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WO2019173701A1 - Procédé et système de bioraffinage catalytique hybride de biomasse en furanes méthylés et lignine technique dépolymérisée - Google Patents

Procédé et système de bioraffinage catalytique hybride de biomasse en furanes méthylés et lignine technique dépolymérisée Download PDF

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WO2019173701A1
WO2019173701A1 PCT/US2019/021326 US2019021326W WO2019173701A1 WO 2019173701 A1 WO2019173701 A1 WO 2019173701A1 US 2019021326 W US2019021326 W US 2019021326W WO 2019173701 A1 WO2019173701 A1 WO 2019173701A1
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catalysts
catalyst
hmf
bimetallic
biomass
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Charles WYMAN
Charles Cai
Phillip Christopher
Bhogeswararao SEEMALA
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University of California Berkeley
University of California San Diego UCSD
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University of California San Diego UCSD
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    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/397—Egg shell like
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/15—X-ray diffraction
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

  • the disclosure relates to support induced control of surface composition in Cu- Ni/Ti0 2 catalysts enabling high yield co-conversion of HMF and furfural to methylated furans, and hybrid catalytic biorefming of biomass to methylated furans and depolymerized technical lignin.
  • Lignocellulosic biomass is one of the most abundant and inexpensive renewable resource that can potentially displace petroleum as a carbon neutral alternative for the production of fungible liquid transportation fuels and commodity chemicals.
  • biomass can include but are not limited to biomass derived from corn, soy beans, tubers (e.g., potatoes, sweet potatoes), sugarcane, sorghum, cassava, grasses (e.g., switchgrass,
  • Miscanthus wheat, rice, barley, oats, millet, cassava
  • legumes wood (e.g., maple, oak, poplar, pine) and other cellulose substrates, such as agricultural wastes (e.g., sugarcane bagasse, com fiber, com stover, wheat husk, rice husk).
  • wood e.g., maple, oak, poplar, pine
  • agricultural wastes e.g., sugarcane bagasse, com fiber, com stover, wheat husk, rice husk.
  • target chemicals and gasoline range fuels from lignocellulosic biomass has been economically challenging due to the need for multiple processing steps and associated high product yields required in each step.
  • Biomass is rich in both C 6 (glucan) and C 5 (xylan) polymeric sugars that can be converted by acid-catalyzed dehydration into 5-(hydroxymethyl)furfural (HMF) and furfural (FF), respectively, with relatively high yields.
  • HMF and FF have been identified as valuable fuel precursors suitable for the production of dimethyl furan (DMF) and methyl furan (MF), respectively, through selective hydrodeoxygenation (HDO)
  • DMF and MF methylated furans
  • Unwanted side reactions include ring hydrogenation of MF or FOL to form methyl tetrahydrofuran (MTHF), or tetrahydrofurfural alcohol (THFOL) and decarbonylation of FF to form furan, see Scheme 1 (FIG. 11).
  • MTHF methyl tetrahydrofuran
  • THFOL tetrahydrofurfural alcohol
  • Cu catalysts minimize decarbonylation and ring hydrogenation due to their full valence d-band and effectively hydrogenate FF to FOL at relatively low temperatures (e.g., ⁇ 200 °C).
  • Cu-based bimetallic catalysts have been proposed to overcome the low reactivity of monometallic Cu for hydrogenation reactions.
  • Various formulations have been proposed, such as Cu-Fe, Cu- Pd, Cu-Cr, and Cu-Ni, to increase reactivity or selectivity, but further enhancements in reactivity, selectivity towards MF, and catalyst stability are needed for economical implementation.
  • Base metal catalysts are generally most suitable for HDO of FF and HMF to methyl furans due to their low costs, but limited demonstrations of these catalysts are reported to achieve high reactivity, selectivity, and stability. Furthermore, it has recently been demonstrated that high yield co-production of HMF and FF can be achieved directly from biomass in a single step process using THF as a co-solvent, thereby enabling integrated downstream catalytic strategies to process a single product stream containing both HMF and FF to reduce overall processing costs. However, most previous reports on HMF and FF HDO have considered their catalytic conversion separately. It is expected that coupling base metal catalysts capable of simultaneously converting HMF and FF to methylated furans with recently developed biomass pre-treatment technologies could realize significant cost savings for an integrated processing strategy that avoids separating biomass sugar streams.
  • HMF hydroxy methylfurfural
  • FF furfural
  • Cu-Ni/Ti0 2 catalyst simultaneous co-processing of HMF and FF over Cu-Ni/Ti0 2 catalysts is disclosed, achieving 87.5% yield of DMF from HMF and 88.5% yield of MF from FF in a one pot reaction.
  • the Cu-Ni/Ti0 2 catalyst also exhibited improved stability and regeneration compared to Cu/Ti0 2 and Cu/Al 2 0 3 catalysts for FF HDO, exhibiting an approximate 7% loss in FF conversion over 4 sequential recycles, compared to an approximate 50% loss in FF conversion for Cu/Al 2 0 3 and an approximately 30% loss in conversion for Cu/Ti0 2.
  • characterization of the Cu-Ni/Ti0 2 catalyst by X-ray Photoelectron Spectroscopy, Scanning Transmission Electron Microscopy, and H 2 -Temperature Programmed Reduction and comparison to monometallic Cu and Ni on Al 2 0 3 and Ti0 2 and bimetallic Cu-Ni/Al 2 0 3 catalysts suggest that the unique reactivity and stability of Cu-Ni/Ti0 2 derives from support-induced metal segregation in which Cu is selectively enriched at the catalyst surface, while Ni is enriched at the Ti0 2 interface.
  • a catalyst for hydrodeoxygenating (HDO) furfural (FF) and 5-hydroxymethylfurfural (HMF) to methylated furans, the catalyst comprising: copper-nickel (Cu-Ni) particles supported on titanium dioxide (Ti0 2 ), and wherein the copper-nickel particles form core-shell structures in which copper (Cu) is enriched at a surface of the catalyst.
  • a method is disclosed of synthesizing a catalyst for hydrodeoxygenating furfural (FF) and 5-hydroxymethylfurfural (HMF) to methylated furans, the method comprising: synthesizing monometallic copper (Cu) catalysts and monometallic nickel (Ni) catalysts; mixing the monometallic Cu and Ni catalysts in deionized water (Di-water) to form a bimetallic Cu-Ni catalyst; drying the mixture of the bimetallic Cu- Ni catalyst; calcining the dried mixture of the bimetallic Cu-Ni catalyst; and synthesizing the bimetallic Cu-Ni catalyst onto titanium dioxide (Ti0 2 ) to form a Cu-Ni/Ti0 2 catalyst, and wherein the copper-nickel particles form core-shell structures in which copper (Cu) is enriched at a surface of the catalyst.
  • a method for converting biomass into a fuel additive comprising: liquefying the biomass to form a liquor;
  • neutralizing the liquor comprises: adding calcium dihydroxide (Ca(OH) 2 ), calcium carbonate (CaC0 3 ), or ammonium hydroxide (NH 4 OH) to the liquor to neutralize the acidic moieties and precipitate iron hydroxide ions and a portion of lignin.
  • Ca(OH) 2 calcium dihydroxide
  • CaC0 3 calcium carbonate
  • NH 4 OH ammonium hydroxide
  • the method further comprises extracting furfural (FF) and 5-hydroxymethylfurfural (HMF) from the liquor using an organic solvent treated with Ca(OH) 2.
  • the organic solvent contains one or more of methanol, ethanol, butanol, isopropyl alcohol, butanediol, pentanediol, toluene, dioxane, methyl- tetrahydrofuran (MTHF), tetrahydrofuran, hexane, decane, nonane, and methyl- isobutylketone (MIBK).
  • MTHF methyl- tetrahydrofuran
  • MIBK methyl- isobutylketone
  • FIGS. 1(a)- 1(h) are (a) representative STEM image of the Cu-Ni/Al 2 0 3 catalyst and associated (b) Cu, (c) Ni, and (d) overlayed Cu/Ni/Al elemental mapping (e) Representative STEM image of the Cu-Ni/Ti0 2 catalyst and associated (f) Cu, (g) Ni, and (h) overlayed Cu/Ni/Ti elemental mapping.
