WO2018219996A1 - Procédé pour la préparation de 1,3-butadiène à partir de n-butènes par déshydrogénation oxydative par recyclage de gaz avec un gaz de recyclage enrichi en co2 - Google Patents

Procédé pour la préparation de 1,3-butadiène à partir de n-butènes par déshydrogénation oxydative par recyclage de gaz avec un gaz de recyclage enrichi en co2 Download PDF

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WO2018219996A1
WO2018219996A1 PCT/EP2018/064159 EP2018064159W WO2018219996A1 WO 2018219996 A1 WO2018219996 A1 WO 2018219996A1 EP 2018064159 W EP2018064159 W EP 2018064159W WO 2018219996 A1 WO2018219996 A1 WO 2018219996A1
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gas stream
stream
butenes
butadiene
hydrocarbons
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PCT/EP2018/064159
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German (de)
English (en)
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Jan Ungelenk
Ulrich Hammon
Oliver HAMMEN
Christian Walsdorff
Marco Oskar KENNEMA
Jan Pablo Josch
Ulrike Wenning
Anton Wellenhofer
Christine TOEGEL
Hendrik Reyneke
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Basf Se
Linde Ag
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Publication of WO2018219996A1 publication Critical patent/WO2018219996A1/fr

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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
    • 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
    • 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
    • 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 preparation of 1, 3-butadiene from n-butenes by oxidative dehydrogenation (ODH).
  • Butadiene (1,3-butadiene) is an important basic chemical and is used for example for the production of synthetic rubbers (butadiene homopolymers, styrene-butadiene rubber or nitrile rubber) or for the production of thermoplastic terpolymers (acrylonitrile-butadiene-styrene copolymers ) used.
  • Butadiene is further converted to sulfolane, chloroprene and 1, 4-hexamethylenediamine (over 1, 4-dichlorobutene and adiponitrile). By dimerization of butadiene it is also possible to produce vinylcyclohexene, 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) in the presence of molecular oxygen.
  • oxidative dehydrogenation oxydehydrogenation, ODH
  • any n-butenes containing mixture 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 the feed gas stream.
  • n-butenes containing gas mixtures obtained by catalytic fluid cracking (FCC) can be used as the feed gas stream.
  • the reaction gas mixture usually contains inert components.
  • Inert components here mean that they are converted under the reaction conditions of the ODH to less than 90%.
  • Inert components are, for example, water vapor and nitrogen, but also, for example, alkanes, such as methane.
  • the molar ratio of the inert component to molecular oxygen is usually higher than that in air, especially to prevent the risk of explosions. This can be done, for example, by using air as the oxygen-containing gas and diluting it with molecular nitrogen. However, the provision of large quantities of concentrated nitrogen is expensive and unfavorable from an economic point of view. Furthermore, this can be done by using a molecular oxygen-depleted air (lean air) as the oxygen-containing gas. Furthermore, this can be done by diluting air with lean air.
  • lean air molecular oxygen-depleted air
  • US 2012 / 0130137A1 describes such a process using catalysts containing oxides of molybdenum, bismuth and, as a rule, other metals.
  • a critical minimum oxygen partial pressure in the gas atmosphere is required in order to avoid too extensive a reduction and thus a loss of performance of the catalysts.
  • ODH reactor oxydehydrogenation reactor
  • the N2 / O2 ratio in the reaction gas mixture is adjusted to the desired value by diluting air as the oxygen-containing gas with nitrogen gas.
  • the concentration of flammable gas constituents may be below the lower explosive limit (LEL) or above the upper explosive limit (LEL) to avoid ignitable mixtures.
  • LEL lower explosive limit
  • LEL upper explosive limit
  • 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, a reaction with a reaction gas mixture above the upper explosion limit is preferred.
  • the oxygen concentration is low, which is economically unfavorable.
  • the concentration of combustible gas constituents can be chosen freely, without an explosive gas can train a mixture.
  • JP 2012072086 it is described in paragraph [0014] that as the oxygen-containing gas, a gas in which the hydrocarbons, such as butadiene, n-butene, n-butane, isobutane, are separated from the product gas mixture, can be recycled to the oxydehydrogenation .
  • WO 2015/063091 A1 describes an ODH process in which the reaction of the gas streams containing butene is carried out 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.
  • the C4 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 and thus the oxygen content of the total input stream is generally limited to 12 to 13% by volume.
  • the recycle gas contains between 7 to 9 vol.% Oxygen and 0 to 2 vol.% Carbon monoxide, 0 to 1.5 vol.% Oxygenates, e.g. Acrolein, and 0 to 0.1 vol .-% hydrocarbons.
  • WO 2015/063091 A1 describes an ODH process with cycle gas recirculation, in which the content of aromatic solvents in the circulating gas stream is limited to less than 1% by volume. This is to prevent deposits caused by high-boiling organic secondary constituents and the possible enrichment of organic peroxides in the downstream apparatuses.
