WO2018002771A1 - Procédés de production d'oléfines à partir d'hydrocarbures légers - Google Patents

Procédés de production d'oléfines à partir d'hydrocarbures légers Download PDF

Info

Publication number
WO2018002771A1
WO2018002771A1 PCT/IB2017/053664 IB2017053664W WO2018002771A1 WO 2018002771 A1 WO2018002771 A1 WO 2018002771A1 IB 2017053664 W IB2017053664 W IB 2017053664W WO 2018002771 A1 WO2018002771 A1 WO 2018002771A1
Authority
WO
WIPO (PCT)
Prior art keywords
mol
hydrocarbons
olefins
feed stream
syngas
Prior art date
Application number
PCT/IB2017/053664
Other languages
English (en)
Inventor
Aghaddin Mamedov
Original Assignee
Sabic Global Technologies B.V.
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 Sabic Global Technologies B.V. filed Critical Sabic Global Technologies B.V.
Publication of WO2018002771A1 publication Critical patent/WO2018002771A1/fr

Links

Classifications

    • 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
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/26—Chromium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • 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
    • 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
    • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1082—Composition of support materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1094—Promotors or activators
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1247—Higher hydrocarbons
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1081—Alkanes
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins
    • 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
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—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
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • 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 disclosed subject matter relates to methods and for producing olefins, such as ethylene and propylene, from light hydrocarbons.
  • Light olefins including ethylene and propylene, are important petrochemical feedstocks that can be derived from light hydrocarbons, such as C2-C3 alkanes.
  • Several technologies for producing light olefins are known in the art, for instance by fluid catalytic cracking (FCC), deep catalytic cracking (DCC), advanced catalytic olefins (ACO) processes, and olefin metathesis.
  • FCC fluid catalytic cracking
  • DCC deep catalytic cracking
  • ACO advanced catalytic olefins
  • thermal steam cracking is used to convert saturated hydrocarbons to light olefins.
  • Such cracking processes can create hydrogen (H 2 ) as a byproduct, which can be separated and used as fuel, e.g., in heating applications.
  • composition of syngas can be important in determining which materials are produced when it is used as a feedstock in subsequent chemical processes.
  • Certain techniques for generating olefins and syngas are known in the art. For example, U. S. Patent Publication No. 2009/0152499 is directed to a process for converting a hydrocarbon and an oxygen source into an olefin and syngas in the absence of a catalyst.
  • WO2010/057663 relates to a process for converting light paraffins (e.g., C 2 to C 7 paraffins) and carbon dioxide into light olefins and syngas by oxidative dehydrogenation using a La-Mn catalyst.
  • Chinese Patent No. CN 1087654 relates to a process for converting light paraffins and carbon dioxide to light olefins and syngas by oxidative dehydrogenation.
  • International Patent Publication No. WO2000/015587 is directed to a method of producing a mono-olefin and syngas from a paraffin feedstock by oxidative dehydrogenation in the presence of a Pt and/or Pd catalyst.
  • the disclosed subject matter provides novel methods for producing olefins using an oxidative dehydrogenation reaction.
  • An exemplary method for producing olefins by an oxidative dehydrogenation reaction in accordance with the disclosed subject matter includes introducing a feed stream including C 2 and C 3 hydrocarbons and C0 2 to a Cr oxide catalyst modified with K and Mn, and generating a product stream therefrom including olefins and syngas, where the syngas has a molar ratio of CO to H 2 (CO/H 2 ) from about 1.4 to about 1.8.
