Synthesis of Renewable C8-C10 Alkanes with Angelica Lactone and

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Synthesis of Renewable C8-C10 Alkanes with Angelica Lactone and Furfural from Carbohydrates Jilei Xu, Lin Li, Guangyi Li, Aiqin Wang, Yu Cong, Xiaodong Wang, and Ning Li ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.7b04797 • Publication Date (Web): 15 Mar 2018 Downloaded from http://pubs.acs.org on March 16, 2018

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ACS Sustainable Chemistry & Engineering

Synthesis of Renewable C8-C10 Alkanes with Angelica Lactone and Furfural from Carbohydrates Jilei Xu,† Lin Li,† Guangyi Li,† Aiqin Wang,†,‡ Yu Cong,† Xiaodong Wang,† Ning Li†,‡,*

†

State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, No. 457 Zhongshan Road, Dalian 116023, China

‡

iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), Dalian Institute of Chemical Physics, Chinese Academy of Sciences, No. 457 Zhongshan Road, Dalian 116023, China

* E-mail address of the corresponding author: [email protected] (N. Li).

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ABSTRACT: For the first time, proline based ionic liquids were reported as effective catalysts for the aldol condensation of angelica lactone with furfural, two platform compounds which were obtained by the hydrolysis-dehydration reactions of cellulose and hemicellulose. Among the investigated catalysts, a renewable ionic liquid which was prepared with biomass derived choline and L-proline (denoted as ChPro) demonstrated the highest activity. Over the ChPro catalyst, 86% carbon yield of C10 oxygenate was obtained under mild conditions (353 K, 1 h). After being hydrogenated over the Pd/C catalyst and hydrodeoxygenated under the promotion of the Pd-Cu/SiO2, the aldol condensation product of angelica lactone with furfural was transmuted into C8-C10 alkanes within the carbon chain range of jet fuel and diesel. Compared with the Cu/SiO2 and Pd/SiO2, the bimetallic Pd-Cu/SiO2 demonstrated higher activity and/or selectivity to C8-C10 alkanes for the hydrodeoxygenation of hydrogenated aldol condensation product. According to the characterizations of XRD, TEM, XPS and CO-FT-IR, the excellent catalytic performance of Pd-Cu/SiO2 can be comprehended by the Pd-Cu alloy particles formed during the preparation of this catalyst.

KEYWORDS: Lignocellulose, Diesel and jet fuel, Angelica lactone, Aldol condensation, Hydrodeoxygenation.

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INTRODUCTION Due to the great social concerns about the sustainable development and environment protection, the catalytic transformation of CO2 neutral and renewable biomass to fuels1-11 or chemicals12-23 has become an attractive research field. Lignocellulose is the cheapest and most abundant biomass. Jet fuel and diesel are two important transportation fuels. Recently, great effort has been made for the production of jet fuel and diesel range hydrocarbons from lignocellulosic platform compounds24-32. Angelica lactone33, 34 and furfural35 are two platform compounds manufactured by the hydrolysis-dehydration reactions of cellulose and hemicellulose, respectively. In our recent work36, it has been found that C8-C10 alkanes can be produced via the Mn2O3 catalyzed aldol condensation of angelica lactone and furfural, followed by hydrogenation over Pd/C catalyst and hydrodeoxygenation (HDO) over Pd-FeOx/SiO2 catalysts, respectively. This process has many advantages such as the simultaneous utilization of hemicellulose and cellulose (two major components of agricultural and forestry wastes), high reactivity of angelica lactone in the aldol condensation with furfural, the dispense with the acid-neutralization of aldol condensation product before HDO process, etc.. Proline is an α-amino acid which is used in the proteins biosynthesis. Choline is a water-soluable, non-toxic, cheap, and biodegradable vitamin. In present work, several L-proline based ionic liquids were first utilized as effective catalysts for the aldol condensation of angelica lactone with furfural. Among them, the renewable ChPro 3



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ionic liquid which was prepared with biomass derived L-proline and choline demonstrated the highest activity. The applicability of ChPro ionic liquid for the aldol condensation of angelica lactone with other lignocellulose derived aldehydes was also explored

under

solvent-free

conditions.

