• 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:
    A process is disclosed for preparing tertiary olefins having a high degree of purity and in good yields starting from tertiary ethers such as methyltert.butyl ether and in which the improvement comprises using an extremely efficient catalyst system which consists of a crystalline silica having a high specific surface area and which has been modified by an oxide of a metallic cation having an at least partially amphoteric character. Such catalyst may be, if appropriate, accompanied by an alumina-modified silica as an adjuvant co-catalyst.
    公开号:SU1181533A3
    申请号:SU792781753
    申请日:1979-06-22
    公开日:1985-09-23
    发明作者:Манара Джованни；Фатторе Витторио；Тарамассо Марко；Нотари Бруно
    申请人:Снампрогетти С.П.А.(Фирма)；
    IPC主号:
    专利说明:

    11 The invention relates to the production of high purity tert-olefins by the catalytic decomposition of the corresponding methyl tert-alkyl esters. The aim of the invention is to simplify the process technology by reducing the formation of dialkyl esters at high conversion of the feedstock. Example 1. Alkmine modified crystalline silica (TRS-23) was used as a catalyst for the conversion of methyl tert-butyl ether. The catalyst was prepared as follows. 80 g of tetraethyl ortho-silicate (TEOS) are placed in a pyrex glass vessel under nitrogen and heated to 80 ° C with stirring, then 68 ml of 25 wt.% Aqueous solution of tetraethylammonium hydroxide is added with stirring at the same temperature until fex pore while will not become homogeneous and transparent. Then 80 mg of AlXNOj.) Dissolved in 50 ml of absolute ethanol and 2 g of NaOH (granules) dissolved in 10 m of distilled water are added. A compact gel is formed, to which distilled water is added to a total volume of 200 ml, the stirring is increased, heated to boiling in order to achieve complete hydrolysis and removal of ethanol. The gel is slowly and carefully transferred to a laundry powder, which is the starting material for the preparation of crystalline silica. The volume was adjusted to 150 ml with distilled water, the pyrex glass vessel was placed in an autoclave, and held there at 155 ° C for 18 days. After cooling, the resulting solid is centrifuged at 10,000 rpm for 15 minutes, washed with distilled water and centrifuged again. This rinse operation is repeated four times, the product is dried at 120 ° C which, according to X-ray diffraction, is crystalline. The substance is calcined at 550 ° C in a stream of air. In order to remove more alkaline residues, the sample is repeatedly washed by dispersing in boiling distilled water containing dissolved ammonium acetate. Crystalline silica of composition 0.0012 Al, jO ,, SiOj, specific surface area, determined by the BET (Brunaur Emmett Teller) method, is 470. . Chemical analysis of the sample showed that the residual sodium content was 0.03% NaO. The concentration of hydrogen ions is 4.5 10 meq / g. In an electrically heated tubular reactor having a diameter of 8 mm, 4 ml (2.8 g) of the catalyst obtained with a grain size of 30 to 80 mesh are placed. Methyl tert-butyl ether (MTBE), previously passed through a preheating tube, is fed into the reactor using a calibrated pump. At the bottom of the reactor, a control valve calibrated at 6 bar and a sampling system are placed. Before starting the experiment, the catalyst is heated to 550 ° C for 2 hours in a stream of dry nitrogen to remove adsorbed water. Raw materials are fed at a speed of 6.66 ml / h, 10 ml / h and 20 ml / h, corresponding to a bulk velocity of 2.66; 4, 8; 8 hours respectively. The results are presented in Table. 1. Conversion of methyl tert-butyl ether on a TRS23 catalyst, but not washed with boiling water containing ammonium acetate. The sample contains a higher residual content of Na ,, 0 - 0.12 wt.%. The concentration of hydrogen ions is 151 to 10 meq / g. The results are presented in table. 2. Example 2. Chromium modified silica (TRS-28) is used for the conversion of MTBE. The TRS-28 catalyst is prepared as follows. 40 g of TEOS are placed in a pyrex glass vessel under nitrogen, heated to 80 ° C with stirring, 20 g of a 20% w / w aqueous solution of tetrapropylammonium hydroxide are added and mixing is continued at 80 ° C until the mixture will not become transparent (about 1 h). Then 4 g of Cg (Cs), 9HjO in 50 ml of anhydrous ethanol are added, 0.25 g of KOH in 20 ml of water is added to the resulting compact gel and the mixture is brought to a boil with stirring and the Methanol is removed. At the same time, the gel turns into a pale green powder, which is the starting material 3 for preparing crystalline silica. The treatment is carried out as in Example 1, but the hydrothermal treatment is carried out by holding the sample at 155 ° C for 13 days. Dried and calcined at 550 ° C, the product has a crystalline structure and composition that corresponds to the formula 0,027 SiOj. catalyst surface 380. The residual content in the catalyst is 0.02 wt.