WO2018178005A1 - Verfahren zum abfahren und regenerieren eines reaktors zur oxidativen dehydrierung von n-butenen - Google Patents
Verfahren zum abfahren und regenerieren eines reaktors zur oxidativen dehydrierung von n-butenen Download PDFInfo
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- WO2018178005A1 WO2018178005A1 PCT/EP2018/057632 EP2018057632W WO2018178005A1 WO 2018178005 A1 WO2018178005 A1 WO 2018178005A1 EP 2018057632 W EP2018057632 W EP 2018057632W WO 2018178005 A1 WO2018178005 A1 WO 2018178005A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
- C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/12—Alkadienes
- C07C11/16—Alkadienes with four carbon atoms
- C07C11/167—1, 3-Butadiene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/09—Purification; Separation; Use of additives by fractional condensation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/11—Purification; Separation; Use of additives by absorption, i.e. purification or separation of gaseous hydrocarbons with the aid of liquids
Definitions
- the invention relates to a process for the shutdown and regeneration of a reactor for the preparation of 1,3-butadiene from n-butenes by oxidative dehydrogenation (ODH).
- ODH oxidative dehydrogenation
- Butadiene is an important basic chemical and is used, for example, for the production of synthetic rubbers (butadiene homopolymers, styrene-butadiene rubber or nitrile rubbers).
- thermoplastic terpolymers acrylonitrile-butadiene-styrene copolymers
- Butadiene is further converted to sulfolane, chloroprene and 1, 4-hexamethylenediamine (over 1, 4-dichlorobutene and adiponitrile).
- sulfolane sulfolane
- chloroprene 1, 4-hexamethylenediamine
- 4-dichlorobutene and adiponitrile By dimerization of butadiene, vinylcyclohexene can also be produced, which can be dehydrogenated to styrene.
- Butadiene can be prepared by thermal cracking (steam cracking) of saturated hydrocarbons, usually starting from naphtha as the raw material. Steam cracking of naphtha produces a hydrocarbon mixture of methane, ethane, ethene, acetylene, propane, propene, propyne, allenes, butanes, butenes, butadiene, butynes, methylalls, Cs and higher hydrocarbons.
- Butadiene can also be obtained by oxidative dehydrogenation of n-butenes (1-butene and / or 2-butene).
- ODH oxidative dehydrogenation
- any mixture containing n-butenes can be used.
- a fraction containing n-butenes (1-butene and / or 2-butene) as a main component and obtained from the C 4 fraction of a naphtha cracker by separating butadiene and isobutene can be used.
- gas mixtures which comprise 1-butene, cis-2-butene, trans-2-butene or mixtures thereof and which have been obtained by dimerization of ethylene can also be used as input gas.
- n-butenes containing gas mixtures obtained by catalytic fluid cracking (FCC) can be used as the input gas.
- the reaction of the gas streams containing butenes is generally carried out industrially in tube bundle reactors which are operated in a salt bath as heat carrier.
- the product gas stream is cooled behind the reactor by direct contact with a coolant in a quenching stage and then compressed. Then, the C 4 components are absorbed in an absorption column in an organic solvent. Inert gases, low boilers, CO, CO2 and others leave the column overhead.
- This overhead stream is partly supplied as a circulating gas to the ODH reactor. Hydrocarbons and oxygen can create an explosive atmosphere.
- the concentration of combustible gas constituents (mainly hydrocarbons and CO) may be reduced to avoid ignitable mixtures. below the lower explosion limit (LEL) or above the upper explosion limit (LEL).
- the oxygen concentration can be freely selected without the formation of an explosive gas mixture.
- the concentration of input gas is low, which is economically unfavorable. Therefore, reaction with a reaction gas mixture above the upper explosion limit is preferred. Here it depends on the oxygen concentration, whether it can come to an explosion.
- the LOC limiting oxygen concen- tration
- the concentration of flammable gas constituents can be freely selected without the formation of an explosive gas mixture. Both LEL, OEG and LOC are temperature and pressure dependent.
- coke precursors may be formed, for example styrene, anthraquinone and fluorenone, which may eventually lead to coking and deactivation of the multimetal oxide catalyst.
- the formation of carbonaceous deposits can increase the pressure drop over the catalyst bed. It is possible, for regeneration, to burn off the carbon deposited on the multimetal oxide catalyst at regular intervals with an oxygen-containing gas to restore the activity of the catalyst.
- DE 734026 describes the regeneration of alumina-based dehydrogenation catalysts containing 5% chromium oxide, which are used in particular in a process for the dehydrogenation of butane. The regeneration is carried out at certain intervals under the influence of an oxygen-containing gas. In this case, to keep the regeneration time short, preferably only a portion of the deposited coke burned.
- JP 60-058928 describes the regeneration of a multimetal oxide catalyst containing at least molybdenum, bismuth, iron, cobalt and antimony, for the oxidative dehydrogenation of n-butenes to 1, 3-butadiene with an oxygen-containing Regeneriergasgemisch at a temperature of 300 to 700 ° C, preferably 350 to 650 ° C, and an oxygen concentration of 0.1 to 5%.
- oxygen-containing gas mixture air is supplied, which is diluted with suitable inert gases such as nitrogen, water vapor or carbon dioxide.
- WO 2005/047226 describes the regeneration of a multimetal oxide catalyst for the partial oxidation of acrolein to acrylic acid, containing at least molybdenum and vanadium, by passing an oxygen-containing gas mixture at a temperature of from 200 to 450.degree.
- the oxygen-containing regeneration gas mixture used is preferably lean air with 3 to 10% by volume of oxygen.
- the gas mixture may contain water vapor.
- a low cost oxygen-containing regeneration gas mixture is air. That's how it describes
- the oxygen content of the air is comparatively high at about 20.95% by volume.
- combustion of the coke precursors and carbonaceous deposits uses a regeneration gas with a relatively high oxygen content, which is significantly higher than the oxygen content during the operating phase, rapid combustion can occur in which the carbonaceous deposits are rapidly converted to carbon oxides.
- the associated rapid volume increase due to gas evolution can irreversibly damage the catalyst by flaking off the active mass.
- An oxygen-containing regeneration gas mixture having lower oxygen content than that of the air, or lower in oxygen content than in the operating phase can be adjusted by diluting air with inert gases, e.g. as described in US 2007/0142689 by dilution with nitrogen or water vapor.
- inert gases e.g. as described in US 2007/0142689
- a high water vapor content in the regeneration gas mixture can damage the catalyst, e.g. in the case of Mo-containing catalysts by formation and discharge of volatile molybdenum compounds.
- Inert gases such as nitrogen, argon, neon, helium, carbon dioxide or even mixtures of these, are expensive. Furthermore, large and expensive containers are necessary to keep a sufficient amount of inert gas in stock.
- a likewise favorable gas mixture which is depleted of oxygen compared with air is the circulating gas, which is obtained from the product gas mixture of the oxydehydrogenation by separation of the non-condensable or low-boiling gas constituents and is recycled to the oxide hydrogenation zone.
