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    • 1. 发明公开
    • VERFAHREN ZUR HERSTELLUNG VON 1,3-BUTADIEN AUS N-BUTENEN DURCH OXIDATIVE DEHYDRIERUNG
    • EP3197851A1
    • 2017-08-02
    • EP15763001.3
    • 2015-09-14
    • BASF SELinde AG
    • JOSCH, Jan PabloGRÜNE, PhilippBENFER, ReginaVICARI, MaximilianBIEGNER, AndreBLOCH, GregorBOELT, HeinzREYNEKE, HendrikTOEGEL, ChristineWENNING, Ulrike
    • C07C5/48C07C7/08C07C7/11C07C7/04C07C11/167
    • C07C5/48B01D3/40C07C5/333C07C7/005C07C7/05C07C7/08C07C7/11C07C11/167
    • The invention relates to a process for preparing butadiene from n-butenes, comprising the steps of: A) providing an input gas stream (a) comprising n-butenes, B) feeding the input gas stream (a) comprising n-butenes and a gas containing at least oxygen into at least one oxidative dehydrogenation zone and oxidatively dehydrogenating n-butenes to butadiene, wherein a product gas stream (b) comprising butadiene, unconverted n-butenes, water vapour, oxygen, low-boiling hydrocarbons and high-boiling secondary components, optionally carbon oxides and optionally inert gases is obtained; Ca) cooling the product gas stream (b) by bringing into contact with a cooling medium in at least one cooling zone, the cooling medium being at least partly recycled and having an aqueous phase and an organic phase ; Cb) compressing the cooled product gas stream (b) which may have been depleted of high-boiling secondary components in at least one compression stage, giving at least one aqueous condensate stream (c1) and one gas stream (c2) comprising butadiene, n-butenes, water vapour, oxygen and low-boiling hydrocarbons, optionally carbon oxides and optionally inert gases; D) removing uncondensable and low-boiling gas constituents comprising oxygen and low-boiling hydrocarbons, with or without carbon oxides and with or without inert gases, as gas stream (d2) from the gas stream (c2) by absorbing the C
      4 hydrocarbons comprising butadiene and n-butenes in an absorbent, giving an absorbent stream laden with C
      4 hydrocarbons and the gas stream (d2), and then desorbing the C
      4 hydrocarbons from the laden absorbent stream, giving a C
      4 product gas stream (d1), E) separating the C
      4 product stream (d1) by extractive distillation with a butadiene-selective solvent into a stream (e1) comprising butadiene and the selective solvent and a stream (e2) comprising n-butenes; F) distilling the stream (e1) comprising butadiene and the selective solvent into a stream (f1) consisting essentially of the selective solvent and a stream (f2) comprising butadiene, charactersied in that step Cb) comprises at least two compression stages Cba) and at least two cooling stages Cbb), which are designed as quench columns, in the cooling stage, the cooling takes place by bringing into direct contact with the two phase cooling medium having an aqueous and an organic phase.