%, The proton concentration is 5.8. In the reactor, as in Example 1, 3 ml of TRS-28 catalyst with a grain size of 30-80 mesh are placed. After a 2-hour calcination, MTBE is fed to the catalyst with a bulk velocity of 2.2 and 4.4 hours at various temperatures. The results are presented in table 3 (experiments 1-10). Table 3 also shows the results of the conversion of MTBE on the TRS-28 catalyst, but containing a slightly larger amount of impurity — 0.1 wt.% With a proton concentration of N0 meq / g. (Experiments 11-13). Example 3. Raw materials (MTBE) are converted on a beryllium-modified crystalline cream (TKS-27). . The catalyst was prepared according to the procedure described in Example 1, in the form of 40 g of TEOS with 100 ml of 20 May,%, an aqueous solution of tetrapropylammonium hydroxide and 4 g of Be (NO03) 4, 4H2 O dissolved in 80 ml of ethanol. The mixture is held in an autoclave at 155 ° C. for 17 days. The catalyst has a composition of 0.083. The specific surface is 400,. . the residual content of Na20.02 wt.%; the proton concentration 1.5 h. TO eq / g. The MTBE conversion is carried out as described in Example 1, the results are presented in Table. 4. Example 4. For the conversion of MTBE, granulated, commercial silica, having a specific surface area of 147 and containing 0.36 wt. NajO, 0.48 wt.%, 0.42 wt.% Sulfates with a concentration of zrotons 1 10 meq / g. The test was carried out as described in Example 1. The conversion conditions and the results obtained are presented in Table 5 334. Example 5. A KHFI version of MTBE on the catalyst with aluminum-modified soil (TRS-57) is carried out. The catalyst was prepared according to the procedure described in Example 1, by reacting 240 g of TEOS, 240 g of Alj (NOj) dissolved in 150 ml of absolute ethanol, a solution of 81 g of triethanolamine in 150 ml of distilled water, and 21 g of sodium hydroxide. The hydrothermal treatment is carried out at 194 ° C for 7 days. The resulting catalyst has a composition of 0.0012 AljOj-SiO ,,. Surface area 344, residual C content, 05 wt.%, Proton concentration 1.5 10 mEq / g. 10% of colloidal silica as a binder is added to the obtained powder, extruded to obtain chips with a diameter of 3 mm and a height of 4 mm. After calcination at 500 ° C for 4 hours, the chips are placed in a reactor with a diameter of 20 mm in an amount of 40 ml. Using a calibrated pump, MTBE is fed into the reactor, maintaining a pressure of 6 kg / cm. The results are presented in table. 6. Example 6. The methyl tert-amyl ester is decomposed on the TRS-23 catalyst described in Example 1. To do this, methyl tert-amyl sufir (MTAE) is fed to 2.5 cm of catalyst with a bulk velocity of 2.66. 8 different temperatures. The results are presented in table 6. Example 7. Methyl tert-butyl ether is converted on (catalyst — crystalline silica modified with zinc (tRS-66). To prepare the catalyst under nitrogen atmosphere, 40 g of TEOS and a solution of 4 g of Zn (0) ,,, 0 in 40 ml of ethanol. Next, 20 g of tetrapropylammonium hydroxide are added to the mixture with simultaneous stirring and heating to form a complete gel. The gel is crushed, water is added to it, in which 2 g of KBr is dissolved in advance and heated to remove ethanol. up to 150 ml of distilled water and dsrzhi: - iogl autoclave at 197 ° (: ngg / poiio; iir, ii.
    After cooling, the solid is collected on a filter, washed until the alkaline reaction disappears, and dried. Then, to remove residual alkaline impurities, the sample was calcined at 550 ° C in air flow for 16 hours, washed several times, boiled with distilled water containing ammonium acetate, and calcined at SSOC for 6 hours.
    Get the catalyst composition 0,0666 ZnOSiOj.
    The specimen surface is 380. The residual content of KjO 0.02 wt.%.
    The results of the conversion of MTBE are presented in Table. eight.
    Example 8. For the conversion of MTBE, titanium modified crystalline silica (TRS-64) is used as a catalyst. The catalyst was prepared according to the technology described in Yrimer 1 from 10 g of tetraethyl orutitanate, separately hydrolyzed with water and boiled in 100 ml, 0 (30 wt.% Concentration) to form a clear yellow-orange solution, 20 g of tetrapropylammonium hydroxide ( 10% aqueous solution), 2 g of KBG and colloidal silicon dioxide. The mixture is kept in an autoclave for 10 days.
