Highly selective hydrogenation of furfural to cyclopentanone over a

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Highly selective hydrogenation of furfural to cyclopentanone over a NiFe bimetallic catalyst in a methanol/water solution with a solvent effect Pei Jia, Xiaocheng Lan, Xiaodan Li, and Tiefeng Wang ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.9b02112 • Publication Date (Web): 20 Aug 2019 Downloaded from pubs.acs.org on August 21, 2019

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ACS Sustainable Chemistry & Engineering

Highly selective hydrogenation of furfural to cyclopentanone over a NiFe bimetallic catalyst in a methanol/water solution with a solvent effect Pei Jia, Xiaocheng Lan, Xiaodan Li, Tiefeng Wang* Beijing Key Laboratory of Green Reaction Engineering and Technology Department of Chemical Engineering, Tsinghua University, Shuangqing Road No. 30, Haidian District, Beijing 100084, People’s Republic of China * Corresponding Author E-mail: [email protected] (T. F. Wang)

KEYWORDS: furfural, cyclopentanone, hydrogenation, bimetallic, solvent effect

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ABSTRACT

The aqueous phase hydrogenation of furfural to cyclopentanone over a NiFe bimetallic catalyst was investigated for the efficient utilization of biomass-derived compounds. Catalyst characterization by XRD, EDS mapping and TPR revealed significant synergetic effects in the NiFe/SBA-15 catalyst. With NiFe/SBA-15, cyclopentanone selectivity was increased to 78.4% from 46.1% with Ni/SBA-15. The use of different supports showed that weak acidity favors cyclopentanone formation. The solvent played an important role: methanol/water solutions with different compositional ratios gave significantly changed product distributions. With pure methanol, and methanol-dominated and water-dominated solutions, respectively, the main product was furfuryl alcohol, tetrahydrofurfuryl alcohol and cyclopentanone. Furfural in the water inhibited THFA formation, which led furfural to preferentially produce cyclopentanone. At the optimized reaction temperature, NiFe/SBA-15 in water gave 99.8% furfural conversion and 90% cyclopentanone yield at 300 min, which was much better than most reported non-precious metal catalysts.


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Introduction The depletion of fossil fuels and petroleum chemicals have challenged humanity with an energy crisis and environmental pollution [1-3]. To solve these problems, the utilization of renewable energy resources as chemical feedstock for sustainable development is being developed. Biomass is a renewable resource, and biomass-derived platform compounds can be converted to many valuable chemicals [4, 5]. Furfural is an important biomass platform compound used to produce a wide range of derivatives and downstream products such as furfuryl alcohol (FFA), tetrahydrofurfuryl alcohol (THFA), 2-methylfuran, tetrahydrofuran and pentadiol by hydrogenation using a suitable catalyst [1, 6, 7]. With water as the solvent, cyclopentanone (CPO) can be produced by the aqueous phase hydrogenation rearrangement of furfural [8]. CPO is an important intermediate in the synthesis of medicine, perfume, pesticides, fungicides, rubber chemicals and fragrance chemicals [9, 10]. In current industrial practice, CPO is produced by the pyrolysis of adipic acid and its derivatives or the oxidation of cyclopentene [11]. These processes use petrochemicals as feedstock and have high energy consumption. Recently, a green route for the preparation of CPO was developed that used biomass-derived furfural as feedstock. Hronec et al. [12-16] first described the aqueous phase conversion of furfural to CPO using precious metal catalysts such as Pt/C, Pd/C, Ru/C and Pd-Cu/C. CPO yield was 76.5% over Pt/C and 92% over Pd-Cu. They deduced a reaction pathway (Scheme 1) for the transformation of furfural to CPO in which CPO, FFA and THFA are produced in a hydrogenation rearrangement reaction. Furfural is first hydrogenated to FFA, which is then converted to THFA or CPO by competitive pathways. Byproduct THFA is produced by the further hydrogenation of FFA. CPO


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is produced by using water to form intermediate 4-hydroxy-2-cycloentenone (4-HCP), which is hydrogenated to CPO.

Scheme 1. Reaction pathway for the hydrogenation of furfural to CPO in water.

