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    • 专利摘要:
    A process for the simultaneous manufacture of pure methyl tertiary butyl ether (MTBE) and a substantially isotubene-free mixture of C4-hydrocarbons, by reacting the isobutene contained in the mixture of C4-hydrocarbons with excess methanol in the liquid phase at elevated temperatures on strongly acid, macroporous, organic ion exchange resins. The process has the following steps: (a) methanol and isobutene are reacted in a molar ratio of 2:1 to 5:1 at temperatures between 30 DEG and 100 DEG C.; (b) the unconverted hydrocarbons are then removed as the top product under a pressure of 2 to 10 bars from a first rectification column; (c) the bottom product from this first column is rectified in a second column under normal pressure or under a slight excess pressure of up to 2 bars at the top of the column, the bottom product of this rectification is recycled to reaction zone (a), if necessary, after separating off a portion of the tertiary butanol formed and the C8-olefins; and (d) the distillate from this second column is rectified in a third rectification column under a pressure of 5 to 30 bars, the distillate thus obtained is recycled into the feed to the second column and pure methyl tertiary butyl ether is withdrawn from the bottom of the third column.
    公开号:SU1367854A3
    申请号:SU792853139
    申请日:1979-12-12
    公开日:1988-01-15
    发明作者:Дросте Вильгельм；Обенаус Фритц
    申请人:Хемише Верке Хюльс Аг (Фирма)；
    IPC主号:
    专利说明:

     CM
    This invention relates to a process for the preparation of methyl tert-butyl ether (MTBE), which finds use as an additive to motor fuel.
    The aim of the invention is to increase the purity of the target product.
    The drawing shows the flow chart of the method.
    Example 1. A reactor containing 220 l of strongly acidic ion exchanger (macroporous sulfonated polystyrene, crosslinked with divinylbenzene) and equipped with a cooling device to remove the heat of reaction, consumes 100.02 kg / h of raffinate I containing 45.00 kg / h isobutene, 26.1 kg / h of butene-1 and 0.02 kg / h of water (via pipeline I), 27.88 kg / h of methanol containing about 0.02 kg / h of water (via pipeline), and 76.45 kg / h of recycled methanol containing 0.09 kg / h olefin Cg and 1.44 kg / h tert butanol (via line 3). In this case, the molar ratio of meta is. nola and isobutene is 4: 1.
    When inside the catalyst bed, the isobutene conversion rate is 99., 71%. Pipeline 4 removed 77.23 kg / h of methanol, 0.13 kg / h of n-butobutene, 55 kg / h of olefin mixture with butane, including 26.1 kg / h of butene-1, 70.29 kg / h MTBE, 0.10 kg / h of Cg olefins and 1.60 kg / h of tert-butanol. |
    The reaction product first falls. To column K 1 (pressure in the upper part is 6 atm), from the upper part of which 55.00 kg / h of n-olefins C mixture with butane, 0.13 kg / h isobutene is withdrawn via pipeline 5 and 2.18 kg / h of methanol. The cubic product of the K1 column, containing 75.05 kg / h of methane ol, 70.29 kg / h of MTBE, 0.10. Kg / h of Cg olefins and 1.60 kg / h of tert-butanol, is supplied via pipelines 6 and 7 to K2 column operating at a pressure of 1.35 at. Together with the head product of the KZ column recirculating through pipelines 8 and 7, only 90.23-kg / h of methanol, 88.11 kg / h of MTBE, are supplied to the column K2. 0.10 kg / h olefins C and 1.60 kg / h tert-butanol.
    At a pressure of 1.35 atm, the azeotrope of MTBE with methanol containing 14.7% of methanol, which COOT-I
    A mixture of 88.11 kg / h of MTBE with 15.18 kg / h of methanol is used.
    From the cube of column K2, pipeline 10 discharges a product containing 75.05 kg / h of methanol, 0.10 kg / h of Cg olefins and 1.60 kg / h of tert-butanol. In order to avoid the enrichment of Cp and tert-butanol olefins in the reaction
    A cycle of 10% of the bottom product of column K2 is supplied via pipeline 11 to column K4, and the remaining 90% is recycled through pipelines 12 and 3 directly to the reactor. Of the K4 column at normal pressure, through conduit 13, O, 13 kg / h of methanol, 0.16 kg / h of tert-butanol, and 0.01 kg / h of Ce olefins are withdrawn as bottom product. B quality
    The distillate gives 7.38 kg / h of methanol, which is removed by pipeline. pipe 14 and connected to the main amount of the bottom product of the column K2, so that through line 3 to the reactor
    recycles 74.92 kg / h of metalone, 0.09 kg / h of Cg olefins, and 1.44 kg / h of tert-butanol.
    The main product of the column K2 is supplied via conduit 9 to the short column,.
    which operates at a pressure of 30 at. V. top. The azeotrope of 15.18 kg / h of methanol and 17.82 kg / h of MTBE is removed from the upper part of the short-circuit column, which is recycled via conduit 8 to column K2. From the cube of the short-circuit column, through pipeline 15, 70.29 kg / h of MTBE with a purity of about 99.9 wt.% Is withdrawn.
    Thus, out of 27.88 kg / h of methanol and 100.02 kg / h of raffinate I
    70.29 kg / h of high-purity MTBE and 55.13 kg / h ra, finate II containing 0.24% isobutene (excluding methanol) are obtained.
    Example 2. A reactor containing 200 l of a strongly acidic ion exchanger (macroporous sulphonated polystyrene crosslinked with divinylbenzene) and equipped with a cooling device to remove the heat of reaction, at an inlet pressure of about 10 atm, 100.02 kg / h fraction C is fed (raffinate I) containing 45 kg / h of isobutene, 26.1 kg / h of butene-1 and 0.02 kg / h of water (via pipeline - Bocu 1), 27.94 kg / h of methanol, containing 0.01 kg / h of water (via line 2), and 37.03 kg / h of a mixture of 36.51 kg / h of methanol, 0.04 kg / h of Cg olefins and 0.48 kg / h of tert-butanol (in terms of
    wire 3). The molar ratio of methanol and isobutene is 2.51: 1. At a maximum temperature around the front of the catalyst bed and in the last third of the catalyst bed, isobutene conversion is 99.76%. The reaction product contains 38.86 kg / h of methanol, 0.11 kg / h of isobutene, 55.00 kg / h of mixture n-olefins C4 and butane (including 26.1 kg / h of butene-1), 70.37 kg / h of MTBE, 0.05 kg / h of Co olefins, and 0.60 kg / h of tert-butano10
    methanol, 0.04 kg / h of Cg olefins and 0.48 kg / h of tert-butanol.
