CONVERSION OF ALCOHOLS AND ALDEHYDES TO ENERGY-DENSE HYDROCARBON FUEL MIXTURES

Abstract

The present disclosure relates to a process for preparing long-chain alkanes and alkenes from alcohols, aldehydes, or both. The process proceeds via acceptorless dehydrogenation and decarbonylative coupling using a supported catalyst.

Claims

1. A process for preparing a hydrocarbon comprising (i) reacting an alcohol, and aldehyde, or both, with a catalyst to form a hydrocarbon; wherein the catalyst comprises palladium and a support.

2. The process of claim 1, wherein the process is conducted in the absence of a solvent.

3. The process of claim 1, wherein the process is conducted in the presence of a solvent.

4. The process of claim 3, wherein the solvent is selected from toluene, tetrahydrofuran, ethanol, and any combination thereof.

5. The process of claim 1, wherein the alcohol is a primary alcohol, a secondary alcohol, a tertiary alcohol, a diol, a polyol, or any combination thereof.

6. The process of claim 1, wherein, the alcohol is an aliphatic alcohol having a methylene (—CH.sub.2—) group adjacent to the hydroxyl bearing carbon atom.

7. The process of claim 1, wherein the alcohol in selected from methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, heneicosanol, docosanol, tricosanol, tetracosanol, pentacosanol, hexacosanol, heptacosanol, octacosanol, nonacosanol, triacontanol, glycerol, hexitol, sorbitol, 1,2-butadiol, 1,4-butadiol, arabinol, xylose, 2-deoxyhexopyranose, 1,4-anhydroxylitol, 1,5-gluconolactone, and any combination of any of the foregoing.

8. The process of claim 1, wherein the particle size of the palladium ranges between about sub-nano and about 10 nm.

9. The process of claim 1, wherein the support is a basic support, an acidic support, an amphoteric support, or any combination thereof.

10. The process of claim 1, wherein the support is a clay-based support.

11. The process of claim 1, wherein the support is selected from magnesium oxide, hydrotalcite, montmorillonite, alumina, vermiculite, kaolinite, talc, nontronite, saponite, illite, amosite, chamosite, cookeite, nimite, dickite, nacrite, pyrophyllite, and any combination thereof.

12. The process of claim 1, wherein the particle size of the support ranges between about 10 nm and about 400 nm.

13. The process of claim 1, wherein the support comprises magnesium oxide, alumina, hydrotalcite, or a combination thereof.

14. The process of claim 1, wherein the catalyst comprises between about 0.1 mol. % and about 10 mol % of palladium.

15. The process of claim 1, wherein the support further comprises a dopant.

16. The process of claim 15, wherein the dopant comprises a metal selected from Fe, Cu, Ni, Zn, Co, or any combination thereof.

17. The process of claim 1, wherein the process comprises a deoxygenative coupling reaction.

18. The process of claim 1, wherein the process comprises a tandem dehydrogenation, aldol condensation and decarbonylation reaction.

19. A hydrocarbon prepared by a process according to claim 1.

20. A fuel prepared by a process according to claim 1.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0049] FIG. 1 shows a process for upgrading primary alcohols to longer chain alcohols (FIG. 1(a)) and hydrocarbons (FIG. 1(b)).

[0050] FIG. 2 shows alcohol coupling processes for 2-aryl ethanol derivatives facilitated by homogeneous Ir, Ru and Mn catalysts.

[0051] FIG. 3 shows an exemplary proposed mechanism for the conversion of alcohols to alkenes, alkanes and additional by-products.

[0052] FIG. 4 shows powder XRD patterns of Pd—Al.sub.2O.sub.3 and Al.sub.2O.sub.3(FIG. 4a), 5% Pd-HT and HT (FIG. 4b), Pd—MgO and MgO (FIG. 4c), and doped Pd-x-HTs (5%) (x=Zn, Cu, Ni, Co, Fe) (FIG. 4(d)).

[0053] FIG. 5 shows palladium 3d X-ray photoelectron spectra of (a) Pd—Al.sub.2O.sub.3(FIG. 5a), 5% Pd-HT (FIG. 5b), Pd—MgO (FIG. 5c), and 1% Pd-HT (FIG. 5d).

[0054] FIG. 6 shows bright field TEM images and corresponding palladium particle size distributions for Pd—Al.sub.2O.sub.3(FIGS. 6a and 6b), Pd—MgO (FIGS. 6c and 6d), 1% Pd-HT (FIGS. 6e and 6f), and 5% Pd-HT (FIGS. 6g and 6h).

