WO2019202535A1 - Procédés de déshydroaromatisation d'hydrocarbures en c1 à c4 - Google Patents

Procédés de déshydroaromatisation d'hydrocarbures en c1 à c4 Download PDF

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Publication number
WO2019202535A1
WO2019202535A1 PCT/IB2019/053200 IB2019053200W WO2019202535A1 WO 2019202535 A1 WO2019202535 A1 WO 2019202535A1 IB 2019053200 W IB2019053200 W IB 2019053200W WO 2019202535 A1 WO2019202535 A1 WO 2019202535A1
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Prior art keywords
stream
mole
dehydroaromatization
catalyst bed
hydrocarbons
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PCT/IB2019/053200
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English (en)
Inventor
Eswara Rao MUPPARAJU
Naga Sanyasi Rao VARANASI
Christoph Johannes DITTRICH
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Sabic Global Technologies B.V.
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Publication of WO2019202535A1 publication Critical patent/WO2019202535A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
    • C07C2/78—Processes with partial combustion
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
    • B01J8/0449—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds
    • B01J8/0453—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds the beds being superimposed one above the other
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0492—Feeding reactive fluids

Definitions

  • Dehydroaromatization of gaseous Ci to C 4 hydrocarbons in the presence of a dehydroaromatization catalyst is a promising route for production of benzene.
  • dehydroaromatization catalysts can be used to convert the Ci to C 4 hydrocarbons to aromatics, such as benzene.
  • the dehydroaromatization reaction is highly endothermic and the thermodynamics of the reaction limit the conversion of Ci to C 4 hydrocarbons to aromatics, even at elevated temperatures of 400°C to l,000°C.
  • the conversion of Ci to C 4 hydrocarbons to aromatics can be limited to 10 mole % to 70 mole % for the dehydroaromatization reaction.
  • heat management can present challenges. For instance, heating the feed to the reaction temperatures of 500°C to 800°C can result in high energy duties and/or metallurgical challenges, for example, due to the high reaction temperatures, special metallurgy can be required. These disadvantages can be significant in commercial scale dehydroaromatization processes.
  • a method of Ci to C 4 hydrocarbon dehydroaromatization includes: passing a first stream comprising a first portion of Ci to C 4 hydrocarbons and an oxidant comprising oxygen through a combustion section, wherein a combustion reaction occurs producing a second stream that exits the combustion section; combining the second stream with a second portion of the Ci to C 4 hydrocarbons to form a third stream; passing the third stream through a dehydroaromatization catalyst bed, wherein a dehydroaromatization reaction occurs producing a fourth stream that exits the dehydroaromatization catalyst bed; and removing the fourth stream from the dehydroaromatization catalyst bed; wherein the third stream has a temperature of 400°C to l,000°C.
  • a method of Ci to C 4 hydrocarbon dehydroaromatization includes: passing a first stream comprising a first portion of Ci to C 4 hydrocarbons and oxygen through a combustion section, wherein a combustion reaction occurs producing a second stream that exits the combustion section; combining the second stream with a second portion of the to C 4 hydrocarbons to form a third stream; passing the third stream through a
  • the first stream has a temperature of 400°C to 700°C prior to passing through the combustion section, and wherein the oxygen is present in the first stream an amount of 1 mole % to 10 mole %, preferably 1 mole % to 5 mole % or 2 mole % to 5 mole %, based on the total moles present in the first stream; and wherein the second stream has a temperature of 350°C to l,000°C after exiting the combustion zone; and wherein the third stream has a temperature of 400°C to l,000°C; and wherein the third stream comprises 85 mole % to 98 mole % of Ci to C 4 hydrocarbons, 0.5 mole % to 5 mole % carbon dioxide, up to 5.0 mole % water, 0.5
  • a system for Ci to C 4 hydrocarbon dehydroaromatization includes: a combustion section, through which a first stream comprising a first portion of Ci to C 4 hydrocarbons and oxygen can be passed and a combustion reaction occurs to produce a second stream that exits the combustion section; and a dehydroaromatization catalyst bed through which a third stream formed by combining the second stream and a second portion of the Ci to C 4 hydrocarbons can be passed and a dehydroaromatization reaction occurs to produce a fourth stream that exits the dehydroaromatization catalyst bed.
  • FIG. 1 is a schematic diagram representing a reactor for Ci to C 4 hydrocarbon dehydroaromatization.
  • Ci to C 4 hydrocarbon dehydroaromatization are methods for Ci to C 4 hydrocarbon dehydroaromatization. Desirably, the methods improve the heat management (e.g., heat supply) in Ci to C 4 hydrocarbon dehydroaromatization reactions. Prior processes suffered from conversions of gaseous Ci to C 4 hydrocarbons to aromatics that can be lower that desired due to
  • thermodynamic limitations and heat management to provide heat to the dehydroaromatization reaction can involve high energy inputs.
