Hydrodeoxygenation of Lignin-Derived Phenols - MDPI

catalysts Review

Hydrodeoxygenation of Lignin-Derived Phenols: From Fundamental Studies towards Industrial Applications Päivi Mäki-Arvela and Dmitry Yu. Murzin * Johan Gadolin Process Chemistry Centre, Åbo Akademi University, 20500 Turku/Åbo, Finland; [email protected] * Correspondence: [email protected] Received: 7 August 2017; Accepted: 22 August 2017; Published: 7 September 2017

Abstract: Hydrodeoxygenation (HDO) of bio-oils, lignin and their model compounds is summarized in this review. The main emphasis is put on elucidating the reaction network, catalyst stability and time-on-stream behavior, in order to better understand the prerequisite for industrial utilization of biomass in HDO to produce fuels and chemicals. The results have shown that more oxygenated feedstock, selection of temperature and pressure as well as presence of certain catalyst poisons or co-feed have a prominent role in the HDO of real biomass. Theoretical considerations, such as density function theory (DFT) calculations, were also considered, giving scientific background for the further development of HDO of real biomass. Keywords: hydrodeoxygenation; bio-oil; guaiacol; lignin; heterogeneous catalyst; fuel

1. Introduction Lignocellulosic biomass, which is abundant, and does not compete with the food chain, has mainly been used for production of pulp and paper via the Kraft process, in which lignin and hemicellulose have been conventionally burnt to generate energy. New transformation processes should be developed in order to utilize the above-mentioned fractions more efficiently. The research in biomass transformation to produce bio-oil via flash pyrolysis [1] and utilize different lignin fractions to produce chemicals and fuels [2,3] has been very intensive in the recent years in part due to the depleting fossil based feedstock and strive towards carbon neutral fuels and chemicals. Further transformation of these fractions, can, however, be demanding, since bio-oil is unstable, exhibiting low pH, whereas lignin is a complex polyphenolic polymer difficult to transform selectively. One of the most important research area in transformation of bio-oil [4] and lignin [2,3] is catalytic hydrodeoxygenation (HDO) during which fuels or suitable blending agents are produced including benzene, toluene as well as cycloalkane and–ketones. Several reviews have already been published on HDO of lignin based phenols [5–15]. In these works, the main emphasis has been on different catalysts [5–8,11], deactivation [6,8,9], mechanism [6,8,10], kinetics [6]. Some specific topics, such as the use of carbide catalysts [12] and production of jet fuel from lignin [7] have been recently reviewed. Bio-oil HDO including the patent literature was reviewed by Zacher et al. in 2014 [13]. The recent trends in HDO of bio-oils have been summarized since this research area is highly important and very many new studies are constantly appearing [16–64]. Although HDO of phenolic compounds has already been investigated during several decades [65,66] and was shown to be a promising method to upgrade bio-oil, it is still challenging. The main challenges are catalyst deactivation, polymerization of phenolic compounds at elevated temperatures and the use of real bio-oils which contain various compounds and catalyst poisons.

Catalysts 2017, 7, 265; doi:10.3390/catal7090265

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Catalysts 2017, 7, 265

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In this review, the main emphasis is in depth elucidation of the reaction network in hydrodeoxygenation of phenolic model compounds, especially focusing on which types of model molecules have been used for HDO and comparison of their reactivity. The experimental data will be correlated with the theoretical results using density functional theory and bond dissociation energies for different functional groups. In addition, to bring the HDO process closer to industry, several relevant aspects, such as catalyst deactivation, recycling and reuse have to be properly addressed. Typically, in continuous HDO of phenolic compounds deactivation of catalyst is significant, therefore relevant literature has been described. It is also of utmost importance for industrial processes to know exactly the mass balances and in particular formation of various undesired side products including gaseous ones and coke. The aim in this review is to report the main trends in the HDO of lignin derived model molecules, bio-oil and lignin per se. Special attention was put on the effect of temperature, pressure, metal and support selection. In addition, a reaction network during the HDO of model molecules will be discussed and reactivity of different model molecules in a single feed studies over the same catalyst will be compared. Continuous operation, catalyst reuse and deactivation will also be discussed in depth in order to relate the current state-of-art more closely to industrial applicability. 2. Bio-Oil and Lignin Properties and Need for Upgrading 2.1. Bio-Oil Properties Bio-oil is a product, which is most commonly produced via fast pyrolysis, in which the biomass is treated in the temperature range of 300–600 ◦ C and short residence time from 1 s to 2 s [15]. In this process biomass is deconstructed giving char as well as liquid, gases. The liquid fraction called bio-oil contains typically a large amount of water, varying in the range of 10–30 wt %, and different chemicals including aldehydes, acids, carbohydrates, phenolics, ketones, alcohols, etc. [15,67]. The composition of bio-oil varies significantly depending on the raw material. Bio-oils being typically non-stable, have a high viscosity, acidity (pH = 2.8–3.8) and low energy content or heating value due to high oxygen content [47,64]. Typically, bio-oils can contain up to 40 wt % oxygen [15], requiring upgrading during which different reactions occur, such as cracking, decarbonylation decarboxylation, hydrogenation, hydrocracking and hydrodeoxygenation. The main aim in hydrodeoxygenation is to reduce the oxygen content in bio-oil, especially present in aromatic hydroxyl and methoxy containing molecules. The HDO reactions of these molecules (e.g., guaiacol), are, however, challenging due to their low stability which causes catalyst deactivation [48]. 2.2. Structure of Different Lignin Types Properties of Organosolv, Kraft and Soda Lignin Organosolv lignin can be prepared under mild extraction conditions using different solvents, such as an ethanol/water mixture at 200 ◦ C [68]. Sulfur-free organosolv lignin suitable for catalytic transformation [69] has a lower average molecular weight compared to other lignin [1]. The organosolv lignin utilized by Kasakov et al. exhibited seven interconnected monolignols in its structure [2]. On the other hand, kraft and soda lignin is more condensed [1]. This can be explained by the preparation method involving alkaline reactions, including degradation of aryl-ethyl bonds and condensation because of carbanions addition to quinine methide during precipitation [1]. 3. HDO of Lignin-Derived Model Compounds, Simulated and Real Bio-Oil and Lignin In the HDO of bio-oil the main target is to decrease the oxygen content of the product and to improve the product heating value. It has been reported that the heating value of, for example, wheat based bio-oil is 21.2 MJ/kg on the dry basis [35] while the corresponding value for yellow poplar based bio-oil is 17.3 MJ/kg dry basis [4]. In the latter work the heating value of the processed


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maximally to 22.8 MJ/kg over Ni/SBA-15 catalyst during HDO at 300 ◦ C 3 of 42 under 30 bar hydrogen being 24% better than in the feed. Furthermore, van Krevelan plot showing the O/C molar ratio of different products gives an idea of how HDO decreases oxygen content during H/O and O/C molar ratio of different products gives an idea of how HDO decreases oxygen content the process (Figure 1). For example, when the light oil fraction in wheat based pyrolysis oil containing during the process (Figure 1). For example, when the light oil fraction in wheat based pyrolysis ◦ Chydrogen, 57% water was 57% hydrodeoxygenated with different catalysts at 250 catalysts °C under bar oil containing water was hydrodeoxygenated with different at80 250 under 80 its bar molar O/C ratio decreased to 0.22 using Ni/ZrO as a catalyst. study with bio‐oil hydrogen, its molar O/C ratio decreased to 0.222using Ni/ZrO2In asanother a catalyst. In another studyfrom with yellow the O/C ratio decreased 0.8 to from 0.2 using Pt/C as a Pt/C catalyst When bio-oil poplar from yellow poplar thewas O/C ratio wasfrom decreased 0.8 to 0.2 using as a [4]. catalyst [4]. considering the fuel properties after HDO, it should be kept in mind that even cyclohexanol, When considering the fuel properties after HDO, it should be kept in mind that even cyclohexanol, cyclohexanone and cyclohexane are valuable products which can be blended with petroleum [70]. cyclohexanone and cyclohexane are valuable products which can be blended with petroleum [70]. Furthermore, Furthermore,for forexample, example,cyclohexane, cyclohexane,toluene tolueneand andxylene xyleneexhibit exhibitsuitable suitablevapor vaporpressures pressuresand and carbon number to be used in gasoline [62]. carbon number to be used in gasoline [62]. bio-oil was increased Catalysts 2017, 7, 265

Figure1. 1.Van VanKrevelan Krevelanplot of plot ofthe thelight lightphase phaseof ofpyrolysis pyrolysisoil oilprepared from prepared fromwheat wheatstraw strawand andits its Figure upgraded products using different catalysts at 250 ◦ C under 80 bar hydrogen [35]. upgraded products using different catalysts at 250 °C under 80 bar hydrogen [35].

In the recent review [7] results from HDO of model molecules, simulated and real bio‐oils and In the recent review [7] results from HDO of model molecules, simulated and real bio-oils and lignin were summarized. Model molecules have been selected among the three phenols derived from lignin were summarized. Model molecules have been selected among the three phenols derived from lignin, p‐coumaryl alcohol, alcohol, coniferyl alcohol sinapyl alcohol 2). The main lignin, namely namely p-coumaryl coniferyl alcohol and and sinapyl alcohol (Figure(Figure 2). The main emphasis emphasis has on been put on of different the proposed reaction pathways and has been put reactivity ofreactivity different molecules, themolecules, proposed reaction pathways and thermodynamics thermodynamics of different reactions. of different reactions.


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HO Catalysts 2017, 7, 265

HO

HO

HO

HO

HO

CH3H3C

O OH

OH

CH3H3C

O

4 of 42

O

CH3

O OH

O

CH3

O

Figure 2. The main phenols from lignin adapted from reference [7].

OH from lignin adapted fromOH OHThe main phenols Figure 2. reference [7].

Figure 2. The main phenols from lignin adapted from reference [7]. 3.1. Conversion and Main Products in the HDO of Lignin‐Derived Model Molecules

3.1. Conversion and Main Products in the HDO of Lignin-Derived Model Molecules

Conversion values and the main products in HDO of lignin derived model molecules are shown 3.1. Conversion and Main Products in the HDO of Lignin‐Derived Model Molecules

HDO (%) Y HDOY(%)

Conversion values and the main HDOis of lignin derived model molecules are shown in Tables 1 and 2 and Figure 3. For products guaiacol, in which one OF the most studied model molecule, Conversion values and the main products in HDO of lignin derived model molecules are shown in Tables 1 andboth 2 and Figureand 3. hydroxyl For guaiacol, which is one to OFobtain the most studied modelunder molecule, containing methoxy group, it is possible complete conversion in Tables 1 and 2 and Figure 3. For which is one OF most complete studied model molecule, either high temperatures [50] or at guaiacol, slightly under high hydrogen pressure containing both methoxy and hydroxyl group,lower it is temperatures possible tothe obtain conversion under containing both methoxy and hydroxyl group, it is possible to obtain complete conversion under (Table 1, entry 1) [46]. However, in most of the cases lower conversion levels have been obtained either high temperatures [50] or at slightly lower temperatures under high hydrogen pressure (Table 1, either high temperatures [50] or at slightly lower temperatures under high hydrogen pressure entry[26,33,38,58]. Complete deoxygenation for guaiacol is also difficult, since these yields vary between 1) [46]. However, in most of the cases lower conversion levels have been obtained [26,33,38,58]. (Table 1, entry 1) [46]. However, in most of the cases lower conversion levels have been obtained 10–75%, except for a high HDO yield with cyclohexane as the main product obtained over Ni/SiO 2‐ Complete deoxygenation for guaiacol is also difficult, since these yields vary between 10–75%, [26,33,38,58]. Complete deoxygenation for guaiacol is also difficult, since these yields vary between ZrO 2 at 300 °C under 50 bar (Figure 3). When, however, the methoxy group is in position 3, HDO is except for a high HDO yield with cyclohexane as the main product obtained over Ni/SiO22-ZrO 2 10–75%, except for a high HDO yield with cyclohexane as the main product obtained over Ni/SiO ‐ easier, most probably due to less steric hindrance (Table 1, entry 2). The reasons for this difficulty to ◦ C under 50 bar (Figure 3). When, however, the methoxy group is in position 3, HDO is at 300 ZrO2 at 300 °C under 50 bar (Figure 3). When, however, the methoxy group is in position 3, HDO is deoxygenate guaiacol and other model molecules are discussed in Section 3.3. easier, most probably due to less steric hindrance (Table 1, entry 2). The reasons for this difficulty to easier, most probably due to less steric hindrance (Table 1, entry 2). The reasons for this difficulty to deoxygenate guaiacol and other model molecules are discussed in Section 3.3. deoxygenate guaiacol and other model molecules are discussed in Section guaiacol3.3. 100

1.