[0055] FIG. 7 shows TEM images and corresponding palladium particle size distributions for Pd-HT (5%) (FIG. 7a) and doped Pd-HTs (5%) (Fe: FIG. 7b, Co: FIG. 7c, Ni: FIG. 7d, Cu: FIG. 7e, and Zn: FIG. 7f).

[0056] FIG. 8 shows the product yield and selectivity for deoxygenative olefination of n-heptanol coupling over supported palladium catalysts. See FIG. 3 for product structures.

[0057] FIG. 9 shows a radial plot of catalytic activity for the three-step deoxygenative olefination of alcohols using Pd—MgO, Pd—Al.sub.2O.sub.3, 1% Pd-HT and 5% Pd-HT catalysts.

[0058] FIG. 10 shows a schematic for the transfer hydrogenation of tridec-6-ene using 2-propanol.

[0059] FIG. 11 shows the differential enthalpy of adsorption as a function of coverage for the adsorption of CO.sub.2 on Pd-HT (5%) and Cu, Ni, Fe and Zn doped Pd-HT (5%) hydrotalcite supports.

[0060] FIG. 12 shows the HRTEM (High resolution TEM) and crystal lattice of 5% Pd-HT (FIG. 12a) showing Pd (111), 5% Pd-HT (FIG. 12b) showing PdO (110) phase, and 1% Pd-HT (FIG. 12c) showing Pd (111) phase.

[0061] FIG. 13 shows temperature-programmed desorption profiles of Pd—MgO, Pd—Al.sub.2O.sub.3, 1% Pd-HT and 5% Pd-HT catalysts using CO.sub.2 (FIG. 13a) and NH.sub.3 (FIG. 13b) as probes for solid base and acid sites, respectively.

[0062] FIG. 14 shows the time course of decarbonylative olefination of heptanal (see Scheme 1) using 5% Pd-HT (FIG. 14a), Pd—Al.sub.2O.sub.3(FIG. 14b) and Pd—MgO (FIG. 14c) at 100° C.

[0063] FIG. 15 shows the time course of decarbonylative olefination of heptanal using Pd-HT (5%) (FIG. 15a), Pd—Al.sub.2O.sub.3(FIG. 15b), and Pd—MgO (FIG. 15c) at 150° C., under air.

[0064] FIG. 16 shows the TEM image (FIG. 16a) of used Pd-HT (5%) and the corresponding particle size distribution (FIG. 16b). The mean particle size is 3.3±0.5 nm.

DETAILED DESCRIPTION OF THE INVENTION

[0065] As used herein, the term “acceptorless dehydrogenation” may refer to the oxidation of an alcohol to an aldehyde or ketone without use of any external oxidant and with extrusion of hydrogen.

[0066] As used herein, the terms “atom-economical” and “atom economy” may refer to the conversion efficiency of a chemical process in terms of all atoms involved and the desired products produced (e.g., equal to the ratio between the mass of desired product to the total mass of products, expressed as a percentage).

[0067] As used herein, the term “deoxygenative coupling” may refer to a reaction in which a carbon-carbon bond is formed between two components and the total oxygen content of the final product is lower than the sum of its parts.

[0068] As used herein, the term “tandem dehydrogenation” may refer to a reaction in which an alcohol undergoes oxidation to an aldehyde, which then undergoes a subsequent reaction to form another product.

[0069] As used herein, the term “aldol condensation” may refer to a reaction in which an enol or an enolate ion reacts with a carbonyl compound to form a β-hydroxyaldehyde or β-hydroxyketone, followed by dehydration to give a conjugated enone.

[0070] As used herein, the term “decarbonylation” may refer to a reaction that involves the loss of carbon monoxide (CO) from an organic substrate to form a new product, such as an aldehyde forming an alkane and CO.

Catalyst Characterization

[0071] Physicochemical properties and palladium composition of Pd—Al.sub.2O.sub.3, Pd—MgO and Pd-HT (1% and 5%) catalysts were investigated by inductively coupled plasma atomic emission spectroscopy (ICP-AES), Brunauer-Emmett-Teller analysis (BET) Barrett-Joyner-Halenda analysis (Bill), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and powder X-ray diffraction (PXRD). The palladium content, surface area, pore volume and size of the catalysts are shown in Table 1. PXRD patterns of (a) Pd—Al.sub.2O.sub.3 and Al.sub.2O.sub.3; (b) 5% Pd-HT and HT; (c) Pd—MgO and MgO, and (d) Cu, Co, Ni and Fe doped Pd-x-HTs are shown in FIG. 4.

