WO2017009665A1 - Procédé de préparation de butadiène à partir de butènes par déshydrogénation oxydative - Google Patents

Procédé de préparation de butadiène à partir de butènes par déshydrogénation oxydative Download PDF

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Publication number
WO2017009665A1
WO2017009665A1 PCT/GB2016/052159 GB2016052159W WO2017009665A1 WO 2017009665 A1 WO2017009665 A1 WO 2017009665A1 GB 2016052159 W GB2016052159 W GB 2016052159W WO 2017009665 A1 WO2017009665 A1 WO 2017009665A1
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Prior art keywords
alkene
steam
catalyst
butene
feed stream
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PCT/GB2016/052159
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English (en)
Inventor
Xavier Elie Baucherel
Paul Mcguire
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Johnson Matthey Public Limited Company
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Publication of WO2017009665A1 publication Critical patent/WO2017009665A1/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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/24—Chromium, molybdenum or tungsten
    • C07C2523/28—Molybdenum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/24—Chromium, molybdenum or tungsten
    • C07C2523/31—Chromium, molybdenum or tungsten combined with bismuth
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/20—Carbon compounds
    • C07C2527/22—Carbides
    • C07C2527/224—Silicon carbide

Definitions

  • the present application concerns a process for the dehydrogenation of an alkene.
  • the reaction proceeds in the presence of a catalyst and steam.
  • the oxygen also combines with some of the butene feedstock to provide heat and may also prolong the active life of the catalyst by burning away coke deposits.
  • Commercial processes operate in the presence of added steam, usually present in amounts to produce a molar ratio in the feed stream of at least 10: 1 (steam : hydrocarbon).
  • steam is used to assist with management of heat in the reactor and to minimise the deactivation of the catalyst by minimising the deposition of carbon onto the catalyst. Whilst all commercial processes use steam, the presence of large volumes of steam brings disadvantages, including the energy requirement involved in generating, pumping and later separating the steam from the reaction products. We have found, surprisingly, that the process may be advantageously operated at very low steam ratios.
  • a process for the production of a diene by dehydrogenation of an alkene comprises the step of reacting a feed stream containing said alkene over a catalyst bed comprising a metal oxide catalyst at a temperature sufficient to effect conversion of said alkene to said diene to form a product stream containing said diene, said feed stream comprising said alkene, oxygen, optionally an inert gas and optionally steam, wherein the molar ratio of alkene : O2 : steam in said feed stream is in the range 1 : 0.5 - 1 : 0 - 5.
  • the process is particularly useful for the production of butadiene from n-butene (1 -butene and/or 2-butene).
  • the process may comprise feeding a mixed butenes feed containing 1 -butene and 2- butene.
  • the alkene may comprise or consist of n-butenes.
  • the alkene may be n-butene(s) and the diene may be butadiene.
  • the catalyst is a metal oxide catalyst.
  • Known catalysts for the oxidative dehydrogenation of alkenes include oxides of bismuth, molybdenum, iron, magnesium, manganese, zinc, aluminium, platinum, tin, vanadium, zirconium, beryllium, calcium, strontium and other transition metals such as Cu, Co, and Ni.
  • catalysts based on mixed oxides of Bi + Mo and on Fe + Mg/Mn are proposed for this reaction.
  • Mixed Bi and Mo oxides include bismuth molybdate catalysts.
  • Bismuth molybdate catalysts may be in the alpha, beta or gamma forms.
  • the catalyst may comprise alpha or beta bismuth molybdate.
  • Other elements e.g.
  • the catalyst may be made by conventional catalyst manufacturing methods. Suitable methods include precipitation, and may include co-precipitation of more than one compound. The precipitated compounds may be converted to catalytically active or stable compounds by methods including heat treatment.
  • the reaction temperature is typically in the range 300 - 600 °C, and may be in the range 350 - 500 °C, especially in the range 400 - 450 °C.
  • the skilled person will adjust the reaction temperature as required in order to maintain a desired rate of conversion of alkene.
  • the dehydrogenation reaction is endothermic, whilst the reaction of oxygen with produced hydrogen is highly exothermic.
