• 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:
    1. METHOD OF OBTAINING ISOBUTE by dehydrating tert-butanol in the form of an aqueous solution on an ion exchange resin — a sulfonated copolymer of styrene and divinylbenzene at 90–140 sec. And an increased pressure. Then, after separation of the reaction products enrichment by distillation with tert-butanol is recycled to dehydration, characterized in that, in order to increase the yield of the target product, the process is carried out in a homogeneous liquid phase on the immobile layer of the ion exchange resin at pressure of 5-25 bar with the use of /) tert-butanol in the form of 60 - 90 wt.% aqueous solution.
    公开号:SU1132787A3
    申请号:SU823527658
    申请日:1982-12-23
    公开日:1984-12-30
    发明作者:Обенаус Фритц；Гревинг Бернд；Бальке Гейнрих；Шольц Бернгард
    申请人:Хемише Верке Хюльс Аг (Фирма)；
    IPC主号:
    专利说明:

    U
    // 1 2, The method according to claim 1, about tl-and h and yu1ts and the fact that the separation of the reaction products is carried out by distillation in a separate column from the reactor with the separation of isobutene as a top product and tert mixture as a cube -butanol and water, which, after being enriched by distillation with tert-butanol, is recycled to dehydration; 3. The method of claim 1, wherein the separation of the reaction product is carried out in a separate column, separating the top of isobutene from TreT -butanol and water, and in the distant part, the enriched tPvT -butanolo is diverted as a side stream , A mixture of tert -butanol and water which is recycled to the dehydration w, and liberation from the column bottom of tert-butanol in
    This invention relates to the preparation of
    isobutene, in particular to a method for producing isobutene by dehydrating TP & T-butyl alcohol. A known method for producing isobutene by dehydrating aqueous solution of tet-butanol at 200-300 ° C: in the presence of a catalyst containing Na X 1 zeolite.
    The disadvantages of this method are high temperature and low selectivity of the process.
    The closest to the present invention is a method for producing isobutene in the form of an aqueous solution with a tert-butanol concentration of 20 to 70 wt.% At 90-180 ° C and a pressure of 1.5-15 atm in the presence of an ion-exchange resin as catalyst, for example, styrene sulfonated copolymer and divinylbenzene. The catalyst is suspended in the boiling reaction mixture during the reaction. The feedstock is fed to the reactor preferably in the form of steam. A mixture of gaseous isobutene, unreacted alcohol and water, which is fed to the separation in a column, is continuously withdrawn from the reactor. Isobutane is withdrawn from the top of the column, and the residue is completely or partially returned to the reactor, while part of the mixture of treT-butanol and water is fed to the distillation column for concentration of TPaT-butyl alcohol f.2l before returning to the reactor.
    A disadvantage of the known method is that the reaction components are a mixture consisting of gas and liquid phases in contact with the solid phase of the catalyst, which inhibits the feed of the raw material to the catalytically active catalyst, resulting in the degree of isobutene formation per volume reactor, i.e. isobutene yield per unit volume / time (TIOV) is unsatisfactory. The aim of the invention is to increase the yield of the target product.
    This goal is achieved by the method of producing isobutene by dehydrating TPe.f -butanol in the form of an aqueous solution with a concentration of 60-90 wt.%. on a stationary layer of an ion-exchange resin — a sulfonated copolymer of styrene and divinylbenzene at a pressure of 90–140 ° C, of 5–25 bar; in a homogeneous liquid phase, followed by separation of the reaction products into gaseous, isobutene and a mixture of TP.T-butyl alcohol and water, which, after being enriched by distillation with trcT-butanol, is recycled to dehydration.
    Separation of the reaction products is carried out by distillation in a separate column from the reactor with separation of isobutene as a top product and as a cube of a mixture of TPET -butanol and water, which, after being enriched by distillation, TPTCT-butanol is recycled to dehydration.