- the recycle gas contains between 7-9 vol% oxygen, which still greatly increases the risk of high local temperature spikes.
- Such a cycle gas is obtained in the ODH process described in WO2015 / 007839, in which n-butenes are reacted with an oxygen-containing gas, preferably air, to form butadiene.
- WO2015 / 007839 deals with the problem of the still relatively high oxygen contents of the recycle gas obtained in the described process for the regeneration operation and proposes the following solution: operating and regeneration phases alternate.
- the supply of air to the reactor is throttled or turned off, but the Oxidehydrier congress continued until the oxygen concentration in the recycle gas has dropped to 5 vol .-%.
- the supply of the gas stream containing n-butenes and the supply of the oxygen-containing gas are stopped.
- the subsequent regeneration step is carried out with the resulting cycle gas having an oxygen content of 5% by volume.
- An essential element of the method described in WO2015 / 007839 is therefore that the oxygen content of the circulating gas in the regeneration phase is significantly below the oxygen content of the circulating gas in the operating phase.
- WO2015 / 007841 describes an ODH process in which two parallel and independently operated tube bundle reactors are located in a common heat transfer medium.
- Each production line comprises a tube bundle reactor, a quench section and a compressor section, after which the two compressed product gas streams are combined in a common absorption column.
- an oxygen-containing recycle gas is obtained by separation of the non-condensable or low-boiling gas constituents of the common product gas of the oxydehydrogenation, and in the operating phase a partial stream is recycled to the two reactors.
- the transition of one of the two reactors from the operating phase to the regeneration phase is designed so that first the oxygen-containing gas stream, preferably air, is switched off while the oxide hydrogenation continues until the concentration of oxygen has fallen below a predetermined value in the product gas stream of this reactor. Then, first the partial stream of the circulating gas stream and then the butene-containing input stream are closed for this reactor, whereupon the regeneration mode is started by the compressed product gas stream of the reactor is discharged before the common absorption column. Then, an inert gas-containing stream is fed to the reactor to be regenerated and then a partial stream of the effluent from the reactor condensed and as oxygen containing regeneration gas returned to the considered reactor. Meanwhile, the second production line remains in production mode.
- the oxygen-containing gas stream preferably air
- the procedure described in WO2015 / 007841 has several disadvantages.
- the two production lines are supplied with one partial flow of the common circulating gas only in the operating phase, but not in the regeneration phase.
- a regeneration gas must be separately generated, preheated, compressed and returned for each line.
- at least two compressor sections per production line must be maintained - one for the operating phase and at least one for the regeneration phase.
- the regeneration gas is generated by the oxygen-containing input streams, preferably air, and a partial flow of the cycle gas are interrupted from the operating phase and an inert gas is fed instead, while the Oxidehydrier devis to deplete the oxygen content of the product gas stream but initially continues, before finally the n- Butene-containing input stream is interrupted.
- the Oxidehydrierresure progressively less selective, so that during the transition from operating to regeneration phase coke precursor and coke are formed.
- This also increases the risk that individual reaction tubes coke more, which can lead to a local overheating of the pipes in question in the subsequent regeneration process, which can lead to damage of the catalyst in the pipe in question and at worst to damage the reactor.
- the increasingly formed coke precursors are recycled to the reactor during the regeneration phase, since a partial flow of the reactor outlet stream is used as the regeneration gas. Thus, the efficiency of the regeneration process is reduced.
- a further disadvantage concerns the work-up, which is operated jointly for both production lines and which is exposed to large fluctuations in both the total flow and the C4 loading.
- the refurbishment section alternates between 100% load operation when both lines are in the operating phase and 50% under load operation when one line is in the operating phase and the other line is in the regeneration phase.
- the requirements for the gas atmosphere, in particular for the oxygen content therefore differ for the operating phase and the regeneration phase.
- the processes described in WO2015 / 007839 and WO2015 / 007841 have disadvantages, such as the increased formation of coke precursors and carbon-containing compounds.
- the oxygen content must not be too high, either in the operating phase or in the regeneration phase, so that no ignitable mixtures are formed.
- the oxygen content When entering the regeneration phase, the oxygen content must not be too high to avoid too rapid burning of carbonaceous compounds and local overheating of possibly heavily coked reaction tubes, which can lead to destruction of the catalyst and the reaction tubes.
- the oxygen content In the operating phase, the oxygen content must not be too low to avoid premature or excessive coking of the catalyst.
- a change in the oxygen content with respect to the n-butenes-containing input gas should be such that neither the coking tendency increases nor premature or too rapid burning takes place, or an ignitable mixture is generated.
- the object of the invention is to provide a safe and economical process for running a reactor for the oxidative dehydrogenation of n-butenes to butadiene.
- the object is achieved by a process for the preparation of butadiene from n-butenes in n parallel-operated reactors R1 to Rn, wherein each of the plurality of parallel-operated reactors undergoes an operating phase and a regeneration phase, wherein the process in the operating phase of a reactor Rm of n reactors the steps includes:
- An advantage of the process according to the invention is that the reoxidation of the catalyst in step iv) can be carried out with the partial cycle gas stream d2m generated by the reactors in the operating state.
- This has a favorable for the reoxidation of the catalyst oxygen content of generally 4 to 10 vol .-%, preferably 6.5 to 9 vol .-%.
- Additional inert gas is required only in steps i) to iii), wherein the partial gas flow d2m must be diluted less strongly with inert gas in order to set the favorable for the burning phase iii) oxygen content of 2 to 3 vol .-%.
- the ratio of oxygen: n-butenes is 0.7 to 1.0 times the ratio in the operating phase.
- the oxygen content in the reactor Rm during step i) is reduced to 3 to 7 vol .-%.
- the n-butene-containing gas stream a1 m is reduced during step i) to 25 to 50% of the gas stream during the operating phase. Further preferably, during step ii), the n-butenes-containing gas stream a1 m is reduced to 12.5 to 25% of the gas stream during the operating phase, and the partial gas stream d2m reduced accordingly, so that the ratio of oxygen: n-butenes 0.7 to 1, 0 times the ratio in the operating phase, and then the n-butenes containing gas stream a1 m reduced to 0.
- the reoxidation of the catalyst is carried out at an oxygen content of 4 to 10% by volume, preferably 6.5 to 9% by volume.
- step iii) is carried out over a period of 5 to 60 minutes.
- the step v) is preferably carried out over a period of 12 to 96 h.
- the ratio of oxygen to hydrocarbons in the operating phase at an n-butenes content of 50 to 100% by volume in the feed gas stream a1 is generally from 1: 1 to 1.65: 1, preferably from 1.3: 1 to 1, 65: 1, more preferably from 1.4: 1 to 1.65: 1.
- the pressure in the reactor Rm during the operating and regeneration phase is 1 to 5 bar.
- the oxygen-containing gas stream a2m is reduced to 0 in step i) or in step ii), preferably in step i).
- the inert gas stream a4m is reduced to 0 in step iv).
- R 1 shows the schematic representation of a plant for carrying out an embodiment of the process according to the invention with a first tube bundle reactor R 1 , a second tube bundle reactor R 2 and optionally further tube bundle reactors R n , a common quench section Q, compressor section K and Have absorption column A.