  • the presence of oxygen in the feed stream may provide heat by burning a hydrocarbon present in the feed stream.
  • the hydrocarbon may comprise a portion of the alkene feed.
  • An inert gas may be added to the reactor in order to control the reaction temperature. Suitable inert gases include nitrogen, for example. Heat management within the reactor may be carried out as necessary, by heating or cooling at least portions of the reactor.
  • the reaction pressure may be typically in the range from 1 to 10 barg (gauge pressure of 0.1 - 1 MPa).
  • Oxygen performs several useful functions in the reaction and is typically co-fed to the reactor with the alkene feed. It is, however, desirable to convert as much of the added O2 as possible in order to avoid the need to separate O2 from the gaseous products of the reaction.
  • One advantage of the process of the invention is that the low steam ratios may promote relatively high conversion of oxygen.
  • the alkene : O2 molar ratio is within the range 1 : 0.5 - 1 .
  • the reaction has been found to run well with an alkene : O2 molar ratio within the range 1 : 0.7 - 0.8, for example about 1 : 0.75.
  • steam may be formed in a vaporisation step and added to the reactor in that form.
  • the feed stream comprising alkene, oxygen, optionally an inert gas and optionally steam may be combined as a single feed stream or the components may be added to the reactor separately or as a combination of co-feeding and separate feeding.
  • the ratio of alkene: steam is in the range 1 :0 to 3, especially 1 : ⁇ 3, for example 1 : 0 - 2 by volume, and 1 : 0 - 1 .5 by volume, including 0 - 1 .0 by volume or 0 - ⁇ 1 by volume.
  • the molar ratio of alkene: steam is in the range 1 :0 to 3, especially 1 : ⁇ 3, for example 1 : 0 - 2, particularly 1 : 0 - 1 .5, including 0 - 1 .0 or 0 - ⁇ 1 . Under the conditions used, any difference between volume ratio and molar ratio is believed to be immaterial so that molar ratio and volume ratio have the same value.
  • the reaction may be carried out continuously under fixed bed conditions.
  • the reaction may take place in an axial or a radial flow reactor.
  • the catalyst may be present as a bed of catalyst particles supported within a reactor space, i.e. in a so-called "fixed bed” reactor.
  • the catalyst particles for such reactors are typically pellets, tablets or other "catalyst units" having a minimum dimension of at least 0.5 mm.
  • the catalyst units may be shaped as cylinders, multi-lobed cylinders (e.g. tri-lobes), spheres, rings, saddles or other shapes. A large number of suitable catalyst shapes and sizes for use in catalyst beds are well-known to the skilled catalyst developer and to process operators.
  • the reactor may be provided with means for controlling the reaction temperature, such as heating and/or cooling means or for measuring the temperature at one or more locations within the reactor.
  • the reaction may take place in a non-adiabatic reactor, especially a reactor having a heat transfer medium for heating or cooling.
  • the heat transfer medium may include any suitable conventional type, including oils and molten salt cooling.
  • the reactor may include one or more reactor tubes, for example in a shell and tube reactor.
  • the reaction may alternatively be carried out under fluid bed conditions.
  • a catalyst for fluidised bed operation typically comprises smaller particles than those used in a fixed bed reactor.
  • Fluidised bed processes are particularly beneficial when rapid catalyst deactivation takes place leading to a requirement for continual catalyst regeneration.
  • a fluidised bed may provide greater opportunity for temperature management of the reaction than a fixed bed reaction, although catalyst particle attrition is a known problem with fluidised bed operation.
  • the process may be operated at a range of conditions.
  • the process is operated in the gas phase.
  • the gas hourly space velocity (GHSV) may be varied within a wide range of parameters.
  • the GHSV may be from about 300 to about 1500 hr .
  • the GHSV is calculated as the volume of alkene fed per hour divided by the volume of catalyst bed. Increasing the space velocity may increase selectivity of the reaction to the desired diene. Increasing the reaction temperature may increase conversion and compensate for any loss of conversion due to increased space velocity.
  • the products of the reaction are usually processed in at least one separation step, which may comprise a distillation or fractionation.
  • the organic components of the product stream, comprising unreacted alkene and product diene are separated.
  • the product diene, optionally after further purification steps may be stored or used directly in a subsequent process.
