WO2023224867A1 - Catalyseurs de zéolite et utilisation dans l'oligomérisation et la production d'éthanol de carburants - Google Patents

Catalyseurs de zéolite et utilisation dans l'oligomérisation et la production d'éthanol de carburants Download PDF

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WO2023224867A1
WO2023224867A1 PCT/US2023/021943 US2023021943W WO2023224867A1 WO 2023224867 A1 WO2023224867 A1 WO 2023224867A1 US 2023021943 W US2023021943 W US 2023021943W WO 2023224867 A1 WO2023224867 A1 WO 2023224867A1
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zsm
zeolite
ethanol
aromatics
heterogeneous catalyst
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Bhogeswararao SEEMALA
Charles E. Wyman
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The Regents Of The University Of California
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    • 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
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/44—Noble metals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/38—Base treatment
    • 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

Definitions

  • the present disclosure relates generally to heterogenous catalysis for bioderived ethanol conversion to sustainable aviation fuel blendstocks, and more specifically to the use of Ga incorporated crystalline-mesoporous zeolite catalysts for ethanol oligomerization and production of fuels, such as jet fuels.
  • a particularly promising route that could facilitate rapid transformation to low carbon emissions by aviation is catalytic conversion of ethanol into SAF that meets energy density and other fit-for-purpose requirements and can build on established US and world ethanol productionof about 14 and 26 billion gallons, respectively, by far the largest amount of biofuel in 2020.
  • ATJ alcohol to jet
  • Many of these alcohol to jet (ATJ) processes being scaled up require 3 to 4 catalytic steps to dehydrate ethanol to C2 to C4 olefins, oligomerize these olefins to C6 to C8 products, further polymerize the oligomers to higher carbon number compounds, and saturate double bonds by hydrogenation.
  • these operations require high temperatures and pressures and can suffer from compounding of the yield losses of each step.
  • CADO consolidated alcohol deoxygenation and oligomerization
  • zeolite catalysts to combine ethanol dehydration/deoxygenation, oligomerization, and further reaction in a single step without the need to add hydrogen.
  • CADO high aromatic content and carbon number distribution from CADO
  • shifting the product distribution to higher carbon number compounds would increase blend levels for jet fuel.
  • this study focuses on determining how changes in ZSM-5 zeolite catalyst features can increase the carbon number range of liquid hydrocarbons made from ethanol by CADO technology and thereby allow higher blend levels in aviation fuels.
  • Si/Al ratio, crystal size, weight hour space velocity(WHSV), temperature, and reaction pressure have been optimized for ethanol conversion into hydrocarbons using H- ZSM-5 supports.
  • 10-13 When ethanol is co-fed with inert gases and reaction pressures are maintained above20 bar for such catalysts, gasoline range paraffins and benzene/toluene/xylene (BTX) are more predominant products while ethylene is the dominant product for reactions at atmospheric pressurewithout an inert gas carrier.
  • BTX benzene/toluene/xylene
  • H-ZSM-5 supports selectively produce BTX by the ethanol HCP process and Ga addition to H-ZSM-5 further promoted BTX production (C6-C8aromatics only).
  • most of the gallium oxide was proven to be on the external zeolite surface due to steric constraints to incorporation inside the pores. 20-24 ’ 26-29 It is still unclear what role gallium oxide inside the zeolite channels plays on ethanol product distributions.
  • the systems and methods provided herein address a need in the art by increasing H-ZSM-5 pore volumes by post synthesis to facilitate greater gallium (Ga) insertion into the zeolite channels. Furthermore, enhanced zeolite pore volumes/size accommodates ethanol reactive intermediates for forming longer hydrocarbon chain lengths (C9+) that are desirable for jet fuel. [0008]
  • a method for selectively producing C9-C12 aromatics comprises converting ethanol in the presence of a heterogeneous catalyst at a temperature suitable to produce a product mixture comprising liquid hydrocarbons.
  • the heterogeneous catalyst comprises zeolite with one or more of the following properties: (i) a zeolite pore volume of at least 0.05 cm 3 /g; (ii) a zeolite surface area of 300-450 m 2 /g; (iii) a crystallinity between 70% and 95% relative to the crystallinity of the zeolite, wherein said crystallinity is determined by powder X-ray diffraction analysis of peaks in the signal area of 22.7° to 24.2° 20 ; (iv) a Ga or Ru loading of 1-10%, 2-8%, or 4-6%; (v) a zeolite surface Si/Ga ratio of 5-30, or 10-20, or 10- 15; (v) a total acid site density between 0.5 mmol/g and 1.5 mmol/g; and (vi) a Ga or Ru particle size between 1 nm and 10 nm.
  • the heterogeneous catalyst is other than unmodified ZSM-5 ze
  • the heterogeneous catalyst is prepared by a process comprising desilicating the zeolite and incorporating Ga or Ru.
  • the zeolite is desilicated by contacting the zeolite with aqueous hydroxide.
  • Ga or Ru is incorporated by wet impregnation.
  • the method further comprises protonating the zeolite prior to incorporating Ga or Ru, for example, by contacting the zeolite with an acidic solution.
  • the method further comprises calcining the zeolite to produce the heterogeneous catalyst used in the methods described herein.
  • a system comprising: a catalytic reactor containing a heterogeneous catalyst, and wherein the catalytic reactor comprises an ethanol inlet configured to receive ethanol at an elevated temperature, and a reactor outlet configured to output liquid products produced from the ethanol; and a pump configured to control ethanol flow through the ethanol inlet through the heterogeneous catalyst.
  • the heterogeneous catalyst used in such a system may be as described in any of the embodiments and variations herein.