100 80

1.

15. 11.

80 60

12. 11.

60 40

12.

15.6.

7.

6. 13. 4. 13. 16. 4.

20 0 0

2.

250

200

250

8.

18. 19. 20. 18. 19. 9. 20.

8.

9.

14. 3. 5.

3.

5. 10. 17.

200

2.

14. 7.

16.

40 20

phenol anisole guaiacol phenol anisole

10.

300

350

400

450

300

350

400

450

17. Temperature (°C) Temperature (°C)

Figure 3. Hydrodeoxygenation (HDO) yield in phenol, anisole and guaiacol HDO over different catalysts as a function of temperature. Notation: For phenol 1. CoNx, 20 bar, cyclohexane [63], 2. Figure 3. Hydrodeoxygenation (HDO) yield in phenol, anisole and guaiacol HDO over different Figure 3. Hydrodeoxygenation (HDO) yield in phenol, anisole and guaiacol HDO over different MoO3/ZrO2, 60 bar, benzene [39], 3. MoO3/ZrO2, 60 bar, benzene [39], 4. ReOx/CNFox, 50 bar, catalysts as aas function of of temperature. Notation:For For phenol 1. CoNx, 20cyclohexane bar, cyclohexane [63], catalysts a function temperature. Notation: phenol 1. CoNx, 20 bar, [63], 2. cyclohexane [37], 5. MoO3, 1 bar, benzene [36], for anisole 6. ReOx/CNFox, 50 bar, cyclohexane [37], 2. MoO /ZrO , 60 bar, benzene [39], 3. MoO /ZrO , 60 bar, benzene [39], 4. ReOx/CNFox, 50 3 3/ZrO 22, 60 bar, benzene [39], 33. 3 2 bar, benzene [39], 4. ReOx/CNFox, 50 bar, bar, MoO MoO 3/ZrO 2, 60 3, 1 bar, benzene [36], 8. MoO /ZrO 2, 60 bar, benzene [39], 9. Pt‐Sn/CNF/Inconel, 1 bar, benzene 7. MoO cyclohexane [37], 5. MoO3 , 13, 1 bar, benzene [36], for anisole 6. ReOx/CNFox, 50 bar, cyclohexane [37], bar, benzene [36], for anisole 6. ReOx/CNFox, 50 bar, cyclohexane [37], cyclohexane [37], 5. MoO [48], 10. Ni‐catalyst, 1.7 bar, benzene [50], for guaiacol: 11. Pt/Alumina silicate, 30 bar, cyclohexane 7. MoO 13, 1 bar, benzene [36], 8. MoO bar, benzene [36], 8. MoO /ZrO [39], 9. S Pt-Sn/CNF/Inconel, 3/ZrO23, 60 bar, benzene [39], 9. Pt‐Sn/CNF/Inconel, 1 bar, benzene 7. MoO 3 , 12. 2 , 60 bar, 2, 100 bar, main product cyclohexanol S = benzene 50%, cyclohexane = 25% [47], 13. [49], Ni/ZrO [48], 10. Ni‐catalyst, 1.7 bar, benzene [50], for guaiacol: 11. Pt/Alumina silicate, 30 bar, cyclohexane 1 bar,Rh/ZrO benzene [48], 10. Ni-catalyst, 1.7 bar, benzene [50],3, for guaiacol: 11. Pt/Alumina 2+aluminosilicate, 40 bar, cyclohexane [45], 14. MoO 1 bar, cyclohexane, [36], 15. Ni/SiOsilicate, 2‐ 100 12. bar, Ni/ZrO main product cyclohexanol S = 50%, cyclohexane S = 25% [47], 13. [49], 12. Ni/ZrO2, [49], 30 bar, cyclohexane , 100 bar, main product cyclohexanol S = 50%, cyclohexane 2, 50 bar, cyclohexane [62], 16. CoMoS, 40 bar, benzene main product [46], 17. Mo 2 N, 50 bar, no ZrO 2 40 bar, cyclohexane [45], 14. MoO3, 1 bar, cyclohexane, [36], 15. Ni/SiO2‐ Rh/ZrO HDO [58], 18. Fe/SiO S = 25% [47],2+aluminosilicate, 13. Rh/ZrO2, 1 bar, benzene and toluene [33], 19. Pt‐Sn/CNF/Inconel, 1 bar, toluene [48], 20. 2 +aluminosilicate, 40 bar, cyclohexane [45], 14. MoO3 , 1 bar, cyclohexane, [36], 2N, 50 bar, no ZrO2, 50 bar, cyclohexane [62], 16. CoMoS, 40 bar, benzene main product [46], 17. Mo Ni‐catalyst, 1.7 bar, benzene and toluene [50]. Notation: Inside the area surrounded by the curve, the 15. Ni/SiO 2 -ZrO2 , 50 bar, cyclohexane [62], 16. CoMoS, 40 bar, benzene main product [46], 17. Mo2 N, HDO [58], 18. Fe/SiO2, 1 bar, benzene and toluene [33], 19. Pt‐Sn/CNF/Inconel, 1 bar, toluene [48], 20. main products are cycloalkanes. 50 bar, no HDO [58], 18. Fe/SiO2 , 1 bar, benzene and toluene [33], 19. Pt-Sn/CNF/Inconel, 1 bar, Ni‐catalyst, 1.7 bar, benzene and toluene [50]. Notation: Inside the area surrounded by the curve, the toluene [48], 20. Ni-catalyst, 1.7 bar, benzene and toluene [50]. Notation: Inside the area surrounded by main products are cycloalkanes.

the curve, the main products are cycloalkanes.


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Catalysts 2017, 7, x FOR PEER REVIEW Table

Entry

Table 1. Single model molecule feed HDO results. Notation: Y denotes yield and S selectivity. X is conversion. Catalyst T (◦ C) P (bar) Solvent Conversion % (Time, h) HDO Selectivity

Reactant

Entry

1. Single model molecule feed HDO results. Notation: Y denotes yield and S selectivity. X is conversion.

Rh/MCM-36

Reactant

Catalyst

T (°C)

Fe/SiO2 Rh/MCM‐36 Fe/SiO2

Mo N

Mo2N 2

Mo Mo 2C/CNF 2 C/CNF Mo 2C/CNF Mo C/CNF 2

OH

1 1

H3C

40

P (bar)

250 400

40

400

1

Mo2 N Mo2N

250

300 300 300

1 50

50

300

300 300 350 350

50 40 55

50 40 55

HDO Selectivity Note Reference (Time, h) Ybenzene+toluene = 71% Co-feed with H2 , CO2 , decane X = 69%, 80 min X = 92%29% hydrocarbons [26] after 21 min time-on-stream CO, H2 O Ybenzene+toluene = 71% after 21 ‐ X = 92% Co‐feed with H 2, CO2, CO, H2O [33] X = 11%min time‐on‐stream Yphenol = 8% Mainly phenol and decalin X = 11% catechol 14,500 s Yphenol = 8% Ycatechol = 2.5% decalin Mainly phenol and catechol [38] 14,500 s Ycatechol = 2.5%

decalin

decalin

X = 40%

X = 40% Yphenol = 22%

Yheavy = 12% dodecane X = 98% (4 h) X = 98% (4 h)Sphenol = 48% dodecane Yphenol = 38% dodecane dodecane X = 100% X = 100% Ycreo = 13%, 6 h WHSV = 4 h−1 1 WHSV = 4 h− Xgua = 100% DODGua = 62% 1‐octanol 1-octanolXoctanol = 30% Xgua = 100%after 80 h TOS Xoctanol = 30% after 78 h TOS after 78 h TOS

250 250

100 100

CoMoS CoMoS

300 300

40

40

‐

-

X = 100%

X = 100%

Ni‐catalyst Ni-catalyst

400 400

1.7 1.7

‐

-

100%

100%

Ni‐SiO2‐ZrO2

300

Ni-SiO2 -ZrO2 Pt/C

Pt/C

Rh/ZrO2 + SiAl Pt/alumina silicate

Rh/ZrO2 + SiAl Ru/C

50

300 300

8 h X = 100

50 1

‐

X = 87%

58– 300 310

40

250

30

58–310

400

40

1

40

Note

29% hydrocarbons

Solvent

Ni/ZrO 2 Ni/ZrO 2

O

guaiacol guaiacol

decane Conversion % X = 69%, 80 min

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decane

X = 100%

hexadecane

76 (1 h)

‐

YHDO = 50% Yphenol = 36% Stoluene = 32% Sbenzene = 30%

Ycyclohexane = 97

8h

Yphenol = 22% Yheavy = 12%

[58]

Sphenol = 48%

Yphenol = 38% Ycreo = 13%, 6 h

Pt/alumina silicate

250

30

hexadecane

76 (1 h)

Ru/C

400

40

-

W/F = 0.067 h−1

[58] [56]

[54]

[54]

YHDO = 50% H2S in the feed, fixed bed [46] H2 S in the feed, fixed bed Yphenol = 36%

[46]

Stoluene = 32%

[50]

[62]

[50]

Sbenzene = 30% Ycyclohexane = 97

Ycyclohexane = 64%

[62]

[31]

[49]

Temperature programmed [16] experiment

[45]

Ycyclohexan = 75%

[49]

Ybenzene = 69%

[16]

X = 34%

Catalysts 2017, 7, 265; doi:10.3390/catal7090265

[38]

[47]

W/F = 0.30 g cat h−1 /ggua

Ybenzene = 69%

[33]

DODGua =Trickle bed, poisons 62% Trickle bed,[47] poisons after 80 h TOS

Ycyclohexan = 75%

X = 34%

[26]

[56]

X = 100 SPhenol = 40% Scyclopentanone = 18% Most stable among Pt, Ru, Rh [31] SPhenol = 40% and Pd/C catalysts, MB = 70% Scatechol = 5% Most stable among Pt, Scyclopentanone = 18% W/F = 0.30 g cat h−1/ggua Ru, Rh and Pd/C X = 87% Temperature programmed Scatechol = 5% Ycyclohexane = 64% [45] = 70% catalysts, MB experiment

decane W/F = 0.067 h−1 X = 100%

Reference

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Table 1. Cont. Catalysts 2017, 7, 265 Catalysts 2017, 7, 265 Catalysts 2017, 7, 265 Entry Reactant Catalysts 2017, 7, 265

T (◦ C)

Catalyst

P (bar)

Solvent

Conversion % (Time, h)

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HDO Selectivity

Note6 of 42

Reference

OH OH OH OH 2 2

2 2 2

CH3 CH CH33 O CH O O 3 4-methoxyphenol O 4‐methoxyphenol 4‐methoxyphenol 4‐methoxyphenol 4‐methoxyphenol

3 3 3 3 3

25 wt % 25 wt % 25 wt % 25 wt % 3/ZrO2 MoO 25 wt % MoO 3 /ZrO 2 33/ZrO 22 MoO /ZrO MoO MoO3/ZrO2 Mo2Mo C 2 C Mo Mo22C C Mo2C

O O O H3C O HH33CC H3C

anisole anisole anisole anisole anisole

CH3 CH CH33 CH3 O O O O

O O O CH 3 O CH CH 33 CH3

4

4 4 4 4

CoNx CoNx CoNx CoNx CoNx

O O H3C O HH33CC O H3C 1,3,5‐trimethoxybenzene

200 200 20 200 20 200 20 200 20

20 dodecane dodecaneX = 100% (2 h) X = 100% Ycyclohexane = 95% (2 h) Ycyclohexane =No sintering 95%