    The head product of column K2 is supplied via pipeline 9 to a short-circuit column operating at a pressure of 8.6 atm in the upper part. Azeotrope 47, 34 kg / h of MTBE and 20.29 kg / h of metalone are removed from the upper part of the short-circuit column, which is recycled through conduit 8 to column K2. 70.37 kg / h of MTBE with a purity of 99.9 wt.% Is withdrawn from the cube of the short-circuit column via pipeline 15.
    Thus, out of 27.94 kg / h of chalk, pipeline 4 is fed to the column-15-tanol and 100.02 kg / h of the raffinate I via K1, operating at a pressure of 6 atm, 70.37 kg / h of high-purity top are obtained. parts. From the top of this MTBE and 55.11 kg / h of raffinate II, the content of the column through line 5 discharges 0.20% isobutene (without taking into account 55.00 kg / h of a mixture of n-olefins C and butamanol).
    20
    tanna, 0.11 kg / h isobutene, 2.18 kg / h methanol. The bottom product of this column is withdrawn through line 6 and fed through line 7 to column K2 operating at a pressure. 1.35 at., It contains 36.68 kg / h of methanol, 70.37 kg / h of MTBE, U, U5 kg / h of Cg olefins and 0.60 kg / h of tert-butanol. Thus, together with the head product of the KZ column supplied via pipeline 8, only 56.97 kg / h of methanol, 117.71 kg / hMTBE, 0.05 kg / h of Cg olefins and 0.60 kg / h are fed to the column K2. tert-butanol. Azeotrope 117.71 kg / h of MTBE and 20.29 kg / h of methanol are removed from the top of column K2. Pipeline 9 azeotrope served in the column KZ. From the cube of column K2, pipeline 10 discharges a product containing 36.68 kg / h of methanol, 0.05 kg / h of Cg olefins and 0.60 kg / h of tert-butanol.
    In order to avoid the enrichment of olefins Cg and tert-butanol in the reaction cycle, 20% of the bottom product of the K2 column is fed via line 11 to the K4 column, and the remaining 80% is recycled directly to the reactor via pipelines 12 and 3. From the cube of the K4 column operating at normal pressure, 0.3 kg / h of product, containing, along with methanol, 0.01 kg / h of Cg olefins and 0.12 kg / h of tert-butanol (pipe 13), is withdrawn. At the same time, 7.17 kg / h of methanol is obtained as a distillate, which is removed via conduit 14 and connected to the main amount of the bottom product of column K2, so that via conduit 3 to the reactor only 36.51 kg / h are recycled
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    Example 3. A reactor containing 200 l of a strongly acidic ion exchanger (macroporous sulfonated polystyrene crosslinked with divinylbenzene) and equipped with a cooling device to remove the heat of reaction is fed 100.02 kg / h of raffinate I containing 45,000 kg / h of isobutene, 26.1 kg / h of butane-1 and 0.02 kg / h of water, pipeline 2 contains 28.04 kg / h of methanol containing 0.02 kg / h of water, and pipeline 3 is 63.71 kg / h recycle- ing methanol containing 0.09 kg / h of Cg olefins and 1.44 kg / h of tert-butanol. The molar ratio of methanol and isobutene is 3.51: 1.
    At a maximum temperature of about 80 ° C, the isobutene conversion in the front part of the catalyst bed and in the last third of the catalyst bed is 99.84%. A product containing 64.62 kg / h of methanol, 0.08 kg / isobutene, 55.00 kg / h of a mixture of C 4 n-olefins with butanol (including 21.6 kg / h butene-1), 70.38 kg / h MTBE, 0.10 kg / h olefins With tert-butanol.
    Pipeline 4
    served in the column K1, operating at a pressure of 6 at the top. Only 55.00 kg / h of a mixture of C. n-olefins with butane, 0.07 kg / h of isobutene and 2.18 kg / h of methanol are withdrawn from the top of this column via pipeline 5. The bottom product of the K1 column contains 62.44 kg / h of methanol, 70j38 kg / h of MTBE, 0.10 kg / h of olefins
    and 1, 60 kg / h
    reaction product
    methanol, 0.04 kg / h of Cg olefins and 0.48 kg / h of tert-butanol.
    The head product of column K2 is supplied via pipeline 9 to a short-circuit column operating at a pressure of 8.6 atm in the upper part. Azeotrope 47, 34 kg / h of MTBE and 20.29 kg / h of metalone are removed from the upper part of the short-circuit column, which is recycled through conduit 8 to column K2. 70.37 kg / h of MTBE with a purity of 99.9 wt.% Is withdrawn from the cube of the short-circuit column via pipeline 15.
    Thus, out of 27.94 kg / h I
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    Example 3. A reactor containing 200 l of a strongly acidic ion exchanger (macroporous sulfonated polystyrene crosslinked with divinylbenzene) and equipped with a cooling device to remove the heat of reaction is fed 100.02 kg / h of raffinate I containing 45,000 kg / h of isobutene, 26.1 kg / h of butane-1 and 0.02 kg / h of water, pipeline 2 contains 28.04 kg / h of methanol containing 0.02 kg / h of water, and pipeline 3 is 63.71 kg / h recycle- ing methanol containing 0.09 kg / h of Cg olefins and 1.44 kg / h of tert-butanol. The molar ratio of methanol and isobutene is 3.51: 1.