  • Figures la and lb show the effect of NaOH treatment concentration on X-ray diffraction spectra and crystallinity of Ga/ZSM-5 catalysts and N2 adsorption-desorption isotherms for Ga(5 wt.%)/ZSM-5 and Ga(5 wt.%)/modified-ZSM-5 catalysts.
  • Figures 2a-f depict the following: (a) STEM images of Ga(5%)/ZSM-5, (b) Ga, and (c) overlaid Ga/Si/Al elemental mapping. STEM images of (d) Ga(5%)/ZSM-5 0 . 8M , (e) Ga, and (f) overlaid Ga/Si/Al elemental mapping.
  • Figures 3a and 3b show XPS spectra of Ga(5 wt.%)/ZSM-5 and Ga(5 wt.%)/ZSM-5xM catalysts in the binding energy range for the Ga 2p3/2 peak, and H 2 -TPR profiles of Ga(5 wt.%)/ZSM-5 and Ga(5 wt.%)/ZSM-5xM..
  • Figures 4a-4c show the effect of temperature on liquid product distribution from ethanol reactions on Ga(5 wt.%)/ZSM-5 and Ga(5 wt.%)/ZSM-5xM catalysts at 1.6h -1 HSV. Product selectivity is calculated based on the total mass of liquid hydrocarbons.
  • Figures 5a-5c show the effect of WHSVs on selectivities for formation of C5-C6 paraffins, BTX, and C9-C10 aromatics from reaction of ethanol over Ga(5 wt.%)/ZSM-5 and Ga(5 wt.%)/ZSM-5xM catalysts at 350°C.
  • Product selectivity is calculated based on the total mass of liquid hydrocarbons.
  • Figures 6a and 6b show selectivity to C5-C6 paraffins, BTX, and C9-C10 aromatics produced by ethanol oligomerizations at 350°C and 0.4h -1 WHSV over ZSM-5 and ZSM-5XM supports without loading Ga, and selectivity to C5-C6 paraffins, BTX, and C9- C10 aromatics produced by ethanol oligomerizations over Ga(5 wt.%)/ZSM-5 and Ga(5 wt.%)/ZSM-5xM at 350°C and 0.4h -1 WHSV.
  • Product selectivity is based on the total mass of just liquid hydrocarbons.
  • Figure 7 depicts the correlation between C9-C10 aromatics selectivity and pore volume and surface Si/Ga ratios (LP: Liquid Product).
  • Product selectivity is based on the total mass of liquid hydrocarbons produced.
  • Figures 8a-8b show the effect of (a) catalyst synthesis time and (b) Ga content on liquid hydrocarbon product selectivity following reaction of ethanol on Ga(5%)/ZSM-50.8M catalysts at 350°C with a 0.4h -1 WHSV. Product selectivity is based on total liquid hydrocarbons.
  • Figure 9a depicts product selectivity over time for Ga/ZSM-5 0.8M fed ethanol for 32 hours at 350°C and 0.4h -1 WHSV.
  • Figure 9b depicts XPS spectra of used Ga(5%)/ZSM- 5O.8M in the binding energy range forthe Ga 2p3/2 peak (red color: washed catalyst and black color: washed catalyst followed by calcination). Product selectivity is based on total liquid hydrocarbons.
  • Figure 9c shows H2-TPR profiles of fresh catalyst and used catalysts for ethanol and wet-ethanol stream.
  • Figures lOa-lOb depict TPO profiles of catalysts following their use for conversion of pure ethanol and wet-ethanol to hydrocarbons.
  • Figure 11 depicts a scheme that shows progressive in carbon number as ethanol dehydrates, aromatizes, and alkylates to longer chained hydrocarbons and C9-C10 aromatics along H-ZSM-5 meso-micropores before exiting through large pores through which they can fit. If the hydrocarbon grows to a size that is too large to exit, it must either crack to form smaller molecules that can leave or pyrolyze to form carbon deposits that block access to active sites or restrict hydrocarbons from entering or leaving pores.
  • Figure 12 shows BJH pore size distribution curves derived from N2 adsorptiondesorption studies for Ga(5 wt.%)/ZSM-5 and Ga(5 wt.%)/modified-ZSM-5 catalysts.
  • Figure 13 shows the effect of Ga loading on ZSM-5 0.8M support porosity and surface area.
  • Figure 14 shows STEM images for: (a) Ga(5 wt.%)/ZSM-5 (a) support, (b) Ga distribution, and (c) overlaid Ga/Si/Al elemental mapping.
  • STEM images for Ga(5 wt.%)/ZSM-5o.8M (d) support, (e) Ga distribution, and (f) overlaid Ga/Si/Al elemental mapping.
  • Figures 15a-15b show Ga average particle diameters in Ga(5 wt.%)/ZSM-5 and Ga(5 wt.%)/ZSM-5 0.8M .
  • Figure 16 shows Ga 2p3/2 XPS spectra of 2, 5, and 8% gallium loadings for 4, 16 and 32 hours Ga wet-impregnation synthesis times.
  • Figure 18 shows the effect of temperature on ethanol oligomerizations over Ga(5 wt.%)/ZSM-5 and Ga(5 wt.%)/ZSM-5xM catalysts at 1.6h WHSV.
  • Figure 19 X-ray diffraction spectra of fresh Ga/ZSM-5o.8M and used Ga/ZSM- 5O.8M after reacting pure ethanol (red color) and 40% wet ethanol (black) to form hydrocarbons.