320 320 320 320 320

1

1 1 1 1

dodecane dodecane dodecane

150 150 1.1 1.1 150 1.1 150 1.1 150 1.1

‐ ‐ ‐ ‐

Ni catalyst Ni catalyst Ni catalyst Ni catalyst Ni catalyst

350 350 1.7 1.7 350 1.7 350 1.7 350 1.7

Pt/H‐Beta Pt/H-Beta Pt/H‐Beta Pt/H‐Beta Pt/H‐Beta

400 400 400 400 400

‐ ‐ ‐ ‐

1 1 1 1

1

Rh/MCM‐36 250 40 Rh/MCM‐36 Rh/MCM‐36 250 250 40 40 Rh/MCM-36 250 Rh/MCM‐36 250 40

40

-

-

X = 100% (2 h) X = 100% (2 h) X = 100% (2 h)

Ycyclohexane = 95% Ycyclohexane = 95% Ycyclohexane = 95%

No sintering No sintering No sintering

S = 41%, aromatic X = 41% X S = 41%, aromatic compounds =S = 41%, aromatic compounds 41% X = 41% X = 41% S = 41%, aromatic compounds compounds X = 41% S = 41%, aromatic compounds Time‐on‐stream Time‐on‐stream Time‐on‐stream Scyclohexane = 20% Time-on-streamScyclohexane = 20% 60,000 s Scyclohexane =CO co‐feed 20% Scyclohexane = 20% 60,000 s Time‐on‐stream 60,000 s CO co‐feed 60,000 s CO co‐feed Sbenzene = 80% X = 3.5% Sbenzene = 80% Scyclohexane = 20% Sbenzene = 80% Sbenzene = 80% X = 3.5% 60,000 s CO co‐feed X = 3.5% X = 3.5% Sbenzene = 80% Yphenol = 38% Yphenol = 38% X = 3.5% Yphenol = 38% h WHSV = 0.54 h WHSV = 0.54Yphenol = 38% WHSV = 0.54 h WHSV = 0.54 h Ybenzene = 22% Ybenzene = 22% Yphenol = 38% Ybenzene = 22% Ybenzene = 22% X = 100% X = 100% WHSV = 0.54 h X = 100% X = 100% Ycresol = 27% Ycresol = 27% Ybenzene = 22% Ycresol = 27% Ycresol = 27% X = 100% X = 98%, Ycresol = 27% X = 98%,Ybenzene = 48% X = 98%, X = 98%, Ybenzene = 48% Ybenzene = 48% W/F = 0.2 X = 98%, W/F = 0.2Ybenzene = 48% W/F = 0.2 W/F = 0.2 Ybenzene = 48% W/F = 0.2

decane X = 7%, 80 min SHDO = 62% decane SHDO = 62% decane X = 7%, 80 min SHDO = 62% decane X = 7%, 80 min X = 7%, 80 min decane X = 7%, 80 min SHDO = 62%

SHDO = 62%

[63] No sintering [63] [63] [63]

[51] [51] [51] [51] [44] CO co-feed [44] [44]

[63]

[51] [44]

[44] [50] [50] [50] [50]

[50]

[24] [24] [24] [24]

[24]

[26] [26] [26] [26]

[26]

1,3,5-trimethoxybenzene 1,3,5‐trimethoxybenzene 1,3,5‐trimethoxybenzene OH 1,3,5‐trimethoxybenzene OH OH

4

4 4 4 4

O H3C OO HH33CC O H3C

OH

O OO CH 3 CH O CH 33 CH3

syringol syringol syringol Catalysts 2017, 7, 265 syringol 5 syringol 5 5 5

CoNx CoNx CoNx CoNx

CoNx

CoNx CoNx CoNx CoNx

OH

200 200 200 200 200 200 200 200

CoNx

5

MoO3/ZrO2,

20 20 20 20

200 350

MoO3 /ZrO2 , phenol

200

20 20 20 20

dodecane dodecane dodecane dodecane

X = 44% (2 h) X = 44% (2 h) X = 44% (2 h) h) 20 dodecane X = 44% (2 h) X = 44% (2Yguaiacol = 10% Yguaiacol = 10% Yguaiacol = 10% Yguaiacol = 10% dodecane X = 100% (2 h) Ycyclohexane = 91% dodecane X = 100% (2 h) Ycyclohexane = 91% dodecane X = 100% (2 h) Ycyclohexane = 91% dodecane X = 100% (2 h) Ycyclohexane = 91%

20 60

350

Ycyclohexane = 9% Ycyclohexane = 9% Ycyclohexane = 9% Ycyclohexane = 9% Ycyclohexane = 9%

dodecane n‐decane

60

X = 100% (2 h)

Yguaiacol = 10%

[63]

[39]

Ybenzene = 97

[39]

phenol

OH Ycyclohexane = 52%

HO 6

CoNx catechol

OH

200

20

dodecane

X = 100% (2 h)

Ycyclohexanol = 62%

[63]

7 of 42 [63] [63] [63] [63]

Ycyclohexane = 91%

Ybenzene = 97

n-decane

[63] [63] [63] [63]

[63]

Catalysts 2017, 7, 265 Catalysts 2017, 7, 265 Catalysts 2017, 7, 265 Catalysts 2017, 7, 265

7 of 42 7 of 42 7 of 42

OH OH OH

Entry

6 6 6 6

Reactant

8

T (◦ C)

60 60 60

CoNx CoNx CoNx CoNx

200 200 20 200 20 200 20

CoNx CoNx CoNx CoNx

Catalysts 2017, 7, 265 o‐cresol o‐cresol o-cresol o‐cresol

Solvent

1. Cont. Table

Ybenzene = 97 Ybenzene = 97 Ybenzene = 97


HDO Selectivity

Note

Ycyclohexane = 52% Ycyclohexane = 52% Ycyclohexane = 52% (2 h) 20 dodecane dodecane X = 100% (2 h) X = 100% Ycyclohexane = 52% dodecane X = 100% (2 h) dodecane X = 100% (2 h) Ycyclohexanol = 62% Ycyclohexanol = 62% Ycyclohexanol = 62% Ycyclohexanol = 62% Ycyclohexane = 45% Ycyclohexane = 45% Ycyclohexane = 45%

200 20 200 200 20 200 20

[39] [39] [39]

[63] [63] [63]

Reference

[63]

Ycyclohexane = 45%

dodecane X = 100% (2 h) [63] 20 dodecane dodecaneX = 100% (2 h) X = 100% (2 h) [63] dodecane X = 100% (2 h) [63] Ycyclohexanol = 43% Ycyclohexanol = 43% Ycyclohexanol = 43% Ycyclohexanol = 43% CO co‐feedTemperature 150 1.2 ‐ toluene [59] Mo2C CO co‐feedTemperature programmed reaction 150 1.2 ‐ toluene [59] Mo2C CO co-feedTemperature CO co‐feedTemperature programmed reaction 8 h Mo C 150 1.2 toluene 150 1.2 ‐ toluene [59] reaction Mo2C 2 programmed programmed reaction Ni/SiO2‐ZrO2 300 50 Stoluene = 93% [62] 8 h X = 100% Ni/SiO2‐ZrO2 300 50 Stoluene = 93% [62] 8 h 8h X = 100% Ni/SiO Ni/SiO 2‐ZrO 2 Stoluene = 93% [62] 300 50 50 Stoluene = 93% 2 -ZrO 2 300 8 h X = 100% X = 100% Ni/SiO2‐ZrO2 300 50 Stoluene = 93% [62] 8 h X = 100% 8 h Stoluene = 93% Ni/SiO2‐ZrO2 300 50 [62] 8 h 8 of 42 X = 100% Ni/SiO 300 50 50 Stoluene = 93% 2 -ZrO 2 300 Ni/SiO 2‐ZrO 2 Stoluene = 93% [62] X = 100% X = 100%

OH OH 1,3‐dihydroxybenzene OH 1,3-dihydroxybenzene 1,3‐dihydroxybenzene OH 1,3‐dihydroxybenzene OH CH3 OH CH3 CH3

8

n‐decane n‐decane n‐decane

P (bar)

OH OH

HO HO HO

catechol OH catechol OH OH

8 8

350 350 350

Catalyst

phenol phenol OH phenol

catechol catechol

7 7 7 7

MoO3/ZrO2, MoO3/ZrO2, MoO3/ZrO2,

7 of 40

[63]

[59] [62]

[62]

OH

9 9

H3C

CoNx CoNx

200

200 20

CoNx

200

20

20

dodecane Yisopropylcyclohexane = 99.2% dodecaneX = 100% (2 h) X = 100% (2 h) Yisopropylcyclohexane = 99.2%

[63]

dodecane

[63]

CH3

4-isopropylphenol 4‐isopropylphenol

OH

10

CH3 CH3

X = 100% (2 h)

3‐isopropylphenol

OH

Hydrogen 40

1 h

Yisopropylcyclohexane = 99.9%

[63]


8 of 42

OH Catalysts 2017, 7, 265

8 of 40

9

CoNx

200

20

dodecane

X = 100% (2 h)


[63]

Table 1. Cont. H3C Entry

CH3

Reactant 4‐isopropylphenol

T (◦ C)

Catalyst

P (bar)

Solvent


HDO Selectivity

Note

Reference

OH

1010

CH3 CH3

CoNx CoNx

200

200 20

dodecane 20

Pt/AC(N) Pt/AC(N)

280

40 Hydrogen 40 water 280 Loade at Loade at RT

X = 100% (2 h) dodecane

Yisopropylcyclohexane = 99.9% X = 100% (2 h)


[63]

[63]

[57]

[57]

3-isopropylphenol 3‐isopropylphenol

OH

Hydrogen

1111

1 h

water X = 100%

1h X = 100%

Ypropylcyclo‐hexane = 97% Ypropylcyclo-hexane = 97%

RT

CH3 Catalysts 2017, 7, 265 4-propylphenol 4‐propylphenol OH

12

9 of 42

CH3

Pt/AC(N)

280

O Pt/AC(N) Pd/C + HSM‐5

12

CH3

4-propylguaiacol 4‐propylguaiacol

OH

Hydrogen 40 water Loade at Hydrogen 40 RT

water

280 240

Pd/C + HSM-5

6 h X = 100%

50

Loade at RT

240

X = 86%, 4 h

50

Ypropylcyclo‐hexane = 65 Ypropylcyclopentane = 5

6h X = 100% Ypropenylcyclohexane = 75%

X = 86%, 4 h

[57]

Ypropylcyclo-hexane = 65 Ypropylcyclopentane = 5

[57] [27]

Ypropenylcyclohexane = 75%

[27]

CH3 O

13

Pt/AC(N)

O CH3

4‐(2‐propenal)‐guaiacol

CH3 O

OH

CH3 O

280

Hydrogen 40 Loade at RT

water

6 h X = 100%

Ypropylcyclo‐hexane = 65 Ypropylcyclo‐pentane = 6

[57]

OH OH

CH CH33 O O


Pd/C + HSM‐5 Pd/C + HSM‐5

240 240

50 50

X = 86%, 4 h X = 86%, 4 h

Ypropenylcyclohexane = 75% Ypropenylcyclohexane = 75%

9 of 40

[27] [27]

Table 1. Cont. CH CH33 Entry

Reactant 4‐propylguaiacol 4‐propylguaiacol

OH OH

T (◦ C)

Catalyst

P (bar)

Solvent


HDO Selectivity

Note

Reference

CH CH33 O O

1313 13

Pt/AC(N) Pt/AC(N) Pt/AC(N)

280 280

280

Hydrogen Hydrogen 40 40 Hydrogen 40 water water Loade at Loade at RT Loade at RT RT

water

Pt/AC(N) Pt/AC(N) Pt/AC(N)

280 280

Hydrogen Hydrogen 40 40 Hydrogen 40 water water 280 Loade at Loade at Loade at RT RT RT

water

O O CH CH33

6 h 6 h X = 100% X = 100%

Ypropylcyclo‐hexane = 65 6h Ypropylcyclo‐hexane = 65 Ypropylcyclo‐pentane = 6 X = 100% Ypropylcyclo‐pentane = 6