    At a maximum temperature of about 80 ° C, the isobutene conversion in the front part of the catalyst bed and in the last third of the catalyst bed is 99.84%. A product containing 64.62 kg / h of methanol, 0.08 kg / h of isobutene, 55.00 kg / h of a mixture of C4 n-olefins with butanol (including 21.6 kg / h of butene-1), 70.38 kg / h of MTBE, 0.10 kg / h of olefins With tert-butanol.
    Pipeline 4
    served in the column K1, operating at a pressure of 6 at the top. Only 55.00 kg / h of a mixture of C. n-olefins with butane, 0.07 kg / h of isobutene and 2.18 kg / h of methanol are withdrawn from the top of this column via pipeline 5. The bottom product of the K1 column contains 62.44 kg / h of methanol, 70j38 kg / h of MTBE, 0.10 kg / h of olefins
    and 1, 60 kg / h
    reaction product
    with and 1.60, kg / h tert-butanol. Through pipelines 6 and 7, it is fed to the column K2, operating at a pressure of 1.35 at the top.
    Thus, together with the head product of the short-circuit column supplied through pipelines 8 and 7, only 77.62 kg / h of methanol, 20 kg / h of MTBE, OjlO kg / h of olefins are fed to the column K2.
    Of
      Ln, J f Wj
    , And 1.60 kg / h tert-butanol ..
    from the top of column K2, the azeotrope of 88.20 kg / h of MTBE and 15.18 kg / h of methanol is removed via pipe-line water 9, and from the bottom of the column of K2 through pipeline 10, the product containing 62.44 kg / h of methanol, 0 , 10 kg / h of Cg olefins and 1.60 kg / h of tert-butanol.
    To avoid the enrichment of olefins Cg and tert-butanol in the reaction cycle, 10% of the bottom product of the column K2. The pipeline 11 is fed to the column K4, and the remaining 90% through pipelines 2 and 3 are recycled directly to the reactor. From the cube of the K4 column operating at normal pressure, the pipeline 13 discharges 0.43 kg / h of the product, which, in addition to methanol, contains 0.01 kg / h of Cg olefins and Ojl6 kg / h of tert-butanol. As distillate, 5.98 kg / h of methanol is obtained, which is removed via conduit 14 and connected to the main amount of the bottom product of column K2, so that only 62.18 kg / h of methanol is recirculated through the Zhno pipeline, 0, 09 kg / h olefins Cg and 1 ,, 44 kg /. tert-butanol. .
     Pipeline 9 of the overhead of column K2 is fed to a short-circuit column operating at a pressure of 30 at. In the upper part. From the upper part of this column, an azeotrope of 17.82 kg / h of MTBE and 15.18 kg / h of methanol is removed, which via pipeline 8 is recycled to column K2. 70.38 kg / h of MTBE with a purity of about 99.9 wt.% Is withdrawn from the cube of the short-circuit column via pipeline 15.
    Thus, out of 28.04 kg / h of methanol and 100.02 kg / h of raffinate I, 70.38 kg / h of high-purity MTBE and 55.07 kg / h of raffinate II containing O, -13% isobutene (excluding methanol).
    Example 4 A reactor containing 900 l of a strongly acidic ion exchanger (macroporous sulphonated polystyrene crosslinked with divinylbenzene) and equipped with a cooling
    t
    15
    -20
    367854. 6
    the method for removing the heat of reaction, serves 100.02 kg / h of raffinate I, containing 45.00 kg / h of isobutene, 26.1. kg / h of butene-1 and 0.02 kg / h of water (via pipeline 1), 27.75 kg / h of methanol containing 0.01 kg / h of water (via pipeline 2), and 27.39 kg / h of recycling methanol containing Q = 0.09 kg / h of Cg olefins and 1.08 kg / h of tert-butanol (via line 3). The molar ratio of methanol and isobutene is 2: 1.
    At 30 ° C inside the catalyst bed, the degree of isobutene conversion is 99.71%. 28.40 kg / h of methanol, 0.13 kg / h of isobutene, 55 kg / h of a mixture of n-olefins are withdrawn from the reactor: C with butane (including 26.1 kg / h of 1-butene), 70.33 kg / h MTBE, O, 10 kg / h
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    olefins Cg and 1.20 kg / h tert-butanol.
    The reaction product is first fed to the column K1 (pressure in the upper part 6 atm), from the upper part of which 55.0 kg / h of the mixture of n-olefins C with butane, 0.13 kg / h of isobutene and 2.18 kg / h of methanol., The bottom product of the column K1 ,. containing 26.22 kg / h. methanol, 7D, 33 kg / h MTBE, 0.10 kg / h Cg olefins and 1.20 kg / h tert-butanol, through pipelines 6 and 7 are fed to column K2, operating at a pressure 1 at. Together with the head product of the short-circuit column recirculating via pipelines 8 and 7, only 52.28 kg / h of methanol, 160, 18 kg / h of MTBE, 0.10 kg / h of Cg olefins and 1.20 kg are fed into the column K2. / h tert-butanol.
    At a pressure of 1 atm, azeotropic MTBE with methanol containing 14% methanol, which corresponds to a mixture of 160.10 kg / h of MTBE and 26.06 kg / h of methanol, is withdrawn from line 2 at the top of column K2.
    From the cube of column K2, pipeline 10 discharges a product containing 26.22 kg / h of methanol, 0.10 kg / h of olefins C and 1.20 kg / h of tert-butanol.
    In order to avoid the enrichment of olefins with Cg and, tert-butanol in the reaction cycle, 10% of the bottom product of column K2 is fed through pipeline 1 1 to column K4, and the remaining 90% through pipelines 12 and 3 are recycled directly to the reactor. From the K4 column operating under normal pressure through pipeline 13 as a bottom product
    0.12 kg / h of t-butanol and 0.01 kg / h of C „olefins are withdrawn. Obtained in
    about
    as a distillate, methanol is withdrawn through conduit 14, it is connected to the main amount of the bottom product of the K2 column and is recycled to the reaction
    The head product of column K2 is supplied via conduit 9 to a short column, which operates at a pressure of 5 at. In the upper part. From the upper part, the azeo.trop of 26.06 kg / h of methanol and 89.77 kg / h of MTBE is withdrawn from the short-circuit to the column, which is recycled via line 8 to column K2. 70.33 kg / h of MTBZ with a purity of more than 99.9% by weight is withdrawn from the cube of the short-circuit column via pipeline 15.
