WO2014102292A1 - Procédé de préparation d'éthylène et de propylène à partir d'un composé oxygéné - Google Patents

Procédé de préparation d'éthylène et de propylène à partir d'un composé oxygéné Download PDF

Info

Publication number
WO2014102292A1
WO2014102292A1 PCT/EP2013/078006 EP2013078006W WO2014102292A1 WO 2014102292 A1 WO2014102292 A1 WO 2014102292A1 EP 2013078006 W EP2013078006 W EP 2013078006W WO 2014102292 A1 WO2014102292 A1 WO 2014102292A1
Authority
WO
WIPO (PCT)
Prior art keywords
hydrocarbons
fraction
stream
process according
saturated
Prior art date
Application number
PCT/EP2013/078006
Other languages
English (en)
Inventor
Leslie Andrew Chewter
Jeroen Van Westrenen
Original Assignee
Shell Internationale Research Maatschappij B.V.
Shell Oil Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shell Internationale Research Maatschappij B.V., Shell Oil Company filed Critical Shell Internationale Research Maatschappij B.V.
Publication of WO2014102292A1 publication Critical patent/WO2014102292A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
    • C10G9/36—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Definitions

  • the invention relates to a process for preparing ethylene and propylene from an oxygenate.
  • lower olefins such as ethylene and propylene are produced via steam cracking of paraffinic hydrocarbon feedstocks including ethane, propane, naphtha, gasoil and hydrowax.
  • An alternative route to lower olefins is the so-called oxygenate-to-olefin process.
  • an oxygenate such as methanol or dimethylether (DME) is provided to a reaction zone containing a suitable oxygenate conversion catalyst, typically a molecular sieve-comprising catalyst, and converted into ethylene and propylene.
  • a substantial part of the oxygenate is converted into C4 + olefins and paraffins.
  • WO2009/065848 an oxygenate-to-olefin process is disclosed wherein the yield of lower olefins is increased by recycling a fraction comprising C4 + olefins to the reaction zone. At least part of the C4 + olefins in the recycle are converted into the desired lower olefins.
  • a disadvantage of the process of WO2009/065848 is, however, that at least part of the recycle stream needs to be purged in order to avoid undesired accumulation of paraffins in the recycle stream. With the purge, also valuable C4 + olefins will be removed from the process without being converted into lower olefins. The purged part of the recycle comprising C4 + olefins can be reduced to achieve a higher yield of lower olefins, but then an increasing volume of recycle is needed, which is undesirable from an economic point of view.
  • the invention relates to a process for preparing ethylene and propylene from an oxygenate, the process comprising the following steps:
  • step b) subjecting the fraction comprising C4 hydrocarbons obtained in step b) to partial dehydrogenation by contacting the fraction with a dehydrogenation catalyst under partial dehydrogenation conditions to obtain a partially dehydrogenated C4 hydrocarbon stream;
  • the recycled C4 hydrocarbon fraction is partially
  • hydrocarbon fraction has at least a certain value before it is subjected to partial dehydrogenation.
  • This may for example be achieved by recycling the C4 hydrocarbon fraction in the start-up phase of the process directly to oxygenate conversion step a), i.e. without subjecting the fraction to partial dehydrogenation, until a certain value of the ratio of saturated C4 hydrocarbons to mono- unsaturated hydrocarbons in the recycled C4 hydrocarbon fraction is obtained. Once such ratio is obtained, the recycled fraction is subjected to partial dehydrogenation step c) .
  • the C4 hydrocarbon fraction may be recycled after subjection to partial dehydrogenation already in the start-up phase, but under application of much milder dehydrogenation conditions.
  • a high ratio of saturated to mono-unsaturated C4 hydrocarbons may be achieved in a start-up phase by combining an external stream comprising saturated and mono- unsaturated C4 hydrocarbons with a relatively high ratio of saturated to mono-unsaturated C4 hydrocarbons with the C4 hydrocarbon fraction to form a combined C4 hydrocarbon stream that is subjected to partial dehydrogenation.