Other precious metal catalysts, such as Ru-based [17, 18], Pd-based [16], Pt-based [19] and Aubased [8] catalysts were also studied for the hydrogenation of furfural to CPO. Au/TiO2-A [8] and Ru/CNTs [18] gave high activity and good selectivity. However, the use of precious metals is hindered by their high cost and limited availability. Recently, several non-precious metal catalysts were investigated for the conversion of furfural to CPO. Cu-based [10, 11, 20-25] and Ni-based [26, 27] catalysts showed promising performance. CPO selectivity was relatively high over Cu-based catalysts, while Ni-based catalysts showed good activity. Nevertheless, it remains difficult to get a satisfactory CPO selectivity at high conversion with these catalysts. Therefore, there is still a need to develop highly selective and active non-precious metal catalysts for the efficient conversion of furfural to CPO. Bimetallic catalysts were reported to give better performance than monometallic catalysts [2830]. This work reports the development of a non-precious bimetallic catalyst with high selectivity and activity for the aqueous phase hydrogenation of furfural to CPO. We studied Ni


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monometallic and NiFe bimetallic catalysts with low metal loadings supported on SBA-15. We also studied the effects of the oxide support and solvent. With solutions of methanol and water as the solvent, we could effectively control the product distribution by changing the methanol/water ratio. At the optimum reaction temperature, a high CPO yield of 90% was obtained with a NiFe/SBA-15 catalyst.

Experimental The Ni monometallic and bimetallic supported catalysts were prepared by incipient wetness coimpregnation to get the best bimetallic bond interaction [31, 32]. X-ray diffraction (XRD), N2 adsorption, hydrogen temperature programmed reduction (H2-TPR), temperature programmed desorption of ammonia (NH3-TPD), and transmission electron microscopy (TEM) were used to characterize the catalysts. The supported catalysts were tested using the liquid phase hydrogenation of furfural with the products analyzed by GC. Complete information of catalyst preparation, evaluation and characterization are given in Supporting Information.

Results and discussion Catalyst characterization The BET surface area and pore volume of the NiFe bimetallic catalysts on different supports are listed in Table 1. NiFe/SBA-15 has the highest BET surface area and pore volume, while NiFe/CeO2 has the smallest surface area and pore volume. The BET surface area and pore volume showed the trend of NiFe/SBA-15 > NiFe/Al2O3 > NiFe/SiO2 > NiFe/ZrO2 > NiFe/CeO2.


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Table 1. Physical and chemical properties of NiFe catalysts on different supports

Catalyst

BET surface area (m2/g) a

Pore volume

Average crystallite

(cm3/g) a

size of NiO (nm)

NiFe/SiO2

144

0.53

3.5

0.01

NiFe/SBA-15

515

0.76

4.3

0.08

NiFe/Al2O3

203

0.56

5.2

0.56

NiFe/ZrO2

42

0.16

3.6

0.05

NiFe/CeO2

30

0.07

2.8

0.02

Acidity (mmol/g) c

b

a

N2 physisorption. The surface area and pore volume were calculated by the BET and BJH methods, respectively.

b

Calculated by the Scherrer equation from the XRD NiO peak.

c

Calculated by NH3-TPD.

Wide angle XRD patterns of the NiFe catalysts and low angle XRD patterns of SBA-15 and NiFe/SBA-15 are shown in Figure 1. In Figure 1(a), the diffraction peaks of NiO are at 2 = 37.2o, 43.3o and 62.9o for NiFe/SiO2 and NiFe/SBA-15. These two samples also gave a broad peak at 15o-30o due to amorphous silica [33]. For NiFe/Al2O3, the peaks at 37.2o and 62.9o were due to NiO, and 46.2o and 66.5o to Al2O3. In the XRD pattern of NiFe/ZrO2, the diffraction peaks of ZrO2 were at 2 = 24o, 28.2o, 31.5o, 34.2o, 35.3o, 41o, 45o, 49.3o, 50.5o, 54.1o, 55.5o and 60o, and the NiO peaks were at 37.2o and 62.9o. For NiFe/CeO2, the diffraction peaks at 2 = 28.5o, 33.1o, 47.5o, 56.3o and 76.7o were attributed to CeO2, and the peaks at 37.2o and 79.4o were attributed to NiO. As listed in Table 1, the crystallite sizes of NiO followed the order of NiFe/Al2O3 (5.2 nm) > NiFe/SBA-15 (4.3 nm) > NiFe/ZrO2 (3.6 nm) > NiFe/SiO2 (3.5 nm) > NiFe/CeO2 (2.8 nm). In Figure 1(b), three well-resolved diffraction peaks at 2 = 0.9o, 1.6o and 1.8o were assigned to the hexagonally ordered structure of SBA-15 [34]. After Ni and Fe were loaded, this ordered structure was well preserved in NiFe/SBA-15. However, the addition of Ni


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and Fe decreased the intensity of the low angle diffraction peaks, which was attributed to that some metal particles were embedded in the SBA-15 [33, 35].