  • a combustion reaction of a first stream comprising a first portion of Ci to C 4 hydrocarbons and an oxidant to produce a second stream which can be combined with a second portion of the Ci to C 4 hydrocarbons
  • a third stream at a temperature of 400°C to l,000°C can be formed.
  • This third stream can pass through a dehydroaromatization catalyst bed, wherein a dehydroaromatization reaction can occur can convert Ci to C 4 hydrocarbon to aromatics.
  • heat management to provide the feed at or near the dehydroaromatization reaction temperature can be simplified and efficiently achieved.
  • a method of Ci to C 4 hydrocarbon dehydroaromatization includes passing a first stream comprising a first portion of Ci to C 4 hydrocarbons and an oxidant comprising oxygen through a combustion section, wherein a combustion reaction occurs producing a second stream that exits the combustion section, combining the second stream with a second portion of the Ci to C 4 hydrocarbons to form a third stream, passing the third stream through a dehydroaromatization catalyst bed, wherein a dehydroaromatization reaction occurs producing a fourth stream that exits the dehydroaromatization catalyst bed, and removing the fourth stream from the dehydroaromatization catalyst bed.
  • the third stream can have a temperature of 400°C to l,000°C, for example, 450°C to 950°C, or 450°C to 850°C, or 500°C to 850°C, preferably, 500°C to 800°C.
  • the Ci to C 4 hydrocarbons comprise greater than or equal to 75 mole %, for example, greater than or equal to 80 mole %or greater than or equal to 90 mole %, methane
  • the third stream can have a temperature of 600°C to l,000°C, for example, 650°C to 950°C, or 650°C to 850°C, or 700°C to 850°C, preferably, 700°C to 800°C.
  • the third stream can have a temperature of 400°C to 800°C, for example, 450°C to 750°C, or 450°C to 650°C, or 500°C to 650°C, preferably, 500°C to 600°C.
  • the gaseous to C 4 hydrocarbons can include methane, ethane, propane, butane, or a combination comprising at least one of the foregoing.
  • a first portion of the to C 4 hydrocarbons can be mixed with an oxidant to obtain a first stream.
  • the first stream can include methane in an amount of, for example, greater than or equal to 90 mole %, in particular, 90 mole % to 95 mole %, and C 2 to C 5 hydrocarbons, for example, in an amount of 5 mole % to 10 mole %, based on the total moles present in the first stream.
  • the first stream can include ethane in an amount of, for example, greater than or equal to 90 mole %, in particular, 90 mole % to 95 mole %, and and C 3 to C 5 hydrocarbons, for example, in an amount of 5 mole % to 10 mole %, based on the total moles present in the first stream.
  • the first stream can include propane in an amount of, for example, greater than or equal to 90 mole %, in particular, 90 mole % to 95 mole %, and Ci, C 2 , C 4 , and C 5 hydrocarbons, for example, in an amount of 5 mole % to 10 mole %, based on the total moles present in the first stream.
  • the first stream can include butane in an amount of, for example, greater than or equal to 90 mole %, in particular, 90 mole % to 95 mole %, and Ci to C 3 and C 5 hydrocarbons, for example, in an amount of 5 mole % to 10 mole %, based on the total moles present in the first stream.
  • the oxidant can be an oxygen-containing compound that is capable of combusting the gaseous Ci to C 4 hydrocarbons under the combustion reaction conditions.
  • the oxidant can be, for example, hydrogen peroxide (H 2 0 2 ), dioxygen (0 2 ), ozone (0 3 ), an anthraquinone, a C 2-32 alkyl peroxide, a C 2-32 alkyl hydroperoxide, a C 3-32 ketone peroxide, a C 2-32 diacyl peroxide, a C 2-22 diperoxy ketal, a C 2-32 peroxyester, a C 2-32 peroxydicarbonate, a C 2-32 peroxy acid, a C 6-32 perbenzoic acid, a C 2-32 peracid, a periodinane, a periodate, or a combination comprising at least one of the foregoing.
  • oxidants include 2-butanone peroxide, cyclohexanone peroxide, benzoyl peroxide, lauryl peroxide, di-ieri-butyl peroxide, ieri-butyl cumyl peroxide, dicumyl peroxide, ieri-butyl hydroperoxide, cumene hydroperoxide, / ⁇ ? / -butyl peroxybenzoate, tert- amyl peroxybenzoate, ieri-butyl peroxyoctoate, 2,2-di(/er/-butylperoxy)butane,
  • the oxidant can be present in the first stream an amount of 1 mole % to 10 mole %, for example, 1 mole % to 5 mole %, or 2 mole % to 5 mole %, based on the total moles present in the first stream.