Subsequently,

the

3-(furan-2-ylmethylene)-5-methylfuran-2(3H)-one (that is compound 1A in Scheme 1) obtained from the ChPro catalyzed aldol condensation of angelica lactone with furfural was further hydrogenated (to transfer from solid to liquid state) and hydrodexoygenated to C8-C10 alkanes under solvent-free conditions. The Pd-Cu/SiO2 was utilized a selective and stable catalyst for the HDO of the hydrogenated aldol condensation products (i.e. compound 1B and 1C in Scheme 1). To understand the good HDO performance of Pd-Cu/SiO2, we characterized the investigated catalysts by several techniques.

Scheme 1. Strategy for the Synthesis of C8-C10 Alkanes with Angelica Lactone and Furfural in this Work.

4


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EXPERIMENTAL SECTION Catalyst Preparation. The proline-based ionic liquids used in the solvent-free aldol condensation reactions of angelica lactone were synthesized with L-proline and different acids or bases according to the methods described in literature37. Typically, 20 mL (10 mmol) of aqueous solution of choline (or other acids and bases) was slowly added into 20 mL of L-proline solution (1.2 g, 10.4 mmol) at 273 K. The mixture as obtained was magnetically agitated in dark for 48 h at room temperature. Subsequently, the water in the system was removed by vacuum distillation. An aqueous solution of acetonitrile and methanol (at a volumetric ratio of 9:1) was added to precipitate the excess L-proline which was removed by filtration. After removal the solvent in filtrate by evaporation, a light-yellow liquid was obtained. This liquid was further dried under vacuum for 48 h at 333 K and used in the activity tests. The Pd/C catalyst utilized in the hydrogenation of 1A was purchased from Aladdin Industrial Inc. The Pd content in the catalyst was 5% by weight (denoted as 5wt.%). The Pd/SiO2 and Cu/SiO2 catalysts for the HDO tests were obtained via conventional incipient wetness impregnation method using commercial SiO2 support and the PdCl2 or Cu(NO3)2 solution. For comparison, the theoretical Pd and Cu contents in these catalysts were fixed as 5wt.%. Analogously, the bimetallic Pd-Cu/SiO2 catalyst (in which the theoretical contents of both Pd and Cu were 2.5wt.%) was synthesized by co-impregnation method. The mixtures as obtained were firstly desiccated at 333 K for 12 h and calcined in air for 2 h at 623 K. Finally, the

5



solid products were reduced by hydrogen flow for 2 h at 623 K. After being cooled down to room temperature in hydrogen, the catalysts were passivated by 1% O2 in N2. Characterization of Catalysts. The XRD patterns of catalysts were acquired by a PANalyticl X’Pert-Pro powder X-ray diffractometer which was manipulated at 40 kV and 40 mA using Cu Kα radiation (λ = 0.1541 nm). Prior to characterization, these catalysts were pretreated with hydrogen flow for 2 h at 623 K. The high-resolution transmission electron microscopy (HRTEM) images of catalysts were collected by a JEM-2100F field emission electronic microscope. Prior to characterization, the catalysts were pretreated in hydrogen flow for 2 h at 623 K. The element distribution of the Pd-Cu/SiO2 catalyst was analyzed by a TEM (JEOL JEM-2100F) which was equipped with energy dispersive X-ray spectroscopy (EDX) instrument. Before microscopy examination, the sample was firstly suspended in ethanol by ultrasonic method then loaded on a holey carbon film supported by a nickel TEM grid. In-situ XPS analysis was carried out by an ESCALAB 250Xi spectrometer employing Al Kα X-ray (pass energy: 20 eV, analysis chamber base pressure > 1 × 10-8 Pa). Prior to analysis, the catalysts were pretreated with hydrogen flow for 2 h at 623 K. The FT-IR spectra were acquired at a spectral resolution of 4 cm-1 and an accumulation of 120 scans by a Bruker spectrometer (EQUINOX55) with a MCT detector. CO was used as the probe molecule. Prior to the tests, the samples were pretreated with hydrogen flow for 2 h at 623 K, evacuated for 1 h, and cooled down to 6