(a)

NiO

Al2O3

CeO2

(b)

ZrO2

NiFe/SBA-15

NiFe/CeO2

Intensity

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


NiFe/ZrO2 NiFe/Al2O3 NiFe/SBA-15

SBA-15 NiFe/SiO2

20

40

60

80

2 (degree)

1.0

1.5

2.0

2.5

3.0

3.5

2 (degree)

Figure 1. (a) Wide angle XRD patterns of NiFe catalysts with different supports, and (b) low angle diffraction patterns of SBA-15 and NiFe/SBA-15.

TPR profiles of the NiFe catalysts are shown in Figure 2. NiFe/SiO2 showed a main peak at 421 oC

and a broad peak centered at 530 oC. Compared with Ni/SiO2, which exhibited the peak of the

reduction of NiO to metal Ni at 473 oC in our previous work [31], the main reduction peak of the Ni bimetallic catalyst was shifted to a lower temperature and was separated into two peaks. For Ni/SBA-15, the main peak at 433 oC corresponds to the reduction of bulk NiO, and the shoulder peak at 560 oC corresponds to the reduction of NiO that has a strong interaction with the SBA-15 support [36]. Two reduction peaks at 409 oC and 663 oC were observed for Fe/SBA-15, which were attributed to the reduction of Fe2O3 to Fe3O4 and Fe3O4 to metallic Fe, respectively [37]. NiFe/SBA-15 gave a similar TPR profile to Ni/SBA-15 with a peak at 417 oC and a broad peak centered at 592 oC. After the addition of Fe, the first peak was close to that of Ni/SBA-15, while the second peak, which was attributed to NiO with a strong interaction with the support, shifted


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to a higher temperature and increased in intensity [38]. These results indicated that the introduction of the second metal Fe into the Ni catalyst shifted the reduction temperature, and confirmed an interaction between Ni and the second metal in the bimetallic catalysts [39]. NiFe/Al2O3 showed three reduction peaks at 396 oC, 476 oC and 681 oC. The first and second peaks were assigned to non-interacting and weakly interacting nickel oxide, respectively, while the third peak was assigned to the reduction of NiO associated with Al2O3 [40, 41]. In addition, NiFe/ZrO2 showed a main peak at 369 oC, and NiFe/CeO2 showed two peaks at 330 oC and 382 oC,

which were attributed to the reduction of nickel oxide [42, 43].

NiFe/CeO2 NiFe/ZrO2

Intensity (mV)

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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NiFe/Al2O3 NiFe/SBA-15 NiFe/SiO2 Fe/SBA-15

Ni/SBA-15 200

300

400

500

600

700

o

Temperature ( C)

Figure 2. H2-TPR profiles of NiFe catalysts on different supports, and Ni/SBA-15 and Fe/SBA-15.

TEM images and metal particle size distribution of NiFe/SBA-15 are shown in Figures 3(a) and (b). The uniform channel structure of SBA-15 and a uniform dispersion of NiFe bimetallic particles on the support were observed. The metal particle size on NiFe/SBA-15 ranged from 4 to 10 nm with an average of 7.2 nm. HAADF-STEM and the corresponding EDS mapping are shown in Figure 3(c). Ni and Fe showed a similar particle distribution on SBA-15. The Ni, Fe, Si and O peaks in the EDS spectrum gave 0.51 ± 0.09% Ni and 0.19 ± 0.04% Fe atomic loading,