TABLE-US-00001 TABLE 1 Pd phases Pd/PdO identified Palladium Surface Pore Pore particle size by High loadingª area.sup.b volume.sup.b size.sup.c (nm) Resolution Catalyst (wt. %) (m.sup.2/g) (cm.sup.3/g) (nm) TEM PXRD TEM (HRTEM) Pd—Al.sub.2O.sub.3 1.95 83 0.116 8.8 3.7 ± 0.9 — Pd (111) Pd—MgO 2.30 45 0.588 46.5 3.5 ± 1.0 4.7 ± 0.8 could not be identified 5% Pd-HT 5.15 53 0.132 6.6 2.4 ± 0.4 — Pd (111) 1% Pd-HT 0.99 1.5 ± 0.5 Pd (111) PdO (110) .sup.aData from ICP-AES; .sup.bData from BET analysis; .sup.cData from BJH analysis.

[0072] Powder XRD of Pd—Al.sub.2O.sub.3 and Pd-HT (1% and 5%) only show reflections for the respective supports, indicating that the palladium is highly dispersed. The diffractogram of Pd—MgO, however, shows reflections associated with crystalline PdO phases, in addition to reflections characteristic of brucite nanocrystals. See FIG. 4.

[0073] XPS revealed significant differences in palladium surface speciation for the three catalysts. See FIG. 5. All catalysts comprise Pd.sup.2+ as the major species in addition to Pd.sup.0, with Pd—MgO and Pd—Al.sub.2O.sub.3 also exhibiting a low level of Pd.sup.4+. The Pd.sup.2+ surface concentration was highest for Pd—Al.sub.2O.sub.3, whereas Pd-HT shows the greatest Pd.sup.0 concentration, suggesting that the support acid-base properties impact Pd speciation.

[0074] Corresponding TEM images (see FIG. 6) reveal oxide agglomerates decorated with palladium nanoparticles typical of wet impregnation syntheses. Nanoparticles (NPs) dispersed over Al.sub.2O.sub.3 5% HT and 1% HT supports exhibited size and shape uniformity, with mean diameters of 3.7 nm, 2.4 nm and 1.5 nm, respectively. HRTEM of 1% Pd-HT show Pd(111) and PdO(110) phases, while Pd-Al.sub.2O.sub.3 shows only Pd(111). No lattice fringes were observable by TEM for Pd—MgO, and hence the nature of the corresponding Pd phase could not be directly assigned. However, XRD identified reflections consistent with PdO (101), (112) and (220) planes. TEM images and corresponding particle size distributions for the Fe, Co, Ni, Cu and Zn doped Pd-HTs are shown in FIG. 7.

[0075] The palladium catalysts were subsequently tested for alcohol coupling using heptanol 1 as the substrate at 180° C. The proposed mechanism for the process is shown in FIG. 3. Initial dehydrogenation produces aldehyde 6, which can either undergo ketal hydrogenolysis to form ether 2, alcohol coupling and dehydrogenation to form ester 3, or aldol condensation to form 7. Double transfer hydrogenation (TH) of 7 (with hydrogen atoms from alcohol dehydrogenation) forms the Guerbet alcohol 5. Alternatively, decarbonylation of 7 forms alkene 8, which can be hydrogenated to alkane 9 over palladium metal. The selectivity for Guerbet alcohol 5 is promoted by co-operative acid and base catalysis, as possible for Pd-HT. [0076] Control reactions with Pd-free MgO, HT and γ-Al.sub.2O.sub.3 supports showed no heptanol conversion. Pd—Al.sub.2O.sub.3 afforded>90% alcohol conversion in 48 hours, with diheptyl ether as the major product (2, 97% selectivity). Only trace heptyl heptanoate 3 was observed and no alkene products were observed. See FIG. 8 and Table 2 below. This high ether selectivity may be attributed to Pd-catalyzed ketal hydrogenolysis, proceeding via heptanal, or acid-catalyzed alcohol dehydration over strong Lewis acidic Pd.sup.δ+ sites. Palladium participation may be inferred from the fact that γ-Al.sub.2O.sub.3 affords no conversion with either heptanol, nor heptanal and heptanol.