  • the feed stream can include from about 30 mol-% to about 60 mol-% C 2 and C 3 hydrocarbons.
  • the feed stream can further include from about 40 mol-%) to about 90 mol-%> C0 2 .
  • the feed stream can include about 35 mol-%> C 2 and C 3 hydrocarbons and about 65 mol-%> C0 2 .
  • the C 2 hydrocarbons can include C 2 H 6 and the C 3 hydrocarbons can include C 3 H 8 .
  • the Cr oxide catalyst can be supported on either A1 2 0 3 or Si0 2 .
  • the Cr oxide catalyst can include about 2 mol-% K, about 8 mol-% Cr, and about 15 mol-% Mn supported on Si0 2 .
  • the method can further include reacting the feed stream in the presence of the Cr oxide catalyst at a temperature from about 600°C to about 900°C. In particular embodiments, the temperature can be from about 800°C to about 830°C. In certain embodiments, the method can include reacting the feed stream in the presence of the Cr oxide catalyst at a space velocity of about 2800 h "1 .
  • the oxidative dehydrogenation reaction generates an olefins yield of greater than about 55%.
  • Embodiments 1 to 14 are described.
  • Embodiment 1 is a method for producing olefins by an oxidative dehydrogenation reaction, including (a) introducing a feed stream comprising C 2 and C 3 hydrocarbons and C0 2 to a Cr oxide catalyst modified with K and Mn; and (b) generating a product stream therefrom comprising olefins and syngas, wherein the syngas has a molar ratio of CO to H 2 (CO/H 2 ) from about 1.4 to about 1.8.
  • Embodiment 2 is the method of Embodiment 1, wherein the feed stream includes from about 30 mol-% to about 60 mol-% C 2 and C 3 hydrocarbons.
  • Embodiment 3 is the method of any one of Embodiments 1 and 2, wherein the feed stream includes from about 40 mol-% to about 90 mol-% C0 2 .
  • Embodiment 4 is the method of any one of Embodiments 1 to 3, wherein the feed stream comprises about 35 mol-% C 2 and C 3 hydrocarbons and about 65 mol-% C0 2 .
  • Embodiment 5 is the method of any one of Embodiments 1 to 4, wherein the C 2 hydrocarbons comprise C 2 H 6 and the C 3 hydrocarbons comprise C 3 H 8 .
  • Embodiment 6 is the method of any one of Embodiments 1 to 5, wherein the Cr oxide catalyst is supported on either A1 2 0 3 or Si0 2 .
  • Embodiment 7 is the method of any one of Embodiments 1 to 6, wherein the Cr oxide catalyst includes about 2 wt-% K, about 8 wt-% Cr, and about 15 wt-% Mn supported on Si0 2 .
  • Embodiment 8 is the method of any one of Embodiments 1 to 7, further including the step of reacting the feed stream in the presence of the Cr oxide catalyst at a temperature from about 600°C to about 900°C.
  • Embodiment 9 is the method of any one of Embodiments 1 to 8, wherein the temperature is from about 800°C to about 830°C.
  • Embodiment 10 is the method of any one of any one of Embodiments 1 to 9, further including the step of reacting the feed stream in the presence of the Cr oxide catalyst at a space velocity of about 2800 h "1 .
  • Embodiment 11 is the method of Embodiment 5, wherein at least about 75 mol-% of the C 2 H 6 is converted.
  • Embodiment 12 is the method of Embodiment 5, wherein at least about 80 mol-% of the C 3 H 8 is converted.
  • Embodiment 13 is the method of any one of Embodiments 1 to 12, wherein at least about 50 mol-% of the C0 2 is converted.
  • Embodiment 14 is the method of any one of Embodiments 1 to 13, wherein the oxidative dehydrogenation reaction generates an olefins yield of greater than about 55%.
  • the method of the present invention can "comprise,” “consist essentially of,” or “consist of particular steps, components, and use include the compositions such as catalysts, etc. disclosed throughout the specification.
  • the catalysts used in accordance with the present invention can "comprise,” “consist essentially of,” or “consist of particular ingredients, components, compositions, etc. disclosed throughout the specification.
  • FIG. 1 depicts a method of producing olefins by an oxidative dehydrogenation reaction according to one exemplary embodiment of the disclosed subject matter.
  • the presently disclosed subject matter provides methods for producing olefins from light hydrocarbons, e.g., by oxidative dehydrogenation.