  • Figures 20a-c show: (a) N2 adsorption-desorption isotherms and (b) surface area (SA), external surface area, and micropore surface area for fresh Ga(5 wt.%)/ZSM-5o.8M and used Ga(5 wt.%)/ZSM-5o.8M catalysts, (c) Pore volumes for fresh Ga(5 wt.%)/ZSM-5o.8M and used Ga(5 wt.%)/ZSM-5o.8M catalysts.
  • Figure 21 shows NH3-TPD profiles of fresh catalyst and used catalysts for pure ethanol and wet ethanol.
  • Figure 22 shows ethanol conversions using 5 wt% Ga loaded ZSM-5, beta and Y- zeolites at 350 C and 0.4h-l SV.
  • Figure 23 shows ethanol conversions over Ru(0.5 wt%)/ZSM-5, Ru(2 wt%)/ZSM-5, Ru(2 wt%)/ZSM-5o.8M and Ru(5 wt%)/ZSM-5o,8 catalysts.
  • Jet fuel from petroleum provides energy densities and other attributes vital for aviation but adds to greenhouse gas emissions.
  • Biomass provides an inexpensive resource that is uniquely suited for large-scale conversion into low carbon footprint sustainable aviation fuels (SAF) for the immediate future and likely longer.
  • SAF sustainable aviation fuels
  • novel consolidated alcohol deoxygenation and oligomerization (CADO) zeolite catalysts including for example ZSM-5, offer low-cost, one-step, complete conversion of biomass ethanol into hydrocarbons without adding hydrogen.
  • CADO novel consolidated alcohol deoxygenation and oligomerization
  • CADO products mostly contain less than 8 carbon atoms while jet fuel includes up to 16, likely restricting jet fuel blending to 50% or less.
  • the larger pores enhanced 5 wt.% gallium oxide migrationinto ZSM-5 0.8M channels and promoted strong interactions between gallium oxide and the support that coupled with retained crystallinity and greater capacity for larger molecules increased liquid hydrocarbon yields (LHYs) from pure ethanol to 46.1% and C9-C10 aromatics selectivity to 45.8%, the first reported direct increase in C9-C10 aromatics selectivity from ethanol.
  • LHYs liquid hydrocarbon yields
  • cofeeding 60% water with ethanol further enhanced LHY and C9-C10aromatics selectivity to 53.1% and 55.1%, respectively, while extending catalyst stability.
  • a simple, efficient, and reproducible desilication process that is selective for extracting framework silica without disturbing framework alumina/Bronsted acid sites and for creating new mesopores was adopted for H- ZSM-5.
  • Desilication of ZSM-5 with NaOH concentrations of 0.2, 0.6, 0.8, and 1.0M resulted in continual increases in pore volume/size, but crystallinity dropped significantly for 1.0M NaOH as determined by XRD and N2-physisorption studies.
  • STEM and XPS studies revealed greater Ga migration into the channels of ZSM-5 that had been treated with 0.8 and 1 ,0M NaOH than for parent ZSM-5 catalyst.
  • a method for selectively producing C9-C10 aromatics comprising converting ethanol in the presence of a heterogeneous catalyst at a temperature suitable to produce a product mixture comprising liquid hydrocarbons.
  • the method further comprises isolating the liquid hydrocarbons from water produced.
  • the ethanol may be sourced from any commercially available sources or produced according to any known methods in the art.
  • the ethanol used in the methods provided is delivered in vapor form, such as wet-ethanol vapor.
  • the heterogeneous catalyst comprises Ga or Ru loaded onto zeolite, wherein the heterogeneous catalyst has one or more of the following properties: (i) a zeolite pore volume of at least 0.05 cm 3 /g, or between 0.05-0.5 cm 3 /g; (ii) a zeolite surface area of 300-450 m 2 /g; (iii) a crystallinity between 70% and 95% relative to the crystallinity of the zeolite, wherein said crystallinity is determined by powder X-ray diffraction analysis of peaks in the signal area of 22.7° to 24.2° 20 ; (iv) a Ga or Ru loading of 1-10%, 2-8%, or 4-6%; (v) a zeolite surface Si/Ga ratio of 5-30, or 10-20, or 10-15; (vi) a total acid site density between 0.5 mmol/g and 1.5 mmol, or between 0.8 mmol/g and 1.2 mmol;
  • the heterogeneous catalyst comprises Ga loaded onto zeolite. In other variations, the heterogeneous catalyst comprises Ru loaded onto zeolite. In one variation, the heterogeneous catalyst is other than unmodified ZSM-5 zeolite.
  • the heterogeneous catalyst has a catalyst stability of greater than 30 hours.
  • Reaction conditions suitable to produce a product mixture comprising liquid hydrocarbons from the ethanol provided may be employed.
  • the temperature is between 350°C and 500°C.
  • the methods provided yield a product mixture that has: (a) less than 50% for C5-C6 paraffins; (b) less than 80% for benzene, toluene and xylene (BTX); and/or (c) at least 10% for C9-10 aromatics.
  • the product mixture has all three properties (a)-(c) above.
  • the methods provided yield a product mixture that has: (a) less than 30% for C5-C6 paraffins; (b) less than 60% for benzene, toluene and xylene (BTX); and (c) at least 20% for C9-10 aromatics.
  • the product mixture has all three properties (a)-(c) above.
  • the produce mixture has at least 50% for C9-10 aromatics.
  • the liquid hydrocarbon yield is at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%.
  • the product mixture comprises C9-C10 aromatics such as trimethyl benzene, ethyl methyl benzene, or ethyl dimethyl benzene, or any combination thereof.
  • the product mixture further comprises gaseous hydrocarbons (C2-C4).
  • the product mixture further comprises C2-C5 olefins.