TABLE-US-00002 TABLE 2 Conversion Catalyst 2 3 5 8 9 6 (%) 5% Pd—HT 2 11 23 3 12 0 51 1% Pd—HT 3 21 5 14 15 0 58 Pd/MgO 0 4 0 5 8 0 17 Pd/Al.sub.2O.sub.3 88 3 0 0 0 0 91 2% Ag—CuHT 0 24 25 0 0 50 Pd/C 0 78 4 83 Ru/HT 0 17 25 5 60 5% Pd—FeHT 0 9 60 1 6 1 99 5% Pd—CoHT 0 12 11 1 4 1 32 5% Pd—NiHT 0 2 2 1 1 0 5 5% Pd—CuHT 0 31 0 1 8 1 84 (<5% Cu) 5% Pd-CuHT 0 48 14 0 0 1 95

[0077] A comparable reaction with Pd-HT (1% and 5%) affords negligible quantity of the ether 2. Instead, near complete selectivity for products arising from initial alcohol dehydrogenation is observed (FIG. 3): 46% selectivity for Guerbet alcohol 5, 7% for 6-E-tridecene 8, 22% for tridecane 9 and 22% for ester 3 (with 50% alcohol conversion). Pd-HT is therefore significantly more efficient at facilitating the initial alcohol dehydrogenation than Pd—Al.sub.2O.sub.3, likely due to the higher concentration of palladium metal sites..sup.12 Product selectivity is dictated by the subsequent fate of heptanal: reaction with the parent alcohol and dehydrogenation forms the ester 3, whereas aldol condensation affords 7, which in turn unlocks access to saturated oxygenates 4 and 5, or alkenes/alkanes 8/9. The molar ratio of ester 3 to the observed aldol reaction products (5, 8 and 9) of 1:3.6 evidences that the strong basic sites in the HT support promote aldol condensation..sup.14 In contrast, the lack of basic sites and weak acidic sites on γ-Al.sub.2O.sub.3 promote ether 3 formation by either dehydration or ketal hydrogenolysis.

[0078] Since downstream hydrogenation is dependent on the rate of the upstream dehydrogenation, the selectivity for 5 versus hydrocarbons 8 and 9, (˜2:1 for Pd-HT) reflects the relative rates of re-hydrogenation versus decarbonylation of the reactively-formed aldol product 7. High selectivity to hydrocarbons requires faster decarbonylation, which is dependent on the Pd speciation.

[0079] Pd-HTs with Fe, Cu, Zn and Co dopants were also examined. Compared to the Pd-HT, Pd-ZnHT and Pd-FeHT afforded significantly more Guerbet alcohol 5, suggesting they are more efficient at transfer hydrogenation vs. decarbonylation. Pd-CuHT afforded primarily the ester 3, consistent with the expected lower basicity of the CuHT which disfavors aldol at the expense of dehydrogenation. Varying the amount of Cu in the Pd-CuHTs affected the selectivity significantly, showing that the dopant quantity can be used to further optimize selectivity.

[0080] Compared to the other catalysts, Pd—MgO was significantly less active for heptanol conversion (16%) but exhibited the highest selectivity for hydrocarbons 8 (29%) and 9 (50%), alongside ester 3. These observations suggest that Pd—MgO possesses few or weak Lewis acidic sites and limited palladium metal sites, accounting for slow dehydrogenation and no dehydration. These features also favor decarbonylation over re-hydrogenation of the aldol condensate 7.