Ypropylcyclo-hexane = 65 Ypropylcyclo-pentane = 6

[57] [57]

[57]

6 h 6 h X = 97% X = 97%

Ypropylcyclo‐hexane = 58 6h Ypropylcyclo‐hexane = 58 Ypropylcyclopentane = 10 Ypropylcyclopentane = 10 X = 97%

Ypropylcyclo-hexane = 58 Ypropylcyclopentane = 10

[57] [57]

[57]

(1 h) X = 100% (1 h) X = 100%

Ypropylcyclo‐hexane = 17% Ypropylcyclo‐hexane = 17%

4-(2-propenal)-guaiacol 4‐(2‐propenal)‐guaiacol 4‐(2‐propenal)‐guaiacol

CH CH33

OH OH

CH CH33

O O

O O

14 1414

CH CH22

4-propenalsyringol 4‐propenalsyringol 4‐propenalsyringol Catalysts 2017, 7, 265 15 15

250 250 Pt/Silica alumina

OH O

30 30

hexadecane hexadecane

Ydihydroeugenol = 75%

Pt/Silica alumina

250

30

hexadecane

10 of 42 [49] [49]

Ypropylcyclo-hexane = 17%

(1 h) X = 100%

CH3

[49] Ydihydroeugenol = 75%

8 h

15 Ni/SiO2‐ZrO2

CH2

300

Ni/SiO2 -ZrO2

50

300

50

Spropylcyclohexane = 98% 8h

[62]

Spropylcyclohexane = 98%

X = 100%

[62]

X = 100%

eugenol eugenol

O

16

O OH

CH3

Ni/SiO2‐ZrO2

300

50

dodecane

(5) Xvan = 83%

Smethylcyclo‐hexane = 65% Scyclohexane = 31

[62]

Pd/TiO2‐N‐C

150

10

water

X = 91% (2 h)

Y 2‐methoxy‐4‐methylphenol = 78%

[29]

Vanillin

Pd‐


10 of 42 Pt/Silica alumina

OH O

Ydihydroeugenol = 75%

CH3 8 h

Catalysts 2017, 7, 265 Ni/SiO22‐ZrO22

300

50

10 of 40

Spropylcyclohexane = 98%

[62]

Table 1. Cont. X = 100%

CH2 Reactant eugenol

Entry

T (◦ C)

Catalyst

P (bar)

Solvent


HDO Selectivity

Note

Reference

O

16 16

Ni/SiO Ni/SiO 22‐ZrO 22 2 -ZrO 2 300

CH3

O OH

300 50

50 dodecane dodecane

150

10

(5) Smethylcyclo-hexane = 65% Smethylcyclo‐hexane = 65% Xvan = 83% Scyclohexane = 31 Scyclohexane = 31

(5) Xvan = 83%

[62]

[62]

Vanillin Vanillin

Pd/TiO -N-C

2 Pd/TiO22‐N‐C

150

Pd-carbonaceous Pd‐ microspheres

carbonaceous Mo2 C/AC microspheres Mo22C/AC

10

90 90

100

100

water

water

5.5 5.5

10

10

Y 2‐methoxy‐4‐methylphenol = X = 91% (2 h) Y 2-methoxy-4-methylphenol = 78%

X = 91% (2 h)

78%

water

X = 99% (3 h)

water

X = 99% (3 h)

water

X = 100% (3 h)

water

Sp‐creosol = 50%

X = 100% (3 h)

Sp‐creosol = 60%

[29]

Sp-creosol = 50%

[60]

[60]

[25]

Sp-creosol = 60%

[29]

[25]

HO X ≥ 99%

17 17

O

ZnCl 22 ZnCl 2

CH3

Y1,4-dimethoxy-phenol Y1,4‐dimethoxy‐phenol = 60% = 60%

MeOH MeOH

8 h

OH

X ≥ 99% [21] [21]

8h

Catalysts 2017, 7, 265 alcohol Vanillyl Vanillyl alcohol

11 of 42 CH3

8 h

18

18

O

Ni/SiO2‐ZrO2

Ni/SiO2 -ZrO2

CH3

300

300

50

50

Spropylcyclohexane = 99% Spropylcyclohexane = 99%

19

[62]

X = 100%

transanthole transanthole O

8h

X = 100% CH3

O

Pt/Al2O3

325

5

X = 75% W/F = 1 kg cat.s/mol

Sphenol = 87% Sbenzene = 20%

H2/O = 23

[61]

CoNx

200

20

dodecane

X = 100%

Ycyclohexane = 92%

[63]

CoNx

200

20

dodecane

C = 100%

Ycyclohexane = 99.9%

[63]

phenylacetate

O 20 Biphenyl ether O

21

HO

OH

4,4‐dihydroxydiphenyl ether OH

H3C

O

[62]

Catalysts 2017, 7, 265 Catalysts 2017, 7, 265 Catalysts 2017, 7, 265

11 of 42 11 of 42 11 of 42


18 18 18

11 of 40

CH CH333 CH

8 h 8 h 8 h

O O O

Ni/SiO Ni/SiO222‐ZrO 2‐ZrO ‐ZrO222 2 Ni/SiO

CH CH333 CH

Entry

Catalyst

2O33 O Pt/Al Pt/Al 2O Pt/Al 22O 3 3 2 Pt/Al 3

O O O

50 50 50

Table 1. Cont.

T (◦ C)

325 325 325 325

P (bar)

5 5 5

5

Solvent

phenylacetate phenylacetate phenylacetate phenylacetate

Spropylcyclohexane = 99% Spropylcyclohexane = 99% Spropylcyclohexane = 99%

[62] [62] [62]

X = 100% X = 100% X = 100%

transanthole Reactant transanthole transanthole O CH O CH333 O CH

19 19 19 19

300 300 300

Conversion % (Time, h) X = 75% X = 75% X = 75% Sphenol = 87% X = 75% Sphenol = 87% Sphenol = 87% W/F = 1 kg W/F = 1 kg W/F = 1 kg Sbenzene = 20% W/F = 1 kg cat.s/mol Sbenzene = 20% Sbenzene = 20% cat.s/mol cat.s/mol cat.s/mol

HDO Selectivity

Sphenol = 87%H2/O = 23 H22/O = 23 2/O = 23 H Sbenzene = 20%

Note

Reference

[61] H2 /O[61] = 23 [61]

[61]

O O O 20 20 20 20

CoNx CoNx CoNx CoNx

200 20 200 200 20 20 200

dodecane X = 100% 20 dodecane dodecane X = 100% dodecane X = 100%

Ycyclohexane = 92% X = 100% Ycyclohexane = 92% Ycyclohexane = 92% Ycyclohexane = 92%

[63] [63] [63]

[63]

CoNx CoNx CoNx CoNx

200 20 200 200 20 20 200

20 dodecane dodecane C = 100% dodecane C = 100% dodecane C = 100%

C = 100% Ycyclohexane = 99.9% Ycyclohexane = 99.9% Ycyclohexane = 99.9% Ycyclohexane = 99.9%

[63] [63] [63]

[63]

Zn/Pd/C Zn/Pd/C Zn/Pd/C Zn/Pd/C

150 21 150 150 21 21 150

21

Y2‐methoxy‐4‐propylphenol = Y2‐methoxy‐4‐propylphenol = Y2‐methoxy‐4‐propylphenol = Y2-methoxy-4-propylphenol 2h 85% 85% 85% = 85% X = 100%Yguaiacol = 85% Yguaiacol = 85% Yguaiacol = 85% Yguaiacol = 85%

[21] [21] [21]

[21]

Biphenyl ether Biphenyl ether Biphenyl ether Biphenyl ether O O O O

21 21 21 21

H O O HO O HH

OH OH OH OH

4,4-dihydroxydiphenyl 4,4‐dihydroxydiphenyl 4,4‐dihydroxydiphenyl 4,4‐dihydroxydiphenyl ether ether ether ether H C 3C H HH 3C O 33C O O O

OH OH OH OH

O O O O

22 22 22 22

H O O H O HH O

OH OH OH OH O O O CH O CH 3 CH CH 333

dimer dimer dimer dimer

MeOH MeOH MeOH MeOH

2 h 2 h 2 h X = 100% X = 100% X = 100%


12 of 40

Table 2. Comparative single feed HDO results using one catalyst. Notation: Yi, j is yield in which i is the reactant and j product, X denotes conversion and S selectivity. Comparison of the Reactivity

Catalyst

T (◦ C)

P (bar)

Phenol, anisole, guaiacol

MoO3 /ZrO2

350

Phenol, cresol, anisole, guaiacol, diphenyl ether

Guaiacol, anisole, phenol, o-cresol

Anisole, phenylacetate

Anisole, guaiacol

MoO3

10ReOx /CNFox

Pt/Al2 O3

Pt-Sn/CNF/Inconel

320

300

325

400


Products

Notation

Reference

60

Xphe = 48% Xanisole = 55% Xgua = 51%

Yphe, benzene = 46% Yani, benzene = 40% Ygua, phe = 23%

Trickle bed

[39]

1

-

Xphe = 29% Xani = 79% Xgua = 74% Xcre = 49% Xdip = 83%

Yphe, benzene = 44% Yani, benzene = 31% Ygua, phenol = 31% Ycre, toluene = 49% Ydip, benzene = 72%

With phenol the solvent is mesitylene

[36]

dodecane

(4 h) Xphe = 90% Xanisole = 100% Xgua = 100% Xcre = 44%

Yphe, cyclohexane = 51% Ygua, cyclohexane = 65% Yani, cyclohexane = 79% Ycre, methylcyclohexane = 18% Ycre, toluene = 16%

5

50 h time-on-stream Xani = 50% Xpheac = 58%

Spheac, benzylalcohol = 83% Spheac, benzene = 16% Sani, benzylalcohol = 55% Sani, benzene = 12

1

125 min TOS W/F = 2 g cat/g react h−1 Xgua = 97% Xani = 67%

Y gua, toluene = 63% Y ani, benzene = 38%

50

Solvent

[37]

H2 /O = 23.2

[61]

[48]


13 of 40

Catalysts 2017, 7, x FOR PEER REVIEW Catalysts 2017, 7, x FOR PEER REVIEW

13 of 42 13 of 42

For methoxylated benzenes, such as anisole, and trimethoxybenzene (Table 1, entries 3 and 4), For methoxylated benzenes, such as anisole, and trimethoxybenzene (Table 1, entries 3 and 4), it For methoxylated benzenes, such as anisole, and trimethoxybenzene (Table 1, entries 3 and 4), it it is easier to achieve HDO compared to guaiacol. For example, selectivity to anisole HDO products is easier to achieve HDO compared to guaiacol. For example, selectivity to anisole HDO products is easier to achieve HDO compared to guaiacol. For example, selectivity to anisole HDO products was 100% at relatively mild temperature of 150 ◦ C under atmospheric pressure over Mo2 C catalyst was 100% at relatively mild temperature of 150 °C under atmospheric pressure over Mo 2C catalyst was 100% at relatively mild temperature of 150 °C under atmospheric pressure over Mo 2C catalyst (Table 3, entry 3) [44]. (Table 3, entry 3) [44]. (Table 3, entry 3) [44].