    The crystalline catalyst has a composition of 0.333 TiOjSiOj, specific surface 430. The remaining content of K, 0 0.02 wt.%.
    The results of the conversion of MTBE are presented in Table. eight.
    Example 9. The conversion of methyl tert-butyl ether is carried out on crystalline silica modified with vanadium-catalyzer
    TRS-48. I
    The catalyst was obtained according to the technology described in Example 1 with 8 g of interaction with 200 ml of water containing 20 g of tetrapropylammonium hydroxide until complete dissolution, followed by the addition of 88 g of tetramethyl ortho-silicate and boiling for several hours. After that, 0.25 g of KOH is added and kept in an autoclave at 175 ° C for 6 days.
    The catalyst has a composition of 0.0588 VjO SiOj. The surface area is 410.
    The residual content in the sample is 0.01 wt.%.
    Conversion results. MTBE are presented in table. eight.
    Example 10. The conversion of methyl tert-butyl ether is carried out on crystalline silica modified with iron. The catalyst is obtained by the interaction of 30.8 g of 30% by weight colloidal silica, 1.55 g of FeCNOj) 9H ,, 0 and 6; i g of tetrapropylammonium hydro5 oxide in 72 g of water according to the method described in example 1. The catalyst has the composition 0 , 0071 FejOjSiOj.
    0
    The catalyst surface is 380.
    To convert MTBE, 2.5 cm of catalyst with a particle size of 30-80 mesh are loaded into the reactor. At 230 ° C under a pressure of 6 kg / cm on the catalyst
    5 serves MTBE with bulk velocity
    f
    Conversion MTBE 94.9%, ce6, 7 h
    methanol selectivity of 99.8%, isobutene selectivity of 99.2%.
    Example 11. Conversion of MTBE
    0 is carried out on boron-modified crystalline silica (boralite A). I
    The catalyst is prepared as follows: A 132g 25% by weight aqueous solution of tetramethylammonium hydroxide is placed in a glass pyrex container in an atmosphere free of CO. 18.6 g of boric acid are added with stirring, after dissolution, 187.5 g of TEOS are added. The mixture is heated while being stirred to 60 ° C, a white, milk-like precipitate is formed and the ethanol is separated. After T2 hours, the alcohol is completely removed and 0.18 g of KOH is added to the mixture and the total volume is made up with 300 ml of distilled water. Then the mixture is kept in an autoclave at
    0 for 12 days. The product is rinsed with water, dried and calcined at 750 ° C.
    The product consists of crystals with a size of 0.1-0.5 microns. The composition of the catalyst 0,091 SiO.
    Specific surface 95. The residual content of Na ,, 0 0.01 wt.%. 7 The results of the conversion of MTBE at a pressure of 6 kg / cm at a volumetric feed rate of MTBE 2 are presented in Table. 9. Example 12. Crystalline silica is obtained. Modified with boron (boralite B), for which, under the conditions of Example 10, 140 g of a 25 wt.% Aqueous solution of tetraethylammonium hydroxide, 12 g of boric acid and 100 g of colloidal dioxide cream are mixed. nor (40% - Ludox A). The hydrothermal treatment was carried out for 9 days with an ISOC in 300 ml in a stationary autoclave lined with Teflon. After washing, drying and calcining, a product is obtained, the total formula of 0.146 BjOjSiOj with a specific surface 421. The conversion of MTBE is carried out at a pressure of 6 kg / cm when feeding raw materials with a bulk velocity of 2 and 4 hours. The results are presented in table. 10. Example 13. A boron-modified (boralite C) modified silica was prepared according to the procedure described in Example 10 from 90 g of a 25 wt.% Solution of tetrapropylammonium hydroxide, 37.5 g of boric acid, 125 ml of distilled water and 62, 4 g TEOS. The hydrothermal treatment is carried out at 160 ° C for 11 days. Get the catalyst composition of 0.25 BjOj-SiOj with a specific surface of 375. Residual content of NajO0.02 wt.% Conversion of MTBE is carried out in a heated reactor under a pressure of 6. kg / cm with a space velocity of 2. 