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room temperature. At this time, the spectrum was acquired and used as the background. The CO adsorption was carried out at 2 kPa for 5 min. The excess CO was removed from the system by evacuation for 0.5 h. Finally, the spectra were acquired and subtracted with the background. Activity Test. The aldol condensation of angelica lactone with furfural was carried out in a batch reactor which was heated by water bath to ensure the temperature uniformity. For each test, 10 mmol angelica lactone, 10 mmol furfural and 1 mmol catalyst were used. The mixtures were magnetically stirred (rotation speed: 800 rpm) for 1 h at 353 K (on the basis of Figures S1-S3, these are the optimized reaction conditions for the ChPro catalyst). Subsequently, the reactor was taken out from water bath and quenched to room temperature using ice water. After being diluted with methanol, the products were quantitatively analyzed by an Agilent 1100 HPLC which was equipped with a autosampler, a ZORBAX SB-C18 column (4.6 × 150 mm, 5 µm) and a refractive index detector (RID) using a methanol and water mixture (at a volumetric ratio of 7:3) was as the mobile phase (flow rate: 0.6 mL min-1). The column temperature was set as 303 K. Based on our observation, the proline-based ionic liquids exist as liquids at room temperature. Under the investigated conditions, they are miscible with reactants. Therefore, these proline-based ionic liquids should be considered as homogeneous catalysts. According to the HPLC chromatogram and NMR spectra illustrated in Figures S4 and S5 of supporting information, 1A was obtained as the only identfied product from the aldol condensation of angelica lactone with furfural. At room temperature, this 7



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compound is a solid. To increase its fluidity, we hydrogenated it before the hydrodeoxygenation (HDO) tests which were conducted under solvent-free conditions. The 1A was hydrogenated using the Pd/C catalyst under the system pressure of 4 MPa. Before the test, the Pd/C catalyst (1.2 g) was prereduced with hydrogen flow for 0.5 h at 433 K. Subsequently, the 10wt.% methanol solution of 1A (which has been purified by vaccum distillation) was fed from bottom into the tublar reactor with a HPLC pump along with a hydrogen flow. After passing through the tublar reactor, the products spontaneously turned into two phases in a stainless steel gas-liquid separator. The gas phase products were analyzed on-line by an Agilent 6890N GC equipped with a thermal conductivity detector (TCD) and a flame ionization detector (FID). The liquid phase products were accumulated in the seperator, drained periodically, and analyzed by another Agilent 7890A GC equiped with a FID. Based on our analysis (see Figures S6 and S7 in supporting information), the

1A

was

almost

quantitatively

3-(5-hydroxypentyl)-5-methyldihydrofuran-2(3H)-one

converted

to and

3-(2-hydroxypentyl)-5-methyldihydrofuran-2(3H)-one (i.e. 1B and 1C in Scheme 1) under the investigated conditions, no alkane or C-C cleavage product was identified in the gas phase and liquid phase products. After vacuum distillation (to remove the methanol), we obtained a mixture of 1B and 1C. At room temperature, this mixture is a liquid (see Figure S8 in supporting information). Therefore, it can be directly used for the HDO tests.

8


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The solvent-free HDO of the hydrogenated 1A (i.e. a mixture of 1B and 1C) was conducted by a fixed-bed continuous flow reactor under a system pressure of 6 MPa. Prior to the activity tests, the HDO catalysts (1.8 g) were pretreated with hydrogen flow for 0.5 h at 623 K. From the bottom of the tublar reactor, the hydrogenated 1A (i.e. a mixture of 1B and 1C) was introduced by a HPLC pump along with hydrogen flow. After passing through the tublar reactor, the products spontaneously turned into two phases in a stainless steel gas-liquid separator. The gas phase products passed through a back pressure regulator and were analyzed by an on-line Agilent 6890N GC which was equipped with a TCD and a flame ionization detector FID. The liquid phase products were accumulated in the seperator, drained periodically, and analyzed by another Agilent 7890A GC equiped with a FID. RESULTS AND DISCUSSION Characterization of Catalysts. In the XRD patterns of Pd/SiO2 and Cu/SiO2 catalysts (see Figure 1), only the peaks of metallic Pd (or Cu) phase and SiO2 support were observed. In contrast, there is a new peak between 40.1o and 43.3o in the XRD pattern of Pd-Cu/SiO2. According to literature about Pd-Cu phase diagram38, the composition and the preparation temperature of Pd-Cu/SiO2 catalyst, this peak should be attributed to a PdCu phase with bcc structure. Compared with the metallic Pd or Cu peaks in the XRD patterns of Pd/SiO2 and Cu/SiO2, this peak is evidently weaker and broader. According to literature39, 40, this phenomenon may be rationalized by the generation of smaller Pd-Cu alloy particles during the preparation of the Pd-Cu/SiO2 catalyst. 9