Table 3. Homolytic bond dissociation energies forlignin lignin derived model molecules calculated by Table energies for Table 3. 3. Homolytic Homolytic bond bond dissociation dissociation for lignin derived derived model model molecules molecules calculated calculated by by ◦ C energies B3LYP/6–311 G(d,p) level theory at 320 in the gas phase adapted from reference [36] and comparison B3LYP/6–311 B3LYP/6–311 G(d,p) G(d,p) level level theory theory at at 320 320 °C °C in in the the gas gas phase phase adapted adapted from from reference reference [36] [36] and and withcomparison with other bond dissociation energies from the literature. Bond dissociation energies are other bond dissociation energies from the literature. Bond dissociation energies are given comparison with other bond dissociation energies from the literature. Bond dissociation energies are given in kJ/mol. in kJ/mol. given in kJ/mol. Monolignol Monolignol Monolignol Bond Bond Bond

Guaiacol Guaiacol Phenol M‐Cresol M-Cresol Anisole Anisole Guaiacol Phenol Phenol M‐Cresol Anisole

Ph-OH Ph‐OH Ph‐OH Ph-OCH 33 Ph‐OCH Ph‐OCH Ph-O—CH33 Ph‐O—CH 3 Ph‐O—CH Ph-OPh 3 Ph‐OPh Ph‐OPh aliphatic C-O aliphatic C‐O aliphatic C‐O

472 472 472 384 384 384 218 218 -218 -‐ ‐ ‐ ‐

481 481 481 397 397 397 205 205 205 ‐ - ‐ ‐ ‐

469 469 469 ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐

469 469 469 ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐

‐ ‐ 384 384 384 238 238 238

Diphenyl Diphenyl Diphenyl Ether Ether Ether O O

‐ -‐ ‐ -‐ ‐ ‐ 280 280 280

‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ [43] 339 339 [43] 339 [43]

Phenol HDO giving high conversions of cyclohexane at Phenol HDO is is also giving high and highyields yields cyclohexane at moderate Phenol HDO is also also giving high conversions conversions and and high high yields of of cyclohexane at moderate moderate temperatures under relatively high hydrogen pressures (Table 1, entry 5) [63]. On the other hand, temperatures under relatively high hydrogen pressures (Table 1, entry 5) [63]. On the other hand, temperatures under relatively high hydrogen pressures (Table 1, entry 5) [63]. On the other hand, dihydroxylated catechol was more difficult to deoxygenate compared to phenol, since this molecule dihydroxylated catechol was more difficult to deoxygenate compared to phenol, since this molecule dihydroxylated catechol was more difficult to deoxygenate compared to phenol, since this molecule exhibited sterical restrictions and strong adsorption containing two hydroxyl groups in the vicinity exhibited sterical restrictions and strong adsorption containing two hydroxyl groups in the vicinity exhibited sterical restrictions and strong adsorption containing two hydroxyl groups in the vicinity of each other (see Section 3.5.5). It was also observed that when the other hydroxyl was in the meta of each other (see Section 3.5.5). It was also observed that when the other hydroxyl was in the meta of each other (see Section 3.5.5). It was also observed that when the other hydroxyl was in the meta position, degree of HDO was much higher (Table 1, entry 7). The products in the HDO of guaiacol, position, degree of HDO was much higher (Table 1, entry 7). The products in the HDO of guaiacol, position, degree of HDO was much higher (Table 1, entry 7). The products in the HDO of guaiacol, phenol phenol and and anisole anisole are are mainly mainly aromatic aromatic compounds, compounds, such such as as benzene benzene and and toluene toluene at at high high phenol and anisolewhereas are mainly aromatic compounds, suchbelow as benzene andover toluene at highexhibiting temperatures, temperatures, cyclohexane can be formed 340 °C catalysts temperatures, whereas cyclohexane can be ◦formed below 340 °C over catalysts exhibiting whereas cyclohexane can be formed below 340 C over catalysts exhibiting hydrogenation activity, hydrogenation activity, such as supported Ni, Rh, ReOx, CoNx and MoO 3 [36,37,43,62,63]. hydrogenation activity, such as supported Ni, Rh, ReOx, CoNx and MoO 3 [36,37,43,62,63]. such as supported Ni, Rh, ReOx, CoNx and MoO3 [36,37,43,62,63]. Monooxygenated o‐cresol with a methyl group in ortho position is easy to deoxygenate (Table Monooxygenated o‐cresol with a methyl group in ortho position is easy to deoxygenate (Table 1, entry 8) [62]. For molecules containing three oxygenated groups, such as vanillin, maximally only Monooxygenated o-cresol with a methyl group in ortho position is easy to deoxygenate (Table 1, 1, entry 8) [62]. For molecules containing three oxygenated groups, such as vanillin, maximally only 2‐ZrO2 only entry65% selectivity towards methylcyclohexane was obtained at 300 °C under 50 bar over Ni/SiO 8) [62]. For molecules containing three oxygenated groups, such as vanillin, maximally 65% selectivity towards methylcyclohexane was obtained at 300 °C under 50 bar over Ni/SiO 2‐ZrO2 ◦ catalyst [62]. 65% selectivity towards methylcyclohexane was obtained at 300 C under 50 bar over Ni/SiO2 -ZrO2 catalyst [62]. The propyl substituted phenols, including 4‐isopropyl‐, and 4‐propylphenol easily underwent The propyl substituted phenols, including 4‐isopropyl‐, and 4‐propylphenol easily underwent catalyst [62]. hydrogenation and deoxygenation (Table 1, entries 1 and 9–11), whereas 4‐propylguaiacol and 4‐(2‐ hydrogenation and deoxygenation (Table 1, entries 1 and 9–11), whereas 4‐propylguaiacol and 4‐(2‐ The propyl substituted phenols, including 4-isopropyl-, and 4-propylphenol easily underwent propenyl)‐guaiacol gave slightly lower HDO degree due to presence of three oxygenated substituents propenyl)‐guaiacol gave slightly lower HDO degree due to presence of three oxygenated substituents hydrogenation and deoxygenation (Table 1, entries 1 and 9–11), whereas 4-propylguaiacol and (Table 1, entries 12 and 13). Noteworthy is also that 4‐propensyringol was transformed not only to 4‐ (Table 1, entries 12 and 13). Noteworthy is also that 4‐propensyringol was transformed not only to 4‐ 4-(2-propenyl)-guaiacol gave slightly lower HDO degree due toin presence ofdeoxygenation three oxygenated propylcyclohexane, propylcyclohexane, but also but also to 4‐propylcyclopentane to 4‐propylcyclopentane indicating indicating that that in addition addition to to deoxygenation substituents (Table 1, entries 12 and 13). Noteworthy is also that 4-propensyringol was transformed and ring hydrogenation in this case ring contraction occurred (Table 1, entry 14). and ring hydrogenation in this case ring contraction occurred (Table 1, entry 14). not onlyFor to 4-propylcyclohexane, but also to°C 4-propylcyclopentane indicating that in addition to eugenol bar the however, For eugenol HDO HDO under under 30 30 bar at at 250 250 °C the main main product product was, was, however, dihydroeugenol dihydroeugenol showing difficulties to hydrogenate the phenyl ring at these conditions (Table 1, 15) deoxygenation and ring hydrogenation in this case ring contraction occurred (Table 1, entry 14). showing difficulties to hydrogenate the phenyl ring at these conditions (Table 1, entry entry 15) [49], [49], ◦ whereas at elevated temperature and pressure the main product was 4‐propylcyclohexane [62]. The For eugenol HDO under 30 bar at 250 C the main product was, however, dihydroeugenol whereas at elevated temperature and pressure the main product was 4‐propylcyclohexane [62]. The same was HDO which maximally gave selectivity towards same difficulties was valid valid tofor for HDO of of vanillin vanillin which maximally gave 65% 65% (Table selectivity towards showing hydrogenate the phenyl ring at these conditions 1, entry 15) [49], methylcyclohexane at 300 °C under 50 bar over Ni/SiO 2‐ZrO2 catalyst (Table 1, entry 16). The main methylcyclohexane at 300 °C under 50 bar over Ni/SiO 2‐ZrOproduct 2 catalyst (Table 1, entry 16). The main whereas at elevated temperature and pressure the main was 4-propylcyclohexane [62]. product from vanillyl alcohol HDO is 1,4‐dimethoxyphenol using ZnCl2 as a catalyst in methanol product from vanillyl alcohol HDO is 1,4‐dimethoxyphenol using 2 as a catalyst in methanol The same was valid for HDO of vanillin which maximallyZnCl gave 65% selectivity towards (Table 1, entry 17) [21]. Transanthole contains both propyl and methoxy substituents and it is easy to (Table 1, entry 17) [21]. Transanthole contains both propyl and methoxy substituents and it is easy to methylcyclohexane at 300 ◦ C under 50 bar over Ni/SiO2 -ZrO2 catalyst (Table 1, entry 16). The main deoxygenate (Table 1, entry 18). Phenylacetate formed in bio‐oil via a reaction between acetic acid deoxygenate (Table 1, entry 18). Phenylacetate formed in bio‐oil via a reaction between acetic acid product from vanillyl alcohol HDO is 1,4-dimethoxyphenol using ZnCl 2 as a catalyst in methanol and phenol underwent HDO at 325 °C under 5 bar hydrogen over Pt/Al 2O3 catalyst [61]. At elevated and phenol underwent HDO at 325 °C under 5 bar hydrogen over Pt/Al 2O3 catalyst [61]. At elevated (Table 1, entry 17) [21]. Transanthole contains both propyl and methoxy substituents and it is 1, easy to temperature due to thermodynamic limitations the main product was phenol temperature due to thermodynamic limitations the main product was phenol (Figure (Figure 4, 4, Table Table 1, deoxygenate (Table 1, entry 18). Phenylacetate formed in bio-oil via a reaction between acetic acid entry 19) [61]. entry 19) [61]. ◦ and phenol underwent HDO at 325 C under 5 bar hydrogen over Pt/Al2 O3 catalyst [61]. At elevated temperature due to thermodynamic limitations the main product was phenol (Figure 4, Table 1, entry 19) [61]. Catalysts 2017, 7, 265; doi:10.3390/catal7090265 Catalysts 2017, 7, 265; doi:10.3390/catal7090265

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Table 4. Comparison of the HDO using mixtures or bio-oil. Notation: X is conversion, Y yield and S selectivity. Comparison of the Reactivity

Catalyst

T (◦ C)

P (bar)

Solvent


HDO Selectivity

Reference

25 wt % Guaiacol, 25 wt % o-cresol, 50 wt % phenol mixture

NiFe/H-Beta

300

16

water

(4 h) Xphe = 50% Xcre = 68% Xgua = 88%

Ycycloalkane = 22% Yarom. HC = 29%

[40]

Bio-oil

Pt/C

350

78% HDO, reuse, Van Krevelan

[30]

Phenol, vanillin, cresol, eugenol, trans-anethole

Ni/SiO2 -ZrO2

300

50

dodecane

Xphe = 100% Xtransanethole = 100% Xeug = 100% Xo-cre = 100%

Scyclohexane = 98% Smethylcyclohexane = 93%e

[62]

Bio-oil

Ni/SiO2 -ZrO2

300

50

Dodecane

(8 h) 86% of identified compounds transformed to cyclic hydrocarbons

Yphenolic = 8 wt % Yarom. HC = 8 wt % Ycyclic alkanes = 55 wt %

[62]

Guaiacol, eugenol

Pt/

250

30

hexadecane

(1 h) Xgua = 88% Xeug = 100%

Ydihydroeugenol = 80% Ycyclohexane = 85%

[49]

m-cresol, anisole, 1,2-dimethoxybenzene, guaiacol

Supercritical EtOH

Sbenzene = 66% Mo2 C

280

1.14

-

Stoluene = 27%

[42]

Scyclohexane = 5% Yield 13 g/100 g oil in water and organic phase

[35]

ethanol

Y = 22 wt %

[30]

ethanol

Deoxygenation degree 54.9%

[4]

20

ethanol

Ylignin monomer = 51% HDO degree = 84%

[3]

320

hexadecane

Shydrocarbon = 70%

[2]

Ni/SiO2

250

80 at 25 ◦ C

Water 57%

Bio-oil

Pd/C

350

30

Bio-oil

Ni/SBA-15

300

30

Soda-lignin

CuMgAlOx + NiO/SiO2 containing Ni2 P

340

Organosolv lignin

Ni/H-BEA

20

Bio-oil

Xmixture = 94%

X = 100%, 6 h

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Figure 4. Results from kinetic results of the gas-phase HDO of phenyl acetate over Pt/Al2 O3 catalyst Figure 4. Results from kinetic results of the gas‐phase HDO of phenyl acetate over Pt/Al2O3 catalyst at 325 ◦ C under 5 bar with H2 /O ratio of 23 [61]. at 325 °C under 5 bar with H2/O ratio of 23 [61].