  • FIGS. 2(a)-2(h) illustrate XPS spectra of monometallic and bimetallic catalysts in the Cu 2p3/2 energy window for (a) Cu/Ti0 2 , (b)Cu-Ni/Ti0 2 , (c) Cu/Al 2 0 3 , and (d)Cu- Ni/Al 2 0 3 , and in the Ni 2p3/2 energy window for (e) Ni/Ti0 2 , (f)Cu-Ni/Ti0 2 , (g) Ni/Al 2 0 3 , and (h)Cu-Ni/Al 2 0 3.
  • Metallic peaks (Cu° & Ni°) represented with blue colour and metal oxide peaks (CuO & NiO) peaks represented with green colour.
  • Orange colour represents Ni(OH)x peak.
  • FIG. 3 illustrates relative Cu:Ni surface concentration (%) for pre-reduced Cu- Ni/Ti0 2 and Cu-Ni/Al 2 0 3 catalysts measured by XPS during depth profiling experiments as a function or Ar sputtering time.
  • FIG. 4 illustrates H 2 -TPR spectra for (a) Cu/Ti0 2 , (b) Cu/Al 2 0 3 , (c) Ni/Ti0 2 , (d) Ni/Al 2 0 3 , (e) Cu-Ni/Al 2 0 3 and (f), Cu-Ni/Ti0 2 .
  • FIG. 5 illustrates FF conversion and product yields for Cu/A 2 0 3 catalysts for the reaction conditions shown along the x-axis at four catalyst loadings. All reactions except those noted by a, b, and c were executed at a FF loading of 1 g, 25 mL IPA solvent, and Cu(l0 wt%)/Al 2 0 3 catalyst loading of 0.05 g.
  • the catalyst loadings for the other three were (a) 0.15 g for Cu(l0 wt%)/Al 2 0 3 ], (b) 0.3 g for Cu(l0 wt%)/Al 2 0 3 , and (c) 0.3 g for Cu(25 wt%)/Al 2 0 3 .
  • FIG. 6 illustrates FF conversion and product yields over monometallic Ni and Cu supported on Al 2 0 3 and Ti0 2 catalysts at different reaction times. All reactions were run with FF loading of 1 g, catalyst loading of 0.3 g, 25 mL of 1,4 Dioxane as solvent, temperature of 200 °C, and H 2 pressure of 25 bar.
  • FIGS. 7(a)-7(b) illustrate FF conversion and product yields as function of reaction time over (a) Cu-Ni/Ti0 2 and (b) Cu-Ni/Al 2 0 3 catalysts. All reactions were run at a FF loading of 1 g, catalyst loading of 0.3 g, 25 mL of 1,4 Dioxane as solvent, temperature of 200 °C, and H 2 pressure of 25 bar.
  • FIGS. 8(a)-8(c) illustrate FF conversion and product yields as a function of number of catalyst recycles, R, for (a) Cu/Al 2 0 3 , (b) Cu /Ti0 2 , and (c) Cu-Ni/Ti0 2 catalysts.
  • R4 catalysts were calcined at 450 °C for 5 hours and reduced at 450 °C for 3 hours prior to R5.
  • Reaction conditions were a FF loading of 1 g, catalyst loading of 0.3 g, 25 mL of 1,4 Dioxane as solvent, temperature of 200 °C, H 2 pressure of 25 bar, and 2 hour run time.
  • FIGS. 9(a) and 9(b) illustrate (a) HMF and (b) HMF +FF conversion and product yields as a function of reaction time over the Cu-Ni/Ti0 2 catalyst.
  • (a) reactions were run at a HMF loading of 0.5 g, catalyst loading of 0.3 g, 25 mL of 1,4 Dioxane as solvent, temperature of 200 °C, and H 2 pressure of 25 bar.
  • (b) reactions were run at a FF loading of 0.5 g, HMF loading of 0.25 g, catalyst loading of 0.3 g, 25 mL of 1,4 Dioxane as solvent, temperature of 200 °C, and H 2 pressure of 25 bar.
  • FIG. 10 is a schematic diagram of the proposed operating states of Cu-Ni bimetallic catalysts on Al 2 0 3 and Ti0 2.
  • E INT Energy of interaction between metal (either Ni or Cu) and support (Al 2 0 3 and Ti0 2 ).
  • FIG. 11 illustrates a scheme (Scheme 1) for a reaction pathway for FF conversion.
  • FF Furfural
  • FOL Furfuryl alcohol
  • MF Methyl furan
  • THFOL Tetrahydrofurfuryl alcohol
  • MTHF Methyl tetrahydrofuran.
  • FIG. 12 illustrates a scheme (Scheme 2) for a reaction pathway for HDO of HMF to DMF.
  • HMF 5 -Hydroxymethyl furfural
  • MFF Methyl furfural
  • BHMF Bis
  • FIG. 13 is a table (Table 1) illustrating physicochemical properties of monometallic Cu, Ni and bimetallic Cu-Ni catalysts supported on Al 2 0 3 and Ti0 2 .
  • FIGS. 14(a) and 14(b) are illustrations of XRD spectra of mono Cu, Ni and bimetallic Cu-Ni on Ti0 2 and Al 2 0 3 catalysts
  • FIG. 15 is an illustration of particle size distributions from TEM images of mono (a) Ni/Al 2 0 3 , (b) Ni/Ti0 2 , (c) Cu/Al 2 0 3 , and (d) Cu/Ti0 2 catalysts.
  • FIG. 16 is an illustration of particle size distributions from TEM images of mono Cu, Ni and bimetallic Cu-Ni on Ti0 2 and Al 2 0 3 catalysts.
  • FIG. 17 is an illustration of XPS of calcined Cu(2p3/2) peaks of bimetallic catalysts
  • FIG. 18 is an illustration of XPS of calcined Ni(2p3/2) peaks of bimetallic samples
  • FIG. 19 is an illustration of XPS depth profiling of Cu-Ni/Ti0 2 catalyst.
  • FIG. 20 is an illustration of XPS depth profiling of Cu-Ni/ Al 2 0 3 catalyst.
  • Cu- Ni/Al 2 0 3 data derived by Argon sputtering at different time intervals such as 0, 1, 5, 10, 30 and 60 min.
  • FIGS. 21(a) and 21(b) are illustrations of furfural conversion as function of time over (a) Cu(l0 wt%)/Ti0 2 and (b) Cu(l0 wt%)/Al 2 0 3 catalysts.
  • FIG. 22 is a table (Table 2) illustrating hydrodeoxygenation of FF to methyl furan over Ni & Cu-supported over g-A1 2 0 3 and Ti0 2 (P25)
  • FIG. 23 is a table (Table 3) illustrating activity of bimetallic Ni-Cu/y-Al 2 0 3 catalysts to FF hydrogenation compared to Ni-Cu/ 7z(3 ⁇ 4
  • FIG. 24 is a table (Table 4) illustrating effect of temperature on FF hydrogenation over N ⁇ /g-A1 2 0 3.
  • FIGS. 25(a)-25(c) are representative TEM images of bimetallic Cu-Ni/Ti0 2 catalysts: (a) Cu(5%)-Ni(0.5%)/TiO 2 , (b) Cu(5%)-Ni(l.5%)/Ti0 2 , and (c) Cu(5%)- Ni(3%)/Ti0 2.
  • the black arrows point to bimetallic Cu-Ni particles.
  • FIGS 26(a)-26(c) are relative Cu and Ni concentration derived from deconvolution of the DP-XPS spectra as a function of Argon sputtering time
  • (a), (b), and (c) show the data for Cu(5%)-Ni(0.5%)/TiO 2 and Al 2 0 3 , Cu(5%)-Ni(3%)/Ti0 2 and Al 2 0 3 , and Cu(5%)- Ni(5%)/Ti0 2 and Al 2 0 3 catalysts, respectively.
  • the data in FIG.2(c) is adapted from.
  • the relative Ni concentrations are shown in black and Cu concentrations are shown in blue.
  • Data for Al 2 0 3 supported catalysts are depicted in squares, whereas Ti0 2 are in triangles.
  • the dotted lines are the expected Ni and Cu concentrations based on nominal bulk compositions.
  • FIG. 27 is a scheme (Scheme 1) illustrating FF hydrogenation reaction pathways.
  • Path (a) represents the hydrogenolysis of FOL to MF followed by ring hydrogenation of MF to form MTHF, and wherein Path (b) represents furan ring hydrogenation in FOL to form THFOL followed by further hydrogenolysis THFOL to form MTHF.