  • a method for preparing the heterogeneous catalyst comprising desilicating the zeolite and incorporating Ga or Ru.
  • the zeolite is desilicated by contacting the zeolite with aqueous hydroxide.
  • Suitable hydroxides include, for example, sodium hydroxide.
  • the hydroxide concentration is between 0.2 M and 1.0 M.
  • Ga or Ru is incorporated by wet impregnation.
  • the method for preparing the heterogeneous catalyst further comprises protonating the zeolite prior to incorporating Ga or Ru.
  • the zeolite is protonated by contacting the zeolite with an acidic solution. Suitable acidic solutions include aqueous ammonium nitrate.
  • the method for preparing the heterogeneous catalyst further comprises calcining the zeolite. Any suitable temperatures may be used for calcining. For example, in some variations, the calcining is performed at a temperature of at least 400°C, at least 450 °C, or at least 500 °C.
  • the heterogeneous catalyst produced according to the methods herein has a zeolite pore volume between 0.4-0.5 cm 3 /g; a zeolite surface area between 375-400 m 2 /g; a zeolite crystallinity between 80-85% relative to ZSM-5; and/or a zeolite surface Si/Ga ratio 5 to 30, 10 to 20, or 10 to 15.
  • the heterogeneous catalyst produced according to the methods herein has a zeolite pore volume between 0.4-0.5 cm 3 /g; a crystallinity between 80- 85% relative to the crystallinity of the zeolite; a Ga or Ru loading between 3-7%; a zeolite surface Si/Ga ratio or Si/Ru ratio between 10-15; a total acid site density between 0.85 mmol/g and 0.95 mmol/g; and a Ga or Ru particle size between 3.5 nm and 4.5 nm.
  • a system comprising: a catalytic reactor containing a heterogeneous catalyst, and wherein the catalytic reactor comprises an ethanol inlet configured to receive ethanol at an elevated temperature, and a reactor outlet configured to output liquid products produced from the ethanol; and a pump configured to control ethanol flow through the ethanol inlet through the heterogeneous catalyst.
  • any of the heterogeneous catalysts described herein including any of the heterogeneous catalysts produced according to the methods described herein, may be employed in the system.
  • any of the reaction conditions provided for the methods to selectively producing C9-C10 aromatics may be employed in the system.
  • H-ZSM-5 (Si/Al - 23). 30-34 In particular, H-ZSM-5 (Si/Al-23) supports were desilicated by treatment with NaOH to produce mesopore-crystalline H-ZSM- 5.
  • Ga was loaded onto parent and modified ZSM-5 supports by following incipient wet-impregnation procedures, and theresulting catalysts were used to catalyze ethanol conversions at different temperatures and WHS Vs.
  • the effects of Ga proximity on the zeolite external surface and inside the channels on ethanol product distributions were then determined.
  • This example demonstrates how pore modification, crystallinity, and Ga proximity in zeolite channels affect yields and carbon number distribution of hydrocarbons formed by single step reaction of ethanol on ZSM-5 catalysts.
  • ZSM-5 pore modification with 0.8M NaOH showed significant influence on ethanol liquid hydrocarbon (LHYs) and raised nearly 5x higher in case of ZSM-5 0.8M (27.1%) compared to parent ZSM-5 (LHYs- 5.3%), without adding gallium oxide.
  • Gallium addition to ZSM-5 0.8M further promoted the LHYs and C9-C10 aromatics selectivity to 46.1% and 45.8%, respectively, at 350 °C reaction temperatures and 0.4h'l WHSV. Presence of water in the ethanol feed further increased the product selectivity of C9-C10 aromatic to 55.1%.
  • Ga/ZSM-5 catalysts synthesis' 2, 5 and 8% Ga was loaded onto ZSM-5 and each ZSM-5xMby following the incipient wet-impregnation procedure.
  • the appropriate amount of gallium nitrate precursor was dissolved in water and then added to H-ZSM-5 or ZSM-5XM at a water/ZSM-5 mass ratio of 50: 1.
  • This combination was then mixed on a magnetic hot-plate that also kept the temperature at 80°C for 16 hours for most samples. However, a few samples were wet-impregnatedfor 4 hours and 32 hours.
  • the solid material was separated from the liquid using a rotary evaporator.
  • the solid obtained was dried at 105°C for 6 hours and calcined at 500°C for 5 hours by a muffle furnace at a ramp rate of 10°C/min from 25°C.
  • a similar procedure was followed for 2 wt.% and 8 wt.% Ga impregnations on the ZSM-5 0.8M support.
  • synthesized materials were used for catalytic conversion of ethanol at 350°C, 400°C, 450°C, and 500 °C and space velocities of 1.6, 1.2, 0.8, and 0.4h -1 unless otherwise noted.
  • ICP-OES Inductively Coupled Plasma-Optical Emission Spectroscopy
  • STEM imaging was at 300 kV accelerating voltage on a FEI/Philips Titan Themis 300 instrument fitted with an X-FEG electron source, a three-lens condenser system, and an S-Twin objective lens.
  • STEM images were recorded with a M3000 High Angle Annular Dark Field (HAADF) Detector at a probe current of 0.2 nA, frame size of 2048 x 2048, dwell time of 15 ps/pixel, camera length of 195 mm, and convergence angle of 10 mrad.
  • Elemental X-ray microanalysis and mapping utilized a FEI Super-X EDS system with four symmetrically positioned SDD detectors of 30 mm 2 each, resulting in aneffective collection angle of 0.7 srad. Elemental maps were collected in STEM mode with a beamcurrent of 0.4 to 0.25 nA, a 512 x 512-pixel frame, 30 ps dwell time, and up to 10 min acquisitiontime.