[0081] In order to gain insights into catalyst design for this multi-step process, trends for the activity of the catalysts in the three steps (dehydrogenation, aldol condensation and decarbonylation) were investigated. Dehydrogenation activity was assessed from the total conversion, given that all products are derived from dehydrogenation, including ether 2 in the case of Pd—Al.sub.2O.sub.3. The trend for dehydrogenation follows Pd-Al.sub.2O.sub.3>5% Pd-HT>Pd—MgO. Activity for aldol condensation was assessed from reactions with heptanal at 100° C., where no decarbonylation occurs. Based on the net yields of aldol condensates at 2 hours, the trend for aldol condensation follows Pd-MgO˜5% Pd-HT>>Pd—Al.sub.2O.sub.3, indicating that the strong basic sites on MgO and HT are significantly more effective for aldol condensation than the Lewis acidic sites of Al.sub.2O.sub.3. Trends in decarbonylation activity were assessed from 2-hour reactions with heptanal at 150° C. based on percent of aldol product decarbonylated. Under these conditions, the decarbonylation trend follows Pd—Al.sub.2O.sub.3>Pd-HT>Pd—MgO. Comparing this trend to the lower selectivity observed for hydrocarbons 8 and 9 using Pd-HT vs Pd—MgO (Pd-HT: ˜3:2 ratio of Guerbet alcohol 5 to 8 and 9, vs Pd—MgO: no alcohol 5), it can be concluded that it is not that Pd-HT is a less efficient decarbonylation catalyst than Pd—MgO, but rather that it facilitates competing transfer hydrogenation of 7. The relative competence of the catalysts for the three steps (see FIG. 9) suggests that obtaining high activity and selectivity for the hydrocarbons requires a balanced catalytic efficiency for each of the three steps and limiting competing ketal hydrogenolysis and transfer hydrogenation.

[0082] To rationalize the ratio of alkene 8 versus alkane 9, and thus the ability of the catalyst to facilitate transfer hydrogenation of alkenes, the efficiency of the catalysts for the TH of 6-E-tridecene (8 in FIG. 3) using 2-propanol as hydrogen donor was investigated (see FIG. 10). Pd—MgO afforded ˜4-fold lower yield of alkane than Pd-HT (15% vs 62%), consistent with the lower fraction of 9:8 afforded by Pd—MgO in the heptanol reaction (1:1.7 for and 1:3.4 with Pd—MgO and Pd-HT respectively, see FIG. 8). This trend is also consistent with the faster heptanol conversion observed for Pd-HT compared to Pd—MgO. Pd—Al.sub.2O.sub.3 affords 51% yield of 9, suggesting it too is an efficient TH catalyst.

[0083] However, as previously discussed, Pd—Al.sub.2O.sub.3 favors formation of ether 2, and hence does not form hydrocarbons (see FIG. 8). In a similar experiment with aldol product 7, Pd-HT (1% and 5%) was found to be ˜2-fold more active than Pd—MgO for formation of alcohol 5. Thus, the selectivity of Pd—MgO for 8 and 9 over 5 is the result of its faster decarbonylation and slower TH relative to that of Pd-HT.

[0084] Elemental analysis of the post-reaction (used) Pd-HT shows a small loss of Pd and Mg (<10%). HRTEM images of this used (post reaction) catalyst do not indicate extensive morphological changes, but do show a small increase in mean particle size, from 2.4 to 3.4 nm nanoparticles, and a broadening of the particle size distribution. HRTEM identified two Pd phases: reduced Pd(111), and PdO(101). Powder XRD of the used Pd-HT does not show reflections of Pd phases. To determine whether decarbonylation was driven by soluble Pd species, poisoning tests were conducted with 1,10-phenanthroline as a scavenger of soluble Pd. Addition of 5 equivalents of 1,10-phenanthroline relative to total Pd resulted in a 22% reduction of activity, suggesting catalysis is predominantly heterogeneous for Pd-HT. A hot filtration test was also performed by sampling a portion of the reaction mixture after 3 hours and passing this through a 2 μm hot frit. Product concentrations of the filtrate did not change significantly over the following 5 hours, evidencing catalytically competent soluble species.

EXAMPLES

Materials and Characterization

[0085] Aluminium (III) nitrate nonahydrate (98%) and magnesium (II) nitrate tetrahydrate (98%) were obtained from ACROS Organics. Sodium hydroxide (97%) was obtained from VWR AMRESCO® Life Sciences; sodium carbonate (99.5%) was obtained from Fisher. Palladium (II) nitrate hydrate (40% palladium basis), palladium (II) acetate (98%) and 4-acetylbenzaldehyde (97%) were purchased from Sigma Aldrich. 1-Heptanol (>98%), heptanal (>95%) and 1,3,5-trimethoxybenzene (>98%) were obtained from TCI America. Isopropanol (HPLC grade) was obtained from Fischer Scientific, and tert-butanol (99.5%) was obtained from ACROS Organics.

