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1. 发明申请

US20170233313A1 PROCESS FOR PREPARING 1,3-BUTADIENE FROM N-BUTENES BY OXIDATIVE DEHYDROGENATION 有权
公开(公告)号：US20170233313A1
公开(公告)日：2017-08-17
申请号：US15503189
申请日：2015-08-11
申请人： BASF SE , Linde AG
发明人： Philipp GRÜNE , Oliver HAMMEN , Rainer ECKRICH , Jan Pablo JOSCH , Christian WALSDORFF , Andre BIEGNER , Gergor BLOCH , Heinz BOELT , Hendrik REYNEKE , Christine TOEGEL , Ulrike WENNING
IPC分类号： C07C5/48
CPC分类号： C07C5/48 , C07C7/005 , C07C7/08 , C07C7/09 , C07C7/11 , C07C2523/887 , C07C11/167
摘要： 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 of an organic solvent, wherein the organic solvent is 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 0.015:1 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 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.

2. 发明申请

US20200039901A1 METHOD FOR DECOMMISIONING AND REGENERATING A REACTOR FOR THE OXIDATIVE DEHYDROGENATION OF N-BUTENES 审中-公开
公开(公告)号：US20200039901A1
公开(公告)日：2020-02-06
申请号：US16498693
申请日：2018-03-26
申请人： BASF SE , Linde AG
发明人： Jan UNGELENK , Oliver HAMMEN , Christian WALSDORFF , Rainer ECKRICH , Heinz BOELT , Christine TOEGEL , Ulrike WENNING , Hendrik REYNEKE , Anton WELLENHOFER
IPC分类号： C07C11/167 , C07C7/04 , C07C7/11 , C07C5/333
摘要： The invention relates to a process for preparing butadiene from n-butenes in n reactors R1 to Rn operated in parallel, wherein the process in the production phase of a reactor Rm in the n reactors comprises the steps: A) provision of a feed gas stream a1m comprising n-butenes; B) feeding of the feed gas stream a1m comprising n-butenes, an oxygen-comprising gas stream a2m and a substream d2m of an oxygen-comprising total recycle gas stream d2 into the oxidative dehydrogenation zone of the reactor and oxidative dehydrogenation of n-butenes to butadiene, giving a product gas substream bm comprising butadiene; C) combination of the product gas substream bm with further product gas substreams to form a total product gas stream b and cooling and compression of the total product gas stream b and condensation of at least part of the high-boiling secondary components, giving at least one aqueous condensate stream c1 and a gas stream c2 comprising butadiene; D) feeding of the gas stream c2 into an absorption zone and separation of incondensable and low-boiling gas constituents as gas stream d from the gas stream c2 by absorption of the C4-hydrocarbons in an absorption medium, giving an absorption medium stream d1 loaded with C4-hydrocarbons and a recycle gas stream d2, and recirculation of a substream d2m of the total recycle gas stream d2 into the reactor Rm, and during the regeneration phase of the reactor Rm further reactors are in the production phase and the regeneration phase of the reactor Rm comprises the steps in the order i) to v): i) reduction of the feed gas stream a1m comprising n-butenes and of the oxygen-comprising gas stream a2m and the feeding of an inert gas stream a4m into the reactor Rm; ii) further reduction of the feed gas stream a1m comprising n-butenes down to 0, reduction of the recycle gas substream d2m and increase of the inert gas stream a4m until the oxygen content in the reactor Rm is from 2 to 3% by volume; iii) regeneration of the catalyst by burning off carbon-comprising deposits at an oxygen content of from 2 to 3% by volume; iv) reduction of the inert gas stream a4m and increase of the recycle gas substream d2m until the oxygen content in the reactor Rm is from 4 to 10% by volume; v) reoxidation of the catalyst at an oxygen content of from 4 to 10% by volume.