  • the first stream can be heated prior to being passed through the combustion section by a heat exchanger or other heating devices. Heating of the first stream can be accomplished in a furnace using flue gas generated on the shell side using hydrocarbon combustion. The temperature of the first stream can be heated to the auto-ignition temperature of the first stream. Desirably, the first stream can have a temperature of 200°C to 700°C, for example, 400°C to 700°C, prior to passing through the combustion section.
  • the first stream can have a temperature of 400°C to 700°C, for example, 600°C to 700°C, prior to passing through the combustion section, and when the Ci to C 4 hydrocarbons comprise greater than or equal to 75 mole %, for example, greater than or equal to 80 mole % or greater than or equal to 90 mole %, ethane, butane, propane, or a combination comprising at least one of the foregoing, the first stream can have a temperature of 200°C to 500°C, for example, 400°C to 500°C, prior to passing through the combustion section.
  • the combustion section in which the combustion reaction occurs can be a free flame combustion section (e.g., a burner) or a combustion reactor.
  • the combustion reaction can occur in the absence of a catalyst in the combustion section.
  • the combustion reaction occurs in an oxidation catalyst bed.
  • the oxidation catalyst be can be a fixed bed or a monolith.
  • the combustion section can include an oxidation catalyst comprising platinum, redox-active oxides of iron, vanadium, nickel, ruthenium, rhodium, palladium, or a combination comprising at least one of the foregoing.
  • the first stream can be combined with hydrogen prior to passing through the combustion section.
  • the hydrogen can be obtained from the fourth stream from the dehydroaromatization catalyst bed.
  • the combustion section can include a fixed bed or monolith of a combustion catalyst that causes combustion of hydrogen (e.g., over gaseous Ci to C 4 hydrocarbons).
  • a fixed bed or monolith of a combustion catalyst or an oxidation catalyst allows the first stream to be at a temperature lower than the auto ignition temperature of the first stream, prior to passing through the combustion section.
  • a combustion reaction can occur in the combustion section according to Formulae (l)-(4):
  • the combustion reaction produces a second stream that exits the combustion section.
  • the second stream can have a temperature of 500°C to l,200°C.
  • the to C 4 hydrocarbons comprise greater than or equal to 75 mole %, for example, greater than or equal to 80 mole % or greater than or equal to 90 mole %, methane
  • the second stream can have a temperature of 700°C to l,200°C
  • the Ci to C 4 hydrocarbons comprise greater than or equal to 75 mole %, for example, greater than or equal to 80 mole % or greater than or equal to 90 mole %, ethane, butane, propane, or a combination comprising at least one of the foregoing
  • the second stream can have a temperature of 500°C to l,000°C.
  • the temperature of the second stream can depend on the amount of oxygen in the first stream. Desirably, the oxygen concentration can be a limiting reactant in the combustion reaction to produce carbon monoxide.
  • the second stream can further include oxygen, Ci to C 5 hydrocarbons (i.e., hydrocarbons with 1 to 5 carbon atoms), water, or a combination comprising at least one of the foregoing.
  • Water can remove coke from the dehydroaromatization catalyst bed to improve stability of the dehydroaromatization catalyst bed compared to a
  • an amount water of 100 ppm to 5.0 mole %, (preferably 2.0 mole% to 4.5 mole%), based on the total moles present in the second stream can improve stability of the dehydroaromatization catalyst bed and stability of the dehydroaromatization reaction.
  • the catalyst can be sensitive to water present in the second stream.
  • de- alumination can occur on the catalyst (e.g., on the zeolite) and this can permanently damage the catalyst.
  • the amount of water in the second stream can be controlled by adjusting the oxygen in the first stream. For instance, decreasing the amount of oxygen in the first stream can decrease the amount of water in the second stream prior to combining with the second portion of the to C 4 hydrocarbons to form a third stream.
  • the temperature of the first stream can also be adjusted to control the amount of water in the second stream.
  • the amount of water formed in the second stream is proportional to the amount of oxygen added to the first stream. If a lower amount of oxygen is added, the temperature of the first stream is heated to a higher temperature before entering the reactor.
  • the oxygen concentration should desirably be optimized to control the water formation and temperature.
  • the method can further include passing the second stream through a water-gas shift section.
  • Sensitive to water content generally refers to the fact that the catalyst can be sensitive to water present in the first stream.
  • the catalyst can tolerate up to 2.0 mole % of water without adverse consequences for methane dehydroaromatization, and up to 5.0 mole % of water without adverse consequences for dehydroaromatization of ethane, propane, butane, or a combination comprising at least one of the foregoing. If the water content exceeds this amount, de-alumination can occur on the catalyst (e.g., on the zeolite) which can permanently damage the catalyst.