    Thus, out of 27.75 kg / h of methanol and 100.02 kg / h of raffinate I, 70.33 kg / h of high-quality MTBE and 55.13 kg / h of raffinate II containing 0.24% of isobutene (excluding methanol) are obtained .
    Example 5. A reactor containing 150 l of a strongly acidic ion exchanger (macroporous sulfonated polystyrene crosslinked with divinylbenzene) and equipped with a cooling device to remove the heat of reaction is fed 100.02 kg / h of raffinate I containing 45.00 kg / h of isobutene, 26 , 1 kg / h of butene-1 and 0.02 kg / h of water (via pipeline 1), 27.79 kg / h of methanol containing 0.01 kg / h of water (via pipeline 2), and 101.87 kg / recycled methanol containing 0.08 kg / h of Cg olefins and 1.08 kg / tert-butanol (via line 3). The molar ratio of methanol and isobutene is 5: 1. When in the front and in the last third of the catalyst bed, the isobutene conversion rate is 99.89%. 102.87 kg / h of methanol, 0.05 kg / h of isobutene, 55 kg / h of n-olefins C mixture are removed from the reactor butane (including 26.1 kg / h of butene-1), 70.46 kg / h of MTBE, 0.10 kg / h of Cg olefins, and 1.20 kg / h of tert-butanol.
    The reaction product is first fed to column K1 (pressure in the upper part 6 atm), from the upper part of which 55.00 kg / h of n-olefins C with butane, 0.05 kg / h of isobutene and 2.17 kg are withdrawn via pipeline 5 / h methanol. The bottom product of the K1 column, containing 100.70 kg / h of methanol, 70.46 kg / h
    678548
    MTBE, 0.10 kg / h of olefins Cg and 1.20 kg / h of tert-butanol, through pipelines 6 and 7 are fed to the column K2, pa-g. working at a pressure of 2 at. Vmggte
    with the main product KOJICl-IHh KZ.
    Recycling is carried out on the basis of 8 and 7, a total of 119.35 kg / h of methanol, 92.35 kg / h of 10 MTBE, 0.10 kg / h of olefins C and I, 20 kg / h of tert-butanol are fed to column K2.
    At a pressure of 2 atm, azeotropic MTBE with methanol is withdrawn through line 9 from the upper part of column K2, cf — 15 holding 16.8% methanol, which corresponds to a mixture of 92.35 kg / h of MTBE and 18.65 kg / h of methanol.
    From the cube of column K2, pipeline 10 discharges a product containing 20,100.70 kg / h of methanol, 0.10 kg / h of Cg olefins and 1.20 kg / h of tert-butanol.
    To avoid Cg and tert-butanol Olefin Enrichment in the reaction cycle; 10% of the bottom product of the column K2 25 through line 11 is fed to the column K4, and the remaining 90% is recycled through pipelines 12 and 3 directly to the reactor. From a column K4 operating under normal pressure, 0.12 kg / h of tert-butanol and 0.01 kg / h of Gg olefins are withdrawn as pipeline product 13.
    The methanol produced as distillate is withdrawn through conduit 14, it is combined with the main bottom product of column K2 and is recycled to the reaction.
     The head product. Columns K2 is supplied via conduit 9 to a short column, which operates at a pressure of 30 at. In the upper part. The azeotrope of 18.65 kg / h of methanol and 21.89 kg / h of MTBE is removed from the upper part of the short-circuit column, which is recycled via conduit 8 to 45 column K2. From the cube of the short-circuit column, through the pipeline 10, 70.46 kg / h of MTBE with a purity of more than 99.9% by weight is removed.
    Thus, out of 27.79 kg / h of methanol and 100.02 kg / h of raffinate I, 70–46 kg / h of high-quality MTBE and 55.05 kg / h of raffinate II, containing 0.09% isobutene (excluding methanol), are obtained.
    Example 6.B reactor containing 320 g of strongly acidic ion exchanger (macroporous sulfonated polystyrene, crosslinked with divinylbenzene) and equipped with a cooling device for removing the heat of reaction, 30
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    give 100.02 kg / h of rafinat I, containing 45.00 kg / h of isobutene, 26.1 kg / h of butene-1 and 0.02 kg / h of water (via pipeline 1), 27.78 kg / h of methanol containing 0.01 kg / h of water (via line 2), and 76.18 kg / h of recirculating methanol containing 0.09 kg / h of Cg olefins and 1.08 kg / h of tert-butanol (via line 3 ). The molar ratio of methanol and isobutene is 2: 1. At 50 ° C in the front and 30 ° C in the last third of the catalyst bed, the degree of isobutene conversion is 99.87%. Pipeline 4 removed 77.18 kg / h of methanol, 0.06 kg / h of isobutene, 55 kg / h of a mixture of n-olefins C with butane (including 26.1 kg / h of butene-) 70 from the reactor, 44 kg / h of MTBE, 0.10 kg / h of Cg olefins and 1.20 kg / h of tert-butanol.
    The reaction product is first fed to the column K1 (pressure in the upper part 6 atm), from the upper part of which through the pipeline 5
    55.00 kg / h of a mixture of n-olefins C with butane, 0.06 kg / h of isobutene and 2.17 kg / h of methanol. The bottom product of the K1 column, containing 75.01 kg / h of methanol, 70.44 kg / h of MTBE, 0.10 kg / h of Cg olefins and 1.20 kg / h of tert-butanol, is fed through pipelines 6 and 7 to column K2 operating at a pressure of 1 at. Together with the head product of the KZ column recirculating through pipelines 8 and 7, only 90.90 kg / h of methanol, 92.20 kg / h, MTBE, O, 10 kg / h of Cg olefins and 1.20 kg / t-butanol.