  • the top stream of the absorption column which is recycled as recycle gas into the oxydehydrogenation reactor, typically accumulates under a pressure of> 8 bar (a) and is generally depressurized to a pressure of ⁇ 2.5 bar (a) before entering the oxydehydrogenation reactor ,
  • the circulating gas stream cools down, and condensation of condensable fractions contained therein can occur, provided heat is not supplied to the circulating gas stream to a sufficient extent from the outside.
  • the supply of heat is economically unfavorable.
  • the separation of the cycle gas from the aromatic hydrocarbon solvent is carried out at low temperatures, preferably below 40 ° C. and / or at a high pressure of preferably 10 bar absolute or above.
  • the absorbent used in the absorption column can be cooled to a low temperature. Accordingly, an even larger amount of heat must be supplied to the circulating gas stream before re-entering the oxydehydrogenation reactor for reheating.
  • JP 2016-69352 also discusses a process for the oxidative dehydrogenation of butenes to butadiene and describes the problem that there is a risk of catalyst deactivation by coking in an oxygen-poor driving style in the reaction part.
  • concentrations for fuel gas and oxygen can not be chosen arbitrarily, given the formation of any explosive mixtures.
  • Paragraphs 0045-0046 in particular, describe that the LOC increases with increasing proportions of carbon dioxide when a mixture of nitrogen and carbon dioxide is selected as the inert gas.
  • this approach is economically unfavorable, since the provision of inert gases is expensive and must be provided with carbon dioxide, in addition to nitrogen, another inert gas.
  • the object of the invention is to provide a method which remedies the above-described disadvantages of known methods with cycle gas operation, and is characterized by a greater distance to the explosion range during all operating phases.
  • Db at least partially recycling the gas stream d2 as a circulating gas stream a2 in the oxidative dehydrogenation, characterized in that the content of carbon dioxide in the circulating gas stream a2 is set to at least 4 vol .-%.
  • the method according to the invention which includes a cycle gas mode of operation, helps to overcome the abovementioned disadvantages of known processes with cycle gas operation.
  • a method is provided in which carbon dioxide is produced at low cost in the circulating gas and fed into the input gas mixture via the circulating gas, in order to increase the limiting oxygen concentration and maintain a greater distance from the explosive region. This allows a more stable operation, especially in operating phases in which there may be increased fluctuations in the process parameters, such as when starting up reactors. In the regular operating phase, the greater distance to the explosive area gives greater scope for the intake of air.
  • the method according to the invention furthermore has the advantage that the relaxed circulating gas coming from the high-pressure part of the method is heated.
  • the carbon dioxide content in the circulating gas stream is adjusted to at least 4 vol .-%. In general, it is adjusted to 4 to 8% by volume, preferably to 4 to 5% by volume.
  • the determination of the volume fraction of carbon dioxide and the other gas components is carried out by gas chromatography.
  • the volume fraction of carbon dioxide can also be determined by an infrared measurement.
  • the circulating gas stream a2 is heated to a temperature of at least 500 ° C.
  • the circulating gas stream a2 is expanded from a pressure of at least 8 bar to a pressure of at most 2.5 bar.
  • a thermal or catalytic afterburning is carried out in the circulating gas stream a2.
  • the thermal or catalytic afterburning takes place in the circulating gas stream which is expanded to a pressure of at most 2.5 bar.
  • a catalytic afterburning takes place in such a way that the circulating gas stream a2 is heated to a temperature of at least 500.degree.
  • the exotherm of the post-combustion can be used to preheat the relaxed circulating gas stream before performing the post-combustion.
  • the selection of the coolant in the cooling stage Ca) is not subject to any restrictions. However, in the cooling step Ca), an organic solvent is preferably used.
  • organic solvents used as cooling agents are aromatic hydrocarbons, particular preference is given to toluene, o-xylene, m-xylene, p-xylene, mesitylene, all possible constitutional isomers of mono-, di- and triethylbenzene as well as all possible constitutional isomers of mono-, di-, and triisopropylbenzene or mixtures thereof.
  • aromatic hydrocarbons having a boiling point at 1013.25 hPa of more than 120 ° C. or mixtures thereof.
  • mesitylene is especially preferred.
  • the absorbent used in the separation step Da) is an aromatic hydrocarbon pulp solvent.
  • the same aromatic hydrocarbon solvent is used as in the preceding cooling step Ca) when an organic solvent is used in the cooling step Ca).
  • non-condensable and low-boiling gas constituents comprising oxygen, low-boiling hydrocarbons, optionally carbon oxides and optionally inert gases are obtained as gas stream d2. At least part of this gas stream d2 is recycled as circulating gas stream a2 into the oxidative dehydrogenation (step B)).
  • the content of carbon dioxide in the circulating gas stream a2 is set to at least 4% by volume by means of a thermal or catalytic afterburning of combustible constituents contained in the circulating gas stream.