  • the methane dehydroaromatization catalyst bed can include a heterogeneous catalyst.
  • the dehydroaromatization catalyst bed includes a catalytic metal and a support, wherein the catalytic metal comprises molybdenum, gallium, calcium, zinc, nickel, iron, copper, cobalt, rhodium, ruthenium, or a combination comprising at least one of the foregoing, and wherein the support comprises zeolite Y, zeolite X, mordenite, ZSM-5, HZSM-5, ALPO-5, VPI-5, FSM-16, MCM-22, MCM-41, or a combination comprising at least one of the foregoing.
  • the methane dehydroaromatization catalyst bed can include molybdenum and ZSM-5.
  • the catalyst bed for dehydroaromatization of ethane, propane, butane, or a combination comprising at least one of the foregoing can include a heterogeneous catalyst.
  • the dehydroaromatization catalyst bed includes a catalytic metal and a support, wherein the catalytic metal comprises platinum, molybdenum, gallium, calcium, zinc, nickel, iron, copper, cobalt, rhodium, ruthenium, or a combination comprising at least one of the foregoing, and wherein the support comprises zeolite Y, zeolite X, mordenite, ZSM-5, HZSM-5, ALPO-5, VPI-5, FSM-16, MCM-22, MCM-41, or a combination comprising at least one of the foregoing.
  • the C 2 - C 4 catalyst bed(s) can comprise gallium and ZSM-5, preferably platinum, gallium and ZSM-5.
  • a water-gas shift reaction of the carbon monoxide and hydrogen in the second stream occurs, producing carbon dioxide and hydrogen such that the second stream can include to C 5 hydrocarbons, carbon monoxide, carbon dioxide, water, hydrogen, oxygen, or a combination comprising at least one of the foregoing.
  • the water-gas shift reaction can be according to Formula (5):
  • the hydrogen can be separated from the second stream and removed or combined with the first stream prior to passing through the combustion section.
  • the water-gas shift reaction is exothermic and produces heat such that, for a first stream comprising methane, the second stream exits the water-gas shift section with a temperature of 300°C to l,500°C, for example, 550°C to l,000°C, and for a first stream comprising ethane, propane, butane, or a combination comprising at least one of the foregoing the second stream exits the water-gas shift section with a temperature of, for example, 500°C to 700°C.
  • the method can further include combining the second stream with a second portion of the to C 4 hydrocarbons to form a third stream.
  • the third stream can include hydrocarbons, carbon dioxide, water, hydrogen, carbon monoxide, or a combination comprising at least one of the foregoing.
  • the third stream can include 85 mole % to 98 mole % of Ci to C 4 hydrocarbons, for example, 90 mole % to 95 mole % of Ci to C 4 hydrocarbons, 0.5 mole % to 5 mole % carbon dioxide, 100 parts per million by moles to 5.0 mole % water, 0.5 mole % to 5 mole % or 1 mole % to 5 mole % hydrogen, based on the total moles present in the third stream, with the total percentage of components of the third stream equaling 100 mole %.
  • the carbon dioxide for example, in an amount of 0.5 mole % to 5 mole %, based on the total moles present in the third stream, can reduce coke formation (i.e., coking) on the methane dehydroaromatization catalyst bed.
  • a temperature of the third stream can be 660°C to l,000°C.
  • a temperature of the dehydroaromatization reaction can be 660°C to l,000°C, preferably 700°C to 900°C, and a pressure of the dehydroaromatization reaction can be 101 kiloPascals to 1013 kiloPascals (kPa), preferably, 101 to 709 kiloPascals (1 to 10 atmospheres, preferably, 1 to 7 atmospheres).
  • kPa kiloPascals to 1013 kiloPascals
  • temperature of the third stream can be 450°C to 800°C.
  • a temperature of the dehydroaromatization reaction can be 450°C to 800°C, preferably 500°C to 700°C, and a pressure of the dehydroaromatization reaction can be 101 kiloPascals to 1013 kiloPascals, preferably, 101 to 709 kiloPascals (1 to 10 atmospheres, preferably, 1 to 7 atmospheres).
  • a dehydroaromatization reaction occurs, producing a fourth stream that exits the dehydroaromatization catalyst bed.
  • the fourth stream can include aromatics, hydrogen, to C 4 hydrocarbons, or a combination comprising at least one of the foregoing.
  • the aromatics can include benzene, naphthalene, or a combination comprising at least one of the foregoing.