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which was consistent with the NiFe (Ni/Fe molar ratio = 3:1) bimetallic composition. The EDS results also confirmed the formation of bimetallic composites on NiFe/SBA-15. Surface acidity of the NiFe catalysts on the different supports was measured by NH3-TPD, and shown in Figure 4. The catalysts showed a broad desorption peak between 200 oC and 450 oC, which was attributed to weak and medium acid sites. The amount of desorbed NH3 from NiFe/Al2O3 was the highest among these catalysts, and gave an acidity of 0.561 mmol/g as listed in Table 1. The acidity followed the trend of NiFe/Al2O3 (0.561 mmol/g) > NiFe/SBA-15 (0.078 mmol/g) > NiFe/ZrO2 (0.054 mmol/g) > NiFe/CeO2 (0.022 mmol/g) > Ni/SBA-15 (0.017 mmol/g) > NiFe/SiO2 (0.010 mmol/g). In particular, the addition of Fe increased the acidity from 0.017 mmol/g to 0.078 mmol/g for NiFe/SBA-15. 35

(a)

(b)

NiFe/SBA-15

30

Da=7.2 nm

25

Frequency (%)

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


20 15 10 5 0 2

3

4

5

6

7

8

9

10

11

12

13

14

Diameter (nm)

(c)

Ni

Fe

Si

O

Figure 3. (a) TEM images and (b) metal particle size distribution of NiFe/SBA-15; (c) HAADF-STEM image of NiFe/SBA-15 and EDS elemental mapping of Ni, Fe, Si and O.


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Ni/SBA-15 NiFe/SBA-15 NiFe/SiO2

Intensity

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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NiFe/Al2O3 NiFe/ZrO2 NiFe/CeO2

150

200

250

300

350

400

450

Temperature (oC) Figure 4. NH3-TPD profiles of NiFe catalysts on the different supports, and Ni/SBA-15.

Catalytic evaluation Aqueous phase hydrogenation over NiFe bimetallic catalysts To understand the bimetallic effect in the NiFe catalyst, furfural conversion and product distribution over Ni/SBA-15 and NiFe/SBA-15 were compared, which is shown in Figure 5. Fe/SBA-15 showed no activity for furfural hydrogenation, which is consistent with the results of Sitthisa et al. [30]. Over Ni/SBA-15, furfural conversion was 51.2% with 46.1% CPO selectivity at 360 min. The selectivity to intermediate product FFA decreased with time on stream, and was 30.6% at 360 min. However, the selectivity to byproduct THFA increased to 12.3%. The result with NiFe/SBA-15 showed that the addition of Fe enhanced catalyst activity and CPO selectivity. Furfural conversion increased to 62.9% and CPO selectivity increased to 78.4% at 360 min. FFA selectivity decreased faster than that over Ni/SBA-15, and the formation of THFA was inhibited (7.7% at 360 min). The results showed that the addition of Fe suppressed the formation of THFA, and therefore enhanced CPO selectivity as compared with Ni/SBA-15. Yu


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et al. [29] studied furfural adsorption on a NiFe bimetallic surface by DFT calculations and reported that the addition of Fe changed the adsorption geometry. On Ni, furfural adsorbed through both the furan ring and carbonyl group and was parallel to the surface [29, 44]. On NiFe, the distance from the surface was decreased for the carbonyl oxygen and increased for the carbonyl carbon [29, 30]. These changes made the furan ring more tilted away from the surface, which would inhibit further hydrogenation of the furan ring to THFA [29]. This would explain why the addition of Fe to Ni improved the catalytic performance in the hydrogenation of furfural to CPO. In addition, a higher carbon loss due to the polymerization of furfural and FFA in water at 140 oC over Ni/SBA-15 was observed as compared with that over bimetallic NiFe/SBA-15 [20]. 100

Conv. FFA THFA CPO

(a)

80

(b)

Conversion or Selectivity (%)

100


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


60

40

20

0

0

50

100

150

200

250

300

350

400

Conv. FFA THFA CPO

80

60

40

20

0

0

50

t (min)

100

150

200

250

300

350

400

t (min)

Figure 5. Furfural conversion and CPO, FFA and THFA selectivity over (a) Ni/SBA-15 and (b) NiFe/SBA-15. Reaction conditions: 1.2 g catalyst, 6.0 g furfural, 100 mL water, 140 oC and 3.4 MPa H2.