[0086] Elemental analysis was carried out with inductively coupled plasma atomic emission spectroscopy (ICP-AES) on a Shimadzu ICPE-9820 Plasma Atomic Emission Spectrometer. Powder X-Ray Diffraction (PXRD) patterns were obtained using a Rigaku MiniFlex II X-Ray diffractometer, between 2θ of 0-80°. XPS data was collected both using MgKα (1253.6 eV) anode and monochromatic Al (1486.7 eV) X-ray sources at 240 W and 40 eV pass energy. Charge neutralization was carried out to minimize surface charging. Hydrocarbon C is binding energies were referenced at 284.8 eV. Pd 3d binding energies were confirmed by Mg anode due to the overlapping of Magnesium Auger Electron peaks (Mg KLL) with Pd 3d signals when Al anode was used. Binding energies of other elements were confirmed using the monochromatic Al X-ray source. Transmission Electron Microscope (TEM) images were collected on Talos F200X under 200 kV FEG with Ceta 16M camera. Fast Energy-dispersive X-ray spectroscopy (EDS) mapping was carried out using the built-in Silicon Drift Detector (Super-X EDS Detector). Nitrogen isotherms were measured on a Micrometric TriStar surface analyzer at liquid nitrogen temperature. Samples were degassed under vacuum at 150° C. for 3 hours prior to measurement. Surface area was calculated using the BET method.

[0087] NMR spectra were recorded on an Agilent 400 MHz spectrometer.

[0088] GC-MS analyses were performed on a Shimadzu QP2010S GC-MS fitted with a SHRXI-5MS column with dimensions L=30 m, ID=0.25 and DF=0.25, run in positive ion mode.

[0089] Temperature programmed desorption (TPD) measurements were performed using a Micromeritics AutoChem II. For determination of basic sites, the catalysts were first calcined by heating at a rate of 10° C. min.sup.−1 in flowing He (99.999%) and then held for 1 hour at 700° C. The release of gas from the catalyst during this step was monitored by the TCD detector. Following calcination, the sample was cooled to room temperature (RT) and exposed to flowing CO.sub.2 (Airgas, 99.99%) for 2 hours. The system was then purged with He carrier gas for 1 hour, or until a stable baseline was observed, to remove weakly adsorbed CO.sub.2. The temperature of the sample was then increased at a rate of 10 K min.sup.−1 from RT to 700° C. to desorb CO.sub.2 from the catalyst surface. For determination of acidic sites, the CO.sub.2 in the above method was replaced with a 10% NH.sub.3 (99.999%) in He (99.999%) mixture from Praxair with all other steps remaining the same.

Catalyst Synthesis

[0090] Pd—Al.sub.2O.sub.3 was synthesized via wet impregnation as follows. γ-Alumina (Aldrich, 1 g) was calcined at 450° C. in a muffle furnace for 12 hours, then suspended in deionized (DI) water (10 mL). Palladium nitrate (0.2153 g) was dissolved in 100 mL DI water at room temperature, then added dropwise to the stirred alumina suspension. The slurry was stirred for a further 2 hours, filtered through grade 410 filter paper, and the residue then dried for 12 hours at 110° C. The resulting solid was then calcined at 450° C. under static conditions for 12 hours and stored in a desiccator.

[0091] Pd-HT and doped Pd-xHT were synthesized via a continuous flow method. A nitrate salt solution of Mg(NO.sub.3).sub.2.Math.6H.sub.2O (3.590 g), Al(NO.sub.3).sub.3.Math.9H.sub.2O 6H.sub.2O (1.876 g), and Pd(NO.sub.3).sub.2.Math.xH.sub.2O (0.230 g) was dissolved in 70 mL of deionized (DI) water. A base solution comprising NaOH (0.040 mol) and Na.sub.2CO.sub.3 (0.0025 mol) was dissolved in 70 mL of DI water. The two solutions were mixed in a continuous fashion using syringe pumps (KD Scientific model 230) connected with a Y-connector at a flow rate of 4 mL/min. The solution mixture was dropped into a beaker containing 100 mL of DI water with stirring (200 rpm). The mixture was aged at 65° C. for 2 hours, then cooled to room temperature, filtered, and washed with DI water until the pH of the filtrate was neutral. The resulting powder was dried in air at 110° C. for 12 hours and stored in a desiccator.