Cu/SiO2 Pd/SiO2 Pd-Cu/SiO2 Intensity (a.u.)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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Pd 03-065-2867 Cu 01-085-1326 10

20

30

40

50 o 2θ ( )

60

70

80

Figure 1. XRD patterns of the Pd/SiO2, Cu/SiO2 and Pd-Cu/SiO2 catalysts. From the HRTEM images of Pd/SiO2 and bimetallic Pd-Cu/SiO2 catalysts illustrated in Figure 2, we can see that the mean size of metallic particles on the Pd-Cu/SiO2 (3.9 nm) is evidently smaller than the one over the monometallic Pd/SiO2 catalyst (5.5 nm). Meanwhile, it is also noticed that the metallic particle lattice parameter on the bimetallic Pd-Cu/SiO2 catalyst (0.21 nm) is lower than the one on the Pd/SiO2 catalyst (0.22 nm). These results confirm the generation of smaller Pd-Cu alloy particles on Pd-Cu/SiO2 catalyst. To further verify this speculation, we characterized the Pd-Cu/SiO2 catalyst by energy dispersive X-ray (EDX) spectroscopy. Taking Figures S9 and S10 in supporting information for example, there is always Pd species accompany with Cu species on the randomly chosen areas (or particles) of Pd-Cu/SiO2 catalyst although the atomic ratios of Pd to Cu are different from each other. This result means that the Pd and Cu species on the bimetallic Pd-Cu/SiO2 catalyst are mixed at the atomic level. 10


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25

(a)

Mean size = 5.5 nm

0.22 nm Pd{111}

Count

20 15 10 5 0

(b)

4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 Particle size (nm) Mean size = 3.9 nm

25

0.21 nm PdCu{111}

20 Count

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


15 10 5 0

1

2

3 4 5 6 Particle size (nm)

7

8

Figure 2. HRTEM images of the Pd/SiO2 (a) and Pd-Cu/SiO2 (b) catalysts. We also characterized the catalysts by XPS. From the results illustrated in Figure 3, the binding energies of Cu 2p on the Pd-Cu/SiO2 are slightly lower than those on the Cu/SiO2. In contrast, the binding energies of Pd 3d on Pd-Cu/SiO2 are higher than those on Pd/SiO2. Based on these results, we think that there should be a strong interaction between the Pd and Cu species on the bimetallic Pd-Cu/SiO2 catalyst.

11



932.5

PdCu/SiO2 Intensity (a.u.)

Intensity (a.u.)

Cu/SiO2

952.3

932.1

951.8

Intensity (a.u.)

960 955 950 945 940 935 930 925 960 955 950 945 940 935 930 925 B.E.(eV) B.E.(eV) 335.3 Pd/SiO2 PdCu/SiO2 334.9 340.2 340.6

Intensity (a.u.)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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345

342

339 336 B.E.(eV)

333

330

345

342

339 336 B.E.(eV)

333

330

Figure 3. Cu 2p and Pd 3d XPS spectra of the Pd/SiO2, Cu/SiO2 and Pd-Cu/SiO2 catalysts.

From the FT-IR spectra of Pd/SiO2 catalyst using CO as the probing molecule (see Figure 4a), we can see two peaks at 2088 cm-1 and 1966 cm-1. The peak at 2088 cm-1 can be attributed to the linearly bonded CO on Pd sites, while the peak at 1966 cm-1 can be assigned to the bridge adsorbed CO on the Pd sites41, 42. The intensity of peak at 1966 cm-1 is higher than the peak at 2088 cm-1, indicating the bridge adsorbed CO is predominant over the Pd/SiO2 catalyst. Three evident changes were noticed after the doping of Pd/SiO2 catalyst with copper. 1) Appearance of a new brand at the wavenumber of 2132 cm-1. According to literature43, this peak can be attributed to the 12


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CO which is linearly bonded on copper sites. 2) The CO adsorption bands on Pd sites red shifted to lower wavenumbers, which can be attributed to the strong interaction between the palladium and copper species44, 45. 3) The ratio of the linearly to bridge bonded CO decreased. This can be noticed from the intensity ratio of the peaks at 2100 cm-1 and 1950 cm-1. In some literature41, it was found that CO is usually bonded on monocrystalline Pd surface in bridged form, while linearly bonded CO was noticed on smaller Pd particles because of the higher percentage of low-coordinated Pd atoms. On the basis of FT-IR results, we believe that the doping of copper species (or the generation of Pd-Cu alloy) makes surface Pd atoms more isolated and weakens the interaction between them. Consequently, the linearly adsorbed CO becomes the predominant surface species on bimetallic Pd-Cu/SiO2 catalyst.