  • Flammable components are the low boiling hydrocarbons contained in the recycle gas such as methane, ethane, ethene, propane and propene, carbon monoxide, oxygenates such as aldehydes (acrolein, methacrolein) and the aromatic hydrocarbon solvent used as the absorbent.
  • the recycle gas such as methane, ethane, ethene, propane and propene, carbon monoxide, oxygenates such as aldehydes (acrolein, methacrolein) and the aromatic hydrocarbon solvent used as the absorbent.
  • oxygenates such as aldehydes (acrolein, methacrolein) and the aromatic hydrocarbon solvent used as the absorbent.
  • aldehydes acrolein, methacrolein
  • aromatic hydrocarbon solvent used as the absorbent.
  • further combustible components such as methane, ethane or hydrogen
  • Suitable catalytic afterburning catalysts have been widely described in the literature, see, for example, Prasad et al., Catal. Rev. Sei. Closely. 26 (1984), 1; Trim, Appl. Catal. 7 (1983), 249; Arai et al., Catal. Today 26 (1995), 217; Centi, J. Mol. Catal. A 173 (2001), 287; Kirchnerova, Kor. J. Chem. Eng. 16 (1999), 427; Ciuparu et al., Catal. Rev. Sei. Closely. 44 (2002), 593 and the literature cited therein.
  • the combustion can take place adiabatically, autothermally or isothermally, for example in a fluidized bed, in a tray furnace, in a solid-tube or shell-and-tube reactor or in a plate heat exchanger reactor.
  • the flow through the bed can be oriented both axially and radially.
  • Monolith reactors can be advantageously used as an adiabatic reactor for reactions requiring little catalyst.
  • the inlet temperature of the circulating gas in the catalyst bed is typically above 100 ° C, preferably above 200 ° C.
  • the cycle gas can be preheated. Precombustion preferably takes place in such a way that the circulating gas is heated to a temperature of at least 500.degree.
  • the minimum content of 4% by volume of CO2 and the minimum temperature of 500 ° C. is achieved by exothermic conversion of organic constituents contained in the circulating gas stream into carbon dioxide.
  • the circulating gas stream contains, in addition to carbon monoxide, inter alia mesitylene, methacrolein, acrolein, furan and formaldehyde.
  • mesitylene can be stoichiometrically converted to 9 molecules of carbon dioxide, releasing about 5000 kJ / mol of heat.
  • Each molecule of methacrolein or furan can be stoichiometrically converted to 4 molecules of carbon dioxide, whereby about 3000 kJ / mol or about 2000 kJ / mol of heat are released.
  • Each molecule of acrolein can be stoichiometrically converted to 3 molecules of carbon dioxide, releasing about 1600 kJ / mol of heat.
  • Each molecule of carbon monoxide or formaldehyde can be stoichiometrically converted to a molecule of carbon dioxide, wherein about 300 kJ / mol and about 600 kJ / mol of heat are released.
  • the process according to the invention preferably also comprises the following further process steps:
  • the stage Ca) at least one cooling stage can be connected upstream, in which the product gas stream b is cooled by indirect cooling in a heat exchanger.
  • the stage Ca) can be carried out in several stages in stages Ca1) to Can), preferably in two stages in two stages Ca1) and Ca2). In this case, particularly preferably at least part of the coolant is supplied after passing through the second stage Ca2) as cooling agent of 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 as the cooling agent in step Ca) when an organic solvent is used in the cooling step Ca).
  • at least part of this cooling agent is fed after passing through the at least one cooling stage Cbb) as cooling agent of stage Ca).
  • the cooling stage Cbb) may consist of heat exchangers.
  • 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 Da) the steps Daa) to Dac): Daa) absorption of the C4 hydrocarbons comprising butadiene and n-butenes in an aromatic hydrocarbon solvent as absorption medium, wherein a C 4 -Kohlen- hydrogens laden absorbent stream and the gas stream are obtained d2 .
  • feed gas stream a1 it is possible to use pure n-butenes (1-butene and / or cis-2-butene and / or trans-2-butene), but also gas mixtures containing butenes.
  • a gas mixture can be obtained, for example, by non-oxidative dehydrogenation of n-butane.
  • a fraction which contains n-butenes as the main constituent and from the C4 fraction of the naphtha cracking was obtained by separation of butadiene and isobutene.
  • 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 the feed gas stream.
  • n-butenes-containing gas mixtures obtained by catalytic fluid cracking (FCC) can be used as the feed gas stream.
  • the feed gas stream 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 hydrogenation 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 reaction gas mixture comprising the feed gas stream a1 containing n-butenes, an oxygen-containing gas, an oxygen-containing circulating gas stream a2 and, if appropriate, further components are fed into at least one dehydrogenation zone (the ODH reactor) and the butenes present in the gas mixture are present an oxydehydrogenation catalyst oxidatively dehydrogenated to butadiene.
  • the ODH reactor the ODH reactor
  • Catalysts suitable for oxydehydrogenation are generally based on a Mo-Bi-O-containing multimetal oxide system, which generally additionally contains iron.