  • the methods can further be used to produce syngas in addition to olefins.
  • Oxidative dehydrogenation can be used to convert saturated hydrocarbons to olefins.
  • C 2 and C 3 paraffins i.e., ethane (C 2 H 6 ) and propane (C 3 H 8 )
  • C 2 and C 3 olefins i.e., ethylene (C 2 H 4 ) and propylene (C 3 3 ⁇ 4), as shown in Formulas 1 and 2 below:
  • H 2 is formed as a byproduct.
  • an oxidant such as carbon dioxide (C0 2 )
  • C0 2 carbon dioxide
  • C0 2 can react with the H 2 to form carbon monoxide (CO) and water (H 2 0) in a reverse water gas shift reaction.
  • the reverse water gas shift reaction is illustrated by Formula 3 below:
  • the total reaction will result in a mixture of olefins (i.e., C 2 H 4 and C 3 3 ⁇ 4) and syngas (primarily a mixture of CO and H 2 ).
  • olefins i.e., C 2 H 4 and C 3 3 ⁇ 4
  • syngas primarily a mixture of CO and H 2 .
  • These reactions are equilibrium-driven, and can be performed under conditions resulting in only partial conversion of C0 2 and H 2 , and thus the product stream can include C0 2 and H 2 , as well as olefins, CO, and H 2 0.
  • the product stream can include C0 2 and H 2 , as well as olefins, CO, and H 2 0.
  • syngas having various molar ratios of CO to H 2 (CO/H 2 ).
  • oxidative dehydrogenation in the presence of C0 2 can have advantages over certain conventional techniques. For example, unlike steam cracking, which produces a significant amount of H 2 byproduct and can result in the accumulation of coke (i.e., carbonaceous) deposits, oxidative dehydrogenation can be used to generate syngas and results in less coke formation. For further example, oxidative conversion of hydrocarbons, which can result in full oxidation to C0 2 and as a result, partial loss of the feed stock. On the contrary, oxidative dehydrogenation can be used to generate olefins without creating deep oxidation products, such as C0 2 . Furthermore, compared to oxidation reactions, oxidative dehydrogenation is less prone to cause heat runaway from oxidation by molecular oxygen.
  • FIG. 1 is a schematic representation of a method according to a non-limiting embodiment of the disclosed subject matter.
  • the method 100 can include introducing a feed stream comprising C 2 and C 3 hydrocarbons and C0 2 to a Cr oxide catalyst 101 and generating a product stream therefrom comprising olefins and syngas 102.
  • the feed stream can include C 2 and C 3 hydrocarbons.
  • the hydrocarbons can be sourced from a C 2 and/or C 3 fraction, e.g., derived from natural gas or petroleum processing.
  • the C 2 hydrocarbons can include ethane (i.e., C 2 H 6 ).
  • the C 3 hydrocarbons can include propane (i.e., C 3 H 6 ).
  • the feed stream can further include C0 2 .
  • the C0 2 in the feed stream can originate from various sources.
  • C0 2 can be sourced from other chemical processes, e.g., as a waste product, and/or unconverted C0 2 can be recovered from the product stream and recycled to the feed stream.
  • "Feed stream,” as used herein, can refer to a single feed stream or multiple feed streams, which can be combined before or during the oxidative dehydrogenation reaction.
  • the feed stream can be a single mixture of hydrocarbons and C0 2 .
  • multiple feed streams containing one or more types of hydrocarbons and/or C0 2 can be provided.
  • the feed stream can further include additional components, including heavier hydrocarbons (i.e., C 4 and heavier hydrocarbons), and unsaturated C 2 and C 3 hydrocarbons, e.g., ethylene, propylene, and/or acetylene.
  • heavier hydrocarbons i.e., C 4 and heavier hydrocarbons
  • unsaturated C 2 and C 3 hydrocarbons e.g., ethylene, propylene, and/or acetylene.
  • the feed stream can include from about 10 mol-% to about 60 mol-%, or from about 20 mol-% to about 50 mol-%, or from about 30 mol-% to about 40 mol-%, or about 35 mol-% C 2 and C 3 hydrocarbons.
  • about 50 mol-%) of the hydrocarbons can be C 2 hydrocarbons (e.g., C 2 H 6 ) and about 50 mol-%> of the hydrocarbons can be C 3 hydrocarbons (e.g., C 3 H 8 ).
  • the feed stream can comprise from about 15 mol-%> to about 30-mol%> C 2 hydrocarbons and from about 15 mol-%> to about 30 mol%> C 3 hydrocarbons.