    The separation of the reaction product is carried out in a separate column with separation in the upper part of isobutene from 3 mixtures of tRet-butanol and water, and in the distant part, a mixture of tert-butanol and water enriched with t-butanol and recycled for dehydration is diverted as a side stream , and water freed from TR-butanol from the bottom of the column is withdrawn. The reaction temperature should be 90-140 ° C. At elevated temperatures, for example at 110 ° C, they operate in the adiabatic mode. Preferred is a temperature of 100-130 ° C, so as in this case, VIET and the service life of the catalyst are economically optimal from the economic point of view. . The reaction is carried out under a pressure of 5-25 bar, and the pressure is chosen so that the isobutene formed in the reactor, without forming a gas phase, is completely and homogeneously left dissolved in the reaction mixture. If the reaction pressure is greater than the pressure in the refining column of the reaction mixture, flash evaporation can be used to facilitate the release of isobutene. The content of TPET -butanol in the feed mixture before feeding into the reactor is 40 - 90% by weight, preferably 55 - 85% by weight . Continuously supplied — to the reactor, the initial mixture consists of a freshly supplied TRST -b tanol, preferably in the form of azero ropTT-butanol and water, and a circulating mixture of TPn-butanol and water. The concentration of treh-butanol is -60 to 90% by weight. Achieving a particularly favorable space velocity depends on the water content in the reaction mixture, and also to a large extent on the reaction temperature and the activity of the catalyst used, which should be determined individually for each catalyst. The volumetric rate in liters of raw material per liter of swollen catalyst per hour at 90-100 ° C is 50-100 l / l.h, at 100-130 ° C. 100-300 l / l.h, at 130-140 ° C to LOO l / lh The catalyst used is sulfonated copolymers of styrene and divinshbenzene, which may have a gel-like structure, or, dp increase the surface, spongy macroporous structure, or 7. 4 increase stability to hydrolysis of their catalytically active sulfonic acid groups, hapogenic frame made of artificial resin. The production of pure isobutene and the isolation of water are carried out in a distillation unit separated from the reactor. The pressure in the distillation column is 3–10 bar, preferably 5–7 bar, since within these limits the distillation by condensation of the distillate with the aid of cooling water is particularly economical. The isobutene containing traces of water corresponding to the Trent -butanol azeotrope and water is distilled through the top of the column. The water is then separated in the collection as a separate phase. The main quantity of a mixture of three tons of butanol and water containing less than 0.5% by weight of isobutene as the product of the bottom of the column is fed to the inlet of the reactor. The temperature at the bottom of the column can be set independently of the inlet temperature of the reactor, however, so that, firstly, the distillation process is carried out under the most economical conditions, and secondly, that the temperature limit that must be maintained in order to maintain catalyst stability is not exceeded . The distillation step can also be carried out at lower or higher pressures than 3 to 10 bar, although this is less expedient from an economic point of view. To release water produced in an equivalent amount relative to isobutene and possible water coming from freshly supplied TRST -butanol, a partial stream of the product obtained at the bottom of the column is fed to the concentration, to the distant column, from the top of which a mixture of tert-butanol and water is withdrawn with azeotropic composition, which is returned to the reactor. Excess water is drained from the bottom of this column. Before being concentrated in a separate column, it is possible to distil as a ternary mixture with TPET-butanol and water dihydrogen isobutene .. contained in the initial mixture or formed in a reaction in very small volumes. The concentration and separation columns of the isobutene dimers can be operated at normal or elevated pressures.
    It is advisable to separate the ternary mixture obtained by separating the isobutene dimers with water;; the resulting aqueous phase containing TPET-butanol is fed back to the 5-well separation column. In case the reaction mixture does not contain isobutene dimers, there is no need for the separation stage of isobutene dimers.
    When using an Azeotrope U TRbT-butanol and water (at a normal pressure of about 88 wt.% Tert-butanol) as the feed mixture freshly fed to the reactor, the ratio of the flow from the bottom of the column 15 to the separation of isobutene, circulating without concentration, and the flow returned to the reactor. the concentration is preferably from 2 to 130: 1, in particular from 20 5 to 30: 1.