- R 1 , R 2 , R n denote n parallel-operated reactors
- K is a compression level
- q 1 , q 2 , q n are the discharge streams assigned to the individual reactors.
- a starting gas stream a1m containing the n-butenes is mixed with a gas stream a2m containing oxygen and passed as mixed gas stream over the heterogeneous particulate multimetal oxide catalyst introduced into the contact tubes of the tube bundle reactors Rm.
- the heat transfer medium absorbs the heat of reaction liberated by indirect heat exchange minus the amount of heat consumed to heat the gas mixture stream in the production mode to reaction temperature, and gives it in an external cooler to a secondary heat carrier completely or partially.
- a first reactor R1, a second reactor R2 and, if appropriate, further reactors R3 to Rn have a common quench Q, a common compressor K and a common absorption column A, from which an overhead stream d2 is withdrawn, which is partly used as the first circulating gas stream d21 in the first tube bundle reactor R1, partially as the second cycle gas stream d22 in the second tube bundle reactor R2 and as further circulating gas streams d23 to d2n in any further tube bundle reactors R3 to Rn recycled.
- the remainder of the stream d2 is discharged as purge gas stream p.
- a partial stream of the stream d2 can be recycled as compensation stream d3 into the common quench Q.
- the heterogeneous particulate multimetal oxide catalyst is regenerated by passing an oxygen-containing regeneration gas mixture and burning off the deposits deposited on the heterogeneous particulate multimetal oxide catalyst, the n tubular reactors R1 to Rn preferably having a single heat transfer cycle and always at least one of the two or more shell and tube reactors in the production mode (Operating phase) is operated so that the heat of reaction liberated minus the amount of heat consumed to heat the feed gas stream in the production mode to reaction temperature is sufficient so that the temperature of the heat carrier in the interstices between the catalyst tubes of the two or more shell and tube reactors in a range of maximum +/- 10 ° C is kept constant.
- a tube bundle reactor Rm is traversed by stopping the oxygen-containing input stream a2m to the tube reactor Rm, throttling the n-butene-containing input stream a1m to, for example, about 1/3 of the volume in the operating phase and feeding in an inert gas stream a4m, so that the resulting total gas stream passes through the reactor for example is still 64% of the volume of the total flow in the operating phase.
- the volume of the inert gas a4m to be supplied is variable, since in general the butane content of the n-butene-containing input stream a1m varies and the inert gas flow a4m is adapted to this content.
- the input stream a1 m containing n-butenes is throttled to, for example, 1/6 of the volume flow in the operating phase, the partial cycle gas stream d2m throttled to, for example, 21% by volume of the total gas flow in the operating phase and the inert gas flow a4m to, for example, 39 vol .-% of the total gas flow in the operating phase increased.
- the n-butene-containing input gas stream a1 m is switched off, whereupon the catalyst is regenerated in the first shell-and-tube reactor Rm.
- the inert gas stream a4m is switched off and the first circulating gas stream d2m is increased to up to 90% by volume of the total gas flow in the operating phase.
- the reoxidation of the catalyst takes place at an oxygen content of 4 to 10 vol .-%, preferably over a period of 12 to 19 h.
- the first circulating gas flow d2m can be throttled down to 1%.
- the next operating phase starts, starting from a circulating gas flow d2m of up to 90% by volume of the total gas flow in the operating phase, by re-closing the n-butene-containing input flow a1m, the oxygen-containing input flow a2m and throttling the first cycle gas flow d2m, respectively on the volume flows in the operating phase.
- a partial flow of the circulating gas stream d2 is driven onto the quench Q as a compensation flow d3 with such a volume that the resulting total volume flow (b + d3) on quench Q, compressor K and absorption column A always remains approximately constant.
- the method according to the invention has numerous advantages.
- the exothermicity of the oxydehydrogenation reactors can be utilized as a heat source for the regeneration phase. Since at least one reactor is always in the operating phase while another reactor is in the regeneration phase, it is ensured that the entire system continuously generates value product.
- the use of multiple reactors further requires that recycle gas be continuously obtained by separating the non-condensable or low-boiling gas constituents of the product gas of the oxydehydrogenation in sufficient quantity to (1) maintain a constant volume load on the common work-up by utilizing a compensation current d3 - (2) to be able to support both the operating phase and the regeneration phase of all tube bundle reactors to partial streams d2m of the common circulating gas d2.
- the invention is based on the finding that the regeneration of the catalyst can be subdivided into two phases, each with different requirements for the gas atmosphere, namely into a (a) burn-up phase and a (b) reoxidation phase.
- the process according to the invention meets these requirements by carrying out the combustion phase with a regeneration gas obtained by mixing part of the partial gas flow d2m with an inert gas and an oxygen content of 2 to 3% by volume, preferably 2.3-2, 7 vol .-%. Since the burnup of carbonaceous deposits succeeds within a few minutes, the consumption of expensive inert gas can be significantly reduced and limited to the combustion phase, which lasts only a few minutes. After the burnup of carbonaceous deposits has taken place, which can be determined by monitoring the COx content of the output stream, the reoxidation phase follows immediately.
- a further advantage of the method according to the invention is that the respective tube bundle reactor is flowed through continuously and over all operating and regeneration phases, so that a heat extraction is always provided via the gas flow and no very long residence times occur. High residence times in combination with reduced convection can lead to local hotspots and thus to a high thermal stress of the catalyst.
- the total volume flow is reduced to, for example, 63% of the volume flow during the operating phase, which further reduces (1) the consumption of expensive inert gas and (2) accelerates burn-up due to the lower gas velocity.
- the gas velocity and the contents of oxygen and n-butenes are coordinated so that neither takes place too fast burning, nor is a coking of the catalyst by an unselective reaction.
- the described variant of the process according to the invention in which the reactor output stream of a started reactor, the reactor output stream of the reactor to be run so replaced that the total product gas stream b remains constant, has the further advantage that not only the volume load of the workup remains approximately constant, but also the composition the total product gas flow b remains approximately constant.
- inert gases preference may be given to using nitrogen, but also argon and CO 2.
- water vapor may also be contained in the oxygen-containing regeneration gas mixture. Nitrogen is preferably used to adjust the oxygen concentration, the same applies to water vapor. Water vapor may also be present to remove the heat of reaction and as a mild oxidizer for the removal of carbonaceous deposits.
- steam is introduced into the reactor at the beginning of the regeneration, it is preferable to use a volume fraction of 0-50% by volume, preferably 0-10% by volume and more preferably 0.1-7% by volume.
- the amount of nitrogen is chosen so that the volume fraction of molecular nitrogen in the regeneration gas mixture at the beginning of the combustion phase is preferably 60-90 vol .-% and more preferably 60-65 vol .-%.
- the oxygen-containing regeneration gas mixture may contain hydrocarbons and reaction products of the oxidative dehydrogenation.
- the amount of partial cycle gas flow d2m is selected such that the volume fraction of molecular nitrogen in the regeneration gas mixture at the beginning of the combustion phase is preferably 10-35% by volume and more preferably 30-35% by volume.
