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    • 专利摘要:
    PURPOSE:To obtain tertary butanol, a useful industrial material, in high selectivity, by the hydration of isobutylene in a n-butene-isobutylene mixture at comparatively low temp. in the presence of a specific catalyst. CONSTITUTION:Tertiary butanol is obtained by selectively hydrating isobutlene in the olefinic mixture containing n-butene and isobutylene at <100 deg.C in the presence of a catalyst. The catalyst is used an aqueous solution containing a heteropoly-acid (e.g. phosphomolybdic acid, phosphotungstic acid etc). having at least one element selected from Mo. W, and V as a condensation coordinating element. The reaction pressur is higher than the one under which said olefinic mixture is liquid. After the reaction, the residual olefin in removed at <=70 deg.C and the tertiary butanol is separated and purified at <=70 deg.C, preferably at 60 deg.C.
    公开号:SU1264835A3
    申请号:SU792776755
    申请日:1979-06-07
    公开日:1986-10-15
    发明作者:Аосима Ацуси；Муробуси Тосиаки；Мицуи Риоити；Тамура Набухиро
    申请人:Асахи Касеи Когио Кабусики Кайся (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to a process for the preparation of tertiary butanol by selectively hydrating isoethylene in a mixture of hydrocarbons, including isobutylene and n-butylene. Tertiary butanol is used as an advanced source reagent for the preparation of a variety of products, such as methacrolein, methacrylonitrile. The aim of the invention is to increase the selectivity of the process by carrying out the hydration of isobutylene in a mixture of hydrocarbons in the presence of an aqueous solution of a heteropoly acid of the formula, O .., where D is molybdenum or tungsten; A - phosphorus, silicon, mol k, bo germanium, cobalt or nickel; a is an integer of 1 or 2; n - integer 2 - 6; c is an integer of 5-18; y is an integer Z3 - 62; k is an integer of O or 1; X is an integer of 4 - 37, with an atomic ratio of D to A equal to 2.5 - 18, and the hydration was carried out at a concentration of heteropoly acid of 10 73 wt.% Calculated on the total amount of water and heteropoly acid at a temperature of 40 - EOS and pressure 6-19 atm Product analysis is performed as follows. Using dimethoxyethane as an inert substance to set the titer, the product was diluted by about 5 times with methanol. neutralized with caustic soda and analyzed by gas chromatography under the following conditions: Hitachi device, model 163 Packing Chromosorb 101, manufactured by Waco Yunuaki company Column length, m 2 Column temperature, with Sample inlet temperature, ° C Media (50) Example 1. 0 g of isobutylene, 10 g of 1-butene, 50 g of heteropolyacid and 100 g of water are loaded into an unequal steel autoclave with a capacity of ZRO ml, after which the mixture is stirred at a temperature and pressure of 8.5 atm for 1 h. The results are shown in table 1. Table 1
    12 (Mo) G (R)
    i2 (W) 1 (P)
    12 (W) KSn
    12 (Mo) J (Si)
    100
    89
    100
    77
    100
    79
    63
    100
    12-Wolframborn, (13-20) HjO 12 (W)
    6 (M) +6 (W)} 1 (P)
    ll (Mo) -H (V) TS
    I2 (W) l (As)
    5 (Mo)
    9 (But)
    6 (W)
    12-Wolframgermaniev
     (28-32)
    18-Molybdenum-2-phosphorus
    HgP, jMo, gOgj (33-37) H Under these conditions no formation of secondary butanol is observed, 1-butene remains unreacted. No isobutylene polymers, such as diisobutylene, have been detected. . Example 2. In a stainless steel autoclave (300 ml load
    Continuation of table 4
    (B)
    100
    61
    100
    86
    100
    81
    too
    43
    100
    100
    100
    l (Ge)
    84
    100
    2 (P)
    100
    81 10 g of isobutylene, 10 g of 1-butene, 50 g of 50 g of 2-molybdenum phosphoric acid with an atomic ratio P: Mo equal to l: l2 jJi PMo; jd (29-30) H, 0, and 100 g of water, after which the mixture is stirred under the conditions indicated in Table 2.