    • 本发明涉及由正丁烯制备丁二烯的方法,其包括以下步骤:A)提供包含正丁烯的输入气流(a),B)将包含正丁烯的输入气流(a)和 将至少含氧的气体送入至少一个氧化脱氢区并将正丁烯氧化脱氢成丁二烯,其中产物气流(b)包含丁二烯,未转化的正丁烯,水蒸气,氧气,低沸点烃和高沸点 获得次要组分,任选的碳氧化物和任选的惰性气体; Ca)通过在至少一个冷却区中与冷却介质接触来冷却产物气流(b),冷却介质至少部分地再循环并且具有水相和有机相; Cb)压缩在至少一个压缩阶段中可能已经耗尽高沸点次要组分的冷却产物气流(b),得到至少一种含水冷凝物流(c1)和一种包含丁二烯的气体流(c2),n 丁烯,水蒸汽,氧气和低沸点烃,任选的碳氧化物和任选的惰性气体; D)通过吸收包含丁二烯的C4烃作为来自气流(c2)的气流(d2),从气体流(c2)中除去含有氧气和低沸点烃的含有或不含有碳氧化物和有或没有惰性气体的不可冷凝和低沸点气体成分 和正丁烯在吸收剂中反应,产生充满C4烃和气体物流(d2)的吸收剂物流,然后从装载的吸收剂物流中解吸出C4烃,得到C4产物气流(d1),E) C4产物流(d1)通过用丁二烯选择性溶剂萃取蒸馏到包含丁二烯和选择性溶剂的物流(e1)和包含正丁烯的物流(e2)中; F)将包含丁二烯和选择性溶剂的物流(e1)蒸馏成基本上由选择性溶剂组成的物流(f1)和包含丁二烯的物流(f2),其特征在于该步骤Cb)包括至少两个压缩阶段Cba)和 在冷却阶段中设计为骤冷塔的至少两个冷却阶段Cbb)通过与具有水相和有机相的两相冷却介质直接接触而进行冷却。
    • 2. 发明公开
    • VERFAHREN ZUR HERSTELLUNG VON 1,3-BUTADIEN AUS N-BUTENEN DURCH OXIDATIVE DEHYDRIERUNG
    • EP3180298A1
    • 2017-06-21
    • EP15748049.2
    • 2015-08-11
    • BASF SELinde AG
    • GRÜNE, PhilippHAMMEN, OliverECKRICH, RainerJOSCH, Jan, PabloWALSDORFF, ChristianBIEGNER, AndreBLOCH, GregorBOELT, HeinzREYNEKE, HendrikTOEGEL, ChristineWENNING, Ulrike
    • C07C5/48C07C7/08C07C7/11C07C7/04C07C11/167B01J15/00
    • C07C5/48C07C7/005C07C7/08C07C7/09C07C7/11C07C2523/887C07C11/167
    • The invention relates to a process for preparing butadiene from n-butenes, comprising the steps of: A) providing an input gas stream a comprising n-butenes, B) feeding the input gas stream a comprising n-butenes and a gas containing at least oxygen into at least one oxidative dehydrogenation zone and oxidatively dehydrogenating n-butenes to butadiene, giving a product gas stream b comprising butadiene, unconverted n-butenes, water vapor, oxygen, low-boiling hydrocarbons and high-boiling secondary components, with or without carbon oxides and with or without inert gases; Ca) cooling the product gas stream b by contacting with a cooling medium in at least one cooling zone, the cooling medium being at least partly recycled and having an aqueous phase and an organic phase composed of an organic solvent, the organic solvent being selected from the group consisting of toluene, o-, m- and p-xylene, mesitylene, mono-, di- and triethylbenzene, mono-, di- and triisopropylbenzene and mixtures thereof, and the mass ratio of the aqueous phase to the organic phase in the cooling medium when it is fed into the cooling zones prior to the contacting with the product gas stream being from 0.15:1 to 10:1; Cb) compressing the cooled product gas stream b which may have been depleted of high-boiling secondary components in at least one compression stage, giving at least one aqueous condensate stream c1 and one gas stream c2 comprising butadiene, n-butenes, water vapor, oxygen and low-boiling hydrocarbons, with or without carbon oxides and with or without inert gases; D) removing uncondensable and low-boiling gas constituents comprising oxygen and low-boiling hydrocarbons, with or without carbon oxides and with or without inert gases, as gas stream d2 from the gas stream c2 by absorbing the C
      4 hydrocarbons comprising butadiene and n-butenes in an absorbent, giving an absorbent stream laden with C
      4 hydrocarbons and the gas stream d2, and then desorbing the C
      4 hydrocarbons from the laden absorbent stream, giving a C
      4 product gas stream d1, E) separating the C
      4 product stream d1 by extractive distillation with a butadiene-selective solvent into a stream e1 comprising butadiene and the selective solvent and a stream e2 comprising n-butenes; F) distilling the stream e1 comprising butadiene and the selective solvent into a stream f1 consisting essentially of the selective solvent and a stream f2 comprising butadiene.