  • the catalyst system 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 systems are described, for example, in US 4,547,615 (Moi2BiFeo, iNi 8 ZrCr 3 Ko, 20x and Moi2BiFeo, iNi 8 AICr 3 Ko, 20x), US 4,424,141
  • X 1 Si, Mn and / or Al
  • X 2 Li, Na, K, Cs and / or Rb,
  • the molecular oxygen-containing gas generally contains more than 10% by volume, preferably more than 15% by volume and even 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.
  • a gas mixture which has a molar oxygen: n-butenes ratio of at least 0.5. Preference is given to operating at an oxygen: n-butenes ratio of 0.55 to 1.6.
  • the input gas stream with oxygen or at least one oxygen-containing gas, such as air, and optionally additional inert gas or steam can be mixed.
  • the resulting oxygen-containing gas mixture is then fed to the oxydehydrogenation.
  • inert gases such as nitrogen and also water (as water vapor) may 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.
  • the reaction temperature of the oxydehydrogenation is generally controlled by a heat exchange medium located around the reaction tubes.
  • liquid heat exchange agents e.g. Melting of salts such as potassium nitrate, potassium nitrite, sodium nitrite and / or sodium nitrate and melting of metals such as sodium, mercury and alloys of various metals into consideration. But 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 350 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 may 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 to 150 ° C, preferably between 10 to 100 ° C and more preferably between 20 to 80 ° C.
  • the temperature at the end of the catalyst bed is generally between 0 to 100 ° C, preferably between 0.1 to 50 ° C, more preferably between 1 to 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 inside 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 40,000 or 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 may consist of a single layer or of two or more layers. These layers may consist of pure catalyst or be diluted with a material that does not react with the feed gas stream or components from the product gas of the reaction. Furthermore, the catalyst layers may consist of solid material 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, 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.
  • This may be an indirect shell and tube heat exchanger.
  • the product gas mixture is passed through the tubes, and a heat exchanger medium is passed around the tubes, the nature of which may correspond to the heat exchanger media recommended for the tube bundle reactors.
  • the distance between the reactor and the indirect shell and tube heat exchanger short, for example, such that the tube bundle heat transfer is mounted directly below the reactor.
  • the interior of the tube may be filled with inert packing materials (eg stainless steel spirals, steatite rings, steatite balls, etc.).
  • inert packing materials eg stainless steel spirals, steatite rings, steatite balls, etc.
  • the aftercooler is made of zinc silicate coated stainless steel. The aftercooling described is not mandatory and may be omitted if the route of the product gas mixture from the first reaction stage into the quench is kept short.
  • spiral heat exchangers As an example of further heat exchangers, spiral heat exchangers, plate heat exchangers, Double tube heat exchangers, multi-tube heat exchangers, boiler spiral heat exchangers, shell and shell heat exchangers, liquid-liquid contact heat exchangers, air heat exchangers, direct-contact heat exchangers and finned tube heat exchangers.
  • 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 may be used so long as it is capable of dissolving the high-boiling by-products.
  • aromatic hydrocarbon solvents such as toluene and xylenes
  • alkaline aqueous solvents such as the aqueous solution of sodium hydroxide.
  • This stage is also referred to below as quench.
  • This quench can consist of only one stage or of several stages.
  • the cooling can be effected by contacting with a coolant, preferably an organic solvent.
  • the cooling medium used are organic solvents, preferably aromatic hydrocarbons, particularly preferably toluene, o-xylene, m-xylene, p-xylene, mesitylene, all possible constitutional isomers of mono-, di- and triethylbenzene and all possible constitutional isomers of mono-, di- and triisopropylbenzene or mixtures thereof.
  • aromatic hydrocarbons having a boiling point at 1013.25 hPa of above 120 ° C or 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 product gas depending on the presence and temperature level of a heat exchanger before the quench, a temperature of 100 to 440 ° C.
  • the product gas is brought into contact with the cooling medium in the first quench stage.
  • the cooling medium can be introduced through a nozzle in order to achieve the most efficient possible mixing with the product gas.
  • internals such as further nozzles, can be introduced in the quenching stage, which contain the product gas and the cooling medium in common. to happen.
  • the coolant inlet into the quench is designed to minimize clogging due to deposits in the area of the coolant inlet.
  • the product gas in the first quenching stage is cooled to 5 to 180 ° C, preferably to 30 to 130 ° C and even more preferably to 60 to 1 10 ° C.
  • the temperature of the coolant medium at the inlet may generally be 25 to 200 ° C, preferably 40 to 120 ° C, particularly preferably 50 to 90 ° C.
  • the pressure in the first quenching stage is not particularly limited, but is generally 0.01 to 4 bar (g), preferably 0.1 to 2 bar (g), and more preferably 0.2 to 1 bar (g).
  • the quenching stage is designed as a cooling tower.
  • the cooling medium used in the cooling tower is often used in a circulating manner.