  • Specimens prepared from suspensions in distilled water were deposited on copper grids coated with lacey carbon. Average metal particle sizes were measured based on the diameter of 100 particles from corresponding TEM images of each catalyst.
  • a lOOmg sample was dried in a 2% O 2 /He stream for 1 h at 450°C and then cooled to 150 °C prior to analysis. Then the sample was reduced in a 10% H 2 /He (50 mL/min) stream at a heating rate of 10°C/min to 950°C. TPO characterization techniques were applied in the same system to about lOOmg of catalysts that had been used for ethanol and wet-ethanol streams. Prior to analysis, the samples were dried in a 2% 02/He stream (30 mL/min) at 150°C for 1 h, followed by heating at a ramp up rate of 10°C/min to 950°C.
  • a highprecision peristaltic pump (DRIVE MFLEX L/S 100RPM 115/230 Cole-Parmer, IL) controlled ethanol inlet flows at desired rates through 0.6 g of as-synthesized Ga-ZSM-5 or Ga-Z SM- 5 XM catalyst powder.
  • the catalyst was preheated to 500°C for 1 hour at an ethanol space time velocity of 1.6h -1 prior to heating up to 350, 400, 450, or 500 °C for the catalyst performance evaluations.
  • liquid products were collected every two hours from thereactor outlet.
  • the products usually contained liquid and gaseous hydrocarbons plus a significantamount of water (theoretically 39.07 g of water from 100 g of ethanol) with little ethanol left. Because water would quickly damage the gas chromatograph (GC) packing, liquid hydrocarbons were extracted from the water with dichloromethane before injecting into the GC for liquid hydrocarbon analysis. Hydrocarbon gases were not analyzed to avoid GC column damage by vaporized water.
  • Reported catalyst performance data were based on analyses of the organic liquidproduct collected after at least 4 hours of reactor operation. Catalyst performance and stability were determined for feeding either pure ethanol or 40% ethanol in water for 32 hours. Used catalystrecovered after reaction was washed with dichloromethane to remove organic deposits and then calcined prior to characterization by XRD, N2-physisorption, and XPS.
  • FIG. 1 Figure la pictures X-ray diffraction (XRD) patterns of H-ZSM-5 and alkali treated H- ZSM-5XM catalysts. As shown, typical ZSM-5 diffraction peaks identified in the 29 rangeof 22.8 to 25.0 are consistent with those for reference ZSM-5 (PDF#44-0003). However, the shapeand intensity of diffraction peaks for alkali treated ZSM-5XM catalysts were altered due to extraction of framework silica. Minimal losses in the intensity of ZSM- 5 characteristic reflectionswere observed after treating ZSM-5 with 0.2, 0.6 and 0.8M NaOH, but 1 ,0M NaOH treatment resulted in significant loss of both diffraction peak shape and intensity.
  • XRD X-ray diffraction
  • Figure lb shows N2 adsorption-desorption isotherms for Ga(5 wt%)/ZSM-5 and Ga(5 wt%)/ZSM-5xM catalysts, and the corresponding BET total surface areas (SA), external surface areas, and mesopore volumes are reported in Table 1.
  • SA BET total surface areas
  • Table 1 shows that Ga/ZSM- 5 exhibited a type-I isotherm and no distinct hysteresis loop, indicating a typical micro- porous structure even after Gaincorporation.
  • Table 1 shows mesopore volumes increased by 1.5, 2.6, and 4 times when ZSM-5 was treated with 0.6M,0.8M, and l.OMNaOH, respectively.
  • l.OMNaOH treatment of ZSM-5 resulted in significant improvements in mesopore volume, excessive silica removal from the framework significantly damaged ZSM-5 I.OM crystallinity, as shown by XRD results.
  • the BJH pore size distribution curves in Figure 12 showed H- ZSM-5 mesopore size consistently increased with increasing NaOH concentration.
  • STEM images of Ga(5 wt%)/ZSM-5 and Ga(5 wt%)/ZSM-5o.8M catalysts in Figures 2 and 14 showboth contained large needle shaped gallium oxide particles with sizes of 0.5-1.5pm and 0.25-0.8pm, respectively.
  • Figures 15a and 15b also indicate gallium oxide nanoparticles had an average diameter of 4.1 ⁇ 1 ,3nm and 3.8 ⁇ 1 ,8nm on parent-ZSM- 5 and ZSM-5 0.8M supports, respectively, consistent with a previous report.
  • 36 Alkali treatment of ZSM-5 marginally increased the number of gallium oxide nanoparticles and gallium oxide dispersion by reducing the size of micro size gallium oxide particles on the external ZSM-5 0.8M support.
  • STEM images of the ZSM-5 0.8M support in Figures 2 and 14 clearly suggest that NaOH treatment selectively extracted silica from the zeolite crystals and facilitated mesopores formation.
  • the negatively charged framework tetrahedral alumina zeolite species as determined by ICP-OES and recorded in Tables 2 and 3 are inert under NaOH treatment. 34
  • XPS spectra were collected for Ga(5%)/ZSM-5 and Ga(5%)/ZSM-5xM catalysts to determine Ga binding energy (B.E) and surface Si/Ga ratios.
  • Figure 3 shows Ga 2p3/2 XPS spectra of as-synthesized catalysts, and Tables 1 and 4 list surface Si/Ga ratios.
  • the higher Ga 2p3/2peak B.E for supported Ga 2 O 3 catalysts in the 1117.8 to 1118.5eV range than for bare Ga 2 O 3 particles could result in either strong metal-support interactions or Ga +3 bounded to neighboring oxygen or strong interactions of gallium (GaO) + with zeolite frame work.