- the total cycle gas stream d2 and correspondingly the partial cycle gas stream d2m contain 6.5 to 9% by volume O2 and 87 to 93% by volume inert gases selected from nitrogen, noble gases (in particular argon) and carbon oxides (in particular CO2).
- the common cycle gas stream d2 and corresponding to the partial cycle gas stream d2m 0 to 2 vol .-% carbon monoxide, 0 to 1, 5% by volume oxygenates, eg Acorlein, 0 to 0.5 vol .-% water vapor and 0 to 0.1 vol .-% hydrocarbons.
- the hydrocarbons may be saturated and unsaturated, branched and unbranched hydrocarbons, such as.
- a regeneration phase is carried out in each case between two operating phases.
- the considered reactor can remain in the production mode (operating state) until the deactivation of the catalyst has reached a specific, predetermined value and, for example, the conversion has fallen by 20%, preferably by 10% and particularly preferably by 5%, while the reaction temperature remains the same. Furthermore, the reactor can remain in the production mode until the pressure loss across the reactor has fallen by a certain predetermined value, for example by 500 mbar, preferably by 100 mbar and especially by 100 mbar. Preferably 25 mbar has risen, or a certain predetermined duration of the operating phase has elapsed, for example 2000 h, preferably 1000 h.
- the regeneration phase is followed by a start-up phase with the steps vi) to viii): vi) optionally additional feeding of a water vapor stream a3m into the dehydrogenation zone; vii) additionally feeding the butene-containing feed gas stream a1 m with a lower volume flow than in the operating phase and increasing this volume flow until at least 50% of the volume flow of the feed gas stream a1 m in the operating phase, wherein the total gas flow through the reactor Rm a maximum of 120% of the total gas flow during the operating phase; viii) additional feeding, upon reaching at least 50% of the volume flow of the butene-containing feed gas stream a1 m in the operating phase, the oxygen-containing stream a2m with a lower volume flow than in the operating phase, and increasing the flow rates of the gas flows a1 m and a2m until reaching the volume flows in the operating phase, wherein the total gas flow through the dehydrogenation zone maximum
- the total gas stream comprising the streams a1m, a2m, d2m and optionally a3m is substantially constant throughout the dehydrogenation zone during steps (vi), (vii) and (viii) and corresponds to 90 to 1 10% by volume of the total gas flow through the dehydrogenation zone during the operating phase.
- the amount of water vapor in the dehydrogenation zone during steps vi), vii) and viii) is 0.5 to 10% by volume.
- the pressure in the reactor Rm during the start-up phase is 1 to 5 bar.
- the starting method according to the invention has the advantage over the procedure described in WO 2015/104397 that oxygen-rich conditions are also present at the start of the starting phase, since the circulating gas is not diluted with an inert gas. This counteracts coking of the catalyst.
- the conditions during the start-up phase in terms of load, gas velocity, residence time and composition of the circulating gas flow correspond more to the conditions during the operating phase. Since the gas velocity is essentially constant, a developing hot spot does not migrate within the reactor.
- the stationary operating state and the optimal performance of the catalyst in terms of space-time yield and selectivity are achieved faster overall.
- the circulating gas flow d2m is set to 90 to 1 10% of the total volume flow in the operating phase.
- the total volume flow is the sum of the volume flows a1 m, a2m, d2m and optionally a3m.
- the circulating gas stream d2m is adjusted to 95-105% of the total volume flow in the operating phase, more preferably the circulating gas flow d2m is set to 100% of the total volume flow in the operating phase.
- the set circulating gas flow d2m is reduced in the subsequent steps vii) and viii) so that the total gas flow through the hydrogenation zone, ie the sum of the flows a1m, a2m, d2m and optionally a3m, during the further start-up phase at least 70% and at most 120%, preferably at least 90% and at most 1 15% of the total gas flow during the operating phase.
- the total gas flow during the start-up phase remains essentially constant and varies by a maximum of +/- 10% by volume, in particular +/- 5% by volume, ie during the start-up phase preferably amounts to 90 to 110% by volume, in particular 95% to 105% by volume of the total gas flow during the operating phase.
- the gas stream d2 has a composition corresponding to the circulating gas stream d2 in the operating phase when its oxygen content deviates at most +/- 2% by volume from the oxygen content of the circulating gas stream d2 in the stationary operating phase.
- a steam stream a3m can be fed into the reactor Rm.
- the amount of water vapor during steps vi) to viii) is 0.5 to 10% by volume, preferably 1 to 7% by volume. This can also be humidity.
- the butene-containing feed gas stream a1 m is additionally fed until it reaches at least 50% of the volume flow in the operating phase of the reactor.
- the volume flow is generally increased in stages, for example, starting with 10% of the volume flow in the operating state, in steps of 10% until reaching at least 50% of the volume flow in the operating state.
- the volume flow can also be increased in the form of a ramp. If appropriate, the circulating gas stream d2 is correspondingly reduced so far that the total gas flow through the reactor Rm corresponds to a maximum of 120% of the total gas flow during the operating phase.
- the content of C4 hydrocarbons (butenes and butanes) in the total gas flow through the reactor Rm at the end of step (vii) is generally 7 to 9% by volume.
- the volume flow of butene-containing feed gas stream a1 m can be raised in step vii) until reaching at least 60% of the volume flow in the operating phase, but at most until reaching a maximum of 75% of the volume flow in the operating phase.
- step viii) when at least 50% and at most 75% of the volume flow of the butene-containing feed gas stream a1m have been reached in the operating phase, in addition to Buteneene containing feed gas stream a1 m an oxygen-containing stream a2m with lower flow than in the operating phase fed into the dehydrogenation zone and the volume flows of the feed gas flows a1 m and a2m raised to reach the volume flows in the operating phase.
- the volume flow of the oxygen-containing gas stream a2m is raised in one or more stages until a ratio of oxygen to hydrocarbons corresponding to the ratio of oxygen to hydrocarbons in the operating phase is reached, and then both volume flows a1m and a2m in Raised levels until reaching each 100% of the volume flow of the gas streams a1 m and a2m in the operating phase, wherein the ratio of oxygen to hydrocarbons remains substantially constant and corresponds to the ratio of oxygen to hydrocarbons in the operating phase.
- the volume flow is thereby generally increased in steps, for example beginning with 50% of the volume flow of the gas flow a1 m in the operating state, in steps of, for example, 10%, wherein the steps for the steps for increasing the volume flow of the gas flow a2m are chosen such that the Ratio of oxygen to hydrocarbons during the start-up phase remains substantially constant until reaching 100% of the flow rates in the operating state.
- the content of C4 hydrocarbons (butenes and butanes) in the total gas flow through the reactor Rm at the end of step viii) is generally from 7 to 9% by volume, the oxygen content generally from 12 to 13% by volume.
- the pressure in the dehydrogenation zone during the start-up phase is 1 to 5 bar absolute, preferably 1.05 to 2.5 bar absolute.
- the pressure in the absorption zone during the start-up phase is 2 to 20 bar, preferably 5 to 15 bar.