  • the circulation flow of the cooling medium in liters per hour, based on the mass flow of butadiene in grams per hour, can generally be 0.0001 -5 l / g, preferably 0.001-1 l / g and particularly preferably 0.002-0.2 l / g be.
  • the temperature of the cooling medium in the bottom can generally be 27 to 210 ° C, preferably 45 to 130 ° C, particularly preferably 55 to 95 ° C. Since the loading of the cooling medium with secondary components increases over time, a portion of the loaded cooling medium can be withdrawn from the circulation as a purge stream and the circulation volume can be kept constant by adding unzula- denem cooling medium. The ratio of effluent amount and added amount depends on the vapor load of the product gas and the product gas temperature at the end of the first quench stage.
  • condensation of water may occur in the first quench stage.
  • an additional aqueous phase may form, which may additionally contain water-soluble secondary components. This can then be subtracted in the bottom of the quenching stage. Preference is given to an operation in which no aqueous phase is formed in the first quench stage.
  • the cooled and possibly depleted in secondary components product gas stream can now be fed to a second quenching stage. In this he can now be brought into contact again with a cooling medium.
  • cooling media are organic solvents, particularly preferably aromatic hydrocarbons, in particular toluene, o-xylene, m-xylene, p-xylene, mesitylene, all possible constitutional isomers of mono-, di- and triethylbenzene and all possible constitutional isomers of mono-, di-, and triisopropylbenzene or mixtures thereof.
  • aromatic hydrocarbons having a boiling point at 1013.25 hPa of above 120 ° C or mixtures thereof.
  • the product gas is cooled to 5 to 100 ° C, preferably 15 to 85 ° C and even more preferably 30 to 70 ° C, to the gas exit of the second quench stage.
  • the coolant can be supplied in countercurrent to the product gas.
  • the temperature of the coolant medium at the coolant inlet may be 5 to 100 ° C, preferably 15 to 85 ° C, particularly preferably 30 to 70 ° C.
  • the pressure in the second quenching stage is not particularly limited, but is generally 0.01 to 4 bar (g), preferably 0.1 to 2 bar (g), and more preferably 0.2 to 1 bar (g).
  • the second quenching stage is preferably designed as a cooling tower.
  • the cooling medium used in the cooling tower is often used in a circulating manner.
  • the circulation stream of the cooling medium in liters per hour can generally be from 0.0001 to 5 l / g, preferably from 0.3001 to 1 l / g and particularly preferably from 0.002 to 0, 2 l / g.
  • condensation of water may occur in the second quench stage.
  • an additional aqueous phase may form, which may additionally contain water-soluble secondary components.
  • the temperature of the cooling medium in the bottom can generally be from 20 to 210 ° C., preferably from 35 to 120 ° C., particularly preferably from 45 to 85 ° C. Since the loading of the cooling medium with secondary components increases over time, a portion of the loaded cooling medium can be withdrawn as purge stream from the circulation, and the circulating amount can be kept constant by adding unladen cooling medium.
  • internals may be present in the second quenching stage.
  • Such internals include, for example, bell, centrifugal and / or sieve trays, columns with structured packings, eg sheet metal packings having a specific surface area of 100 to 1000 m 2 / m 3 such as Mellapak® 250 Y, and packed columns.
  • the coolant circulations of the two quench stages can be both separated from each other and connected to each other.
  • the power can be supplied to the power or replace it.
  • the desired temperature of the circulating streams can be adjusted by means of suitable heat exchangers.
  • the cooling stage Ca) is carried out in two stages, with the second-stage coolant Ca 2) loaded with secondary components being led into the first stage Ca1).
  • the coolant removed from the second stage Ca2) contains fewer secondary components than the coolant removed from the first stage Ca1).
  • suitable structural measures such as the installation of a demisters, can be made.
  • high-boiling substances which are not separated from the product gas in the quench can be removed from the product gas by further structural measures, such as, for example, further gas scrubbing.
  • a gas stream is obtained in which n-butane, 1-butene, 2-butenes, butadiene, optionally oxygen, hydrogen, water vapor, in small amounts methane, ethane, ethene, propane and propene, isobutane, carbon oxides, inert gases and Contains parts of the coolant used in the quench.
  • high-boiling components include, for example, methyl vinyl ketone, methyl ethyl ketone, crotonaldehyde, acrylic acid, propionic acid, maleic anhydride, ethylbenzene, styrene, furanone, benzoic acid, benzaldehyde, fluorenone and anthraquinone.
  • this gas stream may contain formaldehyde, methacrolein and / or furan.
  • the product gas stream from the quench is compressed in at least one compression stage and subsequently further cooled in the cooling apparatus, wherein at least one condensate stream containing water is formed. If a coolant other than water is used in the quench, the coolant used in the quench can furthermore condense out and, if appropriate, form a separate phase. There remains a gas stream containing butadiene, 1-butene, 2-butenes, 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. Furthermore, 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). Generally, 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 stage follows, in which the gas stream is cooled to a temperature in the range of 15 to 60 ° C.