  • the partially dehydrogenated stream may be directly recycled to the oxygenate-to-olefin step.
  • the most important by-product, hydrogen may be separated from the olefin products in a separation section that is used for separating the desired olefin products from the effluent obtained in the oxygenate-to-olefin step.
  • Other byproducts, such as for example butadiene, will be partly converted in the oxygenate-to-olefin step into conversion products such as cyclic and aromatic components that can be separated from the desired product in the separation section.
  • the process according to the invention may be any process according to the invention.
  • a process for steam cracking a paraffinic feedstock such as for example naphtha.
  • a product stream comprising ethylene, propylene and C4 hydrocarbons
  • Such hydrogen may advantageously be used for hydrogenation of a stream obtained in the combined oxygenate conversion and steam cracking process according to the invention, for example for hydrotreatment of pyrolysis gas, hydrogenation of acetylene to ethylene, or hydrogenation of butadiene.
  • the steam cracker step may be further integrated in the process according to the invention by using a combined separation section for the effluents of oxygenate-to-olefin step a) and the steam cracker step.
  • a fraction comprising C4 hydrocarbons is obtained that comprises C4 hydrocarbons both from oxygenate conversion and from steam cracking of paraffins.
  • This C4 hydrocarbon fraction is then partially dehydrogenated, preferably after removal of butadiene by means of partial hydrogenation, and recycled to oxygenate- to-olefin step a) .
  • Figure 1 is schematically shown a process according to the invention comprising an oxygenate conversion step.
  • Figure 2 is schematically shown an embodiment of the invention wherein a steam cracking step is integrated in the process according to the invention.
  • oxygenate is first converted into lower olefins by
  • C4 + paraffins such as isobutane, n-butane, n- pentane, iso-pentane
  • C4+ olefins such as isobutene, n- butenes, n-pentenes, iso-pentenes and C5+ naphtenes such as cyclopentane and cyclopentene
  • small amounts of dienes like butadienes may be present in the olefinic product stream.
  • Reference herein to an oxygenate is to a compound comprising at least one alkyl group that is covalently linked to an oxygen atom.
  • at least one alkyl group has up to five carbon atoms, more preferably up to four, even more preferably one or two carbon atoms, most preferably at least one alkyl group is methyl.
  • Mono- alcohols and dialkylethers are particularly suitable oxygenates.
  • Methanol and dimethylether or mixtures thereof are examples of particularly preferred oxygenates.
  • the oxygenate conversion in step a) is carried out by contacting the oxygenate with a molecular sieve-comprising catalyst at a temperature in the range of from 350 to
  • the conversion may be carried out at any suitable pressure, preferably at a pressure in the range of from 1 bar to 50 bar (absolute) , more preferably of from 1 bar to 15 bar (absolute) .
  • a pressure in the range of from 1.5 to 4.0 bar (absolute) is particularly preferred.
  • Any molecular sieve comprising catalyst known to be suitable for the conversion of oxygenates, in particular alkanols and dialkylethers , into lower olefins may be used.
  • the catalyst comprises a molecular sieve having a 8-, 10- or 12-ring structure and an average pore size in the range of from 3 A to 15 A.
  • suitable molecular sieves are silicoaluminophosphates (SAPOs) ,
  • A1PO aluminophosphates
  • SAPOs include SAPO-5, -8,
  • SAPO-17, -18, -34, -35, and -44 are particularly preferred.
  • a particular suitable class of molecular sieves are zeolites.
  • zeolites In particular in case not only oxygenates but also
  • C4+ olefins or compounds that form C4+ olefins under the reaction conditions prevailing in oxygenate conversion step a) are supplied to step a), e.g. a tertiary alcohol such as tertiary butanol or a tertiary alkylether such as methyl tertiary butylether, a zeolite-comprising catalyst is preferred as molecular-sieve comprising catalyst, more preferably a catalyst comprising a zeolite with a 10- membered ring structure.