    A table is added to the remaining aqueous solution containing the catalyst, 2.5 g of isobutanol and 10 g of 1-butene are added, after which the mixture is stirred at 60 ° C and 8.5 atm for 1 h, resulting in a tertiary butanol with 77% yield and 100% selectivity. Example 5. A stainless steel autoclave (300 ml) was charged with 20 g of the mixture of hydrocarbons according to example 3, 50 g of 12-molybdenophosphoric acid with an atomic ratio P: Mo equal to 1:12 (H PW 0), and 100 g of water, after this mixture is stirred at 60 ° C and 8.5 atm for 2 hours and the organic liquid phase of the hydrocarbon mixture is evaporated to form 0.4 g of isobutylene. The aqueous phase is subjected to distillation, as in Example 4, with the formation of 15.9 g of an 80% vrdn solution of tertiary butanol with a tertiary butanol yield of 96% and a selectivity of .100%. No formation of secondary butano is observed. 3.5 g of water, 10 g of isobutylene and 10 g of 1-butene are added to the remaining aqueous solution, and the mixture is stirred at and 8.5 atm for 2 hours. As a result, tertiary butanol is obtained with a yield of 96% and a selectivity of 100 % without the formation of secondary butanol, dimer, trimer and isobutylene polymers. Example 6. A reactor is used that includes one reaction zone (120 ml) and two separation zones (one in the upper part of the reaction zone and the other in the lower one), while the reaction zone is divided into 7 compartments, each of which is mixed with the help of a mixing blade. The spent B-B fraction according to Example 3 is fed at a speed of 50 MP / h to the lowest section of the reactor, and a recycle liquid containing water and 12-tungstophosphoric acid with atomic ratio P: W equal to 1: 1 is fed to the upper section of the reactor. mass ratio I 2, which is passed through a distillation column and sent to the reactor at a speed of 442 g / h. In the reactor, the spent B-B fraction, the mixture of recirculating water and an additional amount of water are countercurrently combined at 358 and 10 atm. The mixture of the remaining hydrocarbons is collected from the upper separation zone of the reactor, while the aqueous solution containing the tertiary butanol formed and I 2 - tungsten phosphonic acid, sent from the lower separation zone of the reactor to the distillation column. The resulting tertiary butanol is then collected after distillation from the upper part of the distillation column, and the aqueous solution containing 1 2-tungstophosphoric acid is recycled from the lower part of the distillation column to the uppermost reactor compartment along with additional water that corresponds to the amount reduced during the reaction and lost from the reaction system, the conversion of isobutylene is 95.4%, and the amount of isobutylene polymers formed, such as digisobutylene, is 1000 ppm in ne eschete formed on the weight of tertiary butanol and the selectivity of the conversion of isobutylene to tert-butanol almost amenable to quantification. Example 7. The operations of Example 6 are repeated, except that the recirculating fluid containing 49.7 wt.% Water, 50.5 wt.% 12-molybdenum phosphoric acid with an atomic ratio P: Mo equal to 1: 12, and 0.3 wt.% Of phosphoric acid, the mass ratio of phosphoric acid to heteropolyacid (0.006), served at a speed of 450 g / h in the uppermost compartment of the reactor. The conversion of isobutylene is 96.5%. After 1000 h of hydration reaction, the conversion of isobutylene is 96.3%. Example 8. A stainless steel autoclave / 300 ml) was charged with 11.2 g of isobutylene, 16.8 g of 1-butea,) 136 g of 2-tungsten silicic acid with an atomic ratio of Si: W equal to 1: 12 (,), 136 g of water and 41.0 g of tertiary butanol, after which this mixture is stirred at 60 ° C and 8.5 atm for 2 hours. The transformation of isobutylene is 83.1%. The reaction mixture is then allowed to stand and separated into two phases, after which the mixture of remaining hydrocarbons is evaporated in the upper phase at atmospheric pressure. The result is a 13.5-g of a concentrated aqueous solution of tertiary butanol containing 90 wt.% Tertiary butanol and p ,, 9.0 wt.% Vrda. The lower phase contains 40.8 g of tertiary butanol. The selectivity of the conversion of isobutylene to tertiary butanol is almost non-existent. quantification, Example 9. The operations of example 8 are repeated, except that the tertiary butanol is fed in the amount of 38.6 g. The transformation from butylene is bb, 6%. After the reaction, the reaction mixture is allowed to stand and separated into two phases, after which the mixture of the remaining hydrocarbons in the upper phase is evaporated at atmospheric pressure. 13.1 g of a concentrated aqueous solution of tertiary butanol containing 90.1 wt.% Is obtained. - tertiary butanol and 8.9 wt.% water. The lower phase contains 39.6 g of tertiary butanol. The selectivity of the conversion of isobutylene to tertiary butanol is almost quantitatively determined. Example 10. A stainless steel autoclave (ZOO ml) was charged with 9.0 g of isobutylene, 12.0 g of 1-butene, 97 g of 12-molybdenum phosphoric acid with an atomic ratio P: Mo of 1: 12, 97 g of water and 56 g of tertiary butanol, after which this mixture is stirred at 60 ° C and 8.5 atm for 3 hours. The conversion of isobutylene is 81.4%. The reaction mixture is then allowed to stand and separate into two phases, after which the mixture of the remaining hydrocarbons is evaporated in the upper phase at atmospheric pressure. As a result, 9.4 g of a concentrated aqueous solution of tertiary butanol containing 90.1% by weight of tertiary butanol and 8.8% by weight of water are obtained. The lower n phase contains 55.8 wt.