  • FIG. 28 is an illustration of FF conversion and product yields as a function of reaction time on Cu/Al 2 0 3 and Cu-Ni/Al 2 0 3 catalysts.
  • the catalyst composition is noted in the 8 hours reaction time bar. All reactions were conducted at FF loading of 1 g, catalyst loading of 0.3 g, 25 ml of l,4-dioxane as a solvent, and at a temperature of 200 °C.
  • the reactor was pressurized with 35 bar H 2 gas at 25 °C.
  • FIG. 29 is an illustration of FF conversion and product yields as a function of time on Cu/Ti0 2 and Cu-Ni/Ti0 2 catalysts.
  • the catalyst composition is noted in the 8 hours reaction time bar. All reactions were conducted at FF loading of 1 g, catalyst loading of 0.3 g, 25 ml of l,4-dioxane as a solvent, and at a temperature of 200 °C.
  • the reactor was pressurized with 35 bar H 2 gas at 25 °C.
  • FIG. 30 is an illustration of MF conversion and MTHF yield over Cu(5%)/Ti0 2 and Cu(5%)-Ni(0.5 & l.5%)/Ti0 2 catalysts. Reactions were conducted at MF loading of 1 g, catalyst loading of 0.3 g, 25 ml of 1, 4-dioxane as a solvent, temperature of 200 °C, 35 bar of H 2 (at 25 °C), and 4 hours reaction time.
  • FIG. 31 is an illustration of FF conversion and product yields as a function of recycles, R, for (a) Cu(5%)/Ti0 2 , (b) Cu(5%)-Ni(0.5%)/TiO 2 ,(c) Cu(5%)-Ni(3%)/Ti0 2 , and (d) Cu(5%)-Ni(5%)/Ti0 2 catalysts. Prior to regeneration (before R5), each catalyst was calcined at 450 °C for 5 hours and reduced at 450 °C for 3 hours under H 2 flow (50 ml/min).
  • Reaction conditions were a FF loading of 1 g, catalyst loading of 0.3 g, 25 mL of 1,4- Dioxane as solvent, temperature of 200 °C, H 2 pressure of 35 bar (at 25 °C), and 2 hour reaction time.
  • FIG. 32 is an illustration of a schematic diagram of the proposed surface
  • composition and structure of bimetallic particles Cu-Ni on Al 2 0 3 and Ti0 2 supports for Cu(5%)-Ni(3%).
  • Cu(5%)-Ni(3%)/Al 2 0 3 significant contiguous surface Ni domains enabled more facile oxidation of the Ni and preferred FF adsorption through furan ring coordination.
  • the catalyst surface is rich with Cu, containing mostly dispersed Ni species, which favored FF adsorption through carbonyl coordination.
  • FIG. 33 illustrates particle size distributions from TEM images of bimetallic Cu-Ni on Ti0 2 catalysts
  • FIG. 34 illustrates XPS depth profiling of Cu(5%)-Ni(l.5%)/Ti0 2 catalyst. Data derived by Argon sputtering at different time intervals such as 0, 1, 5, 10, 30 and 60 min.
  • FIG. 35 illustrates XPS depth profiling of Cu(5%)-Ni(l.5%)/Al 2 0 3 catalyst. Data derived by Argon sputtering at different time intervals such as 0, 1, 5, 10, 30 and 60 min.
  • FIG. 36 illustrates XPS depth profiling of Cu(5%)-Ni(3%)/Ti0 2 catalyst. Data derived by Argon sputtering at different time intervals such as 0, 1, 5, 10, 30 and 60 min.
  • FIG. 37 illustrates XPS depth profiling of Cu(5%)-Ni(3%)/Al 2 0 3 catalyst. Data derived by Argon sputtering at different time intervals such as 0, 1, 5, 10, 30 and 60 min.
  • FIG. 38 illustrates XPS depth profiling of Cu(5%)-Ni(5%)/Ti0 2 catalyst. Data derived by Argon sputtering at different time intervals such as 0, 1, 5, 10, 30 and 60 min.
  • FIG. 39 illustrates XPS depth profiling of Cu(5%)-Ni(5%)/Al 2 0 3 catalyst. Data derived by Argon sputtering at different time intervals such as 0, 1, 5, 10, 30 and 60 min.
  • FIG. 40 illustrates FF conversion as a function of time over supported bimetallic Cu- Ni on Ti0 2 catalysts. Reaction conditions: 1 g of FF, 0.3 g of catalyst, 25 ml of 1, 4-dioxane, 200 °C reaction temperature and 25 bar of H 2 at room temperature.
  • FIG. 41 illustrates XRD of Cu(5%) and Cu(5%)-Ni(3%) on Ti0 2 and Al 2 0 3.
  • FIG. 42 is a table (Table 5) illustrating XPS Binding energy values derived from 2p3/2 peaks of Cu° and Ni° for catalysts of various composition and support. Surface metal- to-metal oxide ratios were calculated from area under the curves of 2p3/2 peaks of Cu and Ni peaks.
  • FIG. 43 is a table (Table 6) illustrating hydrogen pressure effect on FF
  • FIG. 44 illustrates a process flow diagram of integrated hybrid catalytic conversion of lignocellulosic biomass to methylated furans and technical lignins. Highlighted yields (mol %) indicate efficiency of staged yields whereas other yields (mol %) (un-highlighted) calculated based on total available carbon [glucans (45%), xylans(l4%), and lignin (22%)] from biomass.
  • FIG. 45 illustrates optimization of reaction temperature and reaction time for production of HMF, FF, and LA from poplar wood.
  • Reaction conditions 3 : 1 THF : water 5wt% solids loading, and 1 wt% FeCh.
  • FIG. 46 illustrates dependence of yields of FF and HMF from poplar wood chips and total liquefaction/solids conversion on THF:water (1 : 1 to 1 :7) concentrations. Reaction conditions: l80°C, 20 min, and 1 wt% FeCl 3 loading. Legend: FF-furfural, HMF - 5- hydroxymethyl furfural, LA - levulinic acid, XYL - xylose and GLC - glucose.
  • each catalyst Prior to regeneration (before R5), each catalyst was calcined at 450 °C for 5 hours and reduced at 450 °C for 3 hours under H 2 flow (50 ml/min). Reaction conditions were a 25 ml of l,4-dioxane-toluene extracted FF(0.5 g) and HMF(0.25 g) stream, catalyst loading of 0.3 g, temperature of 220 °C, 3 ⁇ 4 pressure of 35 bar (at 25 °C), and 2 hour reaction time.
  • FIG. 48 illustrates FF and HMF extractions from CELF stream to l,4-dioxane- toluene phase
  • FIG. 49 illustrates Influence of Ca(OH) 2 addition on HDO of l,4-dioxane-toluene extracted FF and HMF stream. All reactions were performed with 25 ml of dioxane-toluene extracted FF (0.5 g) and HMF (0.25 g), catalyst [Cu(5%)-Ni(5%)/Ti0 2 ] loading of 0.3 g, 220 °C reaction temperature, H 2 pressure of 35 bar (at 25 °C) and 2 h reaction time.
  • FIG. 50 illustrates chloride ions influence on neat FF and HMF HDO reactions over Cu-Ni/Ti0 2 catalysts. Reaction were conducted at 0.5 g of FF, 0.25 g of HMF, 25 ml of 1 : 1 ratio of l,4-dioxane-toluene as solvent, 0.3 g of catalyst [Cu(5%)-Ni(5%)/Ti0 2 ] loading, temperature of 220°C and H 2 -pressure of 35 bar and 2 h reaction time. 0.250 mg of NaCl in 2 ml water was added to other reaction.
  • FIG. 51 illustrates temperature effect on HDO of l,4-dioxane-toluene extracted FF and HMF stream. Reaction were conducted with 25 ml of dioxane-toluene extracted FF(0.5 g) and HMF(0.25) stream, 0.1 g of Ca(OH) 2 and catalyst [Cu(5%)-Ni(5%)/Ti0 2 ] was loaded to 0.3 g and H 2 pressure of 35 bar (at 25 °C) and for 2 hours.
  • FIG. 52 illustrates aromatic regions of 2D HSQC NMR spectra of CEL and CELF lignin.
  • FIG. 53 illustrates aliphatic regions of 2D HSQC NMR spectra of CEL and CELF lignin.