    A mixture of TET-butanol and water is passed through a fixed bed of catalyst from top to bottom.
    The most economical way of conducting the proposed method is that the resulting homogeneous liquid reaction product is fed to a pressure column, through which pure 30 isobutene is isolated as the azeotrope with water. The water that is carried out is separated in the collection as a separate phase. In the distant part of this column, TRSt -butanol j ot of the flowing water is azeotropically distilled, and the water released from the gene and the tert-butanol is diverted to the bottom of the column. From the intermediate plate, a stream 0 of tert-butanol-rich mixture of TPVT-butanol and water is drained over the side branch pipe over the distant part, which is mixed with a stream of fresh raw material as a circulating stream and then, preferably from the top 45 down, is passed through the reactor. If the reaction mixture contains isobutene oligomers, they can be recovered in the reinforcing part of this column through the side inlet. Jq
    In the described way, it is possible to obtain high purity isobutene from TPET -butanol with a village activity of more than 99.9 mol.%. The conversion rate of the TPn-b-thanol is practically
    100 %. Since the reaction is carried out under mild conditions on a fixed bed
    catalyst, then, when working with conventional organic cation nitmols, it is possible to achieve a technically satisfactory service life. The reaction can be carried out with continuous or intermittent feeding of fresh tert-butanol. Continuous feed is preferred. The purity of the isobutene obtained is% 99.9%. As a rule, they reach values up to 99.99%, the remainder is water. The resulting agreement of the proposed method is high-purity isobutene to obtain polyisobutene, butyl rubber, as well as to conduct an alkylation reaction.
    Example 1. A strongly acidic ion exchanger is used as a catalyst (macroporous, sulphonated, polystyrene resin crosslinked with divinylbenzene with the following characteristic: BET surface 40 m / g dry resin, divinylbenzene content 18% grain size 0.5-1.3 mm, ion capacity hydrogen 3.8 meq dry resin.
    The method is carried out according to the scheme shown in FIG.
    In reactor 1., loaded with 78 l of the described ion-exchange resin, pipeline 2 serves 711 kg / h of fresh raw materials containing 623 kg / h of tert-butanol, 85 kg / h of water and 2.85 kg / h of Cg olefins, - 10455 kg / h of the circulating mixture withdrawn from the bottom of the column 4, containing 6480 kg / h of treT -butanol, 3938 kg / h of water and 36.9 kg / h of olf-oh So, through the pipeline 4 - 565 kg / h of circulating mixture, coming from the head of the column 5, containing 497 kg / h of tert-butanol and 68 kg / h of water. Thus, a total of 11,731 kg / h of the initial mixture containing 64.7 wt.% Of treT-butanol is fed through the pipeline 6 to the reactor. The initial mixture is passed through the catalyst bed from top to bottom. The reaction is carried out in the liquid homogeneous phase at 10
    bar and average temperature120 С. re
    The reaction mixture is fed to column 4 via line 6 to relieve pressure to 6 bar b. Pressure in the head section of the engine 4J.