    • 本发明涉及由正丁烯制备丁二烯的方法,其包括以下步骤:A)提供包含正丁烯的输入气流a,B)将包含正丁烯的输入气流a和至少含有 氧进入至少一个氧化脱氢区并将正丁烯氧化脱氢为丁二烯,得到包含丁二烯,未转化的正丁烯,水蒸气,氧,低沸点烃和高沸点次要组分的产物气流b,其中有或没有 碳氧化物和有或没有惰性气体; Ca)通过在至少一个冷却区中与冷却介质接触来冷却产物气流b,冷却介质至少部分地再循环并具有水相和由有机溶剂组成的有机相,有机溶剂选自 由甲苯,邻,间和对二甲苯,均三甲苯,单,二和三乙基苯,一,二和三异丙基苯及其混合物组成的组,以及水相与有机相的 当冷却介质在与产品气流接触之前进入冷却区时,冷却介质为0.15:1至10:1; Cb)将在至少一个压缩阶段中可能已经耗尽高沸点次要组分的冷却产物气流b压缩,得到至少一种含水冷凝物流c1和一种气体料流c2,所述气体料流包含丁二烯,正丁烯,水蒸气, 氧和低沸点烃,有或没有碳氧化物,有或没有惰性气体; D)通过吸收包含丁二烯和正丁烯的C 4烃,从气体物流c 2中除去不可冷凝和低沸点的含有氧和低沸点烃的气体成分,含或不含碳氧化物和含或不含惰性气体作为气流d 2 在吸收剂中产生负载有C4烃和气流d2的吸收剂流,然后从负载吸收剂流解吸C4烃,得到C4产物气流d1,E)通过萃取蒸馏将C4产物流d1与 丁二烯选择性溶剂转化成包含丁二烯和选择性溶剂的物流e1和包含正丁烯的物流e2; F)将包含丁二烯和选择性溶剂的物流e1蒸馏成基本上由选择性溶剂组成的物流f1和包含丁二烯的物流f2。
    • 5. 发明公开
    • PROCESS FOR PREPARING 1,3-BUTADIENE FROM N-BUTENES BY OXIDATIVE DEHYDROGENATION
    • 由氧化脱氢制备N-丁烯制备1,3-丁二烯的方法
    • EP3215478A1
    • 2017-09-13
    • EP15788406.5
    • 2015-11-02
    • BASF SELinde AG
    • GRÜNE, PhilippDEUBLEIN, StephanWALSDORFF, ChristianJOSCH, Jan PabloRAHM, RainerREYNEKE, HendrikWELLENHOFER, AntonWENNING, UlrikeTOEGEL, ChristineBOELT, Heinz
    • C07C5/48C07C7/04C07C7/08C07C7/11C07C11/167
    • C07C5/48C07C7/005C07C7/04C07C7/08C07C7/11C07C11/167C07C2523/31C07C2523/843C07C2523/847
    • The invention relates to a process for preparing butadiene from n-butenes, comprising the steps of: A) providing an input gas stream a comprising n-butenes; B) feeding the input gas stream a comprising n-butenes and a gas containing at least oxygen into at least one oxidative dehydrogenation zone and oxidatively dehydrogenating n-butenes to butadiene, giving a product gas stream b comprising butadiene, unconverted n-butenes, water vapor, oxygen, low-boiling hydrocarbons and high-boiling secondary components, with or without carbon oxides and with or without inert gases; Ca) cooling the product gas stream b by contacting with a circulating cooling medium in at least one cooling zone, the cooling medium being at least partly recycled and having an aqueous phase and an organic phase comprising an organic solvent; Cb) compressing the cooled product gas stream b which may have been depleted of high-boiling secondary components in at least one compression stage, giving at least one aqueous condensate stream c1 and one gas stream c2 comprising butadiene, n-butenes, water vapor, oxygen and low-boiling hydrocarbons, with or without carbon oxides and with or without inert gases;D) removing uncondensable and low-boiling gas constituents comprising oxygen and low-boiling hydrocarbons, with or without carbon oxides and with or without inert gases, as gas stream d2 from the gas stream c2 by absorbing the C4 hydrocarbons comprising butadiene and n-butenes in an absorbent, giving an absorbent stream laden with C4 hydrocarbons and the gas stream d2, and then desorbing the C4 hydrocarbons from the laden absorbent stream, giving a C4 product gas stream d1; E) separating the C4 product stream d1 by extractive distillation with a butadiene- selective solvent into a stream e1 comprising butadiene and the selective solvent and a stream e2 comprising n-butenes; F) distilling the stream e1 comprising butadiene and the selective solvent into a stream f1 consisting essentially of the selective solvent and a stream f2 comprising butadiene; which comprises G) removing a portion of the aqueous phase of the cooling medium which circulates in step Ca) and has an aqueous phase and an organic phase as aqueous purge stream g; H) distillatively separating the aqueous purge stream g into a fraction h1 enriched in organic constituents and a fraction h2 depleted of organic constituents.