[0092] Pd—MgO was synthesized via wet impregnation using a modified protocol reported by Akuri et al., Catal. Lett., 147, 1285-129, 2017. 600 mL of a 1M solution of Mg(NO.sub.3).sub.2.Math.6H.sub.2O was mixed with 800 mL of a 0.0312 M solution of NaOH in a continuous fashion using syringe pumps connected with a Y-connector at a flow rate of 4 mL/min. The solutions were deposited into a beaker containing 100 mL of DI water while stirring at 200 rpm. The pH of the solution was adjusted to 10±0.1 by addition of NaOH solution, and the mixture was aged at 60° C. for 1 hour. The suspension was further stirred at room temperature for 12 hours. The slurry was then filtered, and the resulting solid dried in a laboratory oven for 12 hours at 110° C. The solid was then calcined at 450° C. for 12 hours in a furnace. The calcined solid was suspended in DI water (10 mL). Palladium nitrate (0.1082 g, Aldrich) was dissolved in 10 mL DI water at room temperature, then added dropwise to the stirred suspension. After completing the addition, the solution was stirred for 2 hours. The slurry was then filtered, and the impregnated solid dried at 110° C. for 12 hours, calcined at 450° C. for 12 hours under static conditions, then stored in a desiccator.

[0093] FIG. 11 shows the differential enthalpy of adsorption as a function of coverage for the adsorption of CO.sub.2 on Cu, Ni. Fe and Zn doped hydrotalcite supports.

[0094] Table 3 shows the characterization of Pd-HTs and control HT (elemental composition and PXRD crystallographic parameters (a, c and L).

TABLE-US-00003 TABLE 3 Elemental composition, metal mol %ª Crystallographic parameters Catalyst Pd.sup.2+ Mg.sup.2+ Al.sup.3+ M.sup.2+/M.sup.3+ a (Å)* c (Å)* L (nm) 5% Pd—HT 5.15 70.1 25.1 2.98 3.052 23.07 10.4 1% Pd—HT 0.99 73.8 25.2 2.97 3.003 23.56 10.6 Mg—Al (HT) — 75.6 24.4 3.09 3.066 23.35 10.8 .sup.aMol % calculated as fraction of all metals present (Mg, Al, Pd); *a, the average cation-cation distance; *c, three times the distance from the center of one brucite-like layer to the next layer; L, the average crystallite size (calculated using Scherrer's formula).

[0095] FIG. 12 shows the HRTEM and crystal lattice of (a) 5% Pd-HT showing Pd (111); (b) 5% Pd-HT showing PdO (110) phase and (c) 1% Pd-HT showing Pd (111) phase.

[0096] FIG. 13 shows the temperature-programmed desorption profiles of four supported Pd catalysts (Pd—O, Pd—Al.sub.2O.sub.3, %% Pd-HT and 1% Pd-HT) using (a) CO.sub.2 and (b) NH.sub.3 as probes for solid base and acid sites, respectively.

Deoxygenative Heptanol Olefination

[0097] A 20-mL reaction tube was charged with a magnetic stir bar, catalyst (mass adjusted to provide 0.028 mmol Pd loading) and heptanol (Millipore Sigma, >98% 2 mL, 14.17 mmol). The mixture was sealed in a 20-mL reaction tube and heated to 180° C. and stirred under air for the time indicated on a Heidolph Radleys Carousel 12 Plus Reaction Station. The tridecane amount was quantified using GC-FID with 1,3,5-trimethoxybenzene as the internal standard. The yields for all other products were determined by .sup.1H NMR using 1,3,5-trimethoxybenzene as the internal standard. Qualitative product characterization was also characterized by GC-MS.

[0098] Table 4 shows the product yields and conversion for n-heptanol deoxygenative olefination over supported Pd catalysts. See FIG. 3 for product structures.

TABLE-US-00004 TABLE 4 2 3 5 8 9 y. sel. y. sel. y. sel. y. sel. y. sel. Conv. Catalyst % % % % % % % % % % % Pd—HT 3 5 21 61 5 9 14 25 15 27 58 ± 3 Pd—MgO 0 0 4 30 0 0 5 47 8 29 17 ± 2 Pd—Al.sub.2O.sub.3 88 97 3 3 0 0 0 0 0 0 91 ± 3 5% Pd—HT 2 4 11 29 23 47 3 6 12 25 51 ± 3 y.: Yield, sel.: Selectivity; Conditions: 2 mL n-heptanol, 0.2 mol % Pd-support, 180° C., 48 h. Yields and conversion based on GC-FID and NMR quantitation with 1,3,5-trimethoxybenzene as the internal standard. Standard errors are based on two runs.

##STR00001##

[0099] FIG. 14 shows the time course of decarbonylative olefination of heptanal (see Scheme 1) using (a) 5% Pd-HT, (b) Pd—Al.sub.2O.sub.3 and (c) Pd—MgO at 100° C.