    In column 4, 7,470 kg / h of pure isobutene is obtained from the top of the pipeline. In this way. VIOV is 6.0 kg / lh. The run contains a corresponding azeotrope amount of water, which is released in the collector as a separate phase and then discharged. Produce: the bottom of column 4 has the following composition: 6980 kg / hTRETT-butanol, 4242 kg / h of water and 39.75 kg / h of Cg olefins. The main amount of this product is returned to the reaction via line 3. Partial flow (806 kg / h) through line 8 after depressurization to a pressure level at the head of column 9 (1.2 bar, is fed to column 9. From the head of column 9 2.85 kg / h of olefins Co, together with 2.2 kg / h of TRST-butanol and 0.65 kg / h of water, are withdrawn as a ternary mixture through conduit 9. The product obtained from the bottom of the column is fed to conduit 10 via conduit 10 5, from the upper part of which (the pressure at the head of 1.02 6apj from the water azeotropic mixture of TPC-T-butanol and water, which the pipeline is recycled. The ratio of the circulating streams of columns 4 and 5 is 18.5: 1. From the bottom of the column, 235 kg / h of water is obtained, which is from d through pipeline 11. The isobutene selectivity is almost 100%. withdrawing from the head of column 9 a mixture of olefins Cg, tert-butanol and water and recycling the resulting aqueous TP-T-butanol, p-phase, the degree of transformation of tert-butanol is also 100% isobutene 99, 99% Example 2. Example 1 is repeated with the difference that the initial mixture ropuskayut through the mash layer was rolled from the bottom up. With this, the VIW is 6.0 kg / lh. Example 3. A strongly acidic ion exchanger (macroporous, sulfonated divinylbenzene crosslinked polystyrene resin with the following characteristics is used as a catalyst: BET 25 surface of dry resin, divinylben ash content 8%, grain size 0.5-1.2 mm capacity of hydrogen ions 4.1 mzhv N / g of dry resin. The method was carried out according to the scheme shown in Fig. 2. The cleavage of TPET -butanol was carried out at 120 ° C and a pressure of 20 b Work in the following sequence.The reactor 12, loaded with 42 l of the described catalyst, by pipeline 13 p 4161 kg / h (80 wt.%) of tert-butanol, 1040 kg / h of water and 3.4 kg / h of olefins are supplied. This stream contains: fresh inflow through pipeline 14, containing 657 kg / h of tert - butanol, 92 kg / h of water and 2.8 kg / h of Cg olefins, and a circulating stream supplied from a pressure column 15 through line 16 to the reaction and consisting of 3486 kg / h TPtT-butanol, 948 kg / h of water and 0.6 olefins C The circulating stream supplied through conduit 16 to the reaction contains 78.6% by weight of tert-butanol. The resulting product from the reactor is fed via conduit 17 to the column 15 pse le to depressurize up to 7 bar (pressure at the head of the column). From the top of column 15, 510 kg / h of 4Hcto isobutene is distilled off via conduit 18. Thus, VIOV is 1.2.1 kg / l. The resulting product contains the amount of water corresponding to the azeotrope, which is separated in the collector as a separate phase. At the bottom of the column 15, 256 kg / h of water are obtained, which is discharged by pipeline 19. Of the reinforcing part of the column 15, 2.9 kg / h of olefins Cg, together with 2.5 kg / h of tert-butanol and 0, 7 kg / h of water. The mixture of olefins Cg, tert-butanol and water is separated by water obtained from the head product in the collector and part of the water withdrawn from the bottom of the column, and the resulting aqueous phase containing tert-butanol is returned to the reaction. From the distant part of the column 15, a circulating stream 16 is withdrawn along a side conduit 16, which is recycled to the reaction. The selectivity of isobutene is 99.98%, the conversion of tert-butanol is almost 100%, and the purity of isobutane is 99.99%. Examples 4-9. Dehydration of tetR-butanol is carried out analogously to Example I. The macroporous strongly acidic ion exchanger used as a catalyst (sulphonated, crosslinked with divinylbenzene, polystyrene resin;) has the following characteristics: dry BET 35 surface, 10% divinylbenzene content , the size of the grains is 0.5-1.2 mm, the capacity of hydrogen ions is 4.5 meq of dry resin. 100 MP of this resin, loaded with gret-butanol and water (12 wt.