13



(a)

Absorbance (a.u.)

1966

Pd/SiO2

2088

2400

2200

(b)

Absorbance (a.u.)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

2400

2000 1800 -1 Wavenumber (cm )

1600

Pd-Cu/SiO2

2076

1954 2132

2200

2000 1800 -1 Wavenumber (cm )

1600

Figure 4. FT-IR spectra of the Pd/SiO2 and Pd-Cu/SiO2 catalysts using CO as the probing molecule.

Activity Test. Solvent-free aldol condensation. In this work, we explored the catalytic performances of several proline-based ionic liquids for the aldol condensation of angelica lactone with furfural. Among them, the renewable ChPro 14


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ionic liquid which was synthesized with biomass derived choline and proline demonstrated the best performance (see Table 1). Over it, high furfural conversion (95.6%) and good carbon yield of 1A (86.2%) were reacheded after the reacting at 353 K for 1 h without removing the water produced during the reaction, which can be explained by the the conjugated structure of 1A. To the best of our knowledge, this is the first report about the ionic liquid catalyzed aldol condensation of angelica lactone with furfural. Compared with the Mn2O3 catalyst reported in our previous work, the ChPro ionic liquid exhibits higher efficiency (0.0956 mol gcatalyst-1 h-1 vs. 0.0158 mol gcatalyst-1 h-1) for the aldol condensation of angelica lactone with furfural. This can be comprehended because ChPro ionic liquid is a homogenous catalyst. Based on the high catalytic efficiency, selectivity and renewability of ChPro ionic liquid, we believe that it will be a good catalyst in future application. According to literature about similar reaction systems46, 47, the reaction mechanism for the ChPro catalyzed aldol condensation of angelica lactone with furfural was proposed in Scheme 2. Firstly, an imine structure is formed by the reaction of ChPro with angelica lactone, followed by dehydration. After the isomerization of imine structure, the carboanion attacks the carbonyl group of furfural which has been activated by the choline-based anion. After being separated with the ChPro catalyst, the aldol reaction product is dehydrated to 1A. Based on this reaction mechanism, the excellent performance of ChPro ionic liquid can be rationalized by the shorter alkyl group in choline which decreases the steric hindrance and makes it more accessible to furfural. Moreover, the presence of -OH group on choline makes this catalyst more 15



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compatible to reactants (i.e. angelica lactone and furfural), which may be another possible explanation for the excellent performance of ChPro ionic liquid. Table 1. Furfural Conversions, the Carbon Yields and Selectivities of 1A under the Catalysis of Different Proline-Based Ionic Liquidsa Catalystb

Furfural

Carbon yield of 1A

Selectivity of 1A

conversion (%)

(%)c

(%)

ChPro

95.6

86.2

90.2

N(C4H9)4Pro

87.5

53.0

60.6

N(C2H5)4Pro

83.1

73.5

88.5

P(C4H9)4Pro

88.7

46.6

52.5

ProHSO4

84.2

1.1

1.3

ProH2PO4

77.9

57.8

74.2

ProOAc

100

77.5

77.5

a

Reaction conditions: 10 mmol furfural, 10 mmol angelica lactone, 1 mmol catalyst;

353 K, 1 h. b

The ChPro, N(C4H9)4Pro, N(C2H5)4Pro, P(C4H9)4Pro, ProHSO4, ProH2PO4 and

ProOAc account for the proline-based ionic liquids which were synthesized with L-proline

and

choline,

tetrabutylammonium

hydroxide,

tetraethylammonium

hydroxide, tetraethylphosphine hydroxide, H2SO4, H3PO4, acetic acid, respectively. 16


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c

According our analysis, 1A was detected as the only product from the aldol

condensation of angelica lactone with furfural. The differences between the furfural conversions and the 1A carbon yields should be attributed to the coke which was formed by the the intermolecular Diels-Alder reaction of 1A.48

Scheme 2. Possible Mechanism for the ChPro Ionic Liquid Catalyzed Aldol Condensation of Angelica Lactone with Furfural.