  • a system and method are disclosed for catalyst and process for simultaneous conversion of Hydroxymethyl furfural and furfural to methylated furans, which can demonstrate approximately 90% yields, high reactivity, good stability, and re-generatable behaviour for Ti0 2 supported Cu-Ni bimetallic catalysts in individual and co-processing of FF and HMF to MF and DMF, respectively.
  • Cu-Ni bimetallic catalysts can comprise Cu-Ni particles that are between between 2.5 wt%, 5 wt%, 10 wt%, 15 wt%, to 20 wt% Cu or any combination thereof and are between between 0.5 wt%, 1.5 wt%, 3 wt%, 5 wt%, 10 wt%, 15 wt%, to 20 wt% Ni or any combination thereof.
  • Cu-Ni particles can be 2.5 wt% Cu - 0.5 wt% Ni, 2.5 wt% Cu - 1.5 wt% Ni, 5 wt% Cu - 3 wt% Ni, 5 wt% Cu - 5 wt% Ni, 10 wt% Cu - 5 wt% Ni, 10 wt% Cu - 10 wt% Ni, 15 wt% Cu - 5 wt% Ni, 15 wt% Cu - 10 wt% Ni, 15 wt% Cu - 15 wt% Ni, 20 wt% Cu - 15 wt% Ni, or 20 wt% Cu - 20 wt% Ni.
  • the solution was mixed and dried at 80 °C in a rotary evaporator.
  • Supported Ni catalysts were prepared similarly to Cu catalysts, where nickel (II) nitrate hexahydrate (Ni(N0 3 ) 2 6H 2 0, Aldrich, purity 99.99%, Louis, MO 63103, USA) was used as a precursor in desired quantities to achieve 10 wt% loadings on Ti0 2 and Q-A1 2 0 3.
  • the resulting solids were dried at 100 °C for 12 hours in an oven and calcined at 450 °C for 5 hours. Prior to reactivity experiments, catalysts were reduced by a pure H 2 flow rate of 50 mL min 1 at 450 °C for 3 hours and cooled to 25 °C under the same environment.
  • X-ray diffraction X-ray diffraction
  • S B ET The total accessible surface area of the catalysts was measured by N 2 physisorption using a Micromeritics ASAP 2020 instrument.
  • STEM imaging was performed at 300 kV accelerating voltage on an FEI Titan Themis 300 instrument fitted with X-FEG electron source, 3 lens condenser system, and S-Twin objective lens. STEM images were recorded with a Fischione Instruments Inc. M3000 High Angle Annular Dark Field (HAADF) Detector at a probe current of 0.2 nA, frame size of 2048x2048, dwell time of 15 psec/pixel, camera length of 195 mm, and convergence angle of 10 mrad.
  • HAADF High Angle Annular Dark Field
  • Elemental X-ray microanalysis and mapping were performed utilizing FEI Super-X EDS system with four symmetrically positioned SDD detectors of 30 mm 2 each resulting in effective collection angle of 0.7 srad. Elemental maps were collected in STEM mode with beam current of 0.4 to 0.25 nA with 512x512 pixel frame, dwell time of 30 ps, and acquisition time of up to 10 mins. Specimens prepared from suspension in distilled water were deposited on copper grids coated with a lacey carbon. Average metal particle sizes were measured based on the diameter of 100 particles from corresponding TEM images each catalyst.
  • X-ray photoelectron spectroscopy XPS characterization was carried out using a Kratos AXIS EILTRADLD XPS system equipped with an Al Ka monochromated X- ray source and a l65-mm mean radius electron energy hemispherical analyzer. Vacuum pressure was kept below 3 x 10 9 torr during analysis. Binding energy calibrations were done with reference to the carbon ls peak by adjusting spectra to 284.8 eV.
  • Depth profiling experiments were conducted by Argon sputtering samples for 0, 1, 5, 10, 30 and 60 min with beam voltage of 4 kV, current of 2.35 A, spot size of 3x3 mm 2 and vacuum pressure of 3xl0 9 Torr during acquisition.
  • XPS Peak fitting for Cu and Ni components was optimized for each support, and parameters of the fit were kept constant.
  • a FWHM of 2 eV (2.15 eV) and a Gaussian/Lorenzian line shape ratio of 30% (60%) was used for all Cu and Ni peak fitting on Al 2 0 3 (Ti0 2 ).
  • Surface composition of bimetallic Cu/Ni catalysts was calculated using sensitivity factors of 5.321 and 4.044 for Cu and Ni, respectively.
  • TPR Temperature Programmed Reduction
  • 0.3 g of freshly reduced catalysts were transferred into a 100 mL stainless-steel Parr reactor containing 1 g of FF and 25 mL of l,4-dioxane.
  • the reactor was pressurized with H 2 to 25 bar, and the reaction was conducted for 2 hours at 200 °C.
  • the reactor was cooled by quickly lowering it into a room temperature water bath (25 °C) and then depressurized.
  • the catalyst was separated by filtration, dried at 100° C for 3 hours, and then reused in four recycle experiments without reduction or re- activation. Regeneration was executed via calcination at 450 °C for 5 hours followed by reduction with pure 3 ⁇ 4 at 450 °C for 3 hours.
  • the reduced monometallic Ni catalysts exhibited clear peaks associated with the (111) reflection of metallic Ni at 44.9°, although in the case of the M/AI2O3 catalyst this peak overlapped with AI2O3 reflections.
  • the Cu-Ni/ AI2O3 catalyst exhibited a diffraction peak at 43.9°, and the Cu-Ni/Ti0 2 catalyst exhibited a diffraction peak at 44.1° and a shoulder at 44.6°.
  • the existence of diffraction peaks between the Cu (111) and Ni (111) reflections for the bimetallic catalysts are evidence of the formation of Cu-Ni alloy phases.
  • FIGS. 1(a), 1(b), and 15 Representative TEM images of the monometallic and bimetallic catalysts are shown in FIGS. 1(a), 1(b), and 15, with corresponding particle size distributions shown FIG. 16 and average particle sizes reported in Table 1 (FIG. 13).
  • the average metallic particle diameter in all catalysts was relatively consistent, with values between 4.9 and 9.9 nm. It was observed that for a given metal composition, the Al 2 0 3 supported catalysts exhibited an approximately 1 nm to 2 nm smaller average particle diameter compared to the T1O2 supported catalysts. In accordance with an exemplary embodiment, this could be due to the approximately 20 m 2 /g greater total surface area of the AI2O3 supported catalysts compared to the Ti0 2 supported catalysts, see Table 1 (FIG. 13).
  • FIG. 2(a)-2(d) shows the Cu 2p3/2 spectra for pre-reduced monometallic Cu and bimetallic Cu-Ni catalysts on Al 2 0 3 and Ti0 2 .
  • FIGS. 2(e)-2(h) the Ni 2p3/2 XPS spectra is shown for monometallic Ni and bimetallic Cu-Ni supported on AI2O3 and Ti02. All supported Ni catalysts showed three peaks between 852.2 to 853.0 eV, 854.5 to 854.8 eV, and 856.2 to 856.6 eV that are assigned to metallic Ni°, NiO, and Ni(OH) 2 , respectively. Binding energies for the Ni° 2p3/2 peaks were in the order Ni-Cu/AkCh ⁇ M/AI2O3 > Ni/Ti02 ⁇ Ni-Cu/Ti02, with the well-known strong interactions between Ni and TiCF driving charge transfer from Ti +3 to Ni d-states.
  • the Cu/Ni surface composition ratio was calculated for bimetallic catalysts after reduction and calcination by summing all contributions to the Cu and Ni 2p3/2 spectra and correction for XPS sensitivity factors.
  • the Cu/Ni surface composition ratio 48.7/51.3 (Table 1) was observed for the reduced catalyst, consistent with the equal weight loadings of Cu and Ni, the miscibility of Cu and Ni, and their expected non-specific interactions with AI 2 O 3 .
  • the surface composition for the TiC> 2 supported bimetallic catalyst was significantly enriched in Cu, with a Cu/Ni ratio of 82.4/17.6.
  • compositional structure of the particles Regardless of this limitation, contrast between the relative Cu and Ni compositions as a function of Ar sputtering time for the AI 2 O 3 and T1O 2 catalysts is strong evidence that T1O 2 induced the formation of core-shell structures where the catalytic surface is Cu enriched and the T1O 2 interface is Ni enriched.