  • the cooling is preferably carried out by contacting with an organic solvent as a cooling agent.
  • heat exchangers can also be used.
  • 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 (aqueous phase) and optionally the refrigerant used in the quench (organic phase). Both streams (aqueous and organic phase) may also contain minor components such as low boilers, C4 hydrocarbons, oxygenates and carbon oxides.
  • the condensed quench coolant can be cooled in a heat exchanger and recycled as coolant into the apparatus. Since the loading of this cooling medium with minor components increases over time, a portion of the loaded cooling medium can be withdrawn from circulation and the circulating amount of the cooling medium can be kept constant by adding uncharged coolant.
  • the coolant, which is added as a cooling medium thus also preferably consists of the aromatic hydrocarbon solvent used as quench coolant.
  • the condensate stream can be returned to the recycle stream of the quench. As a result, the absorbed in the condensate stream C4 components can be brought back into the gas stream and thus the yield can be increased.
  • Suitable compressors are, for example, turbo, rotary piston and reciprocating compressors.
  • the compressors can be driven, for example, with an electric motor, an expander or a gas or steam turbine.
  • Typical compression ratios (outlet pressure: inlet pressure) per compressor stage are between 1, 5 and 3.0, depending on the design.
  • the cooling of the compressed gas is carried out with organic solvent purged heat exchangers or organic quench, which may be designed, for example, as a tube bundle, spiral or plate heat exchanger.
  • coolant cooling water or heat transfer oils are used in the heat exchangers.
  • air cooling using blowers is preferably used.
  • 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 secondary components containing gas stream c2 is as Output current fed to the further treatment.
  • a step Da) 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 from the process gas stream c2 by absorption of C4 hydrocarbons in an aromatic Hydrocarbon solvent as high-boiling absorbent and subsequent desorption of C 4 -hydrocarbons separated.
  • the step Da) comprises the steps Daa) to Dac):
  • the gas stream c2 is brought into contact with the absorbent and the C 4 hydrocarbons are absorbed in the absorbent, wherein a loaded with C 4 hydrocarbons absorbent and the other gas constituents containing gas stream d2 is obtained, which is at least partially recycled as a circulating gas stream in the oxidative dehydrogenation.
  • the C4 hydrocarbons are released from the absorbent again.
  • absorption organic solvents preferably aromatic hydrocarbons, particularly preferably toluene, o-xylene, m-xylene, p-xylene, mesitylene, all possible constitution isomers of mono-, di- and triethylbenzene and all possible constitution isomers of mono-, di- and Triisopropylbenzene or mixtures thereof.
  • aromatic hydrocarbons having a boiling point at 1013.25 hPa of above 120 ° C or mixtures thereof. More specifically, in the separation step Da), the same aromatic hydrocarbon solvent is used as in the preceding cooling step Ca) when an organic solvent is used in the cooling step Ca).
  • Preferred absorbents are solvents which have a solubility for organic peroxides of at least 1000 ppm (mg active oxygen / kg solvent). In a preferred embodiment, mesitylene is used as the absorbent for the absorption.
  • 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, for example, tray columns with bells, centrifugal and / or sieve bottom, columns with structured packings, for example sheet metal packings having a specific surface area of 100 to 1000 m 2 / m 3 such as Mellapak® 250 Y, and packed columns. But there are also trickle and spray towers, graphite block absorbers, surface absorbers such as thick film and
  • an absorption column in the lower region of the butadiene, n-butenes and the low-boiling and non-condensable gas components containing gas stream c2 is supplied.
  • the absorbent is abandoned.
  • a gas stream d2 is withdrawn, which is essentially oxygen, low-boiling hydrocarbons (methane, ethane, ethene, propane, propene), the aromatic hydrocarbon solvent, optionally C4 hydrocarbons (butane, butenes, butadiene), optionally inert gases, if appropriate Carbon oxides and optionally still contains water vapor.
  • This stream is at least partially supplied as a circulating gas stream a2 the ODH reactor. This makes it possible, for example, to adjust the inlet flow of the ODH reactor to the desired C4 hydrocarbon content.
  • 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 recycle stream is preferably subjected to thermal or catalytic afterburning.
  • the absorbent dissolved oxygen can be discharged in a further column by flushing with a gas.
  • the remaining oxygen content is preferably so small that the stream d1 leaving the desorption column and containing butane, butene and butadiene only contains at most 100 ppm oxygen.
  • the stripping out of the oxygen in step Dab) 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 inert gases such as nitrogen, through the loaded absorption solution. With stripped C4 is washed in the upper part of the absorption column back into the absorption solution by the gas stream is fed back into this absorption column. This can be done both by a piping of the stripping column and a direct assembly of the stripping column below the absorber column. Since the pressure in the stripping column part and the absorption column part is the same according to the invention, this direct coupling can take place.