  • the feed stream can further include from about 40 mol-%> to about 90 mol-%>, or from about 50 mol-%> to about 80 mol-%>, or from about 60 mol-%> to about 70 mol-%, or about 65 mol-% C0 2 .
  • the term “about” or “approximately” means within an acceptable error range for the particular value as determined by one of ordinary skill in the art, which will depend in part on how the value is measured or determined, i.e., the limitations of the measurement system. For example, “about” can mean a range of up to 20%, up to 10%, up to 5%), and or up to 1% of a given value.
  • the feed stream can be introduced to a Cr oxide catalyst, e.g., as modified with K and Mn, for the oxidative dehydrogenation reaction.
  • the oxidative dehydrogenation can be performed under any suitable reaction conditions.
  • the reaction can be performed at a temperature ranging from about 600°C to about 900°C, or from about 700°C to about 850°C, or from about 800°C to about 830°C.
  • the pressure can range from atmospheric pressure to about 5 bar.
  • the weight hourly space velocity (WHSV) of the reaction can be from about 1500 h “1 to about 4500 h “1 , or from about 2000 h “1 to about 3500 h “1 , from about 2500 h “1 to about 3000 h “1 , or about 2800 h “1 .
  • the reaction can be performed in any reactor type known in the art to be suitable for the oxidative dehydrogenation of a hydrocarbon stream.
  • the reactor can be a fixed bed reactor, such as a tubular fixed bed reactor or multi-tubular fixed bed reactor, or fluidized bed reactor.
  • the dimensions and structure of the reactor of the presently disclosed subject matter can vary depending on the capacity of the reactor.
  • the capacity of the reactor can be determined by the reaction rate, the stoichiometric quantities of the reactants and/or the feed stream flow rate.
  • the catalyst for use in the presently disclosed subject matter can be a modified chromium (Cr) oxide catalyst.
  • the Cr can be supported on a variety of oxide materials, including, but not limited to aluminum oxide (alumina), magnesia, silica, titania, zirconia, and mixtures or combinations thereof.
  • the support material is alumina (AI 2 O 3 ) or silica (Si0 2 ).
  • the catalyst is a modified Cr/Si0 2 catalyst.
  • a Cr oxide catalyst can be an effective catalyst for the dehydrogenation of C 2 and C 3 hydrocarbons, e.g., as depicted by Formulas 1 and 2 described above.
  • a bifunctional catalyst is preferred for the simultaneous activation of the hydrocarbons and C0 2 , as in oxidative dehydrogenation.
  • the Cr oxide catalyst can be modified with a basic element to form a redox system. Such a redox system can further reduce the accumulation of coke deposits on the Cr oxide catalyst.
  • suitable basic elements for use in the redox system include alkali metals, such as lithium (Li), sodium (Na), potassium (K), rubidium (Rb), or cesium (Cs), or rare earth elements such as lanthanum (La) or gadolinium (Gd).
  • alkali metals such as lithium (Li), sodium (Na), potassium (K), rubidium (Rb), or cesium (Cs), or rare earth elements such as lanthanum (La) or gadolinium (Gd).
  • the Cr oxide catalyst is modified with K.
  • the Cr oxide catalyst can include one or more promoters.
  • the one or more promoters can increase activation of C0 2 , e.g., to promote the generation of syngas.
  • manganese (II) oxide (MnO) can be a suitable promoter. Because the Mn of MnO is a basic element, MnO can further activate C0 2 through the formation of surface carbonates, as demonstrated in Formulas 6 and 7 below. Surface carbonates can block the surface of the Cr oxide catalyst to prevent oxide phase formation that can reduce catalyst activity.
  • a catalyst according to the disclosed subject matter can be a Cr oxide catalyst modified with at least two additional elements.
  • the Cr oxide catalyst can be modified with K and Mn.
  • the catalyst can be K- Cr-Mn/Si0 2 .
  • a K-Cr-Mn/Si0 2 catalyst can include from about 0.5 wt-% to about 5 wt-%, or about 2 wt-% K and further include from about 5 wt-% to about 25 wt-%), or about 15 wt-%> Mn.
  • the K-Cr-Mn/Si0 2 catalyst can also include from about 2 wt-%> to about 15 wt-%), or about 8 wt-%> Cr.