    • 本发明涉及由正丁烯制备丁二烯的方法,其包括以下步骤:A)提供包含正丁烯的输入气流a; B)将包含正丁烯的输入气流a和至少含氧的气体送入至少一个氧化脱氢区,并将正丁烯氧化脱氢为丁二烯,得到含丁二烯的产物气流b,未转化的正丁烯,水 蒸气,氧气,低沸点烃和高沸点次要组分,有或没有碳氧化物,有或没有惰性气体; Ca)通过在至少一个冷却区中与循环冷却介质接触来冷却产物气流b,所述冷却介质至少部分再循环并且具有水相和包含有机溶剂的有机相; Cb)将在至少一个压缩阶段中可能已经耗尽高沸点次要组分的冷却产物气流b压缩,得到至少一种含水冷凝物流c1和一种气体料流c2,所述气体料流包含丁二烯,正丁烯,水蒸气, 氧和低沸点烃,有或没有碳氧化物,有或没有惰性气体; D)除去含有氧和低沸点烃的不可冷凝和低沸点气体成分,有或没有碳氧化物,有或没有惰性气体,如 通过在吸收剂中吸收包含丁二烯和正丁烯的C 4烃,从气流c 2中产生气流d 2,产生负载有C 4烃和气流d 2的吸收剂流,然后从负载吸收剂流解吸C 4烃,得到 C4产物气流d1; E)通过用丁二烯选择性溶剂萃取蒸馏将C4产物流d1分离成包含丁二烯和选择性溶剂的物流e1和包含正丁烯的物流e2; F)将包含丁二烯和选择性溶剂的物流e1蒸馏成基本上由选择性溶剂组成的物流f1和包含丁二烯的物流f2; 其包括G)除去在步骤Ca)中循环的冷却介质的一部分水相并且具有水相和有机相作为含水清洗流g; H)蒸馏分离含水清扫流g成为富含有机成分的部分h1和贫化有机成分的部分h2。
    • 7. 发明授权
    • PROCESS FOR PREPARING 1,3-BUTADIENE FROM N-BUTENES BY OXIDATIVE DEHYDROGENATION
    • EP3215478B1
    • 2018-08-29
    • EP15788406.5
    • 2015-11-02
    • BASF SELinde AG
    • GRÜNE, PhilippDEUBLEIN, StephanWALSDORFF, ChristianJOSCH, Jan PabloRAHM, RainerREYNEKE, HendrikWELLENHOFER, AntonWENNING, UlrikeTOEGEL, ChristineBOELT, Heinz
    • C07C5/48C07C7/04C07C7/08C07C7/11C07C11/167
    • C07C5/48C07C7/005C07C7/04C07C7/08C07C7/11C07C11/167C07C2523/31C07C2523/843C07C2523/847
    • The invention relates to a process for preparing butadiene from n-butenes, comprising the steps of: A) providing an input gas stream a comprising n-butenes; B) feeding the input gas stream a comprising n-butenes and a gas containing at least oxygen into at least one oxidative dehydrogenation zone and oxidatively dehydrogenating n-butenes to butadiene, giving a product gas stream b comprising butadiene, unconverted n-butenes, water vapor, oxygen, low-boiling hydrocarbons and high-boiling secondary components, with or without carbon oxides and with or without inert gases; Ca) cooling the product gas stream b by contacting with a circulating cooling medium in at least one cooling zone, the cooling medium being at least partly recycled and having an aqueous phase and an organic phase comprising an organic solvent; Cb) compressing the cooled product gas stream b which may have been depleted of high-boiling secondary components in at least one compression stage, giving at least one aqueous condensate stream c1 and one gas stream c2 comprising butadiene, n-butenes, water vapor, oxygen and low-boiling hydrocarbons, with or without carbon oxides and with or without inert gases;D) removing uncondensable and low-boiling gas constituents comprising oxygen and low-boiling hydrocarbons, with or without carbon oxides and with or without inert gases, as gas stream d2 from the gas stream c2 by absorbing the C4 hydrocarbons comprising butadiene and n-butenes in an absorbent, giving an absorbent stream laden with C4 hydrocarbons and the gas stream d2, and then desorbing the C4 hydrocarbons from the laden absorbent stream, giving a C4 product gas stream d1; E) separating the C4 product stream d1 by extractive distillation with a butadiene- selective solvent