The support effect on the NiFe bimetallic catalysts was studied. As listed in Table 2, the product distribution depended strongly on the catalyst support. NiFe/SiO2 showed the highest activity (kr = 1.043×10-2 min-1) with furfural conversion of 90.1% at 300 min. However, the selectivity to FFA and THFA was 49.0% and 26.2%, respectively. CPO selectivity over NiFe/SBA-15 was


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much higher than over NiFe/SiO2 and was 75.8% at 300 min, although the rate constant was lower (2.7×10-3 min-1). Over NiFe/Al2O3, although THFA selectivity (3.2% at 300 min) was low, furfural was mainly converted to FFA and the selectivity to CPO was 39.1%. NiFe/ZrO2 and NiFe/CeO2 showed low activity with rate constants of 2.4×10-4 min-1 and 1.4×10-4 min-1, respectively. CPO selectivity over NiFe/ZrO2 and NiFe/CeO2 was higher than the other catalysts at low furfural conversion. Although NiFe/ZrO2 and NiFe/CeO2 gave good selectivity to CPO, their low activity would limit their application. For both good activity and CPO selectivity, NiFe/SBA-15 was the best catalyst. As listed in Table 2, furfural conversion reached 88.9% with 83.8% CPO selectivity at TOS = 480 min over NiFe/SBA-15, which were much higher than the other catalysts. Table 2. Catalytic performance of NiFe catalysts on different supports a

Entry

Catalyst

Conv. (%)

1

NiFe/SiO2

2

Selectivity (%)

kr×104 (min-1)

FFA

THFA

CPO

90.1

49.0

26.2

23.4

104.3

NiFe/SBA-15

53.5

12.5

4.3

75.6

27.0

3

NiFe/SBA-15

88.9 b

3.9 b

9.3 b

83.8 b

4

NiFe/Al2O3

15.7

48.5

3.2

39.1

4.7

5

NiFe/ZrO2

6.8

31.4

1.2

58.0

2.4

6

NiFe/CeO2

3.7

46.3

2.6

41.6

1.4

a

Reaction conditions are the same as in Figure 5 (TOS = 300 min).

b

TOS = 480 min.

Important physical and chemical properties of the catalysts are shown in Table 1 and Figure 4. Catalyst acidity has a significant effect on CPO selectivity. Better CPO selectivity was obtained over catalysts with weak acidity. Hronec et al. [13] compared Pt catalysts on different supports


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and found that CPO selectivity decreased while FFA and THFA selectivity increased over Pt/Al2O3. Yang et al. [45] studied a series of Ni-based catalysts supported on Al2O3 and alkaline earth metal-modified Al2O3. They found that with increased loading of alkaline earth metal, catalyst acidity decreased, and THFA selectivity increased. NiFe/ZrO2 and NiFe/CeO2 also showed good CPO selectivity, but gave low activity due to their low surface area. Overall, NiFe/SBA-15 gave the best performance for the aqueous phase hydrogenation of furfural to CPO. Methanol/water solvent effect The solvent plays an important role in the liquid phase hydrogenation of furfural. For hydrogenation of furfural to FFA or THFA, alcohol solvents gave good performance [35, 46, 47], especially methanol [39]. Meanwhile, the use of water as the solvent is important for the hydrogenation of furfural to CPO [11, 12]. Since the main products are FFA, CPO and THFA over NiFe/SBA-15, the presence of methanol and water can affect the product distribution significantly. A series of methanol/water solutions with different volume ratios was investigated for the hydrogenation of furfural using NiFe/SBA-15. The results at TOS = 300 min are summarized in Table 3 and Figure 6. As listed in Table 3, it is interesting that the use of methanol/water solutions with different volume ratios changed the product distribution. With increased water ratio, furfural conversion decreased, and THFA selectivity first increased and then decreased, while CPO selectivity increased gradually. With pure methanol as the solvent (100 mL, entry 1 in Table 3), the main product was FFA with a high selectivity of 88.3% at 300 min. No CPO was produced and only a small amount of FFA was converted to THFA. Wu et al. [39] studied FFA selectivity with