    At a pressure of 1.35 atm, the azeotrope of MTBE with methanol containing 14.7% of methanol, which corresponds to a mixture of 92.20 kg / h of MTBE and 15.89 kg / h of methanol, is withdrawn through line 9 from the upper part of column K2.
    From the cube of the column K2, the pipeline 10 removes the product containing
    75.01 kg / h of methanol, 0.10 kg / h of olefin Co, and 1.20 kg / h of tert-butanol.
    D
    In order to avoid the enrichment of olefins C and tert-butanol in the reaction cycle 10% of the bottom product of the column K2 through line 11 is fed to the column K4, and the remaining 90% through pipelines 12 and 3 are recycled directly to the reactor. From the K4 column operating at normal pressure through pipeline 13 as a cubic 136

    ten
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    Of this product, 0.12 kg / h of tert-butanol and 0.01 kg / h of C olefins are withdrawn.
    ABOUT
    The methanol produced as distillate is withdrawn through conduit 14, combined with the main amount of bottom product from the column K2 and recycled to the reaction.
    The head product of the column, K2. Along the pipeline 9, is supplied to a short-circuit column, which operates at a pressure of 20 at. In the upper part. The azeotrope is removed from the upper part of the short-circuit column. 15.89 kg / h of methanol and 21.76 kg / h of 5 MTBE, which is re-circulated to column K2 via line 8. 70.44 kg / h of MTBE with a purity of more than 99.9% by weight is withdrawn from the cube of the short-circuit column via pipeline 15.
    Thus, out of 27.78 kg / h of methanol and 100.02 kg / h of raffinate I, 70.44 kg / h of high-quality MTBE and 55.06 kg / h of raffinate II, containing 0.11% of isobutene (without taking into account methanol ).
    Example.7. 100.02 kg / h of raffin I containing 45.00 kg / h of isobutene are fed to a reactor containing 100 l of strongly acidic ion exchanger (macroporous sulphonated polystyrene crosslinked with divinylbenzene) and equipped with a cooling device to remove the heat of reaction. 26.1 kg / h of butene-i and 0.02 kg / h of water (via pipeline 1), 27.78 kg / h of methanol containing 0.01 kg / h of water (via pipeline 2), and 76.18 kg / h of recirculating methanol containing 0.09 kg / h of Cg olefins and 1.08 kg / h of tert-butanol (via pipeline 3) t In this case, molar respectively. the wearing of methanol and isobutene is 2: 1. At 100 ° C in the front and 50 ° C in the last third of the catalyst bed, the degree of isobutene conversion is 99.80%. Pipeline 4 removed 77.19 kg / h of methanol, 0.09 kg / h of isobutene, 55 kg / h of a mixture of n-olefins C with butane (including 26.1 kg / h of butene-1) from the reactor. , 70.40 kg / h MTBE, 0.10 kg / h olefins Cj and 1.20 kg / h tert-butanol.
    The reaction product is first fed to column K1 (pressure in the upper part 6 atm), from the upper part of which 55.00 kg / h of n-olefin C mixture with butane, 0.09 kg / h of isobutene and 2 are withdrawn from pipeline 5; 18 kg / h
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    methanol. The bottom product of the K1 column, containing 75.01 kg / h of methanol, 70.40 kg / h of MTBE, 0.10 kg / h of olefins. Cd and 1.20 kg / h of tert-butanol, through pipelines 6 and 7 are fed to the column K2, operating at a pressure of 1 -at. Together with the head product of the KZ column recirculating through pipelines 8 and 7, a total of 89.18 kg / h of methanol, 87.03 kg / h of MTBE 0.10 kg / h of Cg olefins and 1.20 kg / h of tert are fed into the column K2. -butanol.
    At a pressure of 1 atm from the upper part of the K2.no column, the pipeline 9 is diverted from an MTBE airborne with methanol containing 1D% methanol, which corresponds to a mixture of 87.03 kg / h of MTBE and 14.17 kg / h of methanol. From the cube of column K2, pipeline 10 withdraws a product containing 75.01 kg / h of methanol, 0.10 kg / h of olefins Cd and 1.20 kg / h of tert-butanol.
    13
    In order to avoid the enrichment of Cn and tert-butanol olefins in the reaction
    about
    cycle 10% of the bottom product of the column K2 through line 11 is fed to the column K4, and the remaining 90% through pipelines 12 and 3 are recycled directly to the reactor. 0.12 kg / h of tert-butanol and 0.01 kg / h of Cg olefins are discharged as the bottom product from the column K4 operating at normal pressure of the column K4.
    The methanol produced as distillate is withdrawn through conduit 14, it is combined with the main bottom product of column K2 and is recycled to the reaction.
    The head product of column K2 is supplied via conduit 9 to a short column, which operates at a pressure of 5 at. In the upper part. From the top
    ,
    36785412
    polystyrene crosslinked with divinylbenzene) and equipped with a cooling device to remove the heat of reaction, 100.02 kg / h of raffinate I, containing 45.00 kg / h of isobutene, 26.1 kg / h of butene-1 and 0.02 kg are served / h of water (via pipeline 1), 26.56 kg / h of methanol containing 0.01 kg / h of water
    10 (via line 2), and 76.18 kg / h of recycled methanol containing 0.09 kg / h of Cg olefins and 1.08 kg / h of tert-butanol (via line 3). At 50 ° C in the front and 30 ° C in
    15 of the last third of the catalyst layer
    the degree of conversion of isobutene is 99.87%. Pipeline 4 removed 77.18 kg / h of methanol, 0.06 kg / h of isobutene, 55 kg / h of the mixture from the reactor
    20 n-olefins C4 with butane (including 26.1 kg / h of butene-1), 70.44 kg / h of MTBE, 0.10 kg / h of Cg olefins, and 1.20 kg / h of tert-butanol.