Dimeric asas biphenyl ether andand the corresponding 4,4-dihydroxydiphenyl ether Dimeric compounds, compounds, such such biphenyl ether the corresponding 4,4‐dihydroxydiphenyl can be also easily deoxygenated to cycloalkanes (Table 1, entries 20 and 21), whereas a synthetic ether can be also easily deoxygenated to cycloalkanes (Table 1, entries 20 and 21), whereas a synthetic β-O-4 lignin dimer, guaiacylglycerol-β-4-O-guaiacyl could only be transformed to 2-methoxyphenol ‐O‐4 lignin dimer, guaiacylglycerol‐ ‐4‐O‐guaiacyl could only be transformed to 2‐methoxyphenol and guaiacol via via breaking breakingthe theether ether linkage in HDO its HDO reaction performed with Zn/Pd/C and guaiacol linkage in its reaction performed with Zn/Pd/C system ◦ C in methanol [21]. The minor product was 3-(3-methoxysystem under 21 bar hydrogen at 150 under 21 bar hydrogen at 150 °C in methanol [21]. The minor product was 3‐(3‐methoxy‐4‐ 4-hydroxyphenyl)-1-propanol. Synergy between Pd and Zn promoted the bond cleavage and a further hydroxyphenyl)‐1‐propanol. Synergy between Pd and Zn promoted the bond cleavage and a further reaction of the monomeric units on the catalyst surface with spillover hydrogen. reaction of the monomeric units on the catalyst surface with spillover hydrogen. 3.2. Comparative Studies of a Single Feed Reactant over the Same Catalysts 3.2. Comparative Studies of a Single Feed Reactant over the Same Catalysts From HDO of different model compounds, comprising guaiacol, anisole, phenol and o-cresol From HDO of different model compounds, comprising guaiacol, anisole, phenol and o‐cresol with a single reactant over the same catalyst it is possible to compare their relative reactivity, with a single reactant over the same catalyst it is possible to compare their relative reactivity, which which is of high interest for industrial applications (Table 2) [36,37,39,48]. Results over ReOx/CNF is of high interest for industrial applications (Table 2) [36,37,39,48]. Results over ReOx/CNF catalyst catalyst at elevated temperature, 300 ◦ C and pressure of 50 bar showed that conversion of four at elevated temperature, 300 °C and pressure of 50 bar showed that conversion of four different model different model molecules decreased in the following order: guaiacol = anisole > phenol > cresol molecules decreased in the following order: guaiacol = anisole > phenol > cresol (Figure 5) [37]. In the (Figure 5) [37]. In the work of Prasomsri et al. [36] the corresponding reactivity was the following: work of Prasomsri et al. [36] the corresponding reactivity was the following: diphenyl > anisole > diphenyl > anisole > guaiacol > phenol > o-cresol [36]. Thus, dehydroxylation of the phenyl ring is guaiacol > phenol > o‐cresol [36]. Thus, dehydroxylation of the phenyl ring is difficult [37,39,48,61]. difficult [37,39,48,61]. Reactivity of anisole higher than guaiacol reported in [39] similarly to the work Reactivity of anisole higher than guaiacol reported in [39] similarly to the work of Prasomsri et al. of Prasomsri et al. [36], can be explained by a higher bond dissociation energy required for the aromatic [36], can be explained by a higher bond dissociation energy required for the aromatic hydroxyl hydroxyl compared to methoxyl (Table 3). For o-cresol the preferred route is demethoxylation followed compared to methoxyl (Table 3). For o‐cresol the preferred route is demethoxylation followed by ring by ring hydrogenation [37]. Only when HDO was performed at 400 ◦ C over Pt-Sn/CNF/Inconel hydrogenation [37]. Only when HDO was performed at 400 °C over Pt‐Sn/CNF/Inconel nickel‐ nickel-(Inconel is chromium-based superalloy), guaiacol reactivity was higher than for anisole probably (Inconel is chromium‐based superalloy), guaiacol reactivity was higher than for anisole probably due due to a very high temperature [48]. Biphenyl with an ether bond is easy to break, as experimentally to a very high temperature [48]. Biphenyl with an ether bond is easy to break, as experimentally and and theoretically shown [36]. theoretically shown [36].

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Conversion/ Yield (mol-%)

100

80

60

40

20

0 0

20

40

60

80 100 120 140 160 180 200 220 240

Time (min)

(a)


100

80

60

40

20

0 0

20

40

60

80 100 120 140 160 180 200 220 240

Time (min) (b) Figure 5. Cont.


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100

80

60

40

20

0 0

20

40

60

80 100 120 140 160 180 200 220 240

Time (min)

(c)


100

80

60

40

20

0 0

20

40

60

80 100 120 140 160 180 200 220 240

Time (min)

(d) Figure 5. Comparative HDO of different model compounds over 10 wt % ReOx/CNF in dodecane at Figure 5. Comparative HDO of different model compounds over 10 wt % ReOx/CNF in dodecane at 300 °C under 5 MPa hydrogen adapted from reference [37], HDO of (a) guaiacol; (b) phenol; (c) anisole 300 ◦ C under 5 MPa hydrogen adapted from reference [37], HDO of (a) guaiacol; (b) phenol; (c) anisole and (d) o‐cresol. Notation: (■) conversion, (+) phenol, (x) benzene, (◊) toluene, (o) cyclohexane, (▲) and (d) o-cresol. Notation: () conversion, (+) phenol, (x) benzene, (♦) toluene, (o) cyclohexane, methoxycyclohexane, () cyclohexanol, () cyclohexene, (●) lights. (N) methoxycyclohexane, (∆) cyclohexanol, (∇) cyclohexene, ( ) lights.

In a mixture of guaiacol and eugenol a slightly higher conversion levels were obtained for HDO In a mixture of guaiacol and eugenol a slightly higher conversion levels were obtained with the latter molecule at 250 °C under 30 MPa over Pt/C and Pt/aluminosilicate catalysts [49]. The for HDO with the latter molecule at 250 ◦ C under 30 MPa over Pt/C and Pt/aluminosilicate main product with Pt/SA was 2‐methoxy‐4‐propylphenol, whereas 2‐methoxy‐4‐propylcyclohexanol catalysts [49]. The main product with Pt/SA was 2-methoxy-4-propylphenol, whereas 2-methoxy-4was mainly generated over Pt/C [49]. It is also interesting that when dehydroxylation occurred over propylcyclohexanol was mainly generated over Pt/C [49]. It is also interesting that when an acidic Pt supported on silica alumina, the reaction did not proceed to ring hydrogenation contrary dehydroxylation occurred over an acidic Pt supported on silica alumina, the reaction did not proceed to Pt/C. to ring hydrogenation contrary to Pt/C. Temperature is one of the main parameters affecting product distribution in the HDO of phenolic mixtures. This was visible, for example, in the HDO of mixtures at high temperature, above 350 °C, when aromatic compounds were the main products [39,48], whereas below this temperature


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Temperature is one of the main parameters affecting product distribution in the HDO of phenolic mixtures. This was visible, for example, in the HDO of mixtures at high temperature, above 350 ◦ C, when aromatic compounds were the main products [39,48], whereas below this temperature non-aromatic cyclic hydrocarbons are also formed [36,37]. For example, in guaiacol HDO, phenol was the main product in accordance with a higher bond dissociation energy for Ar-OH compared to that of Ar-OCH3 [39] (Table 3). In case of o-cresol HDO the main products were methylcyclohexane and toluene requiring dehydration with a high bond dissociation energy for Ar–OH probably also explaining a low conversion of o-cresol. In the gas-phase HDO of a mixture of model compounds, m-cresol, anisole, dimethoxybenzene and guaiacol at 280 ◦ C under 114 kPa over Mo2 C catalyst, phenol was seen to decrease with an increase of conversion. Two other main products were benzene and toluene. These results indicated that aromatic –OCH3 bond was preferentially cleaved from guaiacol prior to the cleavage of aromatic –OH group [42]. These results were in accordance with the computational chemistry calculations of the bond dissociation energies being for Ar-OCH3 and Ar-OH in guaiacol equal to 376 kJ/mol and 456 kJ/mol [36]. 3.3. Reaction Pathways and the Thermodynamic Feasibility of Different Reactions during HDO of Model Compounds Since several different reactions occur during HDO of model compounds one of the main aims in using them is to elucidate the reaction pathways during HDO [32,37,48–50]. In addition to kinetic studies, also adsorption studies [48], theoretical DFT (density function theory) calculations [22,71–75] and bond dissociation energy calculations [36] have been performed. 3.3.1. Kinetic Studies Elucidating the Reaction Pathways during HDO of Model Compounds Guaiacol hydrodeoxygenation can proceed via either demethoxylation pathway forming in the first step phenol at 300 ◦ C under 50 bar hydrogen over ReOx/CNF (Figures 5 and 6) [37] and mainly phenol over Ni-catalysts at 350 ◦ C (Figure 7) [50] or alternatively via dehydroxylation pathway forming first phenol and subsequently cyclohexanol and finally cyclohexane at moderate temperature, when hydrogenation is thermodynamically feasible, e.g., over Pt/silica aluminate at 250 ◦ C under 30 bar hydrogen [49] and above 250 ◦ C over an Rh catalyst (Figure 8) [45]. Phenol was also the main product in guaiacol HDO at 400 ◦ C under atmospheric conditions over Co/Al-MCM-41 [34]. These results clearly show that both the metal type and reaction conditions, i.e., pressure and temperature, are decisive for the product distribution, for example, towards ring hydrogenation or HDO products. On acidic catalysts catechol is formed as the major product from guaiacol and anisole having low reactivity for further transformations [32]. Substantial amounts of catechol were also formed over Pt/C catalyst in HDO of guaiacol at 300 ◦ C under atmospheric pressure (Figure 9) [22]. Further reaction is very slow due to strong adsorption on the catalyst surface, in line with DFT calculations (see Section 3.3.2) [22]. It is also interesting to note that catechol formation was more prominent in HDO of guaiacol over Ru/C catalyst at 350 ◦ C than at 400 ◦ C, which was probably also related to temperature dependence of adsorption, namely low desorption of catechol at lower temperature [16]. According to a DFT study for Ru(0001) surface it was concluded that catecholate is formed prior to phenolate, finally yielding phenol as the main product [74].


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12

CH 3

+ CH4 ME CH3

OH CH 3

ME + CH4 ‐ H2 OH

CH 3 O

OH

DMO +H2

‐ CH3OH 1

CH3

+3 H2

+H2

HYD

‐ H2O 10

9

11

OH

+5 H2

+ H2 ‐ H2O

2 +H2

4

3

HYD

5 ‐ CH3OH DMO

+3 H2 +H2 ‐ H2O

DDO

7

+H2

CH 3

+H2

O

HYD

6

CH 3 O

+3 H2 8

Figure 6. Reaction scheme for guaiacol HDO at 300 °C under 50 bar hydrogen over ReOx/CNF catalyst ◦ adapted from reference [37]. Notation: 1. guaiacol, 2, phenol, 3. cyclohexanol, 5. cyclohexene, 5, cyclohexane, 6. methoxybenzene, 7. benzene, 8. methoxycyclohexanol, 9. O‐cresol, 10. toluene, methylcyclohexne and 11. xylene. DMO denotes demethoxylation, DDO direct deoxygenation, ME methanation and HYD hydrogenation.

Figure 6. Reaction scheme for guaiacol HDO at 300 C under 50 bar hydrogen over ReOx/CNF catalyst adapted from reference [37]. Notation: 1. guaiacol, 2, phenol, 3. cyclohexanol, 5. cyclohexene, 5, cyclohexane, 6. methoxybenzene, 7. benzene, 8. methoxycyclohexanol, 9. O-cresol, 10. toluene, methylcyclohexne and 11. xylene. DMO denotes demethoxylation, DDO direct deoxygenation, ME methanation and HYD hydrogenation. Catalysts 2017, 7, x FOR PEER REVIEW

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Figure 7. Proposed reaction network for guaiacol hydrodeoxygenation over Ni-based catalysts at 350 ◦ C [50]. Figure 7. Proposed reaction network for guaiacol hydrodeoxygenation over Ni‐based catalysts at 350 °C [50].