  • Unreacted alkene may be recycled to the dehydrogenation reaction.
  • Steam or water may be separated from the product stream and a portion of it may be recycled to the dehydrogenation reaction if desired, although it is a particular feature of the process of the invention that the reaction takes place in the presence of low steam volumes or no steam, so that the amount of cooling required to separate steam or water from the product stream is much reduced.
  • the process flow sheet includes such other steps as may be conventionally carried out for such a process. Such steps may include, mixing, vaporisation, heating, cooling, purification, effluent treatment etc.
  • Example 1 Preparation of beta bismuth molybdenum oxide ⁇
  • Ammonium paramolybdate (7.04g, 0.0057 mols) was dissolved in de-ionised water (200 ml). Concentrated nitric acid was added dropwise to lower the pH to 1 .8 and the solution was aged for 15 minutes.
  • Bismuth nitrate (19.4g, 0.039mols) was dissolved in a mixture of concentrated nitric acid (15 ml) and water (30 ml). The bismuth nitrate solution was added over a period of 30 minutes to the aged molybdenum solution whilst maintaining a pH 1 .8 using concentrated ammonia.
  • the resulting suspension was filtered, air dried at room temperature (16 hours) followed by a heat treatment at 1 15°C (5°C per min, hold for 1 hour), then 200°C (5 °C per min, hold 3 hours), then 450°C (5°C per min, hold 3 hour). A pale yellow solid was obtained.
  • the resulting solid material was characterised using X-ray diffraction (XRD), Raman spectroscopy and X-ray fluorescence spectroscopy (XRF) to confirm the identity of the product as ⁇ -bismuth molybdate ( ⁇ ).
  • Example 2 Preparation of gamma bismuth molybdenum oxide ⁇ 2 ⁇ 6 Ammonium paramolybdate (10.58g, 8.56mols) was dissolved in de-ionised water (140ml). Bismuth nitrate (58.28g, 0.120mols) was dissolved in a mixture of concentrated nitric acid (15 ml) and water (30 ml). The bismuth nitrate solution was added over 30 minutes to the aged molybdenum solution whilst maintaining a pH of 2 using 28 wt% ammonia.
  • the resulting suspension was filtered, air dried at room temperature (16 hours) followed by a heat treatment at 1 15°C (5°C per min , hold for 1 hour), then 200°C (5 °C per min , hold 3 hours), then 450°C (5°C per min , hold 3 hours).
  • a pale yellow solid was obtained, which was characterised using X-ray diffraction (XRD), Raman spectroscopy and X-ray fluorescence spectroscopy (XRF) to confirm the identity of the product as ⁇ -bismuth molybdate (B MoOe).
  • Ammonium paramolybdate (128.53g, 0.104 mols) was dissolved in de-ionised water (1600 ml). Concentrated nitric acid was added dropwise to pH 1 .5 and the solution aged for 1 hour. Bismuth nitrate (232.83g 0.480mols) was dissolved in a mixture of concentrated nitric acid (140 ml) and water (500 ml). The bismuth nitrate solution was added over 30 minutes to the aged molybdenum solution whilst maintaining a pH 1 .5 using concentrated ammonia.
  • the resulting suspension was aged for 1 hour, filtered, air dried at room temperature (16 h) followed by a heat treatment at 1 1 5 °C (5°C per min , hold for 1 hour), 200°C (5 °C per min, hold for 3 hours), 450°C ( 5°C per min, hold for 3 hours).
  • a pale yellow solid was obtained, which was characterised using X-ray diffraction (XRD), Raman spectroscopy and X-ray fluorescence spectroscopy (XRF) to confirm the identity of the product as a-bismuth molybdate ( ⁇ 2 ⁇ 3 ⁇ 2).
  • the solid a-bismuth molybdate catalyst was formed into 3.3 mm pellets using 1 wt% graphite as lubricant. The pellets were then ground and sieved to 1 .7 to 2 mm fractions before testing for activity.
  • Alpha-Bi2M03Oi2 (2.8ml, 5.4g , particle size between 1 .7 and 2 mm) was mixed with silicon carbide (3.2g, particle size between 300 and 600 ⁇ ).
  • a fixed bed reactor (19 mm diameter) was charged with the catalyst and silicon carbide mixture.
  • Silicon carbide (3g, particle size between 300 and 600 ⁇ ) and alumina rocks are charged on top of the reactor.
  • the reactor is connected to the testing rig.
  • a flow of 10%(by volume) O2 in N2 was passed over the catalyst at 210 ml/min (1 barg). The temperature of the reactor was raised to 470°C and then the temperature was maintained for 1 hour before the temperature was reduced to 440°C.
  • CO, CO2 and O2 are analysed using a thermal conductivity detector using a HayeSep® column and a Molecular Sieve 13X column in series. Helium at a flow of 30 ml/min is used as carrier gas.
  • Table 1 shows results using ⁇ - ⁇ 2 ⁇ 3 ⁇ 2 , as described in Example 3, as catalyst at a reaction temperature of 440°C, GHSV 640lr 1 , butene : O2 volume ratio 1 : 0.7, steam : butene volume ratio as stated in the table.