38 The results are presented in Table 11, Example 14. Silica modified with boron (boralite D) is obtained according to the procedure of Example 10 from 225 g of a 40 wt.% Solution of tetrabutylammonium hydroxide, 20 g of b.oric acid, 200 g of tetraethyl orthosilicate , 0.2 g KOH and distilled water is added to 1 l in the distillation of ethanol. The hydrothermal treatment is carried out in a titanium autoclave equipped with a stirrer at 165 ° C for 12 days. After drying and calcining at 550 ° C, the product has a specific surface of 415 m / g and corresponds to the formula 0.208 B O, SiO,., The residual alkali content per 0.02 wt.%. The MTBE conversion was carried out in an electrically heated tubular reactor with an internal diameter of 8 mm, filled with 3 ml (1.35 g) of boralite D with a particle size of 30-50 mesh, at a pressure of 6 kg / cm. The results are shown in Table 12. From tab. 1-12, when decomposing methyl tert-alkyl ethers, the selectivity for the target product is high, moreover, methanol is released with high selectivity, which reduces its losses, in addition, side reactions of dialkylamine ethers are suppressed, which reduces or eliminates contamination of the target product. Table 1
    five
    6 6 6 6 6 6
    180 185 180 192 200 215
    99.7
    99.6
    99.7 99.6
    100 99.8
    99.9 99.8
    99.9 99.3
    99.9 99.3
    table 2
    Table 5
    Table 6
    2 2
    4 4
    Table 7
    Tables a8
    Table 9
    Table 10
    99.3
    99.8 99.0 99.1 99.1 99.6 99.6 99.9
    权利要求:
    Claims (2)
    [1]
    1. METHOD FOR PRODUCING LOW TRET-OLEPHINS BY contacting the corresponding methyl tert-alkyl esters with a catalyst at elevated temperature and pressure of 6 kg / cm 2 , characterized in that, in order to simplify the process technology, crystalline silica modified with oxides of elements from the group of beryllium, chromium, boron, zinc, titanium, vanadium, iron, of the general formula (0.0071 - 0.333) MnO. SiO 2 , where Mn Ot is beryllium oxide ', chromium, boron, zinc, titanium, vanadium, iron;
    p, m are the coefficients corresponding to the valency of the metal in the oxide, or crystalline silica, modified q with aluminum of the formula
    0.0012 A1 2 0 3 · SiO 2 having a specific surface area of 95-470 m 2 / and the process is carried out at 100-420 C with a volumetric feed rate of 2-150 h '.
    [2]
    2. The method according to p. 1, characterized in that they use a catalyst with a specific surface area of .344-470 m 2 / year
    ςπ
    ED
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    同族专利:
    公开号 | 公开日
    NL7904912A|1979-12-28|
    SE444169B|1986-03-24|
    AR230827A1|1984-07-31|
    DE2924869A1|1980-01-03|
    PH15933A|1983-04-29|
    NO792060L|1979-12-28|
    BR7904019A|1980-03-11|
    JPS6220966B2|1987-05-11|
    IT1096758B|1985-08-26|
    MX151777A|1985-03-08|
    US4254296A|1981-03-03|
    AT371795B|1983-07-25|
    LU81414A1|1979-09-12|
    PL216494A1|1980-02-25|
    PL119866B1|1982-01-30|
    FR2429195A1|1980-01-18|
    CS223964B2|1983-11-25|
    MW1779A1|1980-11-12|
    TR20305A|1981-01-07|
    IT7824845D0|1978-06-22|
    SE7905451L|1979-12-23|
    YU141979A|1982-10-31|
    GR66508B|1981-03-24|
    CA1117986A|1982-02-09|
    AU4780779A|1980-01-03|
    DK240279A|1979-12-23|
    NO151195C|1985-02-27|
    ZM5479A1|1980-10-21|
    FR2429195B1|1984-06-15|
    DE2924869C2|1983-02-17|
    BE877166A|1979-12-21|
    ZA792880B|1980-10-29|
    YU41439B|1987-06-30|
    ATA438379A|1982-12-15|
    GB2025454A|1980-01-23|
    GB2025454B|1982-08-25|
    IN151368B|1983-04-02|
    ES481858A1|1980-03-01|
    RO78443A|1982-03-24|
    NO151195B|1984-11-19|
    AU526262B2|1982-12-23|
    JPS552695A|1980-01-10|
    CH643222A5|1984-05-30|
    IE791170L|1979-12-22|
    EG14412A|1983-12-31|
    IL57581D0|1979-10-31|
    IE48354B1|1984-12-26|
    HU185777B|1985-03-28|
    PT69800A|1979-07-01|
    IL57581A|1983-06-15|
    DD144404A5|1980-10-15|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    IT24845/78A|IT1096758B|1978-06-22|1978-06-22|PROCESS FOR THE PREPARATION OF TERTIARY OLEFINS|
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