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methanol as the solvent over CuNi alloy catalysts and found that the formation of THFA was inhibited. Al-Mawlawi et al. [48] studied the adsorption of different alcohol molecules on Ni and reported that methanol is more strongly adsorbed than ethanol. Therefore, with pure methanol as the solvent, the consecutive hydrogenation of FFA to THFA is suppressed and no CPO is produced. When the methanol/water volume ratio was 75 mL/25 mL (entry 2 in Table 3), the consecutive hydrogenation of FFA to THFA occurred and gave 95.8% selectivity to THFA at 300 min. The intermediate product FFA was almost completely converted to THFA and CPO, but CPO selectivity was just 2.3%. In 50 mL methanol and 50 mL water (entry 3 in Table 3), furfural conversion decreased compared with that in 75 mL methanol/25 mL water solvent. Meanwhile, CPO selectivity increased to 24.1% at 300 min, which was higher than THFA selectivity (17.2%). When the water ratio was further increased, 25 mL/75 mL (entry 4 in Table 3), CPO was the main product. When pure water was used as the solvent (entry 5 in Table 3), CPO selectivity reached 75.6%, and THFA selectivity decreased to 4.3% at 300 min. These results showed that the major furfural hydrogenation product was, respectively, FFA, THFA and CPO with pure methanol, methanol-dominated and water-dominated solutions as the solvent. Table 3. Catalytic performance of NiFe/SBA-15 catalyst in different solvents a

a

Entry

Volume ratio (mL methanol/mL water)

Conv. (%)

1

100/0

2

Selectivity (%)

99.8

FFA 88.3

THFA 1.7

CPO 0

75/25

99.8

1.9

95.8

2.3

3

50/50

79.9

58.7

17.2

24.1

4

25/75

67.8

27.8

13.5

58.6

5

0/100

53.5

12.5

4.3

75.6

Reaction conditions are the same as in Figure 5 except the solvent (TOS = 300 min).


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The highest THFA and CPO selectivity, respectively, were obtained in 75 mL methanol/25 mL water and 100 mL water. As shown in Figure 6(a), in 75 mL methanol/25 mL water, furfural conversion increased to 66.4% and FFA selectivity increased rapidly to 93.4% at 120 min. Meanwhile, THFA and CPO selectivity increased slowly. After 120 min, FFA selectivity began to decrease, but THFA selectivity gradually increased. At 300 min, FFA was almost completely converted to THFA. With water as the solvent (Figure 5(b)), furfural conversion increase was much slower, and THFA selectivity was low. In this case, CPO selectivity increased gradually and reached 75.6% at 300 min. It is notable that the existence of furfural inhibited THFA formation and gave a high CPO selectivity, except with the pure methanol solvent. Yang et al. [20] found that the aldehyde group of furfural affected the formation of THFA in the hydrogenation of furfural over Ni-based catalysts in water. They further used several molecules with the aldehyde group, such as furan derivatives, benzaldehyde and aliphatic aldehyde, and reported that no THFA was detected in the product. Therefore, when a large amount of furfural exists in the system, the subsequent hydrogenation of the furan ring to THFA is inhibited by unconverted furfural, which is the reason why a high CPO selectivity in water is favored. To further confirm the results, the hydrogenation of furfural was carried out over NiFe/SBA-15 in 95 mL methanol/5 mL water solvent. The results are shown in Figure 6(b). The conversion of furfural was 99.5% at 300 min, and FFA selectivity was high at first (95% at 60 min) and then decreased (0.6% at 480 min). THFA selectivity increased rapidly after 120 min, and reached 97% at 480 min. CPO selectivity was low and only 2% at 480 min.


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100

100

(a)

Conversion and Selectivity (%)


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

Conv. FFA THFA CPO

80

60

40

20

0

0

50

100

150

200

250

300

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(b) Conv. FFA THFA CPO

80

60

40

20

0

0

100

t (min)

200

300

400

500

t (min)

Figure 6. Conversion and selectivity versus time in methanol/water solutions: (a) 75mL methanol/25 mL water; (b) 95 mL methanol/5 mL water. Reaction conditions are the same as in Figure 5 except the solvent.

The simplified reaction network shown in Scheme 1 was used to analyze the hydrogenation reaction of furfural in methanol/water solution. The following reactions were used: (1) hydrogenation of furfural to FFA, (2) further hydrogenation of FFA to THFA, (3) rearrangement and deep hydrogenation of FFA produced. The reactions in Scheme 1 were considered as irreversible first order with respect to the organic reactant. The rate expressions for the components are Eqs. (1)-(4). dCF1 / dt = -k1CF1

(1)

dCF2 / dt = k1CF1- k2CF2- k3CF2

(2)

dCF3 / dt = k2CF2

(3)

dCF4 / dt = k3CF2

(4)