  • TPR temperature programmed reduction
  • FIGS. 3(a) and 3(b) show that the TPR spectra of Cu/Al 2 0 3 exhibited a single reduction peak at 191 °C, whereas two peaks were observed for Cu/Ti0 2 at 127 and 192 °C.
  • the low temperature reduction peak for Cu/Ti0 2 is attributed to CuO x species directly interacting with the Ti0 2 support, whereas the approximately 190 °C reduction peak is assigned to bulk-like CuO x.
  • FIG. 3(c) shows that two reduction peaks were observed at 350 °C and 500 °C.
  • the former is assigned to the reduction of amorphous NiO species, while the latter is assigned to reduction of crystalline NiO.
  • non-stoichiometric and stoichiometric Ni-aluminates may also form, although these species (TPR peaks > 500 °C) were not observed here.
  • the TPR spectra of Ni/Ti0 2 in FIG. 3(d) showed three peaks at 250 °C, 350 °C, and 450 °C.
  • the peaks at 250 °C and 350 °C are assigned to strongly interacting amorphous and crystalline NiO on Ti0 2 , due to their significant shift down in temperature compared to Ni/Al 2 0 3 , and the peak at 450 °C is assigned to the onset of Ti0 2 reduction.
  • TPR results from the monometallic catalysts are in agreement with XPS results, providing evidence for significant Ti0 2 interactions with Cu and Ni and that this interaction is stronger for Ni-Ti0 2.
  • Ni catalysts were selective for production of THFOL.
  • the Ni catalysts were significantly more reactive than Cu catalysts, as evidenced by the approximately 1 order of magnitude longer reaction time required for full FF conversion on Cu.
  • FF was completely converted with a 54.5% yield of THFOL and 30.5% yield of MF after 1 hour, and the product selectivity did not change after 4 hours.
  • the Ni/Ti0 2 catalyst was less active than Ni/Al 2 0 3 , with some FOL remaining after 1 hour and the product selectivity stabilizing after
  • THFOL as the primary product over the Ni catalyst is consistent with the known strong interactions between the furan ring in FF and Ni surfaces, which drives ring hydrogenation.
  • the strong interactions between Ni and Ti0 2 observed by XPS and TPR and the enhanced THFOL yields on Ni/Ti0 2 compared to Ni/Al 2 0 3 indicate that Ni sites near the Ti0 2 interface coordinate more selectively with the furan ring in FF rather than the carbonyl (or
  • Cu catalysts were much less active than Ni catalysts and required approximately 8 hours to achieve complete FF conversion, likely due to their weak ability to activate H 2. Similar to the Ni catalysts, Cu/Al 2 0 3 was more active than Cu/Ti0 2. FIG. 6 shows that for Cu/Al 2 0 3 41% of FF was converted to yield 21.5% FOL and 17.2% MF at 1 hour, while for Cu/Ti0 2 , 25.7% of FF was converted to yield 12.1% FOL and 12.7% MF at 1 hour. Further extending reaction times to 8 hours resulted in complete FF conversion for both catalysts with similar final MF yields of 74.9% for
  • FIG. 21 shows FF conversion and product yields over time on both the Cu/Al 2 0 3 and Cu/Ti0 2 catalysts. In both cases, the time dependent yield profile of FOL strongly suggests that this species is an intermediate in the production of MF, as previously reported.
  • the monometallic Cu and Ni catalysts showed FF hydrogenation and HDO reactivity consistent with previous reports, and their reactivity exhibited minimal sensitivity to support composition.
  • the bimetallic Cu-Ni catalysts showed significant support effects for FF HDO.
  • the bimetallic catalyst acted similarly to Ni alone, while on Ti0 2 , the Cu-Ni bimetallic catalyst enhanced rates and MF selectivity compared to Cu alone.
  • the Cu-Ni/Ti0 2 catalyst showed good stability, regenerability, reactivity, and MF selectivity and outperformed monometallic Cu catalysts in all performance metrics at similar conditions.
  • Cu-Ni/Ti0 2 showed excellent selectivity toward methylated furans in HMF and FF/HMF co-processing reactions.
  • FIG. 10 The proposed Cu-Ni bimetallic particle structure on Al 2 0 3 based on the XPS measurements and reactivity results is shown schematically in FIG. 10.
  • SMSI encapsulation states with Ti0 2 are typically observed following greater than (>) 500 °C reduction treatment. Because minimal Ni reduction peaks were observed for the Cu-Ni/Ti0 2 catalysts despite Ni reduction peaks being clearly observable in the Ni-Ti0 2 catalyst, Ni is likely buried subsurface in the bimetallic particles prior to SMSI encapsulation layer formation. This mechanism is further supported by the XPS analysis of surface composition in the pre-reduced and pre-oxidized Cu-Ni/Ti0 2 catalysts that show identical Cu/Ni surface concentration ratios in Table 1 (FIG. 13). Thus, preferential interactions between Ni and Ti0 2 are believed to drive formation of core-shell like particles where Cu is primarily exposed at the catalyst surface, see proposed structures in FIG. 10. In accordance with an exemplary embodiment, support induced bimetallic particle segregation may be quite general for reducible oxide supported bimetallic catalysts, given known metal specific interactions with reducible supports.
  • reconstruction of the as- synthesized catalytic structure under reaction conditions may be expected when significant adsorbate-metal specific interactions exist, for example in a CO atmosphere.
  • significant adsorbate-metal specific interactions exist, for example in a CO atmosphere.
  • it can be concluded that migration of Ni to the catalyst surface is minimal under reaction conditions.
  • Ni serves as an anchoring site for Cu on Ti0 2 , which enhances catalyst stability and provides a stable platform for regeneration of the core-shell Cu-Ni structure to that for high MF selectivity and reactivity. Further reduction of the Ni loading in Cu-Ni/Ti0 2 catalysts may allow for similar enhanced reactivity and stability as observed here while also minimizing the surface exposure of Ni observed with increased time under reaction conditions.
  • CELF co-solvent-enhanced lignocellulosic fractionation
  • Cu-Ni/Ti0 2 is a unique catalytic material that enabled high yield (-90%) conversion of FF and HMF to methylated furans in either single or co-processing schemes, results not possible with monometallic Cu and Ni, or Cu-Ni/Al 2 0 3.
  • the reactivity of Cu-Ni/Ti0 2 is proposed to result from strong and selective Ni-Ti0 2 interactions that favored in formation of Cu-shell and Ni-core structure, allowing for high selectivity in HDO and enhanced reactivity compared to monometallic Cu catalysts.
  • supported bimetallic catalysts have been demonstrated to enhance catalytic activity, product selectivity, and catalyst stability over supported monometallic catalysts for a range of catalytic reactions.
  • the surface structure and composition of bimetallic particles can differ significantly from the bulk due to variations in surface energies and interactions with adsorbates, making the design of bimetallic catalysts with targeted properties and reactivities challenging.
  • the influence of catalyst support (Al 2 0 3 and Ti0 2 ) on the surface composition and structure of bimetallic Cu-Ni nanoparticles is disclosed with varying Ni weight loading (0, 0.5, 1.5, 3, 5, &10 wt%) at a Cu loading of 5 wt% and a correlation to catalytic reactivity and stability in furfural (FF) hydrodeoxygenation (HDO).
  • FF furfural
  • HDO hydrodeoxygenation
  • Oxide-supported bimetallic heterogeneous catalysts consisting of late-transition and noble metals can play a significant role in multifunctional chemical transformations, with demonstrated enhancements in catalytic activity, product selectivity, and catalyst stability compared to supported monometallic catalysts.
  • bimetallic catalysts have been shown to exhibit improvements over monometallic catalysts in various catalytic performance metrics for applications including petrochemical processing, ammonia synthesis, three-way catalysis, among many others. While the idea of exploiting the properties of multiple catalytic materials to optimize performance is appealing, bimetallic catalyst design is complicated by the phase space of physical effects that control the relative geometries and organization of the constituent elements at the surface of bimetallic nanoparticles.
  • compositions and compositional ordering at bimetallic surfaces may vary from the bulk due to differences in surface energies of the metals.
  • the lower surface free energy of noble metals e.g., Pd, Pt, and Au
  • base metals e.g., Fe, Co, Cu, and Ni
  • FF Furfural
  • HDO Hydrodeoxygenation
  • bimetallic or bifunctional catalysts as monometallic surfaces that enable facile H 2 dissociation (e.g., Pt, Pd, Ni etc.) also preferentially coordinate the furan ring, while metal surfaces that selectively interact with the aldehyde (e.g., Cu or Ag) exhibit relatively low rates of H 2 dissociation.