  • Ga 2p3/2 peak B.E observed at 1118.8eV for all catalyst cases indicated Ga to be in as native oxide that formed a thin oxide layer on the outer surface. 42
  • Figure 16 shows that applying 2 and 8% gallium loadings for 4 hours and 32 hours Ga wet-impregnation synthesis times had no effect on the B.E of Ga 2p3/2 peak, thereby indicating similarGa electronic structures for all cases.
  • the surface Si/Ga ratio for all catalysts were calculated fromGa, Si, Al and O metal XPS peak areas and normalized by their relative sensitivity factors.
  • surface Si/Ga ratios nearly doubled for Ga/ZSM-5 0.6,0.8&1.0M catalysts compared to Ga/ZSM-5 and Ga/ZSM-5o.2M due to reduced Ga on the surface.
  • modified-ZSM-5 supports by treating with higher NaOH concentrations promoted greater Ga migration into the zeolite channels 38 .
  • Reducing the Ga loading to 2% on ZSM-5 0.8M increased the surface Si/Ga ratio to 29, while increasing the Ga loading to 8% resulted in a Si/Ga ratio 13, nearly the same as when 5% Ga was loaded onto ZSM-5 0.8M .
  • H2-Temperature Program Reduction' H 2 -TPR was applied to determine gallium oxide reduction temperature, nature of the gallium oxide and metal-support interactions.
  • the H 2 -TPR profiles for Ga(5 wt.%)/ZSM-5 and Ga(5 wt.%)/ZSM-5xM catalysts show broad reduction peaks starting from 500°C to 950°C, suggesting that gallium oxide is in the form of nanoparticles (nano-Ga2O3), gallium oxide ions (GaO + ) and segregated large Ga2CE clusters (extra framework (EF)-Ga2O3; 200nm to 1500 nm) consistent with STEM data and previous reports.
  • nanoparticles nanoparticles
  • GaO + gallium oxide ions
  • EF extra framework
  • gallium oxide nanoparticles are known to be reduced at 500°C to 600°C, whereas the GaO + ions and surface segregated large gallium oxide clusters are reported to be reduced at above 650°C and 800°C, respectively.
  • 46 In the present case of Ga (5 wt.%)/ZSM-5 gallium oxide reduction started at 504°C, whereas the gallium oxide reduction started at higher temperatures for modified support cases that increased in the following order: Ga(5 wt.%)/ZSM-5 0.2M (543°C) ⁇ Ga(5 wt.%)/ZSM-5 0.6M (550 o C) ⁇ Ga(5 wt.%)/ZSM-5 0 . 8M (560°C).
  • TPR profiles of 2, 5, and 8 wt% Ga loadings on ZSM-5, modified-ZSM-5 catalysts and Ga loaded beta and Y-zeolite catalysts were deconvoluted and then compared the data.
  • Peak deconvolution of H2-TPR profiles revealed the presence of nano-Ga2O3, GaO + , and EF-Ga2O3 on ZSM-5, modified-ZSM-5, and beta and Y-zeolite supports.
  • the composition of each gallium oxide species was quantified by considering their corresponding peak area.
  • the GaO + peak composition for modified-ZSM-5 catalysts increased with increasing ZSM-5 modification severity, except for the Ga/ZSM-5 1.0M case.
  • the percentage of GaO + peak is higher in case of Ga(5%)/ZSM-5 0.8M case compared to other catalysts, could be the cause of more gallium migrated into the modified-ZSM-5 channels and interacted strongly with support hydroxyl groups.
  • no GaO + peak observed for Ga/ZSM-5 catalyst suggesting gallium migration into zeolite channels and interaction with hydroxyl groups inside the zeolite pores are negligible.
  • nano-Ga2O3, GaO + , and EF-Ga2O3 were observed for 2, 5, and 8 wt% Ga loadings on ZSM-5O.SM catalysts.
  • the nano-Ga2O3 peak composition is nearly same ( ⁇ 10 %) for 5 and 8 wt% Ga loadings and higher (18%) for 2 wt% Ga loading on ZSM-5 0.8M suggesting lower Ga loading facilitated enhanced Ga dispersion on external ZSM-5 0.8M support.
  • GaO + peak percentage increased from 37% to 54% by increasing the Ga loading from 2 to 5 wt% on ZSM-5 0.8M support and then decreased to 33% with further increase in Ga loading to 8 wt% for the ZSM-5O.8M case.
  • GaO+ peak position was shifted to higher temperature for 5 wt% Ga/ZSM-50.8M case compared to other cases, indicating more gallium oxide migrated into modified zeolite channels and interacted strong with hydroxyl groups presented inside the pores.
  • the peak percentage of gallium oxide clusters (EF-Ga2O3) is higher for 8 wt% Ga catalyst case compared to lower loadings (2 and 5 wt%) of Ga on ZSM-5O.8M cases. It clearly demonstrated that 5 wt% Ga loading is optimal for generating Ga2Ch nanoparticles and GaO + species and further increasing the Ga loading led formation of gallium oxide clusters as EF-Ga 2 O 3 particles.
  • NH 3 -Temperature Program Desorption (TPD) experiments were conducted with a Micrometrics AutoChem II 2090 chemisorption analyzer equipped with a Pfeiffer Omni Star quadrupole mass spectrometer. In a typical experiment, 0.4 g of the sample sample was taken in a U-shaped, flow-through, quartz sample tube. Prior analysis, sample was pretreated in He (50 ml/min; ramp rate 5°C/min) at 550 °C for 1 h. After cooling to 110°C, the catalyst was flushed with 50 ml/min Ar flow for one hour and then exposed to a flow of 100 ml/min 1%NH3 in Ar for 1.5 hour.