  • the presently disclosed method can be used to generate a product stream including olefins, e.g., ethylene and propylene, and syngas (i.e., CO and H 2 ).
  • the product stream can further include additional components, such as unconverted reactants and intermediates, including C 2 and C 3 hydrocarbons and C0 2 .
  • the product stream can further include H 2 0 and/or methane (CH 4 ).
  • the syngas of the product stream can have a ratio of CO to H 2 (CO/H 2 ) from about 1.4 to about 1.8, or from about 1.5 to about 1.7.
  • the conversion of C 2 hydrocarbons e.g., C 2 H 6
  • the conversion of C 3 hydrocarbons can be greater than about 60 mol-%), greater than about 70 mol-%>, or greater than about 80 mol-%>.
  • the conversion of C0 2 can be greater than about 40 mol-%>, greater than about 45 mol-%>, or greater than about 50 mol-%>.
  • the presently disclosed methods of oxidative dehydrogenation can generate an olefins yield of greater than about 45%, greater than about 50%), or greater than about 55%.
  • a product stream including a mixture of olefins and syngas can be used directly for hydro-carbonylation reactions, e.g., involving oxo-synthesis.
  • the olefins and syngas can be separated and used in multiple applications.
  • the generated propylene can be used for the hydro-carbonylation of propylene to butyl aldehyde, which can be further converted to 2- ethylhexanol (2-EH).
  • the syngas can be used in the production of monoethylene glycol (MEG) or methanol carbonylation. Excess hydrogen can be separated and used, for example, as fuel.
  • the methods and systems of the presently disclosed subject matter provide advantages over certain existing technologies. Exemplary advantages include efficient conversion of light hydrocarbons to olefins while creating a valuable syngas byproduct. Additional advantages include increased conversion of light hydrocarbons and olefins yield.
  • a C 2 -C 3 fraction including C 2 and C 3 alkanes was dehydrogenated in the presence of C0 2 .
  • the catalyst used was 2%K-8%Cr-15%Mn/Si0 2 (by weight). Catalyst loading was 8 mL.
  • the space velocity of the reaction was 2800 h "1 .
  • the feed stream contained 35 mol-% of the C 2 -C 3 fraction and 65 mol-% C0 2 .
  • the feed stream was provided to a fixed bed reactor at a flow rate or 373 cc/min.
  • the fixed bed reactor included a 15mm ID. quartz reactor that was heated by an electrical furnace.
  • the C 2 -C 3 fraction contained 50 mol-% C 2 H 6 and 50 mol-% C 3 H 8 .
  • the reaction was carried out at a temperature of 800°C.
  • the product composition was analyzed with a Gas Chromatograph having columns with Porapak Q and a Molecular Sieve with a thermal conductivity detector (TCD).
  • the conversion of C 2 H 6 was 70.5 mol-% and the conversion of C 3 H 8 was 74.6 mol-%.
  • C0 2 conversion was 44.2 mol-%.
  • the product stream contained ethylene (C 2 H 4 ), propylene (C 3 H 6 ), CO, H 2 , and CH 4 .
  • the CO to H 2 ratio (CO/H 2 ) in the product stream was 1.5.
  • the C 2 and C 3 olefins yield was 56%.
  • the conversion of C 2 H 6 was 78.0 mol-% and the conversion of C 3 H 8 was 80.5 mol-%.
  • C0 2 conversion was 50.0 mol-%.
  • the product stream contained ethylene (C 2 H 4 ), propylene (C 3 H 6 ), CO, H 2 , and CH 4 .
  • the CO to H 2 ratio (CO/H 2 ) in the product stream was 1.7.
  • the C 2 and C 3 olefins yield was 61%. Accordingly, oxidative dehydrogenation can be used with a K-Cr-Mn-/Si0 2 catalyst to convert a hydrocarbon stream to olefins and syngas with high conversion and olefins yield.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne des procédés de production d'oléfines par une réaction de déshydrogénation par oxydation. Les procédés peuvent consister à introduire des hydrocarbures en C2 et C3, tels que l'éthane et le propane, dans un catalyseur d'oxyde de Cr en présence de CO2 afin de produire des oléfines, comme l'éthylène et le propylène, ainsi que du gaz de synthèse. Le catalyseur d'oxyde de Cr peut être modifié avec K et Mn.
PCT/IB2017/053664 2016-06-28 2017-06-20 Procédés de production d'oléfines à partir d'hydrocarbures légers WO2018002771A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201662355516P 2016-06-28 2016-06-28
US62/355,516 2016-06-28