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Figure 8. Guaiacol HDO over bifunctional metal supported acidic catalysts [45]. Figure 8. Guaiacol HDO over bifunctional metal supported acidic catalysts [45]. Figure 8. Guaiacol HDO over bifunctional metal supported acidic catalysts [45].

Figure 9. Kinetic for guaiacol HDO over Pt/C catalyst at 300 ◦ C under atmospheric pressure [22]. Figure 9. Kinetic for guaiacol HDO over Pt/C catalyst at 300 °C under atmospheric pressure [22].

In Figure 9. Kinetic for guaiacol HDO over Pt/C catalyst at 300 °C under atmospheric pressure [22]. case of anisole the reaction rate is very high due to demethoxylation occurring more easily In case of anisole the reaction rate is very high due to demethoxylation occurring more easily for for anisole compared to guaiacol, most probably due to a strong adsorption of the hydroxyl group anisole compared to guaiacol, most probably due to a strong adsorption of the hydroxyl group In case of anisole the reaction rate is very high due to demethoxylation occurring more easily for lowering demethoxylation rate of guaiacol [37]. Phenol dehydroxylation is rather slow due to a high lowering demethoxylation rate of guaiacol [37]. Phenol dehydroxylation is rather slow due to a high anisole compared to guaiacol, most to a strong adsorption of the hydroxyl group bond dissociation energy required forprobably phenolic due hydroxyl group as already mentioned. In addition, bond dissociation energy required for phenolic hydroxyl group as already mentioned. In addition, lowering demethoxylation rate of guaiacol [37]. Phenol dehydroxylation is rather slow due to a high dehydroxylation rate is diminished for methyl substituted phenols due to steric hindrance. dehydroxylation rate is diminished for methyl substituted phenols due to steric hindrance. bond dissociation energy required for phenolic hydroxyl group as already mentioned. In addition, In eugenol HDO the following reaction network was proposed over Pd supported on Al2 O3 , In eugenol HDO the following reaction dehydroxylation rate is diminished for methyl substituted phenols due to steric hindrance. ◦ network was proposed over Pd supported on Al2O3, SiO 2 , C and alumina silicate catalysts at 250 C under 30 bar hydrogen in hexadecane (Figure 10): SiO2In , C and alumina silicate catalysts at 250 °C under 30 bar hydrogen in hexadecane (Figure 10): eugenol forming HDO the following reaction network was followed proposed by over supported on Aland 2O3, hydrogenation 2-methoxy-4-propylcyclohexanol itsPd demethoxylation hydrogenation forming 2‐methoxy‐4‐propylcyclohexanol followed by its demethoxylation and SiO2, C and alumina silicate catalysts at 250 °C under 30 bar hydrogen in hexadecane (Figure 10): hydrolysis forming 2-hydroxy-4-propylcyclohexanol and methanol [49]. Over acidic sites dehydration hydrolysis forming 2‐hydroxy‐4‐propylcyclohexanol and methanol [49]. Over acidic sites hydrogenation forming 2‐methoxy‐4‐propylcyclohexanol followed toby demethoxylation and of hydroxypropylcyclohexanol can happen with further hydrogenation theits corresponding saturated dehydration of hydroxypropylcyclohexanol can happen with further hydrogenation to the hydrolysis forming 2‐hydroxy‐4‐propylcyclohexanol and methanol [49]. Over acidic sites compound. In addition, dealkylation can occur on the acidic sites causing cleavage of the propyl corresponding saturated compound. In addition, dealkylation can occur on the acidic sites causing dehydration of hydroxypropylcyclohexanol happen with further hydrogenation the chain, finally forming cyclohexanol. These resultscan show also difficulties of deoxygenation over to Pd/C. cleavage of the propyl chain, finally forming cyclohexanol. These results show also difficulties of corresponding saturated compound. In addition, dealkylation can occur on the acidic sites causing In addition, HDO of 2-methyl-4-propylphenol was tested using a mixture of Pd/C–H-ZSM-5 giving a deoxygenation over Pd/C. In addition, HDO of 2‐methyl‐4‐propylphenol was tested using a mixture cleavage of the propyl chain, finally These [27] results show also difficulties of relatively high conversion and yield forforming mainly cyclohexanol. propylcyclohexene showing that some acidity is of Pd/C–H‐ZSM‐5 giving a relatively high conversion and yield for mainly propylcyclohexene [27] deoxygenation over Pd/C. In addition, HDO of 2‐methyl‐4‐propylphenol was tested using a mixture needed for HDO. In eugenol HDO the best selectivity towards the desired product was achieved using showing that some acidity is needed for HDO. In eugenol HDO the best selectivity towards the of Pd/C–H‐ZSM‐5 giving a relatively high conversion and yield for mainly propylcyclohexene [27] Pd/C and H-ZSM-5 (Figure 11). HDO activity increased with acidity increase. The kinetic diameter showing that some acidity is needed for HDO. In eugenol HDO the best selectivity towards the


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desired product was achieved using Pd/C and H‐ZSM‐5 (Figure 11). HDO activity increased with acidity increase. The kinetic diameter of eugenol is, however, smaller than the pore size of H‐ZSM‐5. of eugenol is, however, smaller than the pore size of H-ZSM-5. Alkali leached H-ZSM-5 exhibiting Alkali leached H‐ZSM‐5 exhibiting mesopores was used in eugenol HDO giving 60% selectivity to mesopores was used in eugenol HDO giving 60% selectivity to hydrocarbons at 240 ◦ C under 50 bar hydrocarbons at 240 °C under 50 bar hydrogen [27]. It was stated by Zhang et al. [27] that the key hydrogen [27]. It was stated by Zhang et al. [27] that the key factors inhibiting transformations of factors inhibiting transformations of polysubstituted phenols are sterical hindrance, for example, the polysubstituted phenols are sterical hindrance, for example, the bulkiness of the alkyl substituent in bulkiness of the alkyl substituent in the aromatic ring. the aromatic ring.

Figure 10. Reaction scheme for eugenol HDO over various Pd catalysts supported on Al2 O3 , Figure 10. aluminosilicate Reaction scheme for eugenol over at various Pd incatalysts supported on Al2O3, SiO2, SiO2 , carbon and under 30 bar HDO hydrogen 250 ◦ C hexadecane as a solvent carbon and aluminosilicate under 30 bar hydrogen at 250 °C in hexadecane as a solvent adapted from adapted from reference [49]. Notation: 1. Eugenol, 2. Isoeugenol, 3. 2-methoxy-4-propylphenol, reference [49]. Notation: 1. 5. Eugenol, 2. Isoeugenol, 3. 2‐methoxy‐4‐propylphenol, 4. 2‐methoxy‐4‐ 4. 2-methoxy-4-propylcyclohexanol, 3-propylmethoxycyclohexane, 6. 4-methyl-2-methoxyphenol, propylcyclohexanol, 5. 3‐propylmethoxycyclohexane, 6. 4‐methyl‐2‐methoxyphenol, 7. 4‐ 7. 4-propylphenol, 8. 4-propylcyclohexanol and 9. propylcyclohexane. propylphenol, 8. 4‐propylcyclohexanol and 9. propylcyclohexane.

In vanillin HDO full deoxygenation was not achieved at 150 ◦ C under 10 bar hydrogen in In vanillin HDO full deoxygenation was not achieved at 150 °C under 10 bar hydrogen in water water over mesoporous Pd/TiO2 -CNx giving the main product 2-methoxy-4-methylphenol with 78% over mesoporous Pd/TiO2‐CNx giving the main product 2‐methoxy‐4‐methylphenol with 78% selectivity at 91% conversion [29]. The reaction proceeded via hydrogenation of the aldehyde group selectivity at 91% conversion [29]. The reaction proceeded via hydrogenation of the aldehyde group followed by dehydroxylation of the formed alcohol (Figure 12). The pressure applied was not sufficient followed by dehydroxylation of the formed alcohol (Figure 12). The pressure applied was not to hydrogenate the phenyl ring while acidity was not enough to catalyze deoxygenation. sufficient to hydrogenate the phenyl ring while acidity was not enough to catalyze deoxygenation. Cleavage of lignin β-O-4-link model molecules has been experimentally investigated over Cleavage of lignin ‐O‐4‐link model molecules has been experimentally investigated over CuO/γ-Al2 O3 catalyst at 150 ◦ C under 25 bar hydrogen. The experimental results have been confirmed CuO/ ‐Al2O3 catalyst at 150 °C under 25 bar hydrogen. The experimental results have been confirmed by calculating the bond dissociation energies of the corresponding compounds [53]. by calculating the bond dissociation energies of the corresponding compounds [53].


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Figure 11. Conversion and product selectivity in HDO of eugenol at 240 ◦ C under 50 bar hydrogen Figure 11. Conversion and product selectivity in HDO of eugenol at 240 °C under 50 bar hydrogen after Figure 11. Conversion and product selectivity in HDO of eugenol at 240 °C under 50 bar hydrogen 4 h over Pd/C catalyst together with HZSM-5 with different acidity [27]. after 4 h over Pd/C catalyst together with HZSM‐5 with different acidity [27]. after 4 h over Pd/C catalyst together with HZSM‐5 with different acidity [27].

Figure 12. Reaction scheme for HDO of vanillin under 10 bar hydrogen in water at 70–150 ◦ C over Figure 12. Reaction scheme for HDO of vanillin under 10 bar hydrogen in water at 70–150 °C over Pd/TiO from reference [29]. Notation (a) vanillin; (b) 4-hydroxymethyl-2-methoxyphenol 2 adapted Pd/TiO 2 adapted from reference [29]. Notation (a) vanillin; (b) 4‐hydroxymethyl‐2‐methoxyphenol Figure 12. Reaction scheme for HDO of vanillin under 10 bar hydrogen in water at 70–150 °C over and (c) 2-methoxy-4-methylphenol. and (c) 2‐methoxy‐4‐methylphenol. Pd/TiO2 adapted from reference [29]. Notation (a) vanillin; (b) 4‐hydroxymethyl‐2‐methoxyphenol and (c) 2‐methoxy‐4‐methylphenol. 3.3.2. Different Reactions and Their Thermodynamic Feasibility in HDO of Model Compounds

3.3.2. Different Reactions and Their Thermodynamic Feasibility in HDO of Model Compounds

Thermodynamic feasibility of different reactions occurring during HDO of lignin based model 3.3.2. Different Reactions and Their Thermodynamic Feasibility in HDO of Model Compounds Thermodynamic feasibility of different reactions occurring during HDO of lignin based model molecules together with the specific catalyst properties are summarized below. During HDO several molecules together with the specific catalyst properties are summarized below. During HDO several Thermodynamic feasibility of different reactions occurring during HDO of lignin based model reactions, such as demethoxylation, hydrogenation, transalkylation, hydrogenolysis, demethylation, reactions, such as demethoxylation, hydrogenation, transalkylation, hydrogenolysis, demethylation, ring opening, decarbonylation, oligomerisation can occur. molecules together with the specific catalyst properties are summarized below. During HDO several ring opening, decarbonylation, oligomerisation can occur. Demethoxylation is one of the main desired reactions for HDO occurring typically at relatively reactions, such as demethoxylation, hydrogenation, transalkylation, hydrogenolysis, demethylation, Demethoxylation is one the main desired reactions forHDO HDO occurring typically of at 1,3,5‐ relatively high temperature prior to of dehydroxylation during guaiacol [50]. Demethoxylation ring opening, decarbonylation, oligomerisation can occur. high trimethoxybenzene followed by ring hydrogenation occurred over Rh/MCM‐36 at 250 °C under 40 temperature prior to dehydroxylation during guaiacol HDO [50]. Demethoxylation of Demethoxylation is one of the main desired reactions for HDO occurring typically at relatively bar hydrogen in decane [26]. It was concluded in [34] that demethoxylation was catalyzed by metal 1,3,5-trimethoxybenzene followed by ring hydrogenation occurred over Rh/MCM-36 at 250 ◦ C under high temperature prior to dehydroxylation during guaiacol HDO [50]. Demethoxylation of 1,3,5‐ 40 barsites using Co‐ and Ni‐catalysts supported with Al‐MCM‐41 at 400 °C under atmospheric pressure hydrogen in decane [26]. It was concluded in [34] that demethoxylation was catalyzed by metal trimethoxybenzene followed by ring hydrogenation occurred over Rh/MCM‐36 at 250 °C under 40 [34]. Cyclopentanone formation occurred during HDO of guaiacol over Pt/C catalyst at 300 °C under sites using Co- and Ni-catalysts supported with Al-MCM-41 at 400 ◦ C under atmospheric pressure [34]. bar hydrogen in decane [26]. It was concluded in [34] that demethoxylation was catalyzed by metal Cyclopentanone formation occurred during HDO of guaiacol over Pt/C catalyst at 300 ◦ C under sites using Co‐ and Ni‐catalysts supported with Al‐MCM‐41 at 400 °C under atmospheric pressure [34]. Cyclopentanone formation occurred during HDO of guaiacol over Pt/C catalyst at 300 °C under