  • the column labelled "A” shows the averaged results for the first five hours on-line and column “B” shows the averaged results obtained between 85 and 90 hours on-line operation of the process.
  • Table 2 shows results using ⁇ - ⁇ 2 ⁇ 3 ⁇ 2 as catalyst at a reaction temperature of 440°C, with GHSV and butene : O2 volume ratio as shown in the table, and no steam.
  • the column labelled "A” shows the averaged results for the first five hours on-line and column “B” shows the averaged results obtained between 85 and 90 hours on-line operation of the process.
  • Table 3 shows results using ⁇ - ⁇ 2 ⁇ 3 ⁇ 2, ⁇ - B12M02O9 and ⁇ - ⁇ 2 ⁇ 6 as catalyst at a reaction temperature of 440°C, GHSV 640lr 1 , butene to O2 volume ratio 1 to 0.7, in the absence of steam. The reactions were carried out using the general method described for the alpha catalyst above.
  • the ⁇ - B12M02O9 and ⁇ - B12M0O6 catalyst particles were obtained by grinding and sieving the material after the heat treatment, without a pelleting step.
  • the column labelled "A” shows the averaged results for the first five hours on-line and column “B” shows the averaged results obtained between 85 and 90 hours on-line operation of the process, with the exception of ⁇ - ⁇ 2 ⁇ 6 for which the column B results represent average results between 60 and 65 hours online, due to deactivation.
  • the rate of deactivation was calculated for each catalyst under the operating conditions shown in Table 4.
  • the rate of deactivation is indicated in Table 4 as the change in butadiene yield per hour between 10 and 90 hours on line. This shows that the ⁇ - ⁇ 2 ⁇ 6 exhibits a high rate of deactivation under the process conditions used.
  • Butene O2 : water (h- 1 ) Catalyst (% BD yield. Ir )
  • An oxidative dehydrogenation process was operated as described above at GHSV 1400 hr 1 , a reaction temperature of 370°C and a volume ratio of butene : O2 of 1 : 0.6.
  • the catalyst used was an oxidic catalyst containing bismuth, molybdenum, iron and cobalt in the form of particles having an average size in the range 1 - 1 .7 mm.
  • the initial ratio of butene : steam in the gas feed to the reactor was 1 :5 by volume. After about 23 hours the ratio was changed to 1 :4. After a total of about 42 hours online, the butene to steam ratio was changed to 1 : 3.
  • the yield of butadiene was calculated as shown above. The rate of change of butadiene yield with time was calculated from the slope of the curve for butadiene yield at each value of butene : steam ratio in order to demonstrate how each set of conditions affected the rate of deactivation of the catalyst. The results are shown in Table 6.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé de production d'un diène par déshydrogénation d'un alcène comprenant l'étape consistant à faire réagir un flux d'alimentation contenant ledit alcène sur un catalyseur de type oxyde métallique à une température suffisante pour permettre la conversion dudit alcène en diène et former un flux de produit contenant ledit diène, le procédé étant caractérisé en ce que le flux d'alimentation comprend ledit alcène, de l'oxygène, éventuellement un gaz inerte et éventuellement de la vapeur d'eau, le rapport molaire alcène:O2:vapeur d'eau dans ledit flux d'alimentation étant dans la plage de 1:0,5 à 1:0-5.
PCT/GB2016/052159 2015-07-16 2016-07-15 Procédé de préparation de butadiène à partir de butènes par déshydrogénation oxydative WO2017009665A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140163292A1 (en) * 2012-12-06 2014-06-12 Basf Se Process for the Oxidative Dehydrogenation of N-Butenes to Butadiene
EP2862626A1 (fr) * 2013-05-06 2015-04-22 LG Chem, Ltd. Catalyseur à oxydes mixtes mésoporeux, procédé pour le préparer et procédé de synthèse de 1,3-butadiène l'utilisant
DE102013226370A1 (de) * 2013-12-18 2015-06-18 Evonik Industries Ag Herstellung von Butadien durch oxidative Dehydrierung von n-Buten nach vorhergehender Isomerisierung

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140163292A1 (en) * 2012-12-06 2014-06-12 Basf Se Process for the Oxidative Dehydrogenation of N-Butenes to Butadiene
EP2862626A1 (fr) * 2013-05-06 2015-04-22 LG Chem, Ltd. Catalyseur à oxydes mixtes mésoporeux, procédé pour le préparer et procédé de synthèse de 1,3-butadiène l'utilisant
DE102013226370A1 (de) * 2013-12-18 2015-06-18 Evonik Industries Ag Herstellung von Butadien durch oxidative Dehydrierung von n-Buten nach vorhergehender Isomerisierung

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GB2548427B (en) 2018-03-21
GB2548427A (en) 2017-09-20
GB201612347D0 (en) 2016-08-31

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