16

Page 17 of 30

where k1, k2, k3 and k4 are the reaction rate constants, and CF1,CF2, CF3 and CF4 are the concentration (mol/mL) of furfural, FFA, THFA and CPO, respectively. The reaction rates of the components were obtained from their concentration-time curve. Then the rate constants were calculated by solving Eqs. (1)-(4) and optimizing the rate constants. The rate constants in the methanol/water solvents are shown in Figure 7. k1 depended strongly on the methanol/water volumetric ratio. With increasing volume ratio of water, k1 decreased from 2.28×10-2 min-1 to 2.70×10-3 min-1. k3 was very small when the water ratio was lower than 25%, but increased significantly with increased water volume ratio. The value of k3 was largest with pure water as the solvent, and reached 1.65×10-2 min-1. k2 first increased and then decreased. The largest value of k2 was 8.32×10-3 min-1 with the solvent volume ratio 75/25. k2 was much smaller in water-dominated solvents, which explained the inhibition of unconverted furfural. These results indicated that the solvent strongly affects this reaction and existing furfural promots the conversion of furfural to CPO. This is consistent with the experimental results that the highest CPO yield was obtained with water as the solvent. 250 k1 k2

200

k (10-4 min-1)

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


k3

150

100

50

0 100/0

75/25

50/50

25/75

0/100

Volume ratio (mL methanol/mL water)

Figure 7. Correlation of reaction rate constants with solvent composition (volume ratio).


17


Effect of reaction temperature The reaction temperature has been reported to be important in the hydrogenation rearrangement of furfural to CPO [15, 20]. The temperature effect was studied from 130 oC to 170 oC to optimize the CPO yield. As shown in Figure 8(a), furfural conversion significantly increased over NiFe/SBA-15 with increasing temperature. At 130 oC, furfural conversion was 31.4% at 300 min. At 160 oC, furfural conversion increased to 99.6%. Meanwhile, significant changes were seen in the product distribution and CPO selectivity. At a low temperature, the activity was low and FFA selectivity was high. With increasing temperature, FFA selectivity decreased and FFA was almost completely converted at 160 oC within 300 min. When increasing temperature from 130 oC to 160 oC, CPO selectivity increased from 56.2% to 90.1% at 300 min. The highest CPO selectivity was obtained at 160 oC. A further increase in temperature decreased CPO selectivity due to polymerization side reactions and the conversion of CPO to CPL. The dependence of the rate constants on temperature obeyed the Arrhenius equation, as shown in Figure 8(b). The activation energy was 104 kJ/mol for this NiFe catalyst. At the optimized reaction temperature, a high furfural conversion of 99.8% and FFA yield of 90% were achieved over NiFe/SBA-15 in water. 100

(a)

80

-8.0

FFA THFA CPO CPL Conv.

(b)

-8.5 -9.0

60

lnk


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

Page 18 of 30

40

-9.5 -10.0 -10.5

20

-11.0 0

130

140

150

160

170

-0.00250 -0.00245 -0.00240 -0.00235 -0.00230 -0.00225

o

Temperature ( C)

-1/T (1/K)


18

Page 19 of 30

Figure 8. (a) Effect of temperature on furfural conversion and product selectivity; (b) reaction rate constants fitted by the Arrhenius equation. Reaction conditions are the same as in Figure 5 except the temperature (TOS = 300 min).

The stability of NiFe/SBA-15 was studied by recycling the catalyst three times with water as the solvent, as shown in Figure 9. After each run, the catalyst was washed, centrifuged and reduced by hydrogen. After three cycles, furfural conversion slightly decreased from 56.5% to 50.1%, and CPO selectivity decreased from 75.4% to 69.5%. This decreased furfural conversion was mainly attributed to catalyst loss during the collection and washing procedure. The CPO selectivity decrease could be attributed to increased FFA selectivity. The characterization results of the used catalyst are shown in Supporting Information.

100


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


Conv.

FFA

THFA

CPO

80 60 40 20 0

1

2

3

Figure 9. Recyclability of NiFe/SBA-15. Reaction conditions are the same as in Figure 5 except T = 160 oC

and TOS = 120 min.