Publications (1)

Publication Number Publication Date
WO2018002771A1 true WO2018002771A1 (fr) 2018-01-04

Family

ID=60787220

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2017/053664 WO2018002771A1 (fr) 2016-06-28 2017-06-20 Procédés de production d'oléfines à partir d'hydrocarbures légers

Country Status (1)

Country Link
WO (1) WO2018002771A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5254788A (en) * 1991-09-10 1993-10-19 Stone And Webster Engineering Corporation Process for the production of olefins from light paraffins
US20100190874A1 (en) * 2007-04-27 2010-07-29 Mamedov Agaddin M Kh Catalytic hyrogenation of carbon dioxide into syngas mixture
US8835347B2 (en) * 2009-06-05 2014-09-16 Basf Corporation Alkane dehydrogenation catalysts
WO2015066117A1 (fr) * 2013-10-29 2015-05-07 Saudi Basic Industries Corporation Procédé d'hydrogénation de dioxyde de carbone d'un gaz synthétique et intégration du procédé dans des procédés de conversion de gaz synthétique
WO2015170258A1 (fr) * 2014-05-06 2015-11-12 Sabic Global Technologies B.V. Performance améliorée de la déshydrogénation par réduction de la formation de coke à l'aide de co2 pré-activé

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5254788A (en) * 1991-09-10 1993-10-19 Stone And Webster Engineering Corporation Process for the production of olefins from light paraffins
US20100190874A1 (en) * 2007-04-27 2010-07-29 Mamedov Agaddin M Kh Catalytic hyrogenation of carbon dioxide into syngas mixture
US8835347B2 (en) * 2009-06-05 2014-09-16 Basf Corporation Alkane dehydrogenation catalysts
WO2015066117A1 (fr) * 2013-10-29 2015-05-07 Saudi Basic Industries Corporation Procédé d'hydrogénation de dioxyde de carbone d'un gaz synthétique et intégration du procédé dans des procédés de conversion de gaz synthétique
WO2015170258A1 (fr) * 2014-05-06 2015-11-12 Sabic Global Technologies B.V. Performance améliorée de la déshydrogénation par réduction de la formation de coke à l'aide de co2 pré-activé

Similar Documents

Publication Publication Date Title
KR102379397B1 (ko) 메탄을 프로판알로 전환하기 위한 방법
TWI289474B (en) Continuous heterogeneously catalyzed partial dehydrogenation
Hargreaves et al. Control of product selectivity in the partial oxidation of methane
KR20180004165A (ko) Co2의 합성가스로의 전환방법
US9695097B2 (en) Ethanol production via dimethylether recycle
JP2013223864A (ja) 天然ガスを高級炭素化合物に転換するための触媒および方法
García et al. Influence of operating variables on the aqueous-phase reforming of glycerol over a Ni/Al coprecipitated catalyst
US20170267607A1 (en) Concurrent reduction for improving the performance of the dehydrogenation of alkanes
US20160376208A1 (en) Method of Producing Higher Value Hydrocarbons by Isothermal Oxidative Coupling of Methane
WO2020021498A2 (fr) Catalyseurs au nitrure de bore fonctionnalisés pour la production d'oléfines légères à partir de charges d'alcanes par déshydrogénation oxydative
KR102583526B1 (ko) 알킬 알카노에이트의 기상 생성
US20060004241A1 (en) Isothermal method for the dehydrogenating alkanes
EP3160924A1 (fr) Performance améliorée de la déshydrogénation par réduction de la formation de coke à l'aide de co2 pré-activé
WO2018002771A1 (fr) Procédés de production d'oléfines à partir d'hydrocarbures légers
KR20110099112A (ko) 파라핀계 저급 탄화수소의 산화적 탈수소반응 방법
Al-Zahrani et al. Isobutane oxydehydrogenation on Al2O3-supported transition and rare-earth metal oxides
CN113597422A (zh) 通过co2再循环的具有较高碳利用率的甲醇生产方法
WO2020176650A1 (fr) Procédé de transfert de chaleur indirect intégré pour la production de gaz de synthèse et d'oléfines par oxydation partielle catalytique et déshydrogénation catalytique sélective
JP2020097543A (ja) ブタジエンの製造方法
US12006280B2 (en) Methanol production process with higher carbon utilization by CO2 recycle
CN113574040B (zh) 甲醇生产方法
Shaymardanov Parovaya i karbonatnaya konversiya metana
JP2004307451A (ja) オレフィン類への二酸化炭素促進脱水素プロセス
EA044090B1 (ru) Способ производства метанола с более высокой утилизацией углерода за счет рецикла co2
WO2020142489A1 (fr) Enrichissement en hydrogène dans un gaz de synthèse produit par oxydation catalytique partielle

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: 17819445

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: 17819445

Country of ref document: EP

Kind code of ref document: A1