  • the dehydroaromatization reaction has a conversion from methane, ethane, propane, butane, or a combination comprising at least one of the foregoing, of 1 mole % to 80 mole %; i.e., the amount of the to C 4
  • the dehydroaromatization reaction has a conversion from methane of 1 % to 20 mole %, for example, 5 mole % to 20 mole % or 10 mole % to 20 mole %, and the dehydroaromatization reaction has a conversion (from ethane, propane, butane, or a combination comprising at least one of the foregoing) of, for example, 20 mole % to 75 mole %, 20 mole % to 65 mole %, or 20 mole % to 55 mole %. Conversion is calculated as
  • the combustion section and the dehydroaromatization catalyst bed can be in separate reactors. Desirably, the combustion section and the dehydroaromatization catalyst bed can be in a single reactor. At least one of the dehydroaromatization catalyst bed and the oxidation catalyst bed can be a fixed bed, a monolith coated with a catalyst, or a combination comprising at least one of the foregoing.
  • Several catalyst layers of (optionally) combustion catalyst, (optionally) water-gas shift catalyst and alkane dehydroaromatization catalyst can be arranged in series with staged dosing of oxygen upstream of each combustion catalyst layer or burner nozzle.
  • a method of to C 4 hydrocarbon dehydroaromatization can include passing a first stream comprising a first portion of Ci to C 4 hydrocarbons and oxygen through a combustion section, wherein a combustion reaction occurs producing a second stream that exits the combustion section, combining the second stream with a second portion of the Ci to C 4 hydrocarbons to form a third stream, passing the third stream through a dehydroaromatization catalyst bed, wherein a dehydroaromatization reaction occurs producing a fourth stream that exits the dehydroaromatization catalyst bed, and removing the fourth stream from the dehydroaromatization catalyst bed.
  • the first stream has a temperature of 400°C to 700°C prior to passing through the combustion section.
  • the oxygen is present in the first stream in an amount of 1 mole % to 10 mole %, for example, 1 mole % to 5 mole % or 2 mole % to 5 mole %, based on the total moles present in the first stream.
  • the second stream has a temperature of 350°C to l,000°C after exiting the combustion zone.
  • the third stream has a temperature of 400°C to l,000°C and includes 85 mole % to 98 mole % of Ci to C 4 hydrocarbons, 0.5 mole % to 5 mole % carbon dioxide, 100 parts per million by moles to 5.0 mole % water, 0.5 mole % to 5 mole % or 1 mole % to 5 mole % hydrogen, based on the total moles present in the third stream, with the total percentage of components of the third stream equaling 100 mole %.
  • the dehydroaromatization reaction has a conversion from methane, ethane, propane, butane, or a combination comprising at least one of the foregoing, of 1 mole % to 80 mole %.
  • a system for Ci to C 4 hydrocarbon dehydroaromatization includes a combustion section, through which a first stream comprising a first portion of Ci to C 4 hydrocarbons and oxygen can be passed and a combustion reaction occurs to produce a second stream that exits the combustion section, and a dehydroaromatization catalyst bed through which a third stream formed by combining the second stream and a second portion of the Ci to C 4 hydrocarbons can be passed and a dehydroaromatization reaction occurs to produce a fourth stream that exits the dehydroaromatization catalyst bed.
  • combustion section and the dehydroaromatization catalyst bed are in a single reactor.
  • FIG. are merely schematic representations based on convenience and the ease of demonstrating the present disclosure, and are, therefore, not intended to indicate relative size and dimensions of the devices or components thereof and/or to define or limit the scope of the exemplary embodiments.
  • a first stream 2 including a first portion of Ci to C 4 hydrocarbons and an oxidant including oxygen can be passed through a combustion section 10.
  • a combustion reaction occurs in the combustion section 10 producing a second stream 4' that exits the combustion section.
  • the second stream 4' passes through a water-gas shift section 20 where a water-gas shift reaction of carbon monoxide and hydrogen in the second stream 4' occurs, producing carbon dioxide and hydrogen.
  • the second stream 4" can be combined with a second portion of Ci to C 4 hydrocarbons 22 to from a third stream 24.
  • the third stream 24 can be passed through a dehydroaromatization catalyst bed 30, where a dehydroaromatization reaction occurs to produce a fourth stream 32 that exits the dehydroaromatization catalyst bed 30.
  • the methods of the present disclosure address the heat management (e.g., heat supply) challenges of Ci to C 4 hydrocarbon dehydroaromatization while improving the stability of the dehydroaromatization catalyst bed due to the production of carbon dioxide and water to be passed through in the dehydroaromatization catalyst bed.
  • heat management e.g., heat supply
  • a simulated method of methane dehydroaromatization was carried out as shown in FIG. 1.
  • Oxygen was present in the first stream 2 in an amount of 2 mole % and methane was present in the first stream 2 in an amount of 98 mole %, based on the total moles present in the first stream 2.
  • the first stream 2 had a temperature of 650°C, prior to passing through the combustion section 10.
  • the second stream 4' exiting the combustion section 10 had a temperature of 748°C.