- the temperature of the heat exchange medium during the start-up phase is between 220 to 490 ° C., and preferably between 300 to 450 ° C., and more preferably between 330 and 420 ° C.
- the duration of the start-up phase is from 15 to 2000 minutes, preferably from 15 to 500 minutes and more preferably from 20 to 120 minutes. Afterwards the operating phase begins.
- step C) comprises steps Ca) and Cb):
- step D) comprises steps Da) and Db):
- the steps E) and F) are then carried out: E) separation of the C 4 product stream d1 by extractive distillation with a butadiene-selective solvent in a butadiene and the selective solvent-containing stream e1 and a n-butenes containing stream e2;
- the gas stream d contained in step Da) is recirculated to at least 10%, preferably at least 30%, as recycle gas stream d2 in step B).
- aqueous coolants or organic solvents or mixtures thereof are used.
- an organic solvent is used in the cooling stage Ca.
- These generally have a much higher solvent power for the high-boiling by-products, which can lead to deposits and blockages in the downstream of the ODH reactor plant components, as water or alkaline aqueous solutions.
- Preferred organic solvents used as coolants are aromatic hydrocarbons, for example toluene, o-xylene, m-xylene, p-xylene, diethylbenzenes, triethylbenzenes, diisopropylbenzenes, triisopropylbenzenes and mesitylene or mixtures thereof.
- mesylene is especially preferred or particularly preferred variants of the method according to the invention:
- the stage Ca) is carried out in several stages in stages Ca1) to Can), preferably in two stages in two stages Ca1) and Ca2). In this case, it is particularly preferred that at least part of the solvent, after passing through the second stage Ca2), be supplied as cooling agent to the first stage Ca1).
- the stage Cb) generally comprises at least one compression stage Cba) and at least one cooling stage Cbb).
- the compressed in the compression stage Cba) gas is brought into contact with a cooling agent.
- the cooling agent of the cooling step Cbb) contains the same organic solvent used in step Ca) as a cooling agent.
- at least part of this cooling agent is fed after passing through the at least one cooling stage Cbb) as cooling agent of the stage Ca).
- the stage Cb) comprises a plurality of compression stages Cba1) to Cban) and cooling stages Cbb1) to Cbbn), for example four compression stages Cba1) to Cba4) and four cooling stages Cbb1) to Cbb4).
- step D) comprises the steps Da1), Da2) and Db):
- step Da2) removal of oxygen from the C4 hydrocarbon loaded absorbent stream from step Da) by stripping with a non-condensable gas stream, and Db) desorbing the C4 hydrocarbons from the loaded absorbent stream to give a C4 product gas stream d1 substantially consists of C4 hydrocarbons and less than 100 ppm oxygen.
- the high-boiling absorbent used in step Da) is an aromatic hydrocarbon solvent, particularly preferably the aromatic hydrocarbon solvent used in step Ca), in particular mesitylene. It is also possible to use, for example, diethylbenzenes, triethylbenzenes, diisopropylbenzenes and triisopropylbenzenes or mixtures containing these substances. Embodiments of the method according to the invention are shown in FIG. 1 and will be described in detail below. As feed gas stream pure n-butenes (1-butene and / or cis- / trans-2-butene), but also containing butene gas mixtures can be used.
- n-butenes (1-butene and cis- / trans-2-butene)
- gas mixtures which comprise pure 1-butene, cis-2-butene, trans-2-butene or mixtures thereof and which have been obtained by dimerization of ethylene can also be used as input gas.
- gas mixtures containing n-butenes which have been obtained by fluid catalytic cracking (FCC) can be used as the input gas.
- the input gas containing n-butenes is obtained by non-oxidative dehydrogenation of n-butane.
- a non-oxidative catalytic dehydrogenation with the oxidative dehydrogenation of the n-butenes formed, a high yield of butadiene, based on n-butane used, can be obtained.
- a gas mixture is obtained which, in addition to butadiene 1-butene, 2-butene and unreacted n-butane, contains minor constituents.
- Common secondary constituents are hydrogen, water vapor, nitrogen, CO and CO2, methane, ethane, ethene, propane and propene.
- the composition of the gas mixture leaving the first dehydration zone can vary greatly depending on the mode of operation of the dehydrogenation.
- the product gas mixture has a comparatively high content of water vapor and carbon oxides.
- the product gas mixture of the non-oxidative dehydrogenation has a comparatively high content of hydrogen.
- step B) the feed gas stream containing n-butenes and an oxygen-containing gas are fed into at least one dehydrogenation zone (one or more ODH reactors R operated in parallel) and the butenes contained in the gas mixture are oxidatively dehydrogenated to form butadiene in the presence of an oxydehydrogenation catalyst.
- the molecular oxygen-containing gas generally contains more than 10% by volume, preferably more than 15% by volume, and more preferably more than 20% by volume of molecular oxygen. It is preferably air.
- the upper limit of the content of molecular oxygen is generally 50% by volume or less, preferably 30% by volume or less, and more preferably 25% by volume or less.
- any inert gases may be contained in the molecular oxygen-containing gas. Possible inert gases include nitrogen, argon, neon, helium, CO, CO2 and water.
- the amount of inert gases for nitrogen is generally 90% by volume or less, preferably 85% by volume or less, and more preferably 80% by volume or less. In the case of components other than nitrogen, it is generally 10% by volume or less, preferably 1% by volume or less.
- n-butenes ratio preference is given to a gas mixture which has a molar oxygen: n-butenes ratio of at least 0.5. Preference is given to working at an oxygen: n-butenes ratio of 1.25 to 1.6.
- the input gas stream may be mixed with oxygen or at least one oxygen-containing gas, for example air, and optionally additional inert gas or steam. The resulting oxygen-containing gas mixture is then fed to the oxydehydrogenation.
- inert gases such as nitrogen and furthermore water (as water vapor) may also be contained together in the reaction gas mixture.
- Nitrogen can be used to adjust the oxygen concentration and prevent the formation of an explosive gas mixture, the same applies to water vapor.
- Steam also serves to control the coking of the catalyst and to dissipate the heat of reaction.
- Catalysts suitable for oxydehydrogenation are generally based on a Mo-Bi-O-containing multimetal oxide system, which generally additionally contains iron.
- the catalyst contains other additional components such as potassium, cesium, magnesium, zirconium, chromium, nickel, cobalt, cadmium, tin, lead, germanium, lanthanum, manganese, tungsten, phosphorus, cerium, aluminum or silicon.
- Iron-containing ferrites have also been proposed as catalysts.
- the multimetal oxide contains cobalt and / or nickel. In a further preferred embodiment, the multimetal oxide contains chromium. In a further preferred embodiment, the multimetal oxide contains manganese.
- Mo-Bi-Fe-O-containing multimetal oxides are Mo-Bi-Fe-Cr-O or Mo-Bi-Fe-Zr-O-containing multimetal oxides.