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Table 2. Conversions of Aldehydes and the Carbon Yields of Aldol Condensation Products from the Reactions of Angelica Lactone with Various Lignocellulosic Aldehydesa Productb

Reactant

O

a

Conversion (%)c

Carbon yield (%)

100

63.2

100

75.3

100

46.6

100

96.5

O

Reaction conditions: 10 mmol furfural, 10 mmol angelica lactone, 1 mmol ChPro

catalyst; 353 K, 1 h. b 1

H-NMR and

13

C-NMR spectra of the aldol condensation products were shown in

Figures S11-S14 of supporting information. c

The differences between the conversions of aldehydes and the carbon yields of aldol

condensation products should be attributed to the coke formed by the Diels-Alder reaction of aldol condensation products.48

Subsequently, we also explored the solvent-free aldol condensation of angelica lactone

with

other

lignocellulose

derived

18


aldehydes

(such

as

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5-hydroxylmethylfurfural49-51,

5-methylfurfural50,

benzene

formaldehyde52

and

butanal53) using ChPro as the catalyst. Under solvent-free conditions (353 K, 1 h), high carbon yields of C9-C12 oxygenates were obtained from the aldol condensation reactions of angelica lactone with investigated aldehydes (see Table 2). The adol condensation products as obtained can be utilized as the precursors in the production of renewable jet fuel and diesel. Hydrodeoxygenation (HDO). Finally, we explored the HDO of 1A to jet fuel and diesel range alkanes. As we mentioned previously, this process contains two stages. In the first stage, 1A was liquefied by hydrogenation over a commerical Pd/C catalyst. The hydrogenated 1A (i.e. a mixture of 1B and 1C) is a liquid at room temperature, which makes it feasible for the solvent-free HDO tests. In the second stage, we explored the activities of the Pd/SiO2, Cu/SiO2 and Pd-Cu/SiO2 catalysts for the HDO of 1B and 1C which were obtained in the first stage. According to our analysis (see Figure S15), the 1B and 1C were totally transformed into alkanes after being hydrodeoxygenated over the Pd/SiO2 and Pd-Cu/SiO2 catalysts at 623 K and 6 MPa. In contrast, 1B and 1C were only partially hydrodeoxygenated to oxygenates over the Cu/SiO2 catalyst. It is very interesting that the carbon yield of C8-C10 alkanes over the bimetallic Pd-Cu/SiO2 catalyst is higher than that over the Pd/SiO2 catalyst (see Figure 5). Based on the excellent performance and the lower Pd content (2.5wt.% vs. 5wt.%), we think the Pd-Cu/SiO2 is a promising catalyst.

19



C1-C4 light alkanes

100

Carbon yield (%)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

C5-C7 gasoline range alkanes

C8-C10 diesel and jet fuel range alkanes

80 60 40 20 0 Pd/SiO2

Pd-Cu/SiO2

Cu/SiO2

Figure 5. Carbon yields of different alkanes from the solvent-free HDO of hydrogenated 1A over the Pd/SiO2, Pd-Cu/SiO2 and Cu/SiO2 catalysts. Reaction conditions: 623 K, 6 MPa; 1.8 g catalyst, hydrogen flow rate: 120 mL min-1, liquid feedstock flow rate: 0.033 mL min-1.

From the carbon distributions of alkane products over the Pd/SiO2 and Pd-Cu/SiO2 catalysts (see Figure 6), it is noticed that the selectivities of C9 and C10 alkanes over the Pd-Cu/SiO2 are much higher than those over the Pd/SiO2. According to Table S1, higher carbon yield of C8-C10 branched alkanes was acheived from the HDO of hydrogenated 1A over the bimetallic Pd-Cu/SiO2 catalyst (28.8%) than that over the Pd/SiO2 catalyst (9.3%), which should be considered as another advantage for Pd-Cu/SiO2 catalyst. It is well known that branched alkanes have lower freezing

20


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points than those of straight alkanes. Therefore, branched alkanes are advantagous when they are used as jet fuel or diesel under cold conditions.