  • the second stream 4' had a composition as summarized in Table la.
  • the second stream 4" exiting the water-gas shift section 20 had a temperature of 752 C.
  • the third stream 24 had a composition as summarized in Table lb.
  • the first stream was heated in a furnace using flue gas generated on the shell side using hydrocarbon combustion.
  • the first stream was heated to 650°C.
  • a temperature of the third stream was 752°C.
  • a temperature of the dehydroaromatization reaction including a catalyst comprising Mo/ZSM-5 was 750°C, and a pressure of the dehydroaromatization reaction was 101 KiloPascals (1 atmosphere).
  • the conversion of methane was 10 mole % ((96.7 moles Ci hydrocarbon in - 87.0 moles Ci hydrocarbon out) / (96.7 moles Ci hydrocarbon in)).
  • the fourth stream 32 exiting the dehydroaromatization reactor had a composition as summarized in Table lc.
  • a simulated method of ethane dehydroaromatization was carried out as shown in FIG. 1.
  • Oxygen was present in the first stream 2 in an amount of 2.5 mole % and ethane was present in the first stream 2 in an amount of 97.5 mole %, based on the total moles present in the first stream 2.
  • the first stream 2 had a temperature of 450°C, prior to passing through the combustion section 10.
  • the second stream 4' exiting the combustion section 10 had a temperature of 533°C.
  • the second stream 4' had a composition as summarized in Table 2a.
  • the second stream 4" exiting the water-gas shift section 20 had a temperature of 539 C.
  • the third stream 24 had a composition as summarized in Table 2b.
  • the first stream was heated in a furnace using flue gas generated on the shell side using hydrocarbon combustion.
  • the first stream was heated to 450°C.
  • a temperature of the third stream was 539°C.
  • a temperature of the dehydroaromatization reaction including a catalyst comprising Pt-Ga/ZSM-5 was 550°C, and a pressure of the dehydroaromatization reaction was 101 KiloPascals (1 atmosphere).
  • the conversion of ethane was 50 mole % ((96.5 moles C 2 hydrocarbon in - 48.3 C 2 hydrocarbon out) / (96.5 moles C 2 hydrocarbon in)).
  • the fourth stream 32 exiting the dehydroaromatization reactor had a composition as summarized in Table 2c.
  • a simulated method of propane dehydroaromatization was carried out as shown in FIG. 1.
  • Oxygen was present in the first stream 2 in an amount of 3.5 mole % and propane was present in the first stream 2 in an amount of 96.5 mole %, based on the total moles present in the first stream 2.
  • the first stream 2 had a temperature of 450°C, prior to passing through the combustion section 10.
  • the second stream 4' exiting the combustion section 10 had a temperature of 53l°C.
  • the second stream 4' had a composition as summarized in Table 3 a.
  • the second stream 4" exiting the water-gas shift section 20 had a temperature of 537 C.
  • the third stream 24 had a composition as summarized in Table 3b.
  • the first stream was heated in a furnace using flue gas generated on the shell side using hydrocarbon combustion.
  • the first stream was heated to 450°C.
  • a temperature of the third stream was 537°C.
  • a temperature of the dehydroaromatization reaction including a catalyst comprising Pt-Ga/ZSM-5 was 530°C, and a pressure of the dehydroaromatization reaction was 101 KiloPascals (1 atmosphere).
  • the conversion of propane was 60 mole % ((95.5 moles C 3 hydrocarbon in - 38.2 C 3 hydrocarbon out) / (95.5 moles C 3 hydrocarbon in)).
  • the fourth stream 32 exiting the dehydroaromatization reactor had a composition as summarized in Table 3c.
  • a simulated method of butane dehydroaromatization was carried out as shown in FIG. 1.
  • Oxygen was present in the first stream 2 in an amount of 4.5 mole % and butane was present in the first stream 2 in an amount of 95.5 mole %, based on the total moles present in the first stream 2.
  • the first stream 2 had a temperature of 450°C, prior to passing through the combustion section 10.
  • the second stream 4' exiting the combustion section 10 had a temperature of 530°C.
  • the second stream 4' had a composition as summarized in Table 4a.
  • the second stream 4" exiting the water-gas shift section 20 had a temperature of 536 C.
  • the third stream 24 had a composition as summarized in Table 4b.
  • the first stream was heated in a furnace using flue gas generated on the shell side using hydrocarbon combustion.
  • the first stream was heated to 450°C.
  • a temperature of the third stream was 536°C.
  • a temperature of the dehydroaromatization reaction including a catalyst comprising Pt-Ga/ZSM-5 was 530°C, and a pressure of the dehydroaromatization reaction was 101 KiloPascals (1 atmosphere).