  • Catalysts were prepared by adding the required amounts of Cu(N0 3 ) 2 3H 2 0 and Ni(N0 3 ) 2 6H 2 0, (Aldrich, purity 99.99%, Louis, MO 63103, USA) precursors simultaneously to achieve 5 wt% of Cu and 0.5, 1.5, 3, 5, and 10 wt% of Ni in 50 ml of DI- water. This solution was added to 5 g of Ti0 2 (P25) or Q-AI2O3 in a round bottom flask. It was thoroughly mixed and dried at 80 °C using rotary evaporator. The obtained material was dried in a vacuum oven at 100 °C for 12 hours followed by calcination at 450 °C for 5 hours. Prior to reactivity experiments, catalysts were reduced by pure 3 ⁇ 4 at a flow rate of 50 mLmin 1 at 450 °C for 3 hours and cooled to 25 °C under the same environment.
  • TEM Transmission Electron Microscopy
  • X-ray photoelectron spectroscopy XPS experiments were carried out using a Kratos AXIS EILTRADLD XPS system equipped with an Al Ka monochromated X-ray source and a l65-mm mean radius electron energy hemispherical analyzer. Vacuum pressure was kept below 3 x 10 9 torr during analysis. Binding energy calibrations were done with reference to the carbon ls peak by adjusting spectra to 284.8 eV. Depth profiling
  • X-ray Diffraction X-ray Diffraction
  • Micromeritics AutoChem 2920 instrument In each experiment, 0.1 g of catalyst was placed in a EG-tube quartz funnel and purged with Ar gas at 50 mL min 1 at 100 °C for 1 h. A gas mixture of H 2 (10%)/ Ar was passed through the quartz funnel at 25 °C for 1 h with a 50 mL min 1 flow rate. The temperature was raised to 350 °C at a heating rate of 10 °C min 1 and then temperature was reduced to 50 °C under Ar (50 mL min 1 ) for chemisorption studies.
  • catalysts were treated with 1000 ppm N 2 0/He with 30 mL min 1 flow rate for 1 hour followed by purging with Ar flow (50 mL min 1 ) for 1 hour at constant temperature. Then the temperature was raised to 350 °C at a heating rate of 10 °C min 1 with 50 mL min 1 flow of H 2 (l0%)/Ar gas and the amount of H 2 consumption was measured. Repeated N 2 0 oxidation followed by H 2 -TPR experiments were conducted and the average hydrogen consumption of 4 sequential experiments was used to calculate dispersion by using a 2: 1 Cu/H 2 ratio. [0136] Reactivity measurements
  • MF and methyl tetrahydrofuran (MTHF) were analyzed using an Hp-5 column that was 30 m long x 0.320 mm internal diameter x 0.25 micron via FID using the following program: 1 min hold at 30 °C, increase from 30-100 °C at a ramp rate of 10 °C/min, 2 min hold, increase from 100-325 °C at a ramp rate of 25 °C/min and hold for 1 min.
  • Molar yields of the final product were quantified by using calibration curves of standard samples in the gas chromatograph. Mass balances accounting for greater than (>) 95% of the carbon content were obtained in all experiments. Reactant conversion and product yield were calculated as follows:
  • 0.3 g of freshly reduced catalyst was transferred into a 100 mL stainless-steel Parr reactor containing 1 g of FF and 25 mL of 1,4- dioxane.
  • the reactor was flushed with H 2 and then pressurized with H 2 to 35 bar.
  • Each reaction was conducted for 2 hours at 200 °C.
  • the reactor was cooled by quickly lowering it into a room temperature water bath (25 °C) and depressurizing in the fume hood.
  • the catalyst was separated from the liquid by filtration and dried at 105 °C for 3 hours and then reused in four recycle experiments without washing (or) regeneration. Regeneration of the used catalysts was performed via calcination at 450 °C for 5 hours followed by reduction with pure 3 ⁇ 4 at 450 °C for 3 hours.
  • the average Cu-Ni particle size was statistically similar in these three representative materials: Cu(5 wt%)-Ni(0.5 wt%) approximately 3.3 ⁇ 0.7 nm > Cu(5 wt%)-Ni(l.5 wt%) approximately 3.1 ⁇ 0.8 nm > Cu(5 wt%)-Ni(3 wt%) approximately 3.0 ⁇ 1.0 nm.
  • the particle size distributions were relatively tight in all cases examined, with only a few metallic particles with diameters > 5 nm for the catalysts containing 1.5 and 3 wt% Ni. The particle sizes are in reasonable agreement with dispersions of 15.9% and 27.1% that give estimated average Cu particle diameters of 6.3 nm and 3.8 nm measured by N 2 Otitration for
  • the relative Cu and Ni concentration were calculated by summing all contributions to the Cu 2p3/2 and Ni 2p3/2 peaks and normalizing by their relative cross-sections (sensitivity factors).
  • Binding energy values for the Cu° and Ni° components of the 2p3/2 peaks were in the range of 931.8 to 932.3 and 851.8 to 852.9 eV, respectively, consistent with values reported in the literature.
  • Increasing the Ni loading from 1.5 to 5% increased the binding energy for the Ni° 2p3/2 peak by -0.4-0.5 eV for both the Ti0 2 and Al 2 0 3 supports (FIG. 42 - Table Sl).
  • Ti0 2 was used as a support
  • the Cu° 2p3/2 peak position shifted up in binding energy by -0.5 eV as the Ni loading increased, while the Cu° 2p3/2 peak position stayed essentially constant as Ni loading was varied on the Al 2 0 3 supported catalysts.
  • FIG. 26(a) shows the DP-XPS profiles for Cu(5%)-Ni(l.5%) on Ti0 2 and Al 2 0 3 , plotted in terms of the relative percent of Cu and Ni at each sputtering time.
  • Ar sputtering time 0
  • the Cu and Ni relative concentrations converged towards the expected nominal loadings on the Ti0 2 and Al 2 0 3 supported catalysts.
  • the Cu and Ni relative concentrations varied only slightly as a function of Ar sputtering time and from the expected nominal concentrations when Al 2 0 3 was used as a support.
  • HDO of FF to MF occurs through sequential steps, where initial hydrogenation of the FF carbonyl group forms FOL and further hydrogenolysis of FOL produces MF, Scheme 1 (FIG. 27).
  • An unwanted side product, THFOL can form from ring hydrogenation of FOL and is commonly observed on catalysts that promote coordination with the furan ring.
  • FIG. 40 shows the FF conversion, MF yield, and FOL yield (the 2 major identified products) over Cu(5%)-Ni (0.5, 1.5, & 3%)/Ti0 2 catalysts as a function of reaction time.
  • FIG. 28 shows FF conversion and product yields over monometallic Cu(5%) and bimetallic Cu(5%)-Ni(0.5, 1.5, and 3%)/Al 2 0 3 catalysts as a function of reaction time.
  • FF conversions were 70% and 100% at 0.5 and 2 hours reaction time, respectively, and a maximum of 94.6% MF yield was obtained at 8 hours reaction time.
  • the addition of 0.5% Ni caused an increase in catalytic reactivity, where complete FF conversion was observed within 0.5 hour.
  • the dominant products were FOL and THFOL at all explored reaction times, with 74.2% and 18.9% yields of THFOL and MTHF observed, respectively, at 8 hours reaction time.
  • MF yields were diminished at longer reaction times for the Cu(5%)-Ni(3 and 5%)/Ti0 2 catalysts due to the formation of MTHF. Further increasing the Ni loadings to 10% showed minimal influence on the FF HDO reactivity compared to lower Ni loadings, and diminished MF selectivity due to an increased rate of MTHF formation and the apparent degradation of FF or hydrogenation products.
  • Rl through R4 probe the change in catalytic reactivity due to carbon deposition and Cu sintering or leaching into solution, while R5 allows analysis of only the influence of Cu sintering or leaching as regeneration removes all carbon deposits. FF conversion was kept below 100% in all experiments.