% Of water) swollen in the azeotrope, are loaded into the lower quarter of a tubular reactor (inner diameter 2.29 cm) with a heating jacket. The remaining volume is occupied by a nozzle made of V4A steel, serving as as a preheating zone. A movable thermoelement is installed in the central part of the reactor. Inspection glasses are installed in the front and rear walls of the reactor for monitoring the homogeneity of the liquid mixture. By automatically adjusting the level, the volume of the bottom columns 4, 9 and 5 is kept constant A fresh, free from tertiary isobutene oligomers mixture of tert-γ-butanol and water of azeotropic composition is fed through line 2. The conditions of work and the results achieved are presented in Table 1. The analysis of the composition of the streams is carried out by gas chromatography. with the exception of example 6) the column 9 does not participate in the process. The purity of the isobutene obtained is 99.99%. Example 10. A cation exchanger according to example 1 is used as a catalyst. In an 80-centimeter tubular steel reactor, the internal diameter of which is 2.29 cm, with shirt boiling in a thermostat having two heated to a different level, the heating zone is charged with 20 ml of swollen azeotrope tert -butanol and water exchanger. The catalyst is located in the lower third of the reactor. The residual volume of the reactor is occupied by a nozzle made of V4A steel, serving as a preheating zone. A movable thermoelement is installed in the central part of the reactor. Installed in the front and. In the rear walls of the reactor, viewing glasses allow control over the homogeneity of the liquid mixture. In a series of experiments, the splitting of TTPT-butanol was carried out almost under the isometric mode (the maximum temperature difference in the fixed catalyst bed of 2 C j according to Example 3, however, the pressure at 710 is 11 bar, and the temperature and treT-butanol concentration change. FreshTet- Butanol is fed through the pipeline 14 as pure GRET -butanol (99%) free of isobutene oligomers. The concentration of TPEG - butanol in the sidestream discharged from the distant part of the column (pipeline 6), with a content in stream 13 equal to 60 wt. % TRST-butanol is 58% by weight, with 70% by weight of tRet -butanol — 68% by weight, with 80% by weight of rptr-butanol — 78% by weight, with, 90% by weight of TEG-butanol — 85% by weight The analysis of the composition of the streams is carried out by gas chromatography. The working conditions and the results achieved are presented in Table 2. The purity of isobutene is 99.99%. G Example 11. Macroporous ion exchanger with a characteristic according to example 1 is deactivated with 1 mmol / g of dry resin of ions sodium. Decontamination. is carried out in such a way that the residual capacity of hydrogen ions is 2.8 meq of dry resin. Into the reactor according to example 10, 30 ml of resin swelled in the azeotrope treg-butanol and vodak dehydration of TRST -butanol are loaded according to example 10. The conditions of operation and the results achieved are presented in Table 3. The isobutene selectivity is in all cases 100 mol.%, Purity is 99.99%. Example 1. (comparative j. The process is carried out similarly to examples 4-9. At an average temperature of 130 ° C, a pressure of 15 bar and a space velocity of 120 l / l "in the reactor, 0.16 kg / h of fresh azeotrope is passed from top to bottom through a pipeline 2, together with their circulated streams, supplied through pipelines 3 and 4. The ratio of the flows through the pipework 2, 3, 4 is 1: 6.45: 0.12. The mixture of TPH-butaiol and water at the outlet of the reactor contains 25 wt.% th.t-butanol and 75% w / w of water. A biphasic liquid product is obtained. The VIW is 1.1 kg / lh, the selectivity is 97, 8 m ol.%. Comparison of the results of examples 4-9 and comparative example 1 indicates that the yield of isobutene is low when the process is carried out at 11.11. If the process is carried out in the gas-liquid phase according to the prototype, then TIOV is also low , which is supported by comparative examples 2-4. Examples 2-4 (comparison. The experiment is carried out analogously to example 3 with the difference that the 80-meter glass reactor (inner diameter 4.5 CMJ with a mobile thermoelement in the central , its parts and with heating the jacket contains a layer of 100 ml of tertiary butanol swollen in an azeotrope and water of the cation exchanger described in Example 1. The pressure is chosen so that at the reaction temperature the reaction mixture boils. A fresh mixture of tert-butanol and azeotropic water composition, free from isobutene oligomers.