into a stream e1 comprising butadiene and the selective solvent and a stream e2 comprising n-butenes; F) distilling the stream e1 comprising butadiene and the selective solvent into a stream f1 consisting essentially of the selective solvent and a stream f2 comprising butadiene; which comprises G) removing a portion of the aqueous phase of the cooling medium which circulates in step Ca) and has an aqueous phase and an organic phase as aqueous purge stream g; H) distillatively separating the aqueous purge stream g into a fraction h1 enriched in organic constituents and a fraction h2 depleted of organic constituents.
    • 8. 发明公开
    • VERFAHREN ZUR HERSTELLUNG VON 1,3-BUTADIEN AUS N-BUTENEN DURCH OXIDATIVE DEHYDRIERUNG
    • EP3274320A1
    • 2018-01-31
    • EP16711007.1
    • 2016-03-23
    • BASF SELinde AG
    • JOSCH, Jan PabloBALEGEDDE RAMACHANDRAN, Ragavendra PrasadWALSDORFF, ChristianBENFER, ReginaWELLENHOFER, AntonWENNING, UlrikeBOELT, HeinzREYNEKE, HendrikTOEGEL, Christine
    • C07C5/48C07C7/00C07C7/09C07C7/11C07C11/167C07C7/08
    • C07C5/48C07C7/005C07C7/08C07C7/09C07C7/11C07C11/167
    • The invention relates to a process for preparing butadiene from n-butenes, comprising the steps of: A) providing a vaporous feedstock gas stream a1 containing n-butenes by evaporating a liquid stream a0 containing n-butenes; B) feeding vaporous feedstock gas stream a1 containing n-butenes and a gas containing at least oxygen into at least one oxidative dehydrogenation zone and oxidatively dehydrogenating n-butenes to butadiene, resulting in a product gas stream b containing butadiene, unconverted n-butenes, steam, oxygen, low-boiling hydrocarbons, and high-boiling secondary components, with or without carbon oxides and with or without inert gases; Ca) cooling product gas stream b by bringing same in contact with a cooling medium, which contains an organic solvent and includes an aqueous phase and an organic phase, in at least one cooling zone, and at least some of the cooling medium is recycled into the cooling zone; Cb) compressing the cooled product gas stream b, which may have been stripped of high-boiling secondary components, in at least one compression stage, resulting in at least one aqueous condensate stream c1 and one gas stream c2 containing butadiene, n-butenes, steam, oxygen and low-boiling hydrocarbons, with or without carbon oxides and with or without inert gases; D) removing uncondensable and low-boiling gas constituents comprising oxygen, low-boiling hydrocarbons, any carbon oxides and any inert gases as a gas stream d2 from gas stream c2 by absorbing the C
      4 hydrocarbons comprising butadiene and n-butenes in an absorbent, resulting in an absorbent stream laden with C
      4 hydrocarbons and gas stream d2, and then desorbing the C
      4 hydrocarbons from the laden absorbent stream, resulting in a C
      4 product gas stream d1. The disclosed method is characterized in that at least some of the recycled cooling medium from step Ca) is brought into thermal contact with liquid stream a0 containing n-butenes in one or more indirect heat exchangers, and at least part of liquid stream a0 containing n-butenes is evaporated with the recycled cooling medium using indirect heat exchange.