  • the conversion of butane was 70 mole % ((94.5 moles C 4 hydrocarbon in - 28.4 moles C 4 hydrocarbon out) / (94.5 moles C 4 hydrocarbon in)).
  • the fourth stream 32 exiting the dehydroaromatization reactor had a composition as summarized in Table 4c.
  • a method of Ci to C 4 hydrocarbon dehydroaromatization comprising: passing a first stream comprising a first portion of Ci to C 4 hydrocarbons and an oxidant comprising oxygen through a combustion section, wherein a combustion reaction occurs producing a second stream that exits the combustion section; combining the second stream with a second portion of the Ci to C 4 hydrocarbons to form a third stream; passing the third stream through a dehydroaromatization catalyst bed, wherein a dehydroaromatization reaction occurs producing a fourth stream that exits the dehydroaromatization catalyst bed; and removing the fourth stream from the dehydroaromatization catalyst bed; wherein the third stream has a temperature of 400°C to l,000°C.
  • Aspect 2 The method of Aspect 1, wherein the combustion section and the dehydroaromatization catalyst bed are in a single reactor.
  • Ci to C 4 hydrocarbons comprise methane, ethane, propane, or a combination comprising at least one of the foregoing.
  • Aspect 4 The method of any of the preceding aspects, wherein the oxygen is present in the first stream an amount of 1 mole % to 10 mole %, preferably 1 mole % to 5 mole % or 2 mole % to 5 mole %, based on the total moles present in the first stream.
  • Aspect 8 The method of any of Aspects 1-5 and 7, wherein combustion section comprises an oxidation catalyst comprising platinum, redox-active oxides of iron, vanadium, nickel, ruthenium, rhodium, palladium, or a combination comprising at least one of the foregoing.
  • Aspect 11 The method of any of the preceding aspects, wherein the at least one of the dehydroaromatization catalyst bed and the oxidation catalyst bed is a fixed bed.
  • Aspect 12 The method of any of the preceding aspects, wherein at least one of the dehydroaromatization catalyst bed and the oxidation catalyst bed comprises a monolith coated with a catalyst.
  • Aspect 13 The method of any of the preceding aspects, wherein the third stream comprises hydrocarbons, carbon dioxide, water, hydrogen, carbon monoxide, hydrogen, or a combination comprising at least one of the foregoing.
  • Aspect 14 The method of any of the preceding aspects, wherein the third stream comprises 85 mole % to 98 mole % of Ci to C 4 hydrocarbons, 0.5 mole % to 5 mole % carbon dioxide, 100 parts per million by moles to 5.0 mole % water, 0.5 mole % to 5 mole % or 1 mole % to 5 mole % hydrogen.
  • Aspect 16 The method of any of the preceding aspects, wherein the fourth stream comprises aromatics, hydrogen, Ci to C 4 hydrocarbons, or a combination comprising at least one of the foregoing.
  • Aspect 17 The method of any of the preceding aspects, wherein the dehydroaromatization reaction has a conversion from methane, ethane, propane, butane, or a combination comprising at least one of the foregoing of 1 mole % to 80 mole %.
  • Aspect 18 The method of any of the preceding aspects, wherein the second stream comprises an amount of water of less than or equal to or 2.0 mole %, preferably 100 ppm to 2.0 mole %, or 0.5 mole% to 2.0 mol%, or 0.5 mole % to 1.5 mole %, based on the total moles present in the second stream; wherein the third stream comprises 75 mole % to 98 mole %, preferably 85 mole % to 98 mole %, of methane, based on the total moles present in the second stream; and preferably wherein the dehydroaromatization catalyst bed comprises molybdenum and ZSM-5.
  • Aspect 19 The method of any of Aspects 1 - 17, wherein the second stream comprises an amount of water of 100 ppm to 5.0 mole %, preferably 2.0 mole% to 4.5 mole%, based on the total moles present in the second stream; wherein the third stream comprises 75 mole % to 98 mole %, preferably 85 mole % to 98 mole %, of ethane, butane, and propane, based on the total moles present in the second stream; and preferably wherein the dehydroaromatization catalyst bed comprises platinum, gallium, and ZSM-5.
  • Aspect 20 The method of Aspect 19, wherein the third stream comprises 75 mole % to 98 mole %, preferably 85 mole % to 98 mole %, of ethane, based on the total moles present in the second stream.
  • Aspect 21 The method of Aspect 19, wherein the third stream comprises 75 mole % to 98 mole %, preferably 85 mole % to 98 mole %, of butane, based on the total moles present in the second stream.
  • Aspect 22 The method of Aspect 19, wherein the third stream comprises 75 mole % to 98 mole %, preferably 85 mole % to 98 mole %, of propane, based on the total moles present in the second stream.