  • FIG. 17 shows NH3- temperature program desorption (TPD) data for Ga(5 wt.%)/ZSM-5 and Ga(5 wt.%)/ZSM-5xM catalysts, with densities of acid sites calculated based on peak areas.
  • Ga(5 wt.%)/ZSM-5 catalyst resulted two NH3 desorption peaks that were centered at 200 °C and 373°C.
  • the low temperature peak corresponds to weak acid sites that allowed NH3 to desorb from extra framework silanol/alumina species, while the high temperature peak is attributed to strong acid sites that require more energy for NH3 desorption from framework bridged hydroxyl groups (Si-OH-Al).
  • Alkali treatment of ZSM-5 with 0.2M NaOH resulted in significant loss in intensity of the high temperature strong acid site peak while further increasing NaOH concentrations from 0.6M to 1.0M for ZSM-5 treatment exhibited a gradual loss of strong acid site peak intensities.
  • a minimal loss in intensities of low temperature weak acid peaks (200 °C) were observed for modified Ga(5 wt.%)/ZSM-5xM catalysts.
  • the loss of total acidity for used Ga/ZSM-5xM catalysts could be due to loss of framework acid species (Si-OH-Al) and partial replacement of Bronsted acid sites (proton H + in hydroxyl group) by gallium cations.
  • Alkali treatment of H-ZSM-5 is very selective for hydrolyzing the framework silica without disturbing framework alumina or Bronsted acid sites much. 30,33,43 But zeolite crystallinity can be damaged if alkali treatment extracts too much framework silica.
  • ZSM-5 crystallinity and pore volume were characterized to determine how the concentration of NaOH impacted theseproperties and their relationship to carbon number distribution of product hydrocarbons. It was found that increasing NaOH concentration consistently increased support pore volume. However, treatment with 0.8M NaOH was optimum for generating mesopores in ZSM-5 0.8M without compromising crystallinity as further increasing the alkali concentration to 1.0M NaOH resulted in excessive extraction of framework silica.
  • the ICP-OES data in Table 2 shows this detrimentalinfluence of 1 ,0M NaOH on ZSM-5 1.0M crystallinity as measured by XRD.
  • J. C. Groen et al foundthat alkali treatment of ZSM-35 that had a Si/Al ratio of 40 produced a high density of Si-O- Si bonds that are more easily hydrolyzed by NaOH, such that treatment with 0.2M NaOH at 60 °C for 30 minutes led to the maximum mesopore volume without disturbing zeolite crystallinity or Bronsted acidity.
  • STEM showed large needle shape gallium oxide particles on the external surface of the parent H-ZSM-5 support in the present study.
  • the enhanced pore volume of H-ZSM-5 0.6,0.8&1.0M supports facilitated gallium oxide migration into zeolite channels, less gallium oxide was left on the external surface with the result that smaller gallium oxide particles were formed compared to parent ZSM-5.
  • Calculating the Si/Ga ratio on the external surface based on XPS measurements reinforced that larger pores resulted in less Ga on the external surface of Ga(5 wt.%)/ZSM-5 0.6,0.8 &1.0M compared to Ga(5 wt.%)/ZSM-5.
  • employing H2-TPR revealed that enhancing pore volume resulted in more gallium migrating into the zeolite channels, thereby increasing interactions between gallium oxide and the modified-ZSM-5xM supports.
  • Figure 4 shows the effect of temperature on ethanol conversion and product distribution using Ga(5%)/ZSM-5 and Ga(5%)/ZSM-5xM catalysts. All catalysts completely converted ethanolover a temperature range of 350°C to 500°C.
  • the liquid hydrocarbon composition as analyzed byGC after separating the organic liquid from the aqueous phase was divided into C5-C6 paraffins, BTX, and C9-C10 aromatics [trimethyl benzene, ethyl methyl benzene and ethyl dimethylbenzene].
  • BTX selectivity in the liquid products dropped in the order of Ga-ZSM-5 (69.3%)
  • Table 3 ICP-OES analysis for Ga (5 wt.%) ZSM-5 0.8M catalysts synthesized at different times.
  • Table 4 XPS derived Si/Ga surface ratios of as-synthesized samples. aCatalyst synthesis time of 4 hours, b catalyst synthesis time of 16 hours, and C catalyst synthesis time of 32 hours. External Si/Ga surface ratios were measured based on relative surface concentration of Ga, Na, Si, Al, and O atoms.
  • the 8 wt.% Ga loading might have blocked zeolite pores and interfered with escapeof C9-C10 aromatics from the pores due to steric constraints, as supported by the N2-physisorption results shown in Figure 13.
  • the result that the surface Si/Ga ratios of 5 wt.% Ga/ZSM-5 0.8M and 8 wt.% Ga/ZSM-5o.8M catalysts as measured by XPS had about the same values suggests that migration of more gallium oxide into zeolite channels for the latter case reduced formation of larger chains by blocking pores.
  • Figure 9a shows that ethanol LHYs and >45% C9-C10 aromatics selectivities were maintained for 32 hours for the Ga(5 wt.%)/ZSM-5o.8M catalyst.
  • enhanced zeolite pore volume and Ga metal insertion into ZSM-5 0.8M channels maintained catalyst activity over these time periods without loss of C9-C10 aromatics selectivity.
  • Ga(5 wt.%)/ZSM-5o.8M stability was also evaluated when fed wet-ethanol vapor (40% vol), about the concentration that would be producedby vaporizing fermentation broth at the feed tray to an ethanol recovery distillation train.