  • FIG. 31(a) shows that for the monometallic Cu(5%)/Ti0 2 catalyst, FF conversion and MF yields decreased from 37.3% (in Rl) to 25.5% (in R4) and 16.8 (Rl) to 4.2% (R4), respectively, showing a significant loss of performance. Regeneration of the catalyst promoted the FF conversion and MF selectivity in R5 to a similar FF conversion and MF yield as observed in Rl.
  • FIG. 31(b) shows that the addition of 0.5% Ni to the Cu(5%)/Ti0 2 catalyst improved the stability of the catalytic activity during R1-R4, with an essentially constant FF conversion of -61-68%, although MF yield decreased from 37% to 11%.
  • the composition of the support influences the structure of bimetallic Cu-Ni nanoparticles is disclosed.
  • a significant Cu surface segregation within the bimetallic particles was observed when Ti0 2 was used as a support, whereas a homogeneous distribution of the metals throughout the bimetallic particles was observed when A1 2 0 3 was used a support. It was argued that this result was due to strong, specific interactions between Ni and Ti0 2 that induced Ni segregation at the Ti0 2 interface and Cu at the catalytic surface to minimize the energy of the supported particle.
  • the relatively similar interaction energy between Cu or Ni and Al 2 0 3 caused the formation of bimetallic particles with homogeneous Ni and Cu distributions to be energetically favorably.
  • FIGS. 26(a)-26(c) shows that regardless of the Ni loading considered (1.5, 3, and 5%), the composition of Cu at the bimetallic particles surfaces is greater than 80% when Ti0 2 was used as a support.
  • Ni at the surface of Cu-Ni/Ti0 2 catalysts is relatively scarce compared to the same Ni content in Cu-Ni/Al 2 0 3 catalysts, and that the dispersion of Ni within Cu induces significant charge transfer between the metals and reduces the propensity for Ni oxidization.
  • the 43.9° peak is assigned to the surface alloy phase where the low Ni concentration existing as dispersed species only slightly expands the Cu lattice, while the 44.6° reflection is assigned to the Cu-Ni alloy phase existing in the bulk of the bimetallic particles.
  • the results agree well with the DP-XPS data that suggest 2 different phases on Cu-Ni alloys.
  • the Cu(l 11) peak position shifted to a >0.2° higher 2Q value compared with CU/A1 2 0 3 , suggesting that Cu exists in predominantly Cu domains within the bimetallic Cu-Ni particles.
  • controlling metal composition and metal-support interactions in Cu-Ni bimetallic catalysts can simultaneously promote catalytic activity, selectivity, and stability for FF conversion to MF, as compared to monometallic Cu catalysts.
  • Detailed analysis of Cu-Ni bimetallic particles on Ti0 2 and Al 2 0 3 supports suggests that over a range of bimetallic compositions, Ti0 2 promotes formation of near surface alloys rich in Cu that primarily contain dispersed Ni species.
  • Cu-Ni bimetallic particles are synthesized on Al 2 0 3 supports, evidence suggests that Cu and Ni are evenly distributed throughout the particles other than segregation of Ni and Cu domains at the particle surface.
  • a method is needed for all-catalytic conversion of lignocellulosic biomass to transportation fuels at high yields.
  • a method and system is disclosed for a hybrid strategy to co- produce the renewable gasoline blendstocks 2-methylfuran (MF) and 2,5-dimethylfuran (DMF) directly from hardwood poplar by combining homogeneous liquefaction with heterogeneous catalytic dehydration, with a depolymerized technical-grade lignin powder as the major solid byproduct.
  • MF 2-methylfuran
  • DMF 2,5-dimethylfuran
  • poplar wood chips are liquefied under a dilute FeCl 3 -catalyzed aqueous THF environment at a sub-pyrolytic 180 °C to yield 93.5% furfural (FF) and 66.0% 5-hydroxymethylfurfural (HMF) from xylan and glucan, respectively.
  • furfurals were extracted from the liquor and hydrodeoxygenated over a non-noble (Cu-Ni over Ti0 2 ) catalyst to yield 87.8% of the maximum possible for MF from furfural and 85.6% of the maximum for DMF from HMF in the extract.
  • first generation feedstocks such as corn-derived sugars and cane sugar syrups to produce fuel ethanol poses food, water, and land sufficiency concerns
  • second generation feedstocks including forestry and agricultural residues and energy crops can provide an abundant, inexpensive resource for sustainable production of renewable transportation fuels.
  • Purely catalytic conversion of second generation feedstocks can produce fungible fuels provided high enough fuel yields can be achieved to be economic.
  • most catalytic methods are unable to achieve high yields directly from raw lignocellulosic biomass due to significant catalyst poisoning, mass transport limitations, and the need for complicated separations, and typically require expensive highly purified sugar feedstocks to be compatible with exotic supported noble-metal catalysts.
  • a high yield integrated method is disclosed, which is capable of processing raw hardwood poplar chips and converting their sugars directly into fungible fuels while achieving higher total carbon utilization from the production of technical lignin.
  • the strategy presented here maintains high molar yields at each step, achieving an overall yield of 60% from the theoretically available xylan, glucan, and acid-insoluble lignin present in the raw material.
  • poplar wood chips were solubilized in mixtures of tetrahydrofuran (THF) with water containing dilute FeCE, representing one variation of the Co-solvent Enhanced Lignocellulosic Fractionation (CELF) process.
  • THF tetrahydrofuran
  • CELF Co-solvent Enhanced Lignocellulosic Fractionation
  • C5 and C6 sugars within the hardwood were simultaneously hydrolyzed to monomers and then co-dehydrated to the fuel precursors FF and HMF, respectively.
  • the high performance of the first homogeneous catalytic step was owed to unique THF -water-biomass interactions during CELF reaction that accelerates cellulose and lignin solubilization, whereas the mild Lewis acidity of FeCl 3 promoted the kinetically favorable open-chain dehydration of sugar monomers to Furfural (FF) and 5-hydoxymethylfurfural (HMF). Furfural and HMF losses to levulinic acid and formic acid were minimized by optimizing reaction conditions.
  • FF Furfural
  • HMF 5-hydoxymethylfurfural
  • the CELF reaction achieved over 94% solubilization of the starting wood chips including extraction of the lignin that was precipitated as a fine solid powder upon removal and recovery of THF from the CELF liquor.
  • This so-called“CELF lignin” yield was similar to that reported in our previous studies.
  • the lower temperatures required for the CELF reaction compared to pyrolysis affords CELF the ability to selectivity produce furanic intermediates that are considered ideal renewable platform chemicals for the production of both fuels and chemicals, while avoiding any solid tar or char formation or gas production.
  • the catalytic HDO of FF and HMF extracted from the CELF liquor was first considered as a function of solvent composition. Following HMF and FF extraction using pure toluene, HDO was executed at 220 °C where 26% of FF and 100% of HMF conversion were observed after 2 hours. However, the total yield of desired products was low: FOL+MF (9.8%) and MFF+DMF (91.2%). It is assumed that the lower catalytic reactivity in toluene, compared to our previous studies in neat l,4-dioxane, was due to the non-polar nature of toluene. The HDO activity derived from l,4-dioxane-toluene extracted FF and HMF streams was lower than for toluene alone, where diminished MF yields and HMF conversion were seen in FIG. 46(a).
  • FIG. 47(b) shows the conversion and product yields from HDO of l,4-dioxane-toluene extracted FF and HMF at 220 °C with the addition of 0.1 g of Ca(OH) 2 as a function of time. It was observed that at 8 hours reaction time, MF yields of 87.8% and DMF yields of 85.6% could be achieved.
  • FIG. 47(c) shows results for R5(a), where the catalyst was regenerated, compared with R5(b), where additional Ca(OH) 2 was added. It clearly observed that the loss in activity is caused by presence of CF ions in the l,4-dioxane-toluene stream instead of carbon deposition or metal sintering and that this could be addressed simply by adding Ca(OH) 2 in each recycle.
  • the lignin was then precipitated from the CELF hydrolyzate prepared at the conditions optimized for producing FF and HMF (l80°C, 20 min, 4: 1 THF/water, 1% FeCE) by boiling the hydrolyzate to remove THF.
  • the molecular weight, relative abundance of the lignin interunit linkage (e.g., b-O-4) and monolignol compositions (e.g., S/G ratio), and the contents of free hydroxyl groups in lignin were determined by Gel Permeation
  • CELF Native-like cellulolytic enzyme lignin
  • FIGS. 52 and 53 present the aromatic and aliphatic regions of HSQC NMR spectra of CEL and CELF lignin, respectively.