    The reaction product is first served in
    25 column K1 (pressure in the upper part 2 at), from the upper part of which 55.00 kg / h, line n-olefins C with butane, 0.06 kg / h isobutene and 0.95 kg / h I -
    30 thanol. The bottom product of the column K1, containing 75.01 kg / h of methanol, 70.44 kg / h of MTBE, 0.10 kg / h of olefins
    C. and 1.20 kg / h tert-butanol, according to
    ABOUT
    pipelines 6 and 7 are fed to column K2, operating at a pressure
    1.35 at. Together with the head product of the short-circuit column recirculating through pipelines 8 and 7 to the column K2-. give a total of 90.90 kg / h of methanol, 92.20 kg / h of MTBE, 0.10 kg / h of C-olefins and 1.20 kg / h of tert-butanol. At a pressure of 1.35 atm, the azeotrope of MTBE with 40 methanol is removed from pipeline at the top of column K2 through conduit 9.
    50
    the short-circuit columns azeotrope 14.17 kg / h 45 of 14.7% methanol, which corresponds to methanol and 16.63 kg / h of MTBE, which
    through pipeline 8 recycles in
    column K2. From the cube of the column KZ
    pipeline 16 removes 70.40 kg / h
    MTBE purity more than 99.9 wt.%.
    Thus, out of 27.78 kg / h of methanol and 100.02 kg / h of raffinate I, 70.40 kg / h of high-quality MTBE and 55.09 kg / h of raffinate II, containing 0.16% isobutene (excluding methanol ).
    Example 8. In a reactor containing 500 l of strongly acidic ion exchanger (macroporous sulphonated
    55
    a mixture of 92.20 kg / h of MTBE and 15.89 kg / h of methanol.
    From the cube of the column K2 through the pipeline. 10 discharged a product containing 75.01 kg / h of methanol, 0.10 kg / h of olefins C and 1.20 kg / h of tert-butanol.
    In order to avoid the enrichment of olefins Cg and tert-butanol in the reaction cycle, 10% of the bottom product of column K2 is fed through line 11 to column K4, and the remaining 90% is transferred directly to the reactor via pipelines 12 and 3. From operating at normal pressure column K4
    14.7% methanol, which is
    a mixture of 92.20 kg / h of MTBE and 15.89 kg / h of methanol.
    From the cube of the column K2 through the pipeline. 10 discharged a product containing 75.01 kg / h of methanol, 0.10 kg / h of olefins C and 1.20 kg / h of tert-butanol.
    In order to avoid the enrichment of olefins Cg and tert-butanol in the reaction cycle, 10% of the bottom product of column K2 is fed through line 11 to column K4, and the remaining 90% is transferred directly to the reactor via pipelines 12 and 3. From operating at normal pressure column K4
    13
    Pipeline 13 discharged 0, 1 2 kg / h of tert-butanol and 0.01 kg / h of olefins C as a bottom product.
    The methanol produced as distillate is withdrawn through conduit 14, combined with the main bottom product of column K2, and recycled to the reaction.
    The head product of column K2 is supplied via conduit 9 to a short-circuit column, which operates at a pressure of 20 at. In the upper part. Azeotrope 15.89 kg / h of methanol and 21.76 kg / h of MTBE are removed from the upper part of the short-circuit column, which is recycled through conduit 8 to column K2. 70.44 kg / h of MTBE with a purity of more than 99.9 wt.% Is removed from the cube of the short-circuit column.
    Thus, out of 26.56 kg / h of methanol and 100.02 kg / h of raffinate I, 70.44 kg / h of high-quality MTBE and 55.06 kg / h of raffinate II containing 0.11% of isobutene (excluding methanol) are obtained .
    Example 9. A reactor containing 280 l of a strongly acidic ion exchanger (macroporous sulfonated polystyrene crosslinked with divinylbenzene) and supplied with a cooling device to remove the heat of reaction is fed 100.02 kg / h of raffinate 1 containing 45.00 kg / h of isobutene, 26.1 kg / h of butane-1 and 0.02 kg / h of water (via pipeline 1), 29.00 kg / h of methanol containing 0.01 kg / h of water (via pipeline 2), and 76.18 kg / h recycled methanol containing 0.09 kg / h of Cg olefins and 1.08 kg / h of tert-butanol (via line 3). At 50 ° C in the front and 30 ° C in the last third of the catalyst bed, the degree of isobutene conversion is 99.87%. Pipeline 4 removed 77.18 kg / h of methanol, 0.06 kg / h of isobutene, 55 kg / h of a mixture of n-olefins C with butane (including 26.1 kg / h of butene-1), 70 , 44 kg / h of MTBE, O, 10 kg / h of C. olefins and 1.20 kg / h of tert-butarol.
    The reaction product is first fed to column K1 (pressure in the upper part 10 atm), from the upper part of which 55.00 kg / h of n-olefin C mixture with butane, 0.06 kg / h of isobutene and 3.39 are withdrawn from pipeline 5. kg / h of methanol. The bottom product of the column K1, containing 75.01 kg / h
    67854 4
    methanol, 70.44 kg / h of MTBE, 0.10 kg / h of olefins Cd and 1.20 kg / h of tert-butanol, through pipelines 6 and 7 as gifts. are in the column K2, operating at a pressure of 1.35 at. Together with the head product of the short-circuit column recirculating through pipelines 8 and 7, a total of 90.90 kg / h of methanol, 92.20 kg / h of MTBE, 0.10 kg / h of Cg and 1 orefins are fed to the column K2, 20 kg / h tert-buta - nola.
    At a pressure of 1.35 atm from the top of column K2 through pipeline 9
    15 azeotrope of MTBE with methanol, containing 14.7% of methanol, corresponds to a mixture of 92.20 kg / h of MTBE and 15.89 kg / h of methanol.
    From the cube of the K2 column through the pipeline
    20 DN 10 diverted product containing 75.01 kg / h of methanol, 0.10 kg / h of Cg olefins and 1.20 kg / h of tert-butanol. In order to avoid the enrichment of olefins Cg and tert-butanol in the reaction
    25 cycle 10% of the bottom product of the column K2 through line 11 is fed to the column K4, and the remaining 90% through pipelines 12 and 3 recycle directly to the reactor. From running
    30 at the normal pressure of the K4 column, through pipeline 13, 0.12 kg / h of tert-butanol and 0.01 kg / h of olefins are taken as the bottom product
    GS. Methanol produced as a distillate is discharged through conduit 14, connected to the main amount of the bottom product, product K2, and recycled to the reaction.