- Preferred catalysts are described, for example, in
- Particularly preferred catalytically active, molybdenum and at least one further metal-containing multimetal oxides have the general formula (Ia):
- X 1 Si, Mn and / or Al
- X 2 Li, Na, K, Cs and / or Rb,
- y a number determined on the assumption of charge neutrality by the valence and frequency of the elements other than oxygen in (1a).
- the reaction temperature of the oxydehydrogenation is generally controlled by a heat exchange medium located around the reaction tubes.
- liquid heat exchange agents come z.
- metals such as sodium, mercury and alloys of various metals into consideration.
- ionic liquids or heat transfer oils are used.
- the temperature of the heat exchange medium is between 220 to 490 ° C and preferably between 300 to 450 ° C and more preferably between 330 and 420 ° C.
- the temperature in certain sections of the interior of the reactor during the reaction may be higher than that of the heat exchange medium and a so-called hotspot is formed.
- the location and height of the hotspot is determined by the reaction conditions, but it can also be regulated by the dilution ratio of the catalyst layer or the flow rate of mixed gas.
- the difference between hotspot temperature and the temperature of the heat exchange medium is generally between 1 and 150 ° C, preferably between 10 and 100 ° C and more preferably between 20 and 80 ° C.
- the temperature at the end of the catalyst bed is generally between 0 and 100 ° C, preferably between 0.1 and 50 ° C, more preferably between 1 and 25 ° C above the temperature of the heat exchange medium.
- the oxydehydrogenation can be carried out in all fixed-bed reactors known from the prior art, such as, for example, in a hearth furnace, in a fixed-bed or shell-and-tube reactor or in a plate heat exchanger reactor.
- a tube bundle reactor is preferred.
- the oxidative dehydrogenation is carried out in fixed bed tubular reactors or fixed bed bundle bundle reactors.
- the reaction tubes are (as well as the other elements of the tube bundle reactor) usually made of steel.
- the wall thickness of the reaction tubes is typically 1 to 3 mm. Their inner diameter is usually (uniformly) at 10 to 50 mm or 15 to 40 mm, often 20 to 30 mm.
- the number of reaction tubes accommodated in the tube bundle reactor is generally at least 1000, or 3000, or 5000, preferably at least 10,000. Frequently, the number of reaction tubes accommodated in the tube bundle reactor is 15,000 to 30,000 or up to 40,000 or up to 50 000.
- the length of the reaction tubes normally extends to a few meters, typical is a reaction tube length in the range of 1 to 8 m, often 2 to 7 m, often 2.5 to 6 m.
- the catalyst layer configured in the ODH reactor (s) R may consist of a single layer or of two or more layers. These layers may be pure catalyst or diluted with a material that does not react with the input gas or components of the product gas of the reaction. Furthermore, the catalyst layers may consist of solid material and / or supported shell catalysts.
- the product gas stream leaving the oxidative dehydrogenation generally contains unreacted 1-butene and 2-butene, oxygen and water vapor.
- the product gas stream leaving the oxidative dehydrogenation generally contains unreacted 1-butene and 2-butene, oxygen and water vapor.
- it furthermore generally contains carbon monoxide, carbon dioxide, inert gases (mainly nitrogen), low-boiling hydrocarbons such as methane, ethane, ethene, propane and propene, butane and isobutane, optionally hydrogen and optionally oxygen-containing hydrocarbons, so-called oxygenates.
- Oxygenates may be, for example, formaldehyde, furan, acetic acid, maleic anhydride, formic acid, methacrolein, methacrylic acid, crotonaldehyde, crotonic acid, propionic acid, acrylic acid, methyl vinyl ketone, styrene, benzaldehyde, benzoic acid, phthalic anhydride, fluorenone, anthraquinone and butyraldehyde.
- the product gas stream at the reactor exit is characterized by a temperature near the temperature at the end of the catalyst bed.
- the product gas stream is then brought to a temperature of 150 to 400 ° C, preferably 160 to 300 ° C, more preferably 170 to 250 ° C. It is possible to isolate the line through which the product gas stream flows to maintain the temperature in the desired range, or to use a heat exchanger. This heat exchanger system is arbitrary as long as the temperature of the product gas can be maintained at the desired level with this system.
- heat exchangers As an example of a heat exchanger, spiral heat exchangers, plate heat exchangers, double-tube heat exchangers, multi-tube heat exchangers, boiler spiral heat exchangers, shell-shell heat exchangers, liquid-liquid contact heat exchangers, air heat exchangers, direct contact heat exchangers and finned tube heat exchangers can be used. Heat exchangers are called. Since, while the temperature of the product gas is adjusted to the desired temperature, a part of the high-boiling by-products contained in the product gas may precipitate, the heat exchanger system should preferably have two or more heat exchangers.
- the two or more intended heat exchangers may be arranged in parallel.
- the product gas is supplied to one or more, but not all, heat exchangers, which are replaced after a certain period of operation of other heat exchangers. In this method, the cooling can be continued, a portion of the heat of reaction recovered and in parallel, the deposited in one of the heat exchangers high-boiling by-products can be removed.
- a solvent can be used as long as it is capable of dissolving the high-boiling by-products.
- aromatic hydrocarbon solvents such as. As toluene and xylenes, diethylbenzenes, triethylbenzenes, diisopropylbenzenes, triisopropylbenzenes. Particularly preferred is mesitylene.
- aqueous solvents These can be made both acidic and alkaline, such as an aqueous solution of sodium hydroxide.
- Cooling is by contacting with a coolant.
- This step is also referred to below as quench Q.
- This quench can consist of only one stage or of several stages.
- the product gas stream is thus brought directly into contact with a preferably organic cooling medium and thereby cooled.
- Suitable cooling media are aqueous coolants or organic solvents, preferably aromatic hydrocarbons, more preferably toluene, o-xylene, m-xylene, p-xylene or mesitylene, or mixtures thereof. It is also possible to use all possible isomers of diethylbenzene, triethylbenzene, diisopropylbenzene and triisopropylbenzene and mixtures thereof.
- the stage Ca comprises two cooling stages Ca1) and Ca2), in which the product gas stream b is brought into contact with the organic solvent.
- the cooling stage Ca) is carried out in two stages, wherein the solvent of the second stage Ca2) loaded with secondary components is passed into the first stage Ca1).
- the solvent removed from the second stage Ca2) contains fewer secondary components than the solvent removed from the first stage Ca1).
- a gas stream is obtained which comprises n-butane, 1-butene, 2-butenes, butadiene, optionally oxygen, hydrogen, water vapor, in small quantities methane, ethane, ethene, propane and propene, isobutane, carbon oxides, inert gases and parts of the solvent used in the quench. Furthermore, traces of high-boiling components can remain in this gas stream, which were not quantitatively separated in the quench.
- the product gas stream from the solvent quench is compressed in at least one compression stage K and subsequently cooled further in the cooling apparatus, whereby at least one condensate stream is formed.
- a gas stream containing butadiene, 1-butene, 2-butene, oxygen, water vapor, optionally low-boiling hydrocarbons such as methane, ethane, ethene, propane and propene, butane and isobutane, optionally carbon oxides and optionally inert gases.
- this product gas stream may still contain traces of high-boiling components.