Carbon distribution (%)

50

(a)

Pd/SiO2

40 30 20 10 0 C1

C2

C3

C4

50 (b) Carbon distribution (%)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


C5

C6

C7

C8

C9

C10

C7

C8

C9

C10

Pd-Cu/SiO2

40 30 20 10 0 C1

C2

C3

C4

C5

C6

Figure 6. Carbon distributions of different alkanes from the solvent-free HDO of hydrogenated 1A over the Pd/SiO2 and Pd-Cu/SiO2 catalysts. Reaction conditions: 623 K, 6 MPa; 1.8 g catalyst, hydrogen flow rate: 120 mL min-1, liquid feedstock flow rate: 0.033 mL min-1.

21



Scheme 3. Possible Reaction Pathways for the Generation of Different Alkanes from the Solvent-Free HDO of 1B and 1C.

Based on our analysis about gas phase products, CO and CO2 were identified in the gas phase product from the HDO of hydrogenated 1A. In comparsion with the monometallic Pd/SiO2 catalyst, significantly lower amounts of CO and CO2 were produced over the bimetallic Pd-Cu/SiO2 catalyst. According to Table S2 in supporting information and the reaction pathways proposed in Scheme 3, these results can be explained because the dopping of Cu significantly supresses the decarbonylation and decarboxylation during the HDO of the 1B and 1C over Pd/SiO2. The inhibiting effect of Cu on the decarbonylation over Pd/SiO2 has been proved by Resasco et al. using 2-methylpentanal as the reactant54. In present work, the inhibiting effect of Cu on decarboxylation was further verfied by the HDO of ethyl 22


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Page 23 of 39

laurate over the Pd/SiO2 and Pd-Cu/SiO2 catalysts (see Figure 7 and Figure S16 in supporting information). Concurring with expectations, the molar ratio of dodecane/undecane in the HDO product over the Pd-Cu/SiO2 is evidently higher than the one over the Pd/SiO2 catalyst. According to these results, we believe that the dopping of Cu species really restrains the decarboxylation over the Pd/SiO2 catalyst.

Undecane

Dodecane

100

Carbon yield(%)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


80 60

40 20 0 Pd/SiO2

Pd-Cu/SiO2

Figure 7. Carbon yields of different alkanes from the solvent-free HDO of ethyl laurate over the Pd/SiO2 and Pd-Cu/SiO2 catalysts. Reaction conditions: 623 K, 6 MPa; 1.8 g catalyst, hydrogen flow rate: 120 mL min-1, liquid feedstock flow rate 0.033 mL min-1.

The inhibiting effect of copper species on the decarbonylation and decarboxylation can be rationalized because the generation of Pd-Cu alloy changes the carbonyl group adsorption mode. On the basis of literature54, 55, the adsorption of aldehyde on metal 23



sites may lead to the formation two kinds of surface species (see Figure 8). One surface species is η2-(C, O). In this species, two adjacent metal sites will be interacted with the O and C atoms of carbonyl group. Another surface species is η1-(O) where the carbonyl group is adsorbed to one metal site by the lone pair of oxygen atom. At high temperature, the η2-(C, O) species can be converted into a more stable acyl surface species which may decompose to CO and alkanes via route 2 (that is decarbonylation reaction). On the contrary, the surface species of η1-(O) may be hydrogenated to alcohol which can be further hydrodeoxygenated to alkanes (route 1). In the earlier work of Resasco group54, 55, it has been suggested that the adsorption of aldehydes on surface Pd sites tend to form the surface species of η2-(C, O). That may explain why significant decarbonylation was observed in the HDO of aldehydes (e.g. 2-methylpentanal) over Pd/SiO2 catalyst. Based on the FT-IR results, the doping of Pd/SiO2 with copper species reduces the coordination number of Pd-Pd on the catalyst. As the result, the Pd sites on Pd-Cu/SiO2 catalyst are more isolated than those on Pd/SiO2 catalyst. This was verified by FT-IR result (the linearly adsorbed CO predominates over bridge adsorbed CO on the surface of bimetallic Pd-Cu/SiO2). Similarly, the η2-(C, O) species that requires two adjacent Pd sites will generated by the adsorption of carbonyl compounds over the Pd/SiO2 catalyst. Such an adsorption model will be inhibited via the doping of Pd/SiO2 catalyst with copper species (which can be comprehended by the lower coordination number of Pd-Pd on the catalyst). Therefore, less decarbonylation was observed over the Pd-Cu/SiO2 catalyst. The impact of copper species can be comprehended by the dilution effect due to the 24


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generation of Pd-Cu alloy. Furthermore, we can also comprehend the inhibiting effect of copper species on decarboxylation because the aldehyde has been suggested as the intermediate during the hydrogenation of carboxylic acid or ester to their corresponding alcohol and alkanes56, 57.