  • Figures 20a-c indicates a marginal lossin total surface area for used catalysts due to partial damage to the micropore surface area of the ZSM-5O.SM support.
  • a marginal loss in mesopore volume was observed for used catalysts compared to fresh catalyst and the pore volume dropped in order of Ga/ZSM-50.8M (0.2483 cm3/g; fresh catalyst) > used Ga/ZSM- 50.8M for wet-ethanol feed (0.2279 cm3/g) > used Ga/ZSM-50.8M for ethanol feed (0.2164 cm3/g).
  • the loss in pore volume for used Ga/ZSM-50.8M catalysts cause either pore blocking by extra framework alumina (EFA1) species which are leached out from zeolite framework or migration of more gallium from the surface into the mesopores for ethanol conversion at 350 °C.
  • EFA1 extra framework alumina
  • Figure 10 shows desorption peaks for carbon dioxide, carbon monoxide, and water produced by burning off the carbon from used catalysts.
  • the high coke combustion temperatures suggest that a substantial amount of hard carbon had been formed on the catalysts, likely via polymerization of aromatic compounds during conversion of both pure and wet ethanol.
  • the amount of carbon produced was lower from used catalyst that had been used with wet (4.8 wt.%) than with pure ethanol (7.1 wt.%).
  • Previous studies showed less than 5% C9+ aromatics formation in addition to light weighthydrocarbons and BTX from an ethanol feed.
  • the high molecular weight C9+ hydrocarbon may occur either on the external ZSM-5 surface or inside its pores by alkylation of C7/C8 aromatics with C1/C2 paraffin. Any chains too long to escape through the pore mouth would needto either crack to smaller molecules that could leave through zeolite micropores or breakdown to deposit carbon on the walls that would interfere with adsorption or block micropores.
  • this study showed the catalyst could maintain stable production of C9-C10 aromatics, mostly as ethyl methyl benzene, trimethyl benzene (mesitylene), and ethyl dimethyl benzene (CIO).
  • the combination of micro and mesopores in modified-ZSM-5 supports could accommodate sequential ethanol dehydration, aromatization, and alkylation and reduce trapping of bulky C9-C10 aromatics that would otherwise either crack to smaller molecules that could escape or pyrolyze to coke that would interfere with catalytic activity inside the pores.
  • the present study provides insights into the roles of zeolite pore volume, crystallinity, andgallium penetration into channels and metal-support interactions on the distribution of hydrocarbon chain lengths produced by reaction of ethanol to liquid hydrocarbons on ZSM-5 catalysts.
  • ZSM-5 alone produced aromatic hydrocarbons, LHYs were very low due to the small support microporosity.
  • Treatment of ZSM-5 with 1.0M NaOH increased pore volume, but selectivity to liquid hydrocarbons containing more than 5 carbon atoms (C6+) dropped significantly due to loss of support crystallinity and metal-support interaction.
  • This example explores the use of various metals loaded on ZSM-5.
  • the zeolite was modified generally in accordance with the procedure set forth in Example 1, and the modified zeolite was used in ethanol conversion experiments in generally in accordance with the procedure set forth in Example 1.

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Abstract

L'invention concerne des procédés et des systèmes qui utilisent une catalyse hétérogène pour une conversion d'éthanol biodérivée en mélanges de carburant d'aviation durables. Plus particulièrement, les procédés et les systèmes utilisent des catalyseurs à base de zéolite mésoporeux et crystallins à Ga ou de Ru incorporés pour l'oligomérisation de l'éthanol et la production de carburants, tels que des carburéacteurs.
PCT/US2023/021943 2022-05-16 2023-05-11 Catalyseurs de zéolite et utilisation dans l'oligomérisation et la production d'éthanol de carburants WO2023224867A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150183694A1 (en) * 2011-11-23 2015-07-02 Virent, Inc. Dehydrogenation of alkanols to increase yield of aromatics
US20190127292A1 (en) * 2014-03-24 2019-05-02 The Regents Of The University Of California Methods for producing cyclic and acyclic ketones
EP3016923B1 (fr) * 2013-07-02 2019-12-18 UT-Battelle, LLC Conversion catalytique d'alcools sélectionnés parmi le n-heptanol et le n-octanol en un mélange d'hydrocarbures
WO2022015971A1 (fr) * 2020-07-15 2022-01-20 The Regents Of The University Of California Procédé pour le recyclage catalytique valorisant de polymères hydrocarbonés en composés alkylaromatiques
US20220098498A1 (en) * 2020-09-29 2022-03-31 IFP Energies Nouvelles Production of aromatics by reverse water gas shift, fermentation and aromatization

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150183694A1 (en) * 2011-11-23 2015-07-02 Virent, Inc. Dehydrogenation of alkanols to increase yield of aromatics
EP3016923B1 (fr) * 2013-07-02 2019-12-18 UT-Battelle, LLC Conversion catalytique d'alcools sélectionnés parmi le n-heptanol et le n-octanol en un mélange d'hydrocarbures
US20190127292A1 (en) * 2014-03-24 2019-05-02 The Regents Of The University Of California Methods for producing cyclic and acyclic ketones
WO2022015971A1 (fr) * 2020-07-15 2022-01-20 The Regents Of The University Of California Procédé pour le recyclage catalytique valorisant de polymères hydrocarbonés en composés alkylaromatiques
US20220098498A1 (en) * 2020-09-29 2022-03-31 IFP Energies Nouvelles Production of aromatics by reverse water gas shift, fermentation and aromatization

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