    40 The head product of column K2 is fed through conduit 9 to a short column, which operates at a pressure of 20 at. In the upper part. From the top of the column. KZ azeotrope abstracted
    45 15.89 kg / h of methanol and 21.76 kg / h of MTBE, which is recycled via conduit 8 to column K2. From the cube of the short-circuit column through pipeline 15, 70.44 kg / h of MTBE purity is removed
    50 more than 99.9 wt.%.
    Thus, out of 29.00 kg / h of methanol and 100.02 kg / h of raffinate I, 70.44 kg / h of high-quality MTBE and 55.06 kg / h of raffinate II, gg containing 0.11% of isobutene, are obtained (excluding methanol ).
    Example 10 (comparative). To a reactor containing 320 l of strongly acidic ion exchanger (macroporous sul35
    I
    100.02 kg / h of raffinate I containing 45.00 kg / h of isobutene, 26, G kg / h of butene-1 and 0.02 kg / h are supplied with a cooling device for cross-linked polystyrene crosslinked with divinylbenzene). water (by pipeline 1), 30.55 kg / h of methanol containing 0.01 kg / h of water (via pipeline 2), and a recycle stream consisting of 33.69 kg / h of methanol, 26.75 kg / MTEEE, 0.09 kg / h of Cd olefins and 1.08 kg / h of tert-butanol (via line 3).
    At 100 ° C in the front and 30 ° C in the last third of the catalyst bed, the degree of isobutene conversion is 98.98%. Pipeline 4 removed 38.90 kg / h of methanol, 0.46 kg / h of isobutene, 55 kg / h, and mixtures of n-olefins C with butane (including 26.1 kg / h of butene-1) from the reactor 96 , 52 kg / h MTBE, 0.10 kg / h olefins Cg and 1, -20 kg / h tert-butanol.
    The reaction product is first fed to column K1 (pressure in the upper part 6 atm), from the upper part of which 55.0 kg / h of the mixture of n-olefins C with butanol, 0.46 kg / h of isobutene and 2.19 are withdrawn via line 5. kg / h of methanol. The bottom product of the K1 column, containing 36.71 kg / h of methanol, 96.52 kg / h of MTBE, 0.10 kg / h of C8 olefins and 1.20 kg / h of tert-butanol, is fed through pipelines 6 and 7 to 10- Taracku column K2, operating at a pressure of 1.5 at. In addition, on the 30th plate of column K2, the head product of a short circuit column consisting of 17.50 kg / h of methanol and 60.28 kg / h of MTBE is supplied. At the same time, a product containing 33.63 kg / h of methanol, 26.75 kg / h of MTBE, 0.09 kg / h of Cg olefins and 1.08 kg / h of tert-butanol is withdrawn from the cube of the K2 column.
    From the upper part of column K2, a stream containing 20.52 kg / h of methanol, 130.05 kg / h of MTBE, 0.01 kg / olefins Sc and 0.12 kg / h of tert-butanol is withdrawn, and fed to the short-circuit column which operates at a pressure of 5 at the top. Azeotrop 17., 50 kg / h of methanol and 60.28 kg / h of MTBE, which is recycled to the column via pipeline 8, K2 to the 30th plate is removed from the upper part of the short-circuit column. The product containing 69.77 kg / h of MTBE, 3.02 kg / h is withdrawn from the cube of the KZ column.
    67854 b
    methanol, 0.01 kg / h of olefins C and 0.12 kg / h of tert-butanol. Thus, MTBE has a purity of 95.68%. with the proposed method allows
    to obtain the target product with a stable purity of 99.9% and a conversion of 99.71-99.8%, while the known method allows to obtain the target product with a purity of 99.4-99.8% . ,
    Carrying out the proposed method under conditions different from those proposed reduces the purity of the target product and causes the deposition of polymer products.
    Ula Invention Form
    20 A method of producing methyl tert-butyl ether by reacting an excess of methanol with isobutylene as a mixture of hydrocarbons C in the liquid phase at a constant high temperature.
    25 those of the catalyst bed or varying within the SO-SC in the presence of macroporous ionic acid, separation from the resulting reaction mixture of unreacted hydrocarbons by distillation under pressure, distilling the resulting bottom product and separating the target product as a vat residue and azeotropic methanol with methyl-tert-butyl ether, which is recirculated, characterized in that, in order to obtain the target product of stable quality, methanol and isobutylene are used at
    dd molar ratio equal to 2-5: 1, with a constant temperature in the catalyst bed equal to 30-52 ° C, or at a temperature of 50-100 ° C in the first two thirds of the reaction zone and 304g 50 ° C in the last third of the reaction the zones, and the separation of unreacted hydrocarbons is carried out under a pressure of 2-10 atm, distillation of the bottoms product is carried out at a pressure of 1-2 atm, followed by distillation of the distillate at a pressure of 5-30 atm to obtain the azeotrope of methanol as a bottoms residue with methyl tert-butyl ether, which is combined with a bottom product Ktoma distillation of unreacted hydrocarbons and together subjected to distillation.
    35
    50
    55
    Ra (rinata
    HOfl
    CB
    权利要求:
    Claims (1)
    [1]
    Claim
    20 A method for producing methyl tert-butyl ether by reacting an excess of methanol with isobutylene in the form of a mixture of C 4 hydrocarbons in the liquid phase at a temperature constant on the catalyst bed 25 or varying between 30-100 ° C in the presence of a strongly acidic macroporous ion exchanger, separation from the obtained the reaction mixture of unreacted hydrocarbons by distillation at elevated pressure, distillation of the obtained bottoms product and separation of the target product in the form of the bottoms and methanol azeotrope with methyl tert-b Tilova ether, which is recycled, characterized in that, in order to obtain the desired product of stable quality, methanol and isobutylene are used in
    40 molar ratio of 2-5: 1 at a constant temperature in the catalyst bed of 30-52 s C, or at a temperature of 50-100 ° C in the first two thirds of the reaction zone and 3050 ° C in the last third of the reaction zone, and separation of unreacted hydrocarbons is carried out at a pressure of 2-10 atm, distillation of the bottled product is carried out at a pressure of 1-2 at, with g0 followed by distillation of the distillate at a pressure of 5-30 atm to obtain the target product and methanol azeotrope distillate with methyl tert -butyl ether, which is combined with bottoms volume distillation of unreacted hydrocarbons and together subjected to distillation.