  • b-aryl ether (b-O-4) were the dominant interunit linkages in poplar CEL along with minor amounts of phenylcoumaran (b- 5) and resinols (b-b).
  • b-b phenylcoumaran
  • b-b resinols
  • the dominant aliphatic hydroxyl group signal in CEL was significantly reduced by approximately ( ⁇ ) 73% after CELF pretreatment; on the other hand, the contents of phenolic OH, and especially the C5 substituted OH, were much higher in CELF lignin compared to CEL.
  • the drop in aliphatic OH could be due to the above mentioned loss of g-methylol group as formaldehyde.
  • the oxidation of aliphatic hydroxyl groups might have occurred as evident by the dramatic increase in the carboxylic OH content.
  • the increase in total phenolic OH supports the HSQC NMR data indicating significant cleavage of lignin interunit linkages during CELF pretreatment.
  • the relatively low content of aliphatic OH and high content of phenolic OH are desired features for potentially using CELF lignin as good antioxidant.
  • Poplar wood was provided by the National Renewable Energy Laboratory (NREL, Golden, CO) and was milled to obtain less than a 1 mm particle size using a laboratory mill (Model 4, Arthur H. Thomas Company, Philadelphia, PA).
  • the composition of poplar wood was measured to be 45 ⁇ 0.5% glucan, l4 ⁇ 0.3% xylan and 22 ⁇ 0.2% K-lignin using NREL laboratory analytical procedure in triplicates. Other materials needed for biomass composition to total 100% were not characterized in this study as small amounts were difficult to quantify using HPLC. All the pentosans were grouped together as xylan and all hexosans as glucan. THF (>99% purity, Fischer Scientific, NJ) was used in all the CELF pretreatment reactions.
  • Hydrated ferric chloride catalyst was purchased from Sigma Aldrich (St.Louis, MO, ETS). l,4-dioxane and toluene (HPLC Grade, Fisher Chemicals) were used as solvents for FF and HMF extraction from CELF stream and further for HDO reactions. FF (99.9% pure, Sigma Aldrich) and HMF (99.9% pure, Sigma Aldrich) were used as starting materials for HDO reactions.
  • Cu(N0 3 ) 2 3H 2 0 purity 99%, CAS: 10031-43-3, Aldrich, New Jersey, USA
  • Ni(N0 3 ) 2 6H 2 0 purity 99.99%, Aldrich, Louis, MO 63103, USA
  • Ti0 2 P25, Batch No. 4161060398, NIPPON AEROSIL Co., LTD, Evonik, Degussa GmbH
  • CELF liquor was neutralized to pH-7 by adding Ca(OH) 2.
  • Toluene was added at 1 :5 ratio to the neutralized CELF liquor and sonicated for 30 minutes. Solids were separated from the CELF stream by vacuum filtration and then THF was removed by distillation into rotavap. Additional l,4-dioxane added to induce phase separation and liquids were sonicated for 10 minutes to improve extraction. In this step, more than 90% of FF and approximately 80% to 85% of HMF were extracted from CELF stream to l,4-dioxane-toluene (1 :1 ratio) organic phase.
  • Organic phase (l,4-dioxane-toluene) was separated from aqueous phase and used for HDO reaction over Cu(5%)-Ni(5%)/Ti0 2 catalysts.
  • FF and HMF concentration in l,4-dioxane- toluene (or) toluene stream were concentrated to 0.5 g and 0.25 g in 25 ml respectively, in each reaction by adding additional FF and HMF.
  • Cu(5%)- N ⁇ (5%)/T ⁇ q 2 catalysts were reduced at 450 °C for 3 hours.
  • 1,4 -dioxane-toluene organic layer containing extracted FF and HMF was reacted in a 100 mL stainless-steel Parr reactor with 0.3 g of freshly reduced catalyst at 450 °C for 3 hours.
  • required amounts of pure FF and HMF were added to as extracted l,4-dioxane-toluene stream to maintain the same concentrations to 0.5 g and 0.250 g in 25 ml, respectively.
  • the reactor was flushed with H 2 and then pressurized with H 2 to 35 bar. Each reaction was conducted for 2 hours at 220 °C.
  • the reactor was cooled by quickly lowering it into a room temperature water bath (25 °C) and depressurizing in the fume hood. Then the catalyst was separated from the liquid by filtration and dried at 105 °C for 3 hours and then reused in four recycle experiments without washing (or) regeneration. Regeneration of the used catalysts was performed via calcination at 450 °C for 5 hours followed by reduction with pure H 2 at 450 °C for 3 hours.
  • lignin samples were acetylated in 2.0 mL of acetic anhydride/pyridine mixture (v/v, 1 : 1) at 25 °C for 24 h. ⁇ 25 mL of ethanol was then added to the reaction to quench the reaction and left for 30 min. The solvent was then removed by a rotary evaporation under reduced pressure. Samples were then dried at 45 °C overnight in a vacuum oven followed by dissolving in THF at a concentration of ⁇ l mg/mL prior to the GPC analysis.
  • the molecular weight of lignin samples was analyzed on a GPC SECurity 1200 system operated on Agilent HPLC 1200 with four Waters Styragel columns (HR1, HR2, HR4, and HR6) and an UV detector (270 nm). Polystyrene narrow standards were used to prepare the calibration curve. THF was used as the mobile phase with a flow rate 1.0 mL/min.
  • HSQC NMR spectra of lignin samples were acquired with a Bruker Avance 400 MHz spectrometer as previously described.
  • a standard Bruker heteronuclear single quantum coherence pulse sequence was used with the following conditions: 210 ppm spectral width in Fl ( 13 C) dimension with 256 data points and 13 ppm spectral width in F2 (1H) dimension with 1024 data points, a 90° pulse, a 1 SC-H of 145 Hz, a 1.5 s pulse delay, and 32 scans.
  • Approximately 50 mg of dry lignin samples was dissolved in deuterated DMSO.
  • the relative lignin monomer compositions and interunit linkage abundance were estimated semi- quantitatively using volume integration of contours in HSQC spectra.
  • the C a signals were used for contour integration for the estimation of interunit linkages such as b- 0-4, b-b, and b-5.
  • Data processing was performed using Top Spin 2.1 software (Bruker BioSpin).
  • the spectra were acquired at a frequency of 161.93 MHz over 32K data points with an acquisition time of 1.29 s using an inverse gated decoupling pulse sequence with a 25 s pulse delay and 128 scans. Data processing was performed suing Top Spin 2.1 software (Bruker BioSpin).

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Abstract

L'invention concerne un procédé de conversion de biomasse en un additif de carburant, le procédé comprenant : la liquéfaction de la biomasse pour former une liqueur; la neutralisation de la liqueur; la précipitation de la lignine contenue dans la liqueur; l'extraction du furfural (FF) et le 5-hydroxyméthylfurfural (H.M.F.) à partir de la liqueur; et l'hydrodéoxygénation (H.D.O.) des furfurals extraits sur un catalyseur Cu-Ni/TiO2. Le catalyseur pour l'hydrodésoxygénation (H.D.O.) du furfural (FF) et du 5-hydroxyméthylfurfural (H.M.F.) en furanes méthylés comprend des particules de cuivre-nickel (Cu-Ni) supportées sur du dioxyde de titane (TiO2), les particules de cuivre-nickel formant des structures noyau-enveloppe dans lesquelles du cuivre (Cu) est enrichi à une surface du catalyseur.
PCT/US2019/021326 2018-03-08 2019-03-08 Procédé et système de bioraffinage catalytique hybride de biomasse en furanes méthylés et lignine technique dépolymérisée Ceased WO2019173701A1 (fr)

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CN117665173A (zh) * 2024-02-01 2024-03-08 深圳天祥质量技术服务有限公司 一种生活消费品中四氢糠醇的测定方法

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CN113559861A (zh) * 2021-07-27 2021-10-29 大连理工大学 一种糠醛直接转化为四氢糠醇Cu-Ni双金属催化剂、制备方法及应用
CN117665173A (zh) * 2024-02-01 2024-03-08 深圳天祥质量技术服务有限公司 一种生活消费品中四氢糠醇的测定方法
CN117665173B (zh) * 2024-02-01 2024-04-30 深圳天祥质量技术服务有限公司 一种生活消费品中四氢糠醇的测定方法

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