    • 9. 发明公开
    • VERFAHREN ZUR HERSTELLUNG VON 1,3-BUTADIEN AUS N-BUTENEN DURCH OXIDATIVE DEHYDRIERUNG
    • EP3274319A1
    • 2018-01-31
    • EP16709473.9
    • 2016-03-14
    • BASF SELinde AG
    • JOSCH, Jan PabloDEUBLEIN, StephanBENFER, ReginaGAITZSCH, FriedemannREYNEKE, HendrikTOEGEL, ChristineWENNING, UlrikeWELLENHOFER, AntonBOELT, Heinz
    • C07C5/48C07C7/09C07C7/11C07C11/167C07C7/00
    • C07C5/48C07C7/005C07C7/08C07C7/09C07C7/11C07C11/167
    • The invention relates to a process for preparing butadiene from n-butenes, comprising the steps of: A) providing a feedstock gas stream a1 containing n-butenes; B) feeding feedstock gas stream a1 containing n-butenes, an oxygenous gas and an oxygenous cycle gas stream a2 into at least one oxidative dehydrogenation zone and oxidatively dehydrogenating n-butenes to butadiene, resulting in a product gas stream b containing butadiene, unconverted n-butenes, steam, oxygen, low-boiling hydrocarbons, and high-boiling secondary components, with or without carbon oxides and with or without inert gases; Ca) cooling product gas stream b and optionally removing at least some high-boiling secondary components and steam, resulting in a product gas stream b'; Cb) compressing and cooling product gas stream b' in at least one compression and cooling stage, resulting in at least one aqueous condensate stream c1 and one gas stream c2 containing butadiene, n-butenes, steam, oxygen and low-boiling hydrocarbons, with or without carbon oxides and with or without inert gases; Da) absorbing the C
      4 hydrocarbons comprising butadiene and n-butenes in an aromatic hydrocarbon solvent as an absorbent stream A1 in an absorption column K1 and removing uncondensable and low-boiling gas constituents comprising steam, oxygen, low-boiling hydrocarbons, any carbon oxides, aromatic hydrocarbon solvent and any inert gases as a gas stream d2 from gas stream c2, resulting in an absorbent stream A1' laden with C
      4 hydrocarbons and a gas stream d2, and then desorbing the C
      4 hydrocarbons from the laden absorbent stream A1', resulting in a C
      4 product gas stream d1; Db) recycling at least part of gas stream d2 as a cycle gas stream a2 into the oxidative dehydrogenation zone. The disclosed method is characterized in that the content of aromatic hydrocarbon solvent in cycle gas stream a2 is limited to less than 1% by volume by bringing gas stream d2 discharged in removal stage Da) into contact with an at least partially circulating liquid absorbent stream A2 for aromatic hydrocarbon solvent A1 in another column K2 and limiting the water content in the liquid absorbent stream A2 to no more than 80% by weight.