  • Suitable stripping columns are tray columns with bells, centrifugal and / or sieve plates, columns with structured packings, eg sheet metal packings with a specific surface area of 100 to 1000 m 2 / m 3 such 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.
  • the C4 hydrocarbon laden absorbent stream may include water. This can be separated as a stream from the absorbent in a decanter, so that a stream is obtained which contains only the redeemed water in the absorbent.
  • the adsorbent stream d2 which has been freed of C4 hydrocarbons and largely freed from water, can be heated in a heat exchanger and subsequently passed into a desorption column.
  • the desorption step De) is carried out by relaxation and / or heating of the loaded absorbent.
  • a preferred process variant is the use of a reboiler in the bottom of the desorption column.
  • the absorbent regenerated in the desorption stage can be cooled in a heat exchanger and returned to the absorption stage.
  • low boilers such as ethane or propane and high-boiling components such as benzaldehyde, maleic anhydride and phthalic anhydride
  • a purge stream can be withdrawn the. This can be separated in a distillation column according to the prior art in low boilers, regenerated absorbent and high boiler.
  • the C4 product gas stream d1 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 1 - Butene, and 0 to 50% by volume of 2-butenes, the total amount being 100% by volume. Furthermore, small amounts of iso-butane may be included.
  • the liquid or gaseous C4 product streams leaving the condenser can subsequently be separated by extractive distillation in step E) with a solvent which is selective for butadiene into a butadiene and the material stream containing the selective solvent and a stream containing n-butenes.
  • the extractive distillation may, for example, as described in "petroleum and coal - natural gas - petrochemistry", Volume 34 (8), pages 343 to 346 or “Ullmann's Encyclopedia of Industrial Chemistry", Volume 9, 4th edition 1975, pages 1 to 18, be performed.
  • the C4 product gas stream is brought into contact with an extraction agent, preferably an N-methylpyrrolidone (NMP) / water mixture, in an extraction zone.
  • NMP N-methylpyrrolidone
  • the extraction zone is generally carried out in the form of a wash column which contains trays, fillers or packings as internals. This generally has 30 to 70 theoretical plates, so that a sufficiently good release effect is achieved.
  • the wash column has a backwash zone in the column head.
  • This backwash zone is used to recover the extractant contained in the gas phase by means of a liquid hydrocarbon reflux, to which the top fraction is condensed beforehand.
  • the mass ratio extractant to C4 product gas stream in the feed of the extraction zone is generally from 10: 1 to 20: 1.
  • the extractive distillation is preferably carried out at a bottom temperature in the range of 100 to
  • the extractive distillation column preferably has from 5 to 70 theoretical plates.
  • Suitable extractants are butyrolactone, nitriles such as acetonitrile, propionitrile, methoxypropionitrile, ketones such as acetone, furfural, N-alkyl-substituted lower aliphatic acid amides such as dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, N-formylmorpholine, N-alkyl-substituted cyclic acid amides (lactams) such as N Alkylpyrrolidones, especially N-methylpyrrolidone (NMP).
  • NMP N-methylpyrrolidone
  • alkyl-substituted lower aliphatic acid amides or N-alkyl substituted cyclic acid amides are used.
  • Particularly advantageous are dimethylformamide, acetonitrile, furfural and in particular NMP.
  • Particularly suitable is NMP, preferably in aqueous solution, preferably with 0 to 20 wt .-% water, particularly preferably with 7 to 10 wt .-% water, in particular with 8.3 wt .-% water.
  • the overhead product stream of the extractive distillation column contains essentially butane and butenes and in small amounts of butadiene and is taken off in gaseous or liquid form.
  • the stream consisting essentially of n-butane and 2-butene contains up to 100% by volume of n-butane, 0 to 50% by volume of 2-butene and 0 to 3% by volume of further constituents, such as isobutane , Isobutene, propane, propene and Cs + hydrocarbons.
  • the stream consisting essentially of n-butane and 2-butenes can be fed wholly or partly to the C 4 feed of the ODH reactor. Since the butene isomers of this recycle stream consist essentially of 2-butenes, and 2-butenes are generally more slowly dehydrogenated to butadiene than 1-butene, this recycle stream can be catalytically isomerized prior to being fed to the ODH reactor. As a result, the isomer distribution can be adjusted according to the isomer distribution present in the thermodynamic equilibrium.
  • the stream comprising butadiene and the selective solvent is fractionated by distillation into a stream consisting essentially of the selective solvent and a stream comprising butadiene.
  • the stream obtained at the bottom of the extractive distillation column generally contains the extractant, water, butadiene and, in minor proportions, butenes and butane and is fed to a distillation column. In this can be obtained overhead or as a side take butadiene.
  • an extractant and, if appropriate, water-containing material stream are obtained, the composition of the extractant and water-containing material stream corresponding to the composition as it is added to the extraction.
  • the extractant and water-containing stream is preferably returned to the extractive distillation. If the butadiene is recovered via a side draw, the extraction solution thus withdrawn is transferred to a desorption zone, wherein from the extraction solution, the butadiene is desorbed again and washed back.