    19.31
    115,51,1
    16.50.9
    I8,21,3
    112,60,6
    I16,00,6
    The table is admixed to a circulating mixture of TRST-butanol and water and passed from top to bottom through the reactor. The turbulence caused by the boiling of the reaction mixture, as well as by the evaporation of the isobutene formed, results in the catalyst being in a dispersion state. Through a plate tray column connected to the head of the reactor (-0 plates, the gas isobutene formed is continuously removed. To separate the catalyst, the liquid reaction phase in the upper part of the reactor is withdrawn from the 1.2 L reaction chamber through the filter plug and proceeds in a similar manner Example 3. The conditions of operation and the results achieved are presented in Table 4. Thus, the proposed method allows to increase the yield of isobutene.
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    权利要求:
    Claims (3)
    [1]
    1. METHOD FOR PRODUCING ISOBUTENE by dehydration of tert-butanol in the form of an aqueous solution on an ion-exchange resin - a sulfonated copolymer of styrene and divinylbenzene at 90 - 140 ° С and increased pressure, followed by separation of the reaction products into isobutene gas and a mixture of tert-butanol and water, which after enrichment by distillation with tert-butanol is recycled to dehydration, characterized in that, in order to increase the yield of the target product, the process is carried out in a homogeneous liquid phase on a non-stable **, ion-exchange resin bed under pressure and 5-25 bar using tert-butanol in the form of a 60 to 90 wt.% aqueous solution.
    g s
    Fig. / I132787
    [2]
    2, The method of π. 1, according to the fact that the separation of the reaction products is carried out by distillation in a column separate from the reactor with separation in the form of the Top product of isobutene and in the form of a cube - a mixture of tert-butanol and water, which, after enrichment by distillation, tert-butanol recycle for dehydration.
    [3]
    3. The method according to π. 1, characterized in that the separation of the reaction product is carried out in a separate column with separation in the upper part of isobutene from a mixture of ТРе) -butanol and water, and in the distillation part enriched with jpeT-butanol, a mixture of ТРеТ-butanol and water, which recycle to dehydration, and from the bottom of the column (Exempted from tert-butanol in water
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    同族专利:
    公开号 | 公开日
    CA1185271A|1985-04-09|
    MY8600321A|1986-12-31|
    JPH0235728B2|1990-08-13|
    PL136974B1|1986-04-30|
    YU282282A|1984-12-31|
    NO824324L|1983-06-27|
    JPS58116427A|1983-07-11|
    PT75507A|1982-10-01|
    BR8207482A|1983-10-18|
    ES518476A0|1983-10-01|
    AR228333A1|1983-02-15|
    FI824381L|1983-06-25|
    SG81585G|1987-09-18|
    RO86213B|1985-04-02|
    PT75507B|1986-09-11|
    GR77080B|1984-09-06|
    NZ202877A|1985-03-20|
    ES8308817A1|1983-10-01|
    FI71926B|1986-11-28|
    HU198164B|1989-08-28|
    KR840002763A|1984-07-16|
    DE3151446A1|1983-07-14|
    NO154306B|1986-05-20|
    YU43108B|1989-02-28|
    AT9682T|1984-10-15|
    MX161992A|1991-03-18|
    FI824381A0|1982-12-20|
    ZA829399B|1984-08-29|
    IL67551A|1986-01-31|
    EP0082937B1|1984-10-03|
    DE3260905D1|1984-11-08|
    AU9188682A|1983-06-30|
    US4423271A|1983-12-27|
    PL239720A1|1983-07-18|
    IL67551D0|1983-05-15|
    CS232745B2|1985-02-14|
    AU567086B2|1987-11-12|
    KR880002271B1|1988-10-21|
    TR21393A|1984-05-10|
    EG16018A|1987-05-30|
    FI71926C|1987-03-09|
    NO154306C|1986-08-27|
    RO86213A|1985-03-15|
    EP0082937A1|1983-07-06|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE19813151446|DE3151446A1|1981-12-24|1981-12-24|METHOD FOR PRODUCING HIGH PURITY ISOBUTEN BY DEHYDRATING TERTIA BUTANOL|
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