  • Zeolite-comprising catalysts are known for their ability to convert higher olefins to lower olefins, in particular C4+ olefins to ethylene and/or propylene.
  • Suitable zeolite-comprising catalysts include those containing a zeolite of the ZSM group, in particular of the MFI type, such as ZSM-5, the MTT type, such as ZSM- 23, the TON type, such as ZSM-22, the MEL type, such as ZSM- 11, the FER type.
  • Other suitable zeolites are for example zeolites of the STF-type, such as SSZ-35, the SFF type, such as SSZ-44 and the EU-2 type, such as ZSM-48.
  • the catalyst comprises at least one zeolite selected from MFI, MEL, TON and MTT type zeolites, more preferably at least one of ZSM-5, ZSM-11, ZSM-22 and ZSM-23 zeolites.
  • the zeolite in the oxygenate conversion catalyst is preferably predominantly in the hydrogen form.
  • the molecular sieve-comprising catalyst may further comprise a binder material such as for example silica, alumina, silica-alumina, titania, or zirconia, a matrix material such as for example a clay, and/or a filler.
  • a binder material such as for example silica, alumina, silica-alumina, titania, or zirconia
  • a matrix material such as for example a clay, and/or a filler.
  • step a) not only lower olefins and C4 +
  • Water is typically separated from the olefinic product stream by means known in the art, for example by cooling the effluent of step a) in a quench water tower.
  • step b) of the process according to the invention the olefinic product stream is subjected to one or more separation steps such that at least ethylene and/or
  • a fraction comprising mainly ethylene is first separated from the olefinic product stream in a de- ethaniser and a fraction mainly comprising propylene is then separated from the bottoms of the de-ethaniser in a de-propaniser .
  • a fraction comprising both ethylene and propylene is then separated from the bottoms of the de-ethaniser in a de-propaniser .
  • propylene may be obtained by directly supplying the olefinic product stream to a de-propaniser .
  • the bottoms of the de-propaniser contain C4 + hydrocarbons.
  • the bottoms of the de-propaniser is further separated into a fraction mainly comprising C4 hydrocarbons and a fraction comprising C5 + hydrocarbons.
  • the fraction comprising C4 hydrocarbons comprises saturated and unsaturated C4 hydrocarbons .
  • the fraction comprising C4 hydrocarbons is in step c) subjected to partial dehydrogenation by contacting the fraction with a dehydrogenation catalyst under partial dehydrogenation conditions to obtain a partially
  • the partially dehydrogenated C4 hydrocarbon stream is, in step d) , recycled to oxygenate conversion step a) .
  • the partially dehydrogenated C4 hydrocarbon stream is preferably heated prior to being recycled in order to bring it to the temperature at which oxygenate conversion in step a) is carried out.
  • the partially dehydrogenated C4 hydrocarbon stream may be directly recycled to step a), i.e. without any further separation or conversion steps, since the most important byproduct formed in the dehydrogenation step, i.e. hydrogen, will act as an inert in oxygenate conversion step a) .
  • Hydrogen may be separated from the olefinic product stream obtained in the one or more separation steps of step b) .
  • a light fraction obtained in one of the separation steps of step b) e.g.
  • a fraction comprising C2 ⁇ hydrocarbons and hydrogen may be used to hydrogenate, in a so-called front-end hydrogenation unit, unsaturated compounds, such as acetylene, methylacetylene, or propadiene, produced in the process.
  • unsaturated compounds such as acetylene, methylacetylene, or propadiene
  • the entire partially dehydrogenated C4 hydrocarbon stream is recycled to step a), i.e. without separating a purge stream from the partially dehydrogenated C4 hydrocarbon stream.
  • dehydrogenation step c) not only saturated C4 hydrocarbons will be dehydrogenated to C4 mono-olefins , i.e. butenes, but also C4 mono-olefins will be