  • the desorption zone can be embodied, for example, in the form of a wash column which has from 2 to 30, preferably from 5 to 20, theoretical stages and, if appropriate, a backwashing zone with, for example, four theoretical stages.
  • This backwash zone is used to recover the extractant contained in the gas phase by means of a liquid hydrocarbon reflux, to which the top fraction is condensed beforehand.
  • As internals packings, trays or packing are provided.
  • the distillation is preferably carried out at a bottom temperature in the range of 100 to 300 ° C, in particular especially in the range of 150 to 200 ° C and a head temperature in the range of 0 to 70 ° C, in particular in the range of 10 to 50 ° C.
  • the pressure in the distillation column is preferably in the range of 1 to 10 bar. In general, in the desorption zone, a reduced pressure and / or elevated temperature prevail over the extraction zone.
  • the product stream obtained at the top of the column generally contains 90 to 100% by volume of butadiene, 0 to 10% by volume of 2-butene and 0 to 10% by volume of n-butane and isobutane.
  • a further distillation according to the prior art can be carried out.
  • the circulating gas stream d2 occurs, if necessary after preheating a purge stream p preheated to 330 ° C and a carbon dioxide content of 1, 9 vol .-%, an oxygen content of 7.6 vol .-% and a total organic content of 1, 6 vol .-% in a converter for catalytic afterburning.
  • the pressure is 2.95 bar absolute. Due to the exothermic reaction, the stream exits the converter at a temperature of 705 ° C. and a carbon dioxide content of 4.5% by volume and an oxygen content of 5.5% by volume as stream a2.
  • the stream a2 is, if necessary, after separation of a purge stream p2, driven back into the reactor. Table 1
  • Pressure bar 3 1 3.0 1, 5 10 10 3.0 3.0 10
  • PROP-SAEURE% by weight 0.00 0.00 0.02 0.00 0.06 0.00 0.00 0.00 0.00

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Abstract

Procédé de préparation de butadiène à partir de n-butènes comprenant les étapes consistant à : A) mettre à disposition un flux de gaz de mise en œuvre contenant des n-butènes a1, B) charger le flux de gaz de mise en œuvre contenant des n-butènes a1, un gaz contenant de l'oxygène et un flux de gaz de recyclage contenant de l'oxygène a2 dans au moins une zone de déshydrogénation oxydative et procéder à la déshydrogénation oxydative des n-butènes en butadiène, ce qui permet d'obtenir un flux de gaz de produit b contenant du butadiène, des n-butènes n'ayant pas réagi, de la vapeur d'eau, de l'oxygène, des hydrocarbures à bas point d'ébullition, des composants secondaires à point d'ébullition élevé, le cas échéant des oxydes de carbone et le cas échéant des gaz inertes, Ca) refroidir le flux de gaz de produit b et le cas échéant séparer au moins partiellement les composants secondaires à point d'ébullition élevé et la vapeur d'eau, ce qui permet d'obtenir un flux de gaz de produit b', Cb) comprimer et refroidir le flux de gaz de produit b' en au moins une étape de compression et de refroidissement, ce qui permet d'obtenir au moins un flux de condensat aqueux c1 et un flux de gaz c2 contenant du butadiène, des n-butènes, de la vapeur d'eau, de l'oxygène, des hydrocarbures à bas point d'ébullition, le cas échéant des oxydes de carbone et le cas échéant des gaz inertes, Da) absorber les hydrocarbures en C4 comprenant du butadiène et des n-butènes dans un solvant hydrocarbure aromatique comme agent d'absorption et séparer les composants gazeux non condensables et à bas point d'ébullition comprenant de l'oxygène, des hydrocarbures à bas point d'ébullition, le cas échéant des oxydes de carbone, le solvant hydrocarbure aromatique et le cas échéant des gaz inertes comme flux de gaz d2 à partir du flux de gaz c2, ce qui permet d'obtenir un flux d'agent d'absorption chargé d'hydrocarbures en C4 et le flux de gaz d2, et procéder ensuite à la désorption des hydrocarbures en C4 à partir du flux d'agent d'absorption chargé, ce qui permet d'obtenir un flux de gaz de produit en C4 d1, Db) renvoyer au moins partiellement le flux de gaz d2 sous forme de flux de gaz de recyclage a2 dans la zone de déshydrogénation oxydative, caractérisé en ce que la teneur en dioxyde de carbone dans le flux de gaz de recyclage a2 est réglée à au moins 4% en volume.
PCT/EP2018/064159 2017-06-02 2018-05-30 Procédé pour la préparation de 1,3-butadiène à partir de n-butènes par déshydrogénation oxydative par recyclage de gaz avec un gaz de recyclage enrichi en co2 WO2018219996A1 (fr)

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US11548839B2 (en) * 2020-09-17 2023-01-10 Indian Oil Corporation Limited Integrated oxidative alkane dehydrogenation and hydrogen generation process

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