  • a method of to C 4 hydrocarbon dehydroaromatization comprising: passing a first stream comprising a first portion of Ci to C 4 hydrocarbons and oxygen through a combustion section, wherein a combustion reaction occurs producing a second stream that exits the combustion section; combining the second stream with a second portion of the to C 4 hydrocarbons to form a third stream; passing the third stream through a dehydroaromatization catalyst bed, wherein a dehydroaromatization reaction occurs producing a fourth stream that exits the dehydroaromatization catalyst bed; and removing the fourth stream from the dehydroaromatization catalyst bed; wherein the first stream has a temperature of 400°C to 700°C prior to passing through the combustion section, and wherein the oxygen is present in the first stream an amount of 1 mole % to 10 mole %, preferably 1 mole % to 5 mole % or 2 mole % to 5 mole %, based on the total moles present in the first stream;
  • a system for to C 4 hydrocarbon dehydroaromatization comprising: a combustion section, through which a first stream comprising a first portion of Ci to C 4 hydrocarbons and oxygen can be passed and a combustion reaction occurs to produce a second stream that exits the combustion section; and a dehydroaromatization catalyst bed through which a third stream formed by combining the second stream and a second portion of the Ci to C 4 hydrocarbons can be passed and a dehydroaromatization reaction occurs to produce a fourth stream that exits the dehydroaromatization catalyst bed.
  • Aspect 25 The system of Aspect 24, wherein the combustion section and the dehydroaromatization catalyst bed are in a single reactor.
  • the invention may alternately comprise, consist of, or consist essentially of, any appropriate components herein disclosed.
  • the invention may additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any components, materials, ingredients, adjuvants or species used in the prior art compositions or that are otherwise not necessary to the achievement of the function and/or objectives of the present invention.
  • the endpoints of all ranges directed to the same component or property are inclusive and independently combinable (e.g., ranges of“less than or equal to 25 wt%, or 5 wt% to 20 wt%,” is inclusive of the endpoints and all intermediate values of the ranges of“5 wt% to 25 wt%,” etc.).
  • composition of all streams herein total 100 mole%.
  • the modifier“about” used in connection with a quantity is inclusive of the stated value and has the meaning dictated by the context (e.g., includes the degree of error associated with measurement of the particular quantity).
  • the notation“+ 10%” means that the indicated measurement can be from an amount that is minus 10% to an amount that is plus 10% of the stated value.
  • the terms“front”,“back”,“bottom”, and/or“top” are used herein, unless otherwise noted, merely for convenience of description, and are not limited to any one position or spatial orientation.“Optional” or“optionally” means that the

Abstract

La présente invention concerne un procédé de déshydroaromatisation d'hydrocarbures en C1 à C4 comprenant les étapes consistant à : faire passer un premier flux comprenant une première partie d'hydrocarbures en C1 à C4 et un oxydant comprenant de l'oxygène à travers une section de combustion, une réaction de combustion produisant un second flux sortant de la section de combustion ; combiner le deuxième flux avec une deuxième partie d'hydrocarbures en C1 à C4 pour former un troisième flux ; faire passer le troisième flux à travers un lit de catalyseur de déshydroaromatisation, une réaction de déshydroaromatisation produisant un quatrième flux sortant du lit de catalyseur de déshydroaromatisation ; et éliminer le quatrième flux du lit de catalyseur de déshydroaromatisation ; le troisième flux ayant une température de 400 °C à 1000 °C.
PCT/IB2019/053200 2018-04-17 2019-04-17 Procédés de déshydroaromatisation d'hydrocarbures en c1 à c4 WO2019202535A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB709035A (en) * 1952-02-06 1954-05-12 Chemical Construction Corp Improvements relating to the production of pyrogenic chemical reactions
US6239057B1 (en) * 1999-01-15 2001-05-29 Uop Llc Catalyst for the conversion of low carbon number aliphatic hydrocarbons to higher carbon number hydrocarbons, process for preparing the catalyst and process using the catalyst
WO2014173791A1 (fr) * 2013-04-23 2014-10-30 Bayer Technology Services Gmbh Procédé de production de benzène à partir de méthane et de dioxyde de carbone avec une cloison étanche aux fluides dans le réacteur

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB709035A (en) * 1952-02-06 1954-05-12 Chemical Construction Corp Improvements relating to the production of pyrogenic chemical reactions
US6239057B1 (en) * 1999-01-15 2001-05-29 Uop Llc Catalyst for the conversion of low carbon number aliphatic hydrocarbons to higher carbon number hydrocarbons, process for preparing the catalyst and process using the catalyst
WO2014173791A1 (fr) * 2013-04-23 2014-10-30 Bayer Technology Services Gmbh Procédé de production de benzène à partir de méthane et de dioxyde de carbone avec une cloison étanche aux fluides dans le réacteur

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