3. 发明申请

US20160355450A1 PROCESS FOR PREPARING 1,3-BUTADIENE FROM N-BUTENES BY OXIDATIVE DEHYDROGENATION 有权
标题翻译：通过氧化脱氢制备N-丁烯的1,3-丁二烯的方法
公开(公告)号：US20160355450A1
公开(公告)日：2016-12-08
申请号：US15033203
申请日：2014-10-27
申请人： BASF SE
发明人： Philipp GRÜNE , Oliver HAMMEN , Christine SCHMITT , Ragavendra Prasad BALEGEDDE RAMACHANDRAN , Jan Pablo JOSCH , Christian WALSDORFF
IPC分类号： C07C5/48 , B01J23/00 , B01J23/887
CPC分类号： C07C5/48 , B01J23/002 , B01J23/8878 , B01J37/0045 , B01J2523/00 , C07C7/08 , C07C7/11 , C07C2523/04 , C07C2523/18 , C07C2523/26 , C07C2523/28 , C07C2523/745 , C07C2523/75 , C07C2523/887 , C07C11/167 , B01J2523/13 , B01J2523/54 , B01J2523/67 , B01J2523/68 , B01J2523/842 , B01J2523/845
摘要： A process for preparing butadiene from n-butenes, comprising the steps of A) providing an input gas stream a1 comprising n-butenes; B) feeding the input gas stream a1 comprising 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, giving a product gas stream b comprising 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 the product gas stream b and optionally at least partly removing high-boiling secondary components and steam, giving a product gas stream b′, Cb) compressing and cooling the product gas stream b′ in at least one compression and cooling stage, giving at least one aqueous condensate stream c1 and one gas stream c2 comprising butadiene, n-butenes, steam, oxygen and low-boiling hydrocarbons, with or without carbon oxides and with or without inert gases, Da) absorbing the C4 hydrocarbons comprising butadiene and n-butenes in an aromatic hydrocarbon solvent as an absorbent and removing uncondensable and low-boiling gas constituents comprising oxygen, low-boiling hydrocarbons, any carbon oxides, aromatic hydrocarbon solvent and any inert gases as gas stream d2 from the gas stream c2, 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, Db) at least partly recycling the gas stream d2 as cycle gas stream a2 into the oxidative dehydrogenation zone, wherein the content of aromatic hydrocarbon solvent in the cycle gas stream a2 is limited to less than 1% by volume.

4. 发明申请

US20190337870A1 METHOD OF STARTING UP A REACTOR FOR THE OXIDATIVE DEHYDROGENATION OF N-BUTENES 审中-公开
公开(公告)号：US20190337870A1
公开(公告)日：2019-11-07
申请号：US16324315
申请日：2017-08-08
申请人： BASF SE , LINDE AG
发明人： JAN UNGELENK , Oliver HAMMEN , Ulrich HAMMON , Rainer ECKRICH , Signe UNVERRICHT , Christian WALSDORFF , Heinz BOELT , Hendrik REYNEKE , Christine TOEGEL , Anton WELLENHOFER , Ulrike WENNING
IPC分类号： C07C5/48 , C07C7/11 , C07C11/167
摘要： Process for preparing butadiene from n-butenes, which has a start-up phase and an operating phase and the operating phase of the process comprises the steps: A) provision of a feed gas stream a1 comprising n-butenes; B) introduction of the feed gas stream a1 comprising n-butenes, an oxygen-comprising gas stream a2 and an oxygen-comprising recycle gas stream d2 into at least one oxidative dehydrogenation zone and oxidative dehydrogenation of n-butenes to butadiene, giving a product gas stream b comprising butadiene; C) cooling and compression of the product gas stream b, giving at least one aqueous condensate stream c1 and a gas stream c2 comprising butadiene; D) introduction of the gas stream c2 into an absorption zone and separation of incondensable and low-boiling gas constituents as gas stream d from the gas stream c2 by absorption of the C4 hydrocarbons in an absorption medium, giving an absorption medium stream loaded with C4 hydrocarbons and the gas stream d, and recirculation of the gas stream d as recycle gas stream d2 to the oxidative dehydrogenation zone, where the start-up phase comprises the steps, in the order i) to iv): i) introduction of a gas stream d2′ having a composition corresponding to the recycle gas stream d2 in the operating phase into the dehydrogenation zone and setting of the recycle gas stream d2 to at least 70% of the total volume flow in the operating phase; ii) optionally additional introduction of a steam stream a3 into the dehydrogenation zone; iii) additional introduction of the feed gas stream a1 comprising butenes at a lower volume flow than in the operating phase and raising of this volume flow until at least 50% of the volume flow of the feed gas stream a1 in the operating phase has been attained, with the total gas flow through the dehydrogenation zone corresponding to not more than 120% of the total gas flow during the operating phase; iv) additional introduction, when at least 50% of the volume flow of the feed gas stream a1 comprising butenes in the operating phase has been attained, of an oxygen-comprising stream a2 at a lower volume flow than in the operating phase and raising of the volume flows of the feed gas streams a1 and a2 until the volume flows in the operating phase have been attained, with the total gas flow through the dehydrogenation zone corresponding to not more than 120% of the total gas flow during the operating phase.

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