    类似技术:
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    同族专利:
    公开号 | 公开日
    IL58936D0|1980-03-31|
    HU182501B|1984-01-30|
    JPS5592326A|1980-07-12|
    AT370713B|1983-04-25|
    FI69052B|1985-08-30|
    FR2444021A1|1980-07-11|
    PL220320A1|1980-08-25|
    ES486823A1|1980-06-16|
    SE7910153L|1980-06-14|
    IL58936A|1983-05-15|
    IT1164090B|1987-04-08|
    YU39574B|1984-12-31|
    GB2040924A|1980-09-03|
    US4282389A|1981-08-04|
    BE880581A|1980-06-12|
    BR7908129A|1980-09-23|
    DE2853769B2|1980-10-09|
    YU297079A|1982-08-31|
    DE2853769A1|1980-06-19|
    FI69052C|1985-12-10|
    PT70318A|1979-11-01|
    NO149659C|1984-06-06|
    NO793925L|1980-06-16|
    JPS6228933B2|1987-06-23|
    NL7908945A|1980-06-17|
    DD147664A5|1981-04-15|
    GB2040924B|1983-02-16|
    FI793844A|1980-06-14|
    CA1128552A|1982-07-27|
    CS236457B2|1985-05-15|
    SE445110B|1986-06-02|
    ATA783179A|1982-09-15|
    AR218791A1|1980-06-30|
    FR2444021B1|1984-03-09|
    DE2853769C3|1989-03-16|
    RO79319A|1982-08-17|
    NO149659B|1984-02-20|
    IT7951047D0|1979-12-11|
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    IT1012686B|1974-05-21|1977-03-10|Snam Progetti|PROCEDURE FOR THE PREPARATION OF TER-ALKYL ETHERS|
    IT1012690B|1974-05-21|1977-03-10|Snam Progetti|PROCEDURE FOR THE PRODUCTION OF TER-ALKYL ETHERS|
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    DE3024147C2|1980-06-27|1983-05-05|Edeleanu Gmbh, 6000 Frankfurt|Process for the separation of the reaction products obtained in the etherification of lower i-olefins with methanol|
    DE3036481A1|1980-09-27|1982-05-19|EC Erdölchemie GmbH, 5000 Köln|METHOD FOR THE SIMULTANEOUS PRODUCTION OF C 4-OLIGOMERS AND ALKYL-TERT.-BUTYL ETHERS|
    DE3116780A1|1981-04-28|1982-11-04|Veba Oel AG, 4660 Gelsenkirchen-Buer|METHOD FOR PRODUCING SEC.-BUTYL ALCOHOL AND SEC.-BUTYL-TERT.-BUTYL ETHER|
    DE3116779A1|1981-04-28|1982-11-04|Veba Oel AG, 4660 Gelsenkirchen-Buer|METHOD FOR PRODUCING ALCOHOLS AND ETHERS|
    US4371718A|1981-07-02|1983-02-01|Phillips Petroleum Company|Using butenes to fractionate methanol from methyl-tertiary-butyl ether|
    DE3148109A1|1981-12-04|1983-06-09|EC Erdölchemie GmbH, 5000 Köln|METHOD FOR THE PRODUCTION OF METHYL-TERT.-BUTYL ETHERAND MOSTLY OF I-BUTEN AND METHANOL-FREE HYDROCARBON REFINATES|
    US4413150A|1981-12-18|1983-11-01|Uop Inc.|Two product process for methyl tertiary butyl ether production|
    US4510022A|1983-08-08|1985-04-09|Lloyd Berg|Separation of isopropyl ether from isopropanol and water by extractive distillation|
    US4558168A|1985-06-19|1985-12-10|Air Products And Chemicals, Inc.|Production of high purity butene-1 from an n-butane feedstock|
    US4571439A|1985-07-22|1986-02-18|Tenneco Oil Company|Method for controlled oligomerization/etherification of propylene|
    US4761504A|1986-12-29|1988-08-02|Uop Inc.|Integrated process for high octane alkylation and etherification|
    US4797133A|1986-12-29|1989-01-10|Uop Inc.|Process for recovery of butene-1 from mixed C4 hydrocarbons|
    US4925989A|1987-06-01|1990-05-15|Texaco Inc.|MTBE preparation from isobutylene/TBA and methanol in presence of an acid resin catalyst|
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    US6660898B1|2000-11-03|2003-12-09|Fortum Oil & Gas Oy|Process for dimerizing light olefins to produce a fuel component|
    EP1388528B1|2002-08-06|2015-04-08|Evonik Degussa GmbH|Process for the oligomerisation of isobutene contained in hydrocarbon streams containing n-butene|
    DE102005062699A1|2005-12-28|2007-09-06|Oxeno Olefinchemie Gmbh|Process for the fine purification of 1-butene-containing streams|
    JP6350259B2|2013-12-27|2018-07-04|東レ株式会社|Process for producing aromatic compound isomers|
    EP3197849A1|2014-09-26|2017-08-02|Total Research & Technology Feluy|Modified crystalline aluminosilicate for dehydration of alcohols|
    CN105859530B|2015-01-23|2018-04-06|上海优华系统集成技术有限公司|A kind of stabilizer and MTBE device catalytic rectifying tower combined cycle equipment|
    WO2017005719A1|2015-07-09|2017-01-12|Total Research & Technology Feluy|Modified crystalline aluminosilicate for dehydration of alcohols|
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    CN113058283A|2021-03-01|2021-07-02|中国石油化工股份有限公司|Methanol recovery system and process of MTBEdevice|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE2853769A|DE2853769C3|1978-12-13|1978-12-13|
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