  • the weight ratio of saturated to mono- unsaturated C4 hydrocarbons in the stream that is contacted with the dehydrogenation catalyst is preferably at least 0.1, more preferably at least 0.25, in order to increase the selectivity of dehydrogenation of alkanes compared to the selectivity of dehydrogenation of mono-olefins into di- olefins.
  • the dehydrogenation catalyst will, however, also result in a relatively high concentration of saturated C4 hydrocarbons in the partially dehydrogenated C4 hydrocarbon stream that is recycled to step a) .
  • the weight ratio of saturated to mono- unsaturated C4 hydrocarbons in the stream that is contacted with the dehydrogenation catalyst is preferably at most 4, more preferably at most 3.
  • a weight ratio of saturated to mono-unsaturated C4 hydrocarbons in the stream that is contacted with the dehydrogenation catalyst in the range of from 0.4 to 2.5 is particularly preferred.
  • the weight ratio of saturated to mono-unsaturated C4 hydrocarbons in the stream that is subjected to partial dehydrogenation catalyst in step c) is at least 0.1 or even higher, it is preferred that during start-up of the process of the invention, the C4
  • hydrocarbon fraction obtained in step b) is directly recycled to oxygenate conversion step a), i.e. without subjecting the fraction to partial dehydrogenation, until sufficient saturated C4 hydrocarbons have built-up in the C4 hydrocarbon fraction.
  • preferably at least 0.25 may be combined during the startup of the process with the C4 hydrocarbon fraction to form a combined C4 hydrocarbon stream that is subjected to partial dehydrogenation.
  • the dehydrogenation catalyst may be any suitable dehydrogenation catalyst known in the art. Such catalysts are for example known from C.H. Bartholomew and R.J.
  • Dehydrogenation catalysts are known to be able both to dehydrogenate alkanes into olefins and to convert saturated hydrocarbons into aromatic compounds, also referred to as catalytic reforming.
  • catalytic reforming in step c) is undesired. Therefore, the dehydrogenation catalyst preferably has a relatively low reforming activity.
  • the dehydrogenation catalyst preferably comprises a Group VIII metal, more preferably Pt, Pd, Ni or Cu or is a chromia-based catalyst.
  • the partial dehydrogenation conditions may be any suitable partial dehydrogenation conditions known in the art. Suitable dehydrogenation conditions are for example disclosed in C.H. Bartholomew and R.J. Farrauto,
  • the dehydrogenation conditions comprise a temperature in the range of from 350 to 750 °C, more preferably in the range of from 450 to 700 °C, even more preferably in the range of from 500 to 650 °C.
  • the partial dehydrogenation is
  • dehydrogenation in step c) comprises less than 5 wt% hydrocarbons with more than 4 carbon atoms, more preferably less than 1 wt% .
  • C5 + hydrocarbons typically comprise cyclic hydrocarbons that easily dehydrogenate to form for example cyclopentadiene , a compound that will contribute to undesired coke formation in oxygenate conversion step a) .
  • the hydrogenation conditions are such that in the range of from 1 to 20 wt% of the saturated
  • hydrocarbons in the stream subjected to partial dehydrogenation in step c) is dehydrogenated into mono- unsaturated C4 hydrocarbons.
  • the dehydrogenation conditions may comprises any suitable weight hourly space velocity (WHSV) , preferably a WHSV in the range of from 0.01 to 20 h -1 , more preferably of from 0.1 to 15 h -1 , even more preferably of from 0.2 to 10 h "1 .
  • WHSV weight hourly space velocity
  • the partial dehydrogenation step may be carried out in any suitable reactor configuration known in the art, for example an adiabatic fixed bed, an isothermal fixed bed, a moving bed or a fluidised bed configuration, preferably an adiabatic or isothermal fixed bed configuration.
  • an external stream comprising saturated and unsaturated C4 hydrocarbons may be added to the hydrocarbons that are recycled to step a) .
  • Such external stream may be added prior to or after such recycled hydrocarbons are subjected to partial