H Route 1

RH + CO η2-(C,O)

Metal surface Route 2

H η1-(O)

3H

RCH3

Figure 8. Two reaction pathways for the deoxygenation of aldehyde over metal catalyst.

Another possible cause for the less C-C cleavage in the HDO of 1B and 1C over the Pd-Cu/SiO2 is that the Pd-Cu alloy formed on the catalyst is less active than Pd for the hydrogenolysis C-C bond. As we can see from Figure 6, small amount of C3-C5 alkanes were detected in the HDO product over Pd/SiO2 catalyst, while these alkanes are undetectable in the HDO product over Pd-Cu/SiO2 catalyst. For real application, we also checked the stabiltiy of the Pd-Cu/SiO2 catalyst in the HDO of hydrogenated 1A (i.e. a mixture of 1B and 1C). From the result illustrated in Figure 9, it is found that the Pd-Cu/SiO2 is a stable catalyst. No significant deactivation was noticed during the 11 h continusous test.

25



100 80

Carbon yield (%)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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C1-C4 light alkanes (%)

60

C5-C7 gasoline range alkanes (%) C8-C10 diesel and jet fuel range alkanes (%)

40 20 0 2

4

6 8 Time on stream (h)

10

12

Figure 9. Carbon yields of different alkanes from the solvent-free HDO of hydrogenated 1A over the Pd-Cu/SiO2 catalyst as the function of time on stream. Reaction conditions: 623 K, 6 MPa; 1.8 g catalyst, hydrogen flow rate: 120 mL min-1, liquid feedstock flow rate 0.033 mL min-1.

CONCLUSIONS ChPro ionic liquid was discovered as an efficient catalyst for the solvent-free aldol condensation of angelica lactone with furfural. Over it, 86.2% carbon yield of C10 oxygenate can be reached under mild reaction conditions. This catalyst is also very active for the aldol condensation of angelica lactone with other lignocellulose derived aldehydes. The aldol condensation product of angelica lactone with furfural can be selectively converted to C8-C10 alkanes by Pd/C catalyzed hydrogenation, followed by 26


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the solvent-free HDO over the bimetallic Pd-Cu/SiO2 catalyst. The doping of copper inhibits the C-C cleavage reactions (decarbonylation, decarboxylation and hydrogenolysis) over the Pd/SiO2 catalyst, which leads to the higher carbon yield or selectivity of C8-C10 alkanes from the HDO process. On the basis of the characterization results, the beneficial effect of copper was rationalized by the generation of Pd-Cu alloy during the preparation of Pd-Cu/SiO2 catalyst.

27



ASSOCIATED CONTENT Supporting Information. The following files are available free of charge. Experimental details. Detail information for the aldol condensation of angelica lactone under different reaction conditions. Copies of HPLC, GC chromatograms and NMR spectra. (PDF) AUTHOR INFORMATION Corresponding Author *N.L.: [email protected].

Notes The authors declare no competing financial interests.

ACKNOWLEDGMENT This work was supported by the National Natural Science Foundation of China (no. 21603221; 21690080; 21690082; 21776273), the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB17020100), the National Key Projects for Fundamental Research and Development of China (2016YFA0202801), Dalian Science Foundation for Distinguished Young Scholars (no. 2015R005), Department of Science and Technology of Liaoning Province (under contract of 2015020086-101). Dr. Xu appreciates the Postdoctoral Science Foundation of China (2015M580235) and the dedicated grant for methanol conversion from DICP for funding this work.

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For Table of Contents Use Only

Bio-derived aldol condensation catalyst

Cost-effective and selective hydrodeoxygenation catalyst

A whole biomass reaction system

ChPro and Pd-Cu/SiO2 were first reported as promising catalysts for the synthesis of C8-C10 alkanes with angelic lactone and furfural.

39


Synthesis of Renewable C8-C10 Alkanes with Angelica Lactone and

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