% Tertiary butanol. The selectivity of the conversion of isobutylene to tertiary butanol is almost quantifiable. Example 11. A stainless steel autoclave was added to steel (ZOO ml was charged with 8.0 g of isobutylene, 12.0 g -button, 200 g of 12-tungsten-phosphoric acid with a P: W atomic ratio of 1: 12, 100 g of water and 65.0 g of tertiary butanol, after which the mixture is stirred at 40 ° C and 6.0 atm for 3 hours. The conversion of isobutylene is 83.0%. The reaction mixture thus obtained is left to stand and separated into two phases the mixture of the remaining hydrocarbons is then ground into the upper phase at atmospheric pressure, resulting in 9.1 g of concentrated Aqueous aqueous solution of a tertiary butanol solution containing 90.2 wt.% tertiary butanol and 8.8 wt.% water. The lower phase contains 65.5 g of tertiary butanol. The selectivity of the conversion of isobutylene to tertiary butanol is almost quantifiable. Example 12. Repeat The procedure of Example 7, except that the amount of phosphoric acid in the autoclave is changed to 0.5 wt.%. The mass ratio of phosphoric acid to the heteropolyacid is 0.01. After 240 hours of hydration reaction, the conversion of isobutylene is 96.7%. Example 13. The procedure of Example 7 is repeated, except that 0.5 wt.% P-toluenesulfonic acid is added instead of 0.3 wt.% Of phosphoric acid. The mass ratio of acid to heteropoly acid is 0.01. After 500 hours of hydration reaction, the conversion of isobutylene is 96.7%. Example 14 (concentration of heteropolyacid 73.3%). 10 g of isobutylene, 10 g of 1-butene, PO of 12-tungstophosphoric acid with an atomic ratio P: W equal to 1: 12, and 40 g of water are loaded into a stainless steel autoclave (ZOO mp). The mixture is stirred at 40 ° C and a pressure of 6 atm for 1 hour. As a result, only (Isobutylene reacts with the formation of its hydrated compound, i.e., tertiary butanol. The following results are obtained: Conversion of isobutylene,% Selectivity of isobutylene to tert-butanol, / Formation of secondary Non-Obnabutanol Production of dimer, trimer and polymer, 11264835 Example 15 (heteropoly acid concentration 10%) 10 g of isobutylene, 10 g of 1-butene, 15 g of 12-molybdenum phosphorous sour You have an atomic ratio P: Mo equal to 1:12 and 135 g of water. The mixture is stirred at 90 ° C and a pressure of 15 atm for 3 hours. The following results are obtained: Yu Conversion of isobutylene,% 81 12 selectivity of isobutylene to tetrad butaiol, 99.9 Weight concentration of secondary butanol versus tertiary butanol0, 07 Formation of dimer, trimer and polymers Not detected
    权利要求:
    Claims (3)
    [1]
    I. METHOD FOR PRODUCING Tertiary butanol from a butylene mixture by selective hydration of isobutylene and a mixture of hydrocarbons including isobutylene and n-butene in the presence of an aqueous solution of heteropoly acid at elevated temperature and pressure, characterized in that, in order to increase the selectivity of the process, as a heteropoly acid take an acid of the formula
    H h A a D e V K 0 у · χΗ 2 0, where D is molybdenum or tungsten;
    A - phosphorus, silicon, arsenic, boron, germanium, cobalt or ni-
    cell; a - the whole number 1 or 2; η - the whole number 2 - 6; from - the whole number 5 - 18; At - the whole number 23 - 62; to - the whole number 0 or 1; X - the whole number 4· -37,
    with an atomic ratio of D to A equal to
    [2]
    2.5-18 and hydration is carried out during concentration. Heteropoly acids
    May 10-73, 2 based on the total amount of water and heteropoly acid at a temperature of 40-90 ° C and a pressure of 6 19 atm.
    2. The method of pop. ^ characterized in that the hydration is carried out in the presence of phosphoric acid with a mass ratio to heteropoly acid of 0.006-0.01.
    [3]
    3. The method of pop. ^ characterized in that the hydration is carried out in the presence of n-toluenesulpha-acid with a mass ratio to the heteropoly acid of not more than 0.01.
    SU «„ 1264835
    1264835 2
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    同族专利:
    公开号 | 公开日
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    引用文献:
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    JPS5345082B2|1972-07-08|1978-12-04|
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    JPS5236757B2|1973-08-01|1977-09-17|
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    JPH03122792U|1990-03-27|1991-12-13|
    KR100969616B1|2005-11-01|2010-07-14|아사히 가세이 케미칼즈 가부시키가이샤|Processes for production of isobutene and tertiary butanol|
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    JP2016034915A|2014-08-01|2016-03-17|旭化成ケミカルズ株式会社|Hydration reaction method for unsaturated hydrocarbons|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP53068326A|JPS5839134B2|1978-06-08|1978-06-08|
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