  • such combined stream preferably has a weight ratio of saturated to mono-unsaturated C4 hydrocarbons of at least 0.1, more preferably at least 0.1, even more preferably in the range of from 0.4 to 2.5.
  • the external stream is a C4 hydrocarbon fraction obtained from a process for cracking a paraffinic feedstock such as for example butane, naphtha or gasoil into ethylene and propylene or a C4 hydrocarbon fraction from an effluent of a fluid catalytic cracking unit.
  • a paraffinic feedstock such as for example butane, naphtha or gasoil into ethylene and propylene
  • a C4 hydrocarbon fraction from an effluent of a fluid catalytic cracking unit.
  • the external stream is subjected to partial hydrogenation or other butadiene removal step in order to remove at least part of any butadiene or other di-olefins present before being combined with the fraction comprising C4 hydrocarbons or with the partially dehydrogenated C4 hydrocarbon stream.
  • An advantage of adding such external stream to the recycle is that additional olefins may be produced from the C4 hydrocarbons present in the external stream. Moreover, additional hydrogen is produced in the partial
  • the external stream comprises a weight ratio of saturated to mono-unsaturated C4 hydrocarbons that is higher than such ratio in the fraction comprising C4 hydrocarbons
  • the external stream is preferably added to the fraction comprising C4 hydrocarbons obtained in step b) to form a combined stream C4 hydrocarbon stream that is subjected to partial dehydrogenation in step c) .
  • Such combined stream then has a relatively high butane
  • the external stream has a ratio of saturated to mono-unsaturated C4 hydrocarbons that is lower than such ratio in the fraction comprising C4 hydrocarbons that is subjected to partial dehydrogenation in step c) , it is preferred to add such external stream to the partially dehydrogenated stream that is recycled to step a) or to supply such external stream directly to oxygenate
  • the weight ratio of saturated to mono-unsaturated C4 hydrocarbons in the external stream is preferably at most 0.4, more preferably at most 0.25.
  • the external stream has an amount of saturated C4 hydrocarbons that exceeds the amount of C4 saturated hydrocarbons that is dehydrogenated in step c)
  • it is preferred to purge part of the recycle stream preferably to purge part of the recycle stream before such stream is subjected to partial dehydrogenation in step c) .
  • steam cracking of a paraffinic feedstock to produce ethylene and propylene is integrated in the process.
  • the process then comprises an oxygenate conversion step (step a)) to produce ethylene and propylene from an oxygenate and a steam cracking step (step e) ) to produce ethylene and propylene from a paraffinic feedstock.
  • step e steam cracking step
  • conversion step a) and from steam cracking step e) is separated into ethylene and/or propylene and a fraction comprising C4 hydrocarbons including saturated and
  • the C4 fraction thus obtained is partially dehydrogenated and recycled to oxygenate conversion step a) as described hereinabove.
  • the C4 fraction thus obtained is, prior to partial dehydrogenation in step c) , subjected to partial hydrogenation or extractive
  • Butadiene is typically formed in steam cracking step e) and, to a lesser extent, in oxygenate conversion step a) .
  • Conditions in partial dehydrogenation step c) are preferably chosen such that the amount of saturated C4 hydrocarbons formed in oxygenate conversion step a) and, if applicable, formed in steam cracking step e) and/or added with the external stream, is balanced by the partial dehydrogenation of saturated C4 hydrocarbons in
  • dehydrogenation step c) dehydrogenation step c) .
  • the amount of saturated C4 hydrocarbons formed in oxygenate conversion step a) and, if applicable, formed in steam cracking step e) and/or added with the external stream exceeds the amount of C4
  • FIG. 1 is shown an embodiment of the invention wherein the C4 hydrocarbon fraction of an oxygenate conversion process is partially dehydrogenated and then recycled to the oxygenate conversion process.