- the compression and cooling of the gas stream can take place in one or more stages (n-stage).
- a total pressure is compressed in the range of 1.0 to 4.0 bar (absolute) to a pressure in the range of 3.5 to 20 bar (absolute).
- a cooling step in which the gas stream is cooled to a temperature in the range of 15 to 60 ° C.
- the condensate stream can therefore also comprise a plurality of streams in the case of multistage compression.
- the condensate stream consists to a large extent of water and optionally the organic solvent used in the quench. Both streams (aqueous and organic phase) may also contain minor components such as low boilers, C 4 hydrocarbons, oxygenates and carbon oxides.
- the butadiene, n-butenes, oxygen, low-boiling hydrocarbons (methane, ethane, ethene, propane, propene, n-butane, isobutane), optionally water vapor, optionally carbon oxides and optionally inert gases and optionally traces of minor components containing gas stream is used as the output stream the further processing supplied.
- step D) are non-condensable and low-boiling gas components comprising oxygen, low-boiling hydrocarbons (methane, ethane, ethene, propane, propene), carbon oxides and inert gases in an absorption column A as a gas stream from the process gas stream by absorption of C 4 hydrocarbons separated in a high-boiling absorbent and subsequent desorption of C 4 hydrocarbons.
- step D) comprises the steps Da1), Da2) and Db):
- step Da2) removal of oxygen from the C 4 -hydrocarbon-laden absorbent stream from step Da) by stripping with a non-condensable gas stream, wherein a C4 hydrocarbons laden absorbent stream is obtained, and
- the gas stream is contacted with an inert absorbent and the C4 hydrocarbons are absorbed in the inert absorbent to obtain an absorbent laden with C4 hydrocarbons and an offgas containing the remaining gas constituents.
- the C4 hydrocarbons are released from the high-boiling absorbent again.
- the absorption stage can be carried out in any suitable absorption column known to the person skilled in the art. Absorption can be accomplished by simply passing the product gas stream through the absorbent. But it can also be done in columns or in rotational absorbers. It can be used in cocurrent, countercurrent or cross flow. Preferably, the absorption is carried out in countercurrent. Suitable absorption columns are z. B. tray columns with bell, centrifugal and / or sieve bottom, columns with structured packings, eg. B. Sheet metal packings with a specific surface area of 100 to 1000 m 2 / m 3 as Mellapak® 250 Y, and packed columns. However, trickle and spray towers, graphite block absorbers, surface absorbers such as thick-layer and thin-layer absorbers as well as rotary columns, rags, cross-flow scrubbers and rotary scrubbers are also suitable.
- an absorption column in the lower region of the butadiene, n-butenes and the low-boiling and non-condensable gas components containing gas stream is supplied.
- the high-boiling absorbent is abandoned.
- Inert absorbent used in the absorption stage are generally high-boiling non-polar solvents in which the C4-hydrocarbon mixture to be separated has a significantly higher solubility than the other gas constituents to be separated off.
- Suitable absorbents are comparatively nonpolar organic solvents, for example aliphatic Cs to Cis alkanes, or aromatic hydrocarbons, such as the paraffin distillation from the paraffin distillation, toluene or ethers with bulky groups, or mixtures of these solvents, these being a polar solvent such as 1, 2 Dimethyl phthalate may be added.
- Suitable absorbers are also esters of benzoic acid and phthalic acid with straight-chain d-Cs-alkanols, as well as so-called heat transfer oils, such as biphenyl and diphenyl ether, their chlorinated derivatives and triaryl alkenes.
- a suitable absorbent is a mixture of biphenyl and diphenyl ether, preferably in the azeotropic composition, in which For example, the commercially available Diphyl ® . Often, this solvent mixture contains di-methyl phthalate in an amount of 0.1 to 25 wt .-%.
- the same solvent is used as in the cooling stage Ca).
- Preferred absorbents are solvents which have a solubility for organic peroxides of at least 1000 ppm (mg active oxygen / kg solvent).
- aromatic hydrocarbons particularly preferably toluene, o-xylene, p-xylene and mesitylene, or mixtures thereof. It is also possible to use all possible isomers of diethylbenzene, triethylbenzene, diisopropylbenzene and triisopropylbenzene and mixtures thereof.
- a gas stream d is withdrawn which comprises essentially oxygen, low-boiling hydrocarbons (methane, ethane, ethene, propane, propene), the hydrocarbon solvent, optionally C 4 -hydrocarbons (butane, butenes, butadiene), optionally inert gases, optionally carbon oxides and optionally also contains water vapor.
- This stream is at least partially supplied as circulating gas stream d2 the ODH reactor.
- the inlet flow of the ODH reactor can be adjusted to the desired C4 hydrocarbon content.
- at least 10% by volume preferably at least
- the recycle stream is 10 to 70% by volume, preferably 30 to 60% by volume, based on the sum of all material streams fed into the oxidative dehydrogenation B).
- the purge gas stream may be subjected to thermal or catalytic afterburning. In particular, it can be thermally utilized in a power plant.
- the stripping of the oxygen in step Da2) can be carried out in any suitable column known to the person skilled in the art.
- the stripping can be carried out by simply passing non-condensable gases, preferably not or only weakly absorbable in the absorbent stream gases such as methane, through the loaded absorption solution. With stripped C4 hydrocarbons are washed in the upper part of the column back into the absorption solution by the gas stream is passed back into this absorption column. This can be achieved both by a piping of the stripping column and a direct
- stripping column carried out below the absorber column. Since the pressure in the stripping column part and the absorption column part is the same, this direct coupling can take place.
- overall suitable stripping columns are z. B. tray columns with bell, centrifugal and / or sieve tray, columns with structured packings, eg. B. Sheet metal packings with a specific surface area of 100 to 1000 m 2 / m 3 as Mellapak® 250 Y, and packed columns. But there are also trickle and spray towers and rotary columns, dishwashers, cross-flow scrubbers and rotary scrubbers into consideration. Suitable gases are for example nitrogen or methane.
- stripping is carried out in step Da2) with a methane-containing gas stream.
- this gas stream (stripping gas) contains> 90% by volume of methane.
- the loaded with C4 hydrocarbons absorbent stream can be heated in a heat exchanger and then passed into a desorption.
- the desorption step Db) is carried out by relaxing and stripping the loaded absorbent by a steam stream.
- the absorbent regenerated in the desorption stage can be cooled in a heat exchanger.
- the cooled stream still contains water in addition to the absorbent, which is separated in the phase separator.
- the C4 product gas stream consisting essentially of n-butane, n-butenes and butadiene generally contains from 20 to 80% by volume of butadiene, from 0 to 80% by volume of n-butane, from 0 to 10% by volume of 1-butene , 0 to 50% by volume of 2-butenes and 0 to 10% by volume of methane, the total amount being 100% by volume. Furthermore, small amounts of iso-butane may be included.
- a portion of the condensed head effluent of the desorption column, which contains mainly C 4 hydrocarbons, can be returned to the top of the column to increase the separation efficiency of the column.