The best results of this work are compared with typical results in the literature as shown in Table 4, where catalyst productivity is used to compare activity [49]. The detailed reaction conditions are given in Table S3. Most precious metal catalysts showed high activity. Au/TiO2-A [8] gave


19


Page 20 of 30

the best catalytic performance. However, the metal loadings of these precious metal catalysts were high (> 3 wt%), except Au/TiO2-A (0.1 wt%). Among the non-precious metal catalysts, NiFe/SBA-15 in this work had the best overall performance for activity and CPO selectivity. Although CuNi0.5@C [24] and Cu-Ni-Al [10] gave high CPO yields, they had much lower activities than NiFe/SBA-15. CuNi0.5@C showed higher CPO selectivity than NiFe/SBA-15, but both the catalyst amount (2 g) and metal loading (50 wt%) were high. A high metal loading (87 wt%) and long reaction time (8 h) were used for Cu-Ni-Al, while in this work, the metal loading was 5 wt% and reaction time was 5 h. Cu-Co-CP-500 [21] was more active than NiFe/SBA-15, but it gave only 65% CPO yield due to the conversion of CPO to CPL. Overall, NiFe/SBA-15 showed it is highly advantageous among the non-precious metal catalysts. Table 4. Comparison of metal catalysts for liquid phase hydrogenation of furfural to CPO

Yield

(MPa)

Conv. (%)

160

4

3% Ru/MIL-101

160

6wt% Ru/CNTs

T (oC)

Au/TiO2-A

PH2

(%)

Catalyst productivity a

Ref.

99

98

13.4

[8]

4

99

95

0.02

[17]

160

1

99

90

1.24

[18]

5% Pd+10% Cu/C

160

3

98

90.3

10.9

[16]

Pd/C

160

3

97.8

65.5

3.26

[12]

5% Pt/C

160

8

100

76.5

13.3

[12]

5wt% Pt/NC

150

3

99

75

0.79

[19]

5% Pt/C

160

3

96.5

49.7

3.22

[12]

CuZn/CNT

140

4

95.1

81.1

0.02

[23]

Cu-Co-CP-500

170

2

97

65

0.62

[21]

CuZnAl-500

150

4

97.9

60.3

0.02

[11]

CuNi0.5@C

130

5

99.3

96.2

0.02

[24]

Catalyst


20

Page 21 of 30 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


Cu-Ni-Al

140

4

100

95.8

0.01

[10]

Raney Ni

180

1

97.8

38.2

0.04

[27]

NiCu-50/SBA-15

160

4

99

61.4

0.07

[20]

NiFe/SBA-15

160

3.4

99.8

90.0

0.33

this work

a Calculated

by furfural consumption per mass metal loading per minute (g·g-1·min-1).

Conclusions The hydrogenation of furfural to CPO was studied over NiFe bimetallic catalysts. NiFe/SBA-15 showed a synergetic bimetallic effect in the aqueous phase hydrogenation. The addition of Fe to Ni inhibited further hydrogenation of the furan ring to THFA and enhanced CPO selectivity. Furfural conversion and CPO selectivity were 62.9% and 78.4% over NiFe/SBA-15, respectively, compared with 51.2% and 46.1% over Ni/SBA-15. The composition (different volume ratios of the components) of the methanol/water solvent affected the product distribution significantly. The main product was, respectively, FFA, THFA and CPO with pure methanol, methanol-dominated and water-dominated methanol/water solutions as the solvent. The existence of furfural in water inhibited the formation of THFA, such that furfural preferentially produced CPO. The best catalytic performance was obtained over NiFe/SBA-15 in water. At 160 oC,

the CPO yield was 90% at complete furfural conversion and the consecutive hydrogenation

of FFA to THFA was inhibited.

SUPPORTING INFORMATION Catalyst preparation, evaluation condition, catalyst characterization, characterization results of the used catalyst and details of reaction conditions are given in Table 4

AUTHOR INFORMATION


21


Page 22 of 30

Corresponding Author * Corresponding Author: Tel.: 86-10-62797490. Fax: 86-10-62772051. E-mail: [email protected] (T. F. Wang)

ACKNOWLEDGMENT This work was supported by the National Natural Science Foundation of China (No. 21676155 and No. 21476122) and PetroChina Innovation Foundation (2016D-5007-0507).

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For Table of Contents Use Only


29


Page 30 of 30

Synopsis: Bimetallic SBA-15 supported NiFe gave 90% CPO yield in the liquid phase hydrogenation of furfural. Product selectivity was different when the composition of the solvent was changed using different volume ratios of methanol and water.


30

Highly selective hydrogenation of furfural to cyclopentanone over a

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