  • methanol is fed via line 1 to oxygenate conversion reaction zone 10 comprising an oxygenate conversion catalyst.
  • reaction zone 10 methanol is converted into olefins and water.
  • Effluent from reaction zone 10 is supplied via line 11 to water quench tower 12 to be separated into water and an olefinic product stream.
  • Water is withdrawn from tower 12 via line 13 and the olefinic product stream is supplied via line 14 to a compression section (not shown) , a caustic treatment (not shown) and then to fractionation section 15.
  • Fractionation section 15 comprises a de-ethaniser, a de- propaniser and a de-butaniser (not shown) .
  • the olefinic product stream is first fractionated by means of the de- ethaniser and de-propaniser into an ethylene-rich stream, a propylene-rich stream, a C4 + hydrocarbon fraction and a lighter stream comprising light by-products such as methane and carbon oxides.
  • the C4 + hydrocarbon fraction is further fractionated in the de-butaniser into a C4 hydrocarbon fraction comprising isobutene and a fraction rich in C5 + hydrocarbons.
  • the lighter stream, the ethylene-rich stream, the propylene-rich stream and the fraction rich in C5 + hydrocarbons are withdrawn from fractionation section 15 via lines 16, 17, 18 and 19, respectively.
  • the fraction comprising C4 hydrocarbons is fed via line 20 to partial dehydrogenation unit 30 comprising a dehydrogenation catalyst.
  • a partially dehydrogenated C4 hydrocarbon stream is obtained in unit 30 and recycled via line 31 to
  • Figure 2 is shown an embodiment of the invention wherein the effluents of a steam cracking process and of an oxygenate conversion process are combined to be separated in a combined separation section and wherein the C4
  • hydrocarbon fraction obtained in the combined separation section is partially dehydrogenated and then recycled to the oxygenate conversion process.
  • Corresponding reference numbers have the same meaning as in Figure 1.
  • naphtha and steam are fed via lines 41 and 42, respectively, to steam cracking zone 40.
  • Cracker effluent is withdrawn from cracking zone 40 and supplied via line 43 to quench tower 12 wherein both the combined effluents from zones 40 and 10 are quenched to separate water from an olefinic product stream.
  • the combined olefinic product stream is supplied via line 14 and via a compression section and a caustic treatment (both not shown) to fractionation section 15.
  • the fraction comprising C4 hydrocarbons thus obtained is first hydrotreated to remove butadiene (not shown) and then fed via line 20 to partial dehydrogenation unit 30 comprising a dehydrogenation catalyst.
  • a partially dehydrogenated C4 hydrocarbon stream is obtained in unit 30 and recycled via line 31 to oxygenate conversion reaction zone 10.
  • hydrocarbons in line 20 is preferably purged (purge not shown) .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne un procédé de préparation d'oléfines inférieures à partir d'un composé oxygéné, le procédé comprenant : a) la mise en contact du composé oxygéné avec un catalyseur comprenant un tamis moléculaire, à une température dans la plage de 350 à 1000°C pour obtenir un flux de produits oléfiniques comprenant de l'éthylène, du propylène et des hydrocarbures en C4; b) la soumission du flux de produits oléfiniques à une ou plusieurs étapes de séparation, de manière à obtenir au moins de l'éthylène et/ou du propylène et une fraction comprenant des hydrocarbures en C4, incluant des hydrocarbures en C4 saturés et monoinsaturés; c) la soumission de la fraction comprenant des hydrocarbures en C4 obtenue dans l'étape b) à une déshydrogénation partielle par la mise en contact de la fraction avec un catalyseur de déshydrogénation dans des conditions de déshydrogénation partielle de manière à obtenir un flux d'hydrocarbures en C4 partiellement déshydrogénés; et d) le recyclage du flux d'hydrocarbures en C4 partiellement déshydrogénés vers l'étape a).
PCT/EP2013/078006 2012-12-28 2013-12-24 Procédé de préparation d'éthylène et de propylène à partir d'un composé oxygéné WO2014102292A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP12199587 2012-12-28
EP12199587.2 2012-12-28