[0100] FIG. 15 shows the time course of decarbonylative olefination of heptanal using (a) Pd-HT, (b) Pd—Al.sub.2O.sub.3 and (c) Pd—MgO at 150° C., under air. Trends in decarbonylation activity were assessed from each time point based on percent of total aldol product decarbonylated, calculated as follows:

[00001]$\mathrm{Total}\mathrm{aldol}\mathrm{product}\mathrm{decarbonylated}=\frac{\mathrm{Yield}\left(8\right)}{.Math.\mathrm{Yields}\left(7,8\right)}\times 100\%$

[0101] The effective decarbonylation yields are shown in Table 5 be: 10

TABLE-US-00005 TABLE 5 Effective Decarbonylation Yield % Reaction time (hr) .fwdarw. 2 8 24 Pd-HT 15 15 68 Pd-MgO 13 10 34 Pd-Al.sub.2O.sub.3 20 40 83

[0102] Table 6 shows the relative catalytic activity for the three-step reactions involved in deoxygenative coupling of heptanol. Dehydrogenation is calculated from conversion to products 2, 3, 5, 8 and 9 using conditions described in FIG. 3. Aldol condensation is calculated from the 2-hour yield of 7 at 100° C. (see FIG. 13). Decarbonylation yield is calculated from ratio of 8 to the sum of 7 and 8, as described above.

TABLE-US-00006 TABLE 6 Catalyst Dehydrogenation Aldol condensation Decarbonylation Pd-HT 58% 58% 62% Pd/MgO 17% 66% 34% Pd/Al.sub.2O.sub.3 88%  0% 83% 5% Pd-HT 50% 74% 68%

[0103] Table 7 shows the elemental composition of Pd-HT (5%) and used Pd-HT (ICP-AES)

TABLE-US-00007 TABLE 7 Mol (±RSD) % Catalyst Pd wt. % Pd Mg Al Pd-HT 5.15 4.62 ± 0.29 69.82 ± 0.31 25.56 ± 0.32 Used Pd-HT 4.65 6.80 ± 0.56 66.23 ± 0.15 26.97 ± 0.35

[0104] FIG. 16 shows (a) the TEM image of used Pd-HT (5%) and (b) the corresponding particle size distribution of used Pd-HT. The mean particle size: 3.3±0.5 nm. .sup.1H NMR data for products depicted in 4G. 3 are provided below,

##STR00002##

Product 2: di(n-heptyl) ether

[0105] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 3.39 (m, 4H), 1.22-1.64 (broad, 20H), 0.88 (t, 6H).

ESI-MS: 214 m/z.

[0106] ##STR00003##

Product 3: n-heptyl heptanoate.

[0107] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 4.01 (t, 2H), 2.25 (t, 2H), 1.57 (m, 4H), 1.32 (m, 14H), 0.85 (t, 6H).

##STR00004##

Product 5: 2-pentyl-1-nonanol

[0108] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 3.70-3.53 (m, 2H), 1.46-1.28 (broad, 22H), 0.90-0.86 (m, 6H).

##STR00005##

Product 6: heptanal

[0109] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 9.33 (s, 1H), 1.81 (t, 2H), 1.31-1.03 (m, 8H), 0.82 (t, 3H).

##STR00006##

Product 7: 2-pentyl-2-nonenal.

[0110] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 9.33 (s, 1H), 6.40 (t, 1H), 2.34 (m, 2H), 2.26-2.17 (m, 2H), 1.53-1.45 (m, 2H), 1.40-1.25 (m, 12H), 0.92-0.83 (t, 6H).

##STR00007##

Product 8: (6E)-Tridecene

[0111] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 5.40-5.33 (m, 2H), 2.03-1.97 (m, 4H), 1.30-1.20 (m, 14H), 0.94-0.86 (t, 6H).

##STR00008##

Product 9: Tridecane.

[0112] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 1.38-1.25 (m, 22H), 0.94-0.86 (t, 6H).

[0113] The description of the present embodiments of the invention has been presented for purposes of illustration but is not intended to be exhaustive or to limit the invention to the form disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art. As such, while the present invention has been disclosed in connection with an embodiment thereof, it should be understood that other embodiments may fall within the spirit and scope of the invention.

[0114] All patents and publications cited herein are incorporated by reference in their entirety.