- liquid or gaseous C4 product streams leaving the condenser can then be separated by extractive distillation in step E) with a solvent which is selective for butadiene into a material stream containing the selective solvent and a stream comprising butanes and n-butenes.
- the tubular reactor (R) consists of stainless steel 1, 4571, has an internal diameter of 29.7 mm and 5 m in length and is filled with a mixed oxide catalyst (2500 ml).
- a thermo-sleeve outer diameter 6 mm
- the tube is lapped with a molten salt to keep the outer wall temperature constant.
- a stream of butenes and butanes (a1), water vapor (a3), air (a2) and oxygen-containing recycle gas (d2) are fed to the reactor.
- nitrogen (a4) can be fed to the reactor.
- the product gas (b) is cooled to 45 ° C.
- a quench apparatus whereby the high-boiling by-products are separated off.
- the stream is compressed in a compressor stage (K) to 10 bar and cooled again to 45 ° C.
- a condensate stream (c1) is discharged.
- the gas stream (c2) is fed to an absorption column (A).
- the absorption column is operated with mesitylene. From the absorption column, a liquid stream rich in organic products and a gaseous stream (d) are obtained at the top of the absorption column. The entire workup is designed so that water and the organic components are completely separated. A portion of the stream (d) is recycled as cycle gas (d2) back into the reactor.
- Figure 1 shows schematically the experimental setup, wherein only one reactor R is considered.
- the oxygen concentration in the circulating gas d2 in the stationary operating state is 7.5% by volume.
- the reactor is fed:
- a stream a1 consisting of 85 vol.% Butenes and 15 vol.% Butanes, with a flow of 516 NL / h,
- a stream a2 in this case air, with a flow of 2431 NL / h,
- the shutdown phase is initiated by closing the current a2 within 10 minutes, throttling the current a1 to 172 NL / h and the current a3 to 175 NL / h and feeding in inert gas with a current a4 of 875 NL / h.
- the inert gas flow a4 is increased to 2175 NL / h, the circulating gas flow d2 throttled to 150 NL / h and the flow a1 throttled to 86 NL / h.
- FIG. 2 shows the metering scheme for the reactor tube with the phases: operating phase (steps 0 and 1), shutdown phase (steps 1 to 4), burnup phase (steps 4 and 5) and reoxidation phase (steps 5 and 6).
- FIG. 3 shows the exploded diagram for the metering scheme.
- FIG. 4 shows the volume flows in Nl / h of C4-hydrocarbons a1, oxygen-containing gas a2, circulating gas flow d2, and the inert gas flow (nitrogen) a4 during the shutdown and regeneration process according to the invention.
- the 02 concentration in the feed is initially 12.3% by volume in order to simulate the O2 concentration in the recycle gas stream d2.
- FIG. 5 shows the resulting residual oxygen content at the outlet of the quench stage Q in% by volume, the salt bath temperature SBT and the hotspot temperature in ° C. during the shutdown and regeneration process according to the invention, corresponding to the flows shown in FIG.
- the 02 concentration in the feed is initially 12.3% by volume in order to simulate the O2 concentration in the recycle gas stream d2.
- the hotspot gradually decreases during the descent, neither does it rise sharply, nor does it decrease sharply in a short time.
- the oxygen concentration behind the reactor is 6.0% by volume and in the cycle gas 7.5% by volume. During shutdown, the value drops behind the reactor.
- the value is below the oxygen concentration of 2.5% by volume set at the reactor inlet.
- the oxygen concentration behind the reactor due to the dilution with water vapor, increases to 7.1% by volume or to 7.5% by volume between quench and absorption column and in recycle gas at.
- the oxygen concentration before and after the reactor and between quench and absorption column can not exceed the value in the cycle gas. Thus, a safe and the catalyst gentle departure is guaranteed.
Abstract
Description
Claims
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JP2019553306A JP2020512980A (ja) | 2017-03-31 | 2018-03-26 | n−ブテンを酸化脱水素するための反応器の停止および再生方法 |
KR1020197031831A KR20190132677A (ko) | 2017-03-31 | 2018-03-26 | n-부텐의 산화성 탈수소화를 위한 반응기의 러닝 다운 및 재생 방법 |
US16/498,693 US20200039901A1 (en) | 2017-03-31 | 2018-03-26 | Method for decommisioning and regenerating a reactor for the oxidative dehydrogenation of n-butenes |
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EP3763694A4 (de) * | 2018-11-30 | 2021-05-19 | Lg Chem, Ltd. | Verfahren zur herstellung von butadien |
JPWO2021006252A1 (ja) * | 2019-07-05 | 2021-09-13 | 積水化学工業株式会社 | 1,3−ブタジエンの製造方法 |
JPWO2021006250A1 (ja) * | 2019-07-05 | 2021-09-13 | 積水化学工業株式会社 | 1,3−ブタジエンの製造方法 |
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US9861976B2 (en) * | 2016-03-01 | 2018-01-09 | Tpc Group Llc | Regeneration of oxidative dehydrogenation catalyst in a reactor |
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- 2018-03-26 KR KR1020197031831A patent/KR20190132677A/ko unknown
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WO2015007841A1 (de) * | 2013-07-18 | 2015-01-22 | Basf Se | Verfahren zur oxidativen dehydrierung von n-butenen zu 1,3-butadien |
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EP3763694A4 (de) * | 2018-11-30 | 2021-05-19 | Lg Chem, Ltd. | Verfahren zur herstellung von butadien |
JP2021518849A (ja) * | 2018-11-30 | 2021-08-05 | エルジー・ケム・リミテッド | ブタジエンの製造方法 |
US11447435B2 (en) | 2018-11-30 | 2022-09-20 | Lg Chem, Ltd. | Method for producing butadiene |
JP7156596B2 (ja) | 2018-11-30 | 2022-10-19 | エルジー・ケム・リミテッド | ブタジエンの製造方法 |
JPWO2021006252A1 (ja) * | 2019-07-05 | 2021-09-13 | 積水化学工業株式会社 | 1,3−ブタジエンの製造方法 |
JPWO2021006250A1 (ja) * | 2019-07-05 | 2021-09-13 | 積水化学工業株式会社 | 1,3−ブタジエンの製造方法 |
CN114364650A (zh) * | 2019-07-05 | 2022-04-15 | 积水化学工业株式会社 | 1,3-丁二烯的制造方法 |
CN114364649A (zh) * | 2019-07-05 | 2022-04-15 | 积水化学工业株式会社 | 1,3-丁二烯的制造方法 |
EP3995474A4 (de) * | 2019-07-05 | 2022-09-07 | Sekisui Chemical Co., Ltd. | Verfahren zur herstellung von 1,3-butadien |
US11472753B2 (en) | 2019-07-05 | 2022-10-18 | Sekisui Chemical Co., Ltd. | Method for producing 1,3-butadiene |
US11479518B2 (en) | 2019-07-05 | 2022-10-25 | Sekisui Chemical Co., Ltd. | Method for producing 1,3-butadiene |
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US20200039901A1 (en) | 2020-02-06 |
JP2020512980A (ja) | 2020-04-30 |
KR20190132677A (ko) | 2019-11-28 |
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