Publications (1)

Publication Number Publication Date
WO2014102292A1 true WO2014102292A1 (fr) 2014-07-03

Family

ID=47458773

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2013/078006 WO2014102292A1 (fr) 2012-12-28 2013-12-24 Procédé de préparation d'éthylène et de propylène à partir d'un composé oxygéné

Country Status (1)

Country Link
WO (1) WO2014102292A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109304197A (zh) * 2017-07-27 2019-02-05 中国石油化工股份有限公司 一种含金属原子碳材料及其制备方法和应用以及一种烃氧化脱氢方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003020667A1 (fr) * 2001-08-30 2003-03-13 Exxonmobil Chemical Patents Inc. Procedes a deux catalyseurs destine a la fabrication d'olefines
US20100298619A1 (en) * 2007-11-19 2010-11-25 Leslie Andrew Chewter Process for the preparation of an olefinic product

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003020667A1 (fr) * 2001-08-30 2003-03-13 Exxonmobil Chemical Patents Inc. Procedes a deux catalyseurs destine a la fabrication d'olefines
US20100298619A1 (en) * 2007-11-19 2010-11-25 Leslie Andrew Chewter Process for the preparation of an olefinic product

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109304197A (zh) * 2017-07-27 2019-02-05 中国石油化工股份有限公司 一种含金属原子碳材料及其制备方法和应用以及一种烃氧化脱氢方法
CN109304197B (zh) * 2017-07-27 2021-06-11 中国石油化工股份有限公司 一种含金属原子碳材料及其制备方法和应用以及一种烃氧化脱氢方法

Similar Documents

Publication Publication Date Title
US20130172627A1 (en) Process for preparing lower olefins
US8822710B2 (en) Process for preparing an epoxide from an oxygenate
US20130237714A1 (en) Process for preparing ethylene and/or propylene and an iso-olefin-depleted c4 olefinic product
AU2005228847A1 (en) Processes for making methanol streams and uses for the streams
WO2012021341A2 (fr) Production de 1-butène à partir d'un système de réaction d'oxygénation en oléfine
US10384986B1 (en) MTO process for enhanced production of propylene and high value products
US8822709B2 (en) Process for preparing an epoxide from an oxygenate
US20150291487A1 (en) Process for preparing ethylene, propylene and isoprene from an oxygenate
US20160168045A1 (en) High pressure swing fixed-bed process with optional ethylene recycle for highly selective methanol to olefins conversion
US8704027B2 (en) Process for preparing ethylene and propylene
WO2015094877A1 (fr) Intégration de mto avec du butadiène produit exprès
WO2014102292A1 (fr) Procédé de préparation d'éthylène et de propylène à partir d'un composé oxygéné
US8946496B2 (en) Process for preparing lower olefins from an oxygenate
US9012713B2 (en) Process for removing oxygenate from an olefin stream
US8889941B2 (en) Process for preparing lower olefins from an oxygenate
US20130165712A1 (en) Integrated process for the preparation of a lower olefin product
EP3040325A1 (fr) Procédé de préparation d'éthylène, de propylène et d'isoprène
US20230159411A1 (en) Integrated process for producing ethylene and propylene from c4 and/or c5 hydrocarbons
US8987540B2 (en) Process for removing oxygenate from an olefin stream
US9115103B2 (en) Process for removing oxygenate from an olefin stream
WO2016094171A1 (fr) Procédé mto "à haute valeur" à pression accrue pour améliorer les performances d'un catalyseur sapo
US9133077B2 (en) Process for the preparation of a lower olefin product
US20130165718A1 (en) Process for the preparation of olefins
US20150191402A1 (en) Process for the preparation of olefins
US20140187834A1 (en) Process for extracting c4+ olefins and a process for converting oxygenates to olefins

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13811998

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13811998

Country of ref document: EP

Kind code of ref document: A1