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atmospheric pressure [31]. The proposed reaction network for guaiacol HDO proposed over Pt/C is atmospheric pressure [31]. The proposed reaction network for guaiacol HDO proposed over Pt/C is shown in Figure 13a. Cyclopentanone was formed via hydroxycycloalkene intermediate and its ring shown in Figure 13a. Cyclopentanone was formed via hydroxycycloalkene intermediate and its ring opening [41]. Slow demethoxylation of guaiacol observed experimentally was in agreement with DFT opening [41]. Slow demethoxylation of guaiacol observed experimentally was in agreement with DFT calculations for HDO on Pt(111) surface (Figure 13b) [22] leading to formation of large amounts of calculations for HDO on Pt(111) surface (Figure 13b) [22] leading to formation of large amounts of catechol. Formation of cyclopentanone was confirmed by DFT calculations made for guaiacol HDO catechol. Formation of cyclopentanone was confirmed by DFT calculations made for guaiacol HDO over Pt(111). This product can be formed by partial hydrogenation of the aromatic ring in guaiacol over Pt(111). This product can be formed by partial hydrogenation of the aromatic ring in guaiacol followed by formation of alpha diketone which undergoes decarbonylation and ring closing [22]. followed by formation of alpha diketone which undergoes decarbonylation and ring Analogous results were reported by Lee et al. [68] who performed DFT calculations for closing Pt(111) [22]. Analogous results were reported by Lee et al. [68] who performed DFT calculations for Pt(111) surface. surface.

(a)

(b) Figure 13. (a) Reaction scheme for HDO of guaiacol over Pt/C catalyst in the temperature range of

Figure 13. (a) Reaction scheme for HDO of guaiacol over Pt/C catalyst in the temperature range 275–325 °C under atmospheric pressure over Pt/C and (b) energy levels for reaction coordinate of 275–325 ◦ C under atmospheric pressure over Pt/C and (b) energy levels for reaction coordinate calculated with DFT for Pt(111) surface [22]. calculated with DFT for Pt(111) surface [22].

Demethoxylation of dihydroeugenol resulting in formation of 4‐propylphenol requires acidity (Figure 10) [49]. In temperature programmed HDO of guaiacol at 280 °C over Rh/ZrO 2 together with Demethoxylation of dihydroeugenol resulting in formation of 4-propylphenol requires acidity ◦ aluminosilicate under 40 bar hydrogen in decane complete demethoxylation of guaiacol was (Figure 10) [49]. In temperature programmed HDO of guaiacol at 280 C over Rh/ZrO2 together with aluminosilicate under 40 bar hydrogen in decane complete demethoxylation of guaiacol was achieved at 280 ◦ C showing clearly its easiness for breaking this bond (Figure 14) (Table 3) [45]. It was also stated in [37] that ReOx/CNF is a promising catalyst favoring C-O bond cleavage and forming


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achieved at 280 °C showing clearly its easiness for breaking this bond (Figure 14) (Table 3) [45]. It was 24 of 40 also stated in [37] that ReOx/CNF is a promising catalyst favoring C‐O bond cleavage and forming phenol at 300 °C under 50 bar hydrogen (Figures 5 and 6) without breaking C‐C bond being thus hydrogen efficient and carbon atom economical catalyst. Demethoxylation was faster compared to phenol at 300 ◦ C under 50 bar hydrogen (Figures 5 and 6) without breaking C-C bond being thus transalkylation in and continuous HDO economical of a phenylacetate anisole mixture at 325 °C compared under 5 bar hydrogen efficient carbon atom catalyst.and Demethoxylation was faster to ◦ hydrogen over inPt/C catalyst HDO [61] of and thus it was proposed anisole is converted transalkylation continuous a phenylacetate and anisolethat mixture at 325 C under 5more bar preferentially to phenol than to m‐cresol. hydrogen over Pt/C catalyst [61] and thus it was proposed that anisole is converted more preferentially to phenol than to m-cresol. Catalysts 2017, 7, 265

a)

b)

Figure 14. (a) Temperature and pressure profiles during HDO of guaiacol; (b) yields of different Figure 14. (a) Temperature and pressure profiles during HDO of guaiacol; (b) yields of different products in HDO of guaiacol as a function of temperature, solvent decane [45]. products in HDO of guaiacol as a function of temperature, solvent decane [45].

Dehydroxylation ring is thermodynamically more demanding thandemanding demethoxylation Dehydroxylation of the of phenyl the phenyl ring is thermodynamically more than (Table 3) [22,36]. Substantial amounts of catechol were formed from guaiacol prior to phenol formation demethoxylation (Table 3) [22,36]. Substantial amounts of catechol were formed from guaiacol prior showing apparent difficulties of direct phenol formation from guaiacol at 300 ◦ C over Pt/C [22]. to phenol formation showing apparent difficulties of direct phenol formation from guaiacol at 300 °C Typically demethoxylation of bulky 1,3,5-trimethoxybenzene was rather slow even over mesoporous over Pt/C [22]. Typically demethoxylation of bulky 1,3,5‐trimethoxybenzene was rather slow even Rh/MCM-36 at 250 ◦ C under 40 bar hydrogen due to the sterical hindrance, despite the fact that it is over mesoporous Rh/MCM‐36 at 250 °C under 40 bar hydrogen due to the sterical hindrance, despite easy to break the methoxy bond compared to the hydroxyl bond connected to the phenyl ring [26]. the fact that it is easy to break the methoxy bond compared to the hydroxyl bond connected to the Substantial demethylation has been observed over Ni-, Fe-based catalysts [50] as well as over phenyl ring [26]. Mo2 S and CoMoS catalysts [46] in HDO of guaiacol at relatively high temperatures. Methanation was also observed in HDO of guaiacol over CoMo/ZrO2 catalyst at 300 ◦ C under 50 bar hydrogen [46] and Co/Al-MCM-41 at 400 ◦ C under 1 bar [34]. In the latter work it was concluded that demethylation


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occurs only on the acid sites especially with high catalyst weight to flow rate [34]. Methanation could however, be inhibited in guaiacol HDO via transalkylation increasing the carbon efficiency [34,50]. On the other hand, a very low methanation activity occurred in HDO of anisole at 320 ◦ C under 1 bar using MoO3 /ZrO2 catalyst [51]. It is also noteworthy that substantial methanation occurred in HDO of guaiacol and anisole over Pt-Sn/CNF [48]. In addition, methanation is especially promoted by Rh and Ru [76]. Methanation in anisole HDO increased with increasing temperature over Mo2 C [43]. Phenol and methanol were the primary products in anisole HDO over Mo2 C, whereas methanol deoxygenated to methane at higher temperatures [43]. It was thus concluded that Mo2 C is capable for breaking phenolic C-O bond in anisole at low temperature. Demethylation of guaiacol involves C(sp3)-Oar and is from the thermodynamic point of view the easiest reaction compared to, e.g., phenol, via C(sp2)-OMe cleavage [46]. Non-promoted MoS2 catalyst was beneficial for demethylation [46]. 2-methylphenol is formed over CoMoS/Al2 O3 via adsorption of the methoxy oxygen group followed by methylation of the phenyl ring. The deoxygenation of methoxyphenol is more difficult than that of phenol [77]. Ring hydrogenation is thermodynamically favored during HDO of phenolic compounds under high pressure using relatively low temperatures [27,37,45,47–49,62,63]. Such ring hydrogenation makes the overall process more expensive because of hydrogen consumption. Typically hydrogenation during HDO is favored over supported Ni catalysts [47,62], CoNx [63], Rh/ZrO2 with the mixture of aluminosilicates [43], Pt/alumina [49] and even with MoO3 [36]. If the target is to perform HDO to produce BTX products, lower hydrogen consumption can be achieved under high temperatures [16,34]. For example, no ring hydrogenation occurred in HDO of guaiacol and anisole at 400 ◦ C and 1 bar over Pt-Sn/CNF [48]. At the same temperature nickel and iron catalysts were also inefficient for hydrogenation [33,50]. Even when using 60 bar at 350 ◦ C in anisole and phenol HDO, the main product was benzene over MoO3 /ZrO2 catalyst showing clearly thermodynamic limitations at this temperature [39]. Ring hydrogenation in HDO of 4-propylphenol occurred with very high selectivity over Pt/AC at 280 ◦ C under 40 bar hydrogen giving propylcyclohexane as the main product [57]. It was also pointed out that under these conditions using water as a solvent, protons can be formed increasing acidity of the reaction media [57]. Slightly lower yields of propylcyclohexane were achieved in HDO of 4-propylguaiacol, since Pt/AC catalyst promoted also formation of propylcyclopentane [57]. In eugenol HDO, ring hydrogenation occurred after demethoxylation over supported Pd catalysts under 30 bar hydrogen at 250 ◦ C in hexadecane as a solvent [49]. It should, however, be noticed that ring hydrogenation could occur already prior to dehydroxylation [49]. Noteworthy is that 10 bar hydrogen was not sufficient to facilitate ring hydrogenation during vanillin HDO over Pd/CNF catalyst in the temperature range of 70–150 ◦ C in water [29]. Acidic catalysts are active in HDO facilitating often complete conversion of phenolic compounds, but not hydrogenation [25,55], for example, vanillin transformation to p-creosol [25]. Transalkylation occurring after demethylation is beneficial for carbon efficiency [50] and it is favored by acidic catalysts [32]. Several transalkylated C7–C12 products were formed in guaiacol HDO at 400 ◦ C under atmospheric pressure due to acidity of Co-Ni-Al-MCM-41 [34]. MoO3 /ZrO2 promoted also transalkylation in anisole HDO at 350 ◦ C under 60 bar hydrogen [39]. It was also proposed based on the product distribution that transalkylation occurred parallel with hydrogenolysis [39]. On the other hand, no transalkylation occurred with Mo2 C in HDO of a mixture of anisole, m-cresol, dimethoxybenzene and guaiacol at 280 ◦ C under 114 kPa [42]. These results suggest that temperature is one of the decisive factors determining the transalkylation activity. A low alkylation ability was, however, observed in HDO of guaiacol at 400 ◦ C over Pt-Sn/CNF catalyst exhibiting low acidity (Figure 15) [48].


O

26 of 40 21 of 42

CH 3

OH

+H2 ‐H2O

+ O

CH 3

O

CH3 CH 3

CH3

CH 3

+H2 ‐CH4

OH

+H2 ‐H2O

Figure 15. Reaction scheme for HDO and transalkylation of anisole at 400 ◦ C under 1 bar over Figure 15. Reaction scheme for HDO and transalkylation of anisole at 400 °C under 1 bar over Pt-Sn/CNF adapted from ref. [48]. Pt‐Sn/CNF adapted from ref. [48].

Oligomerisation [25] formation of gaseous products are also as evidenced from several Oligomerisation [25] and and formation of gaseous products are typical also typical as evidenced from HDO studies regarding lignin derived phenolics. As a result mass balance is very often below 100%. several HDO studies regarding lignin derived phenolics. As a result mass balance is very often below For example, in vanillin HDO, performed over Mo2 C/AC2catalyst under 20 bar hydrogen at 100 ◦ C 100%. For example, in vanillin HDO, performed over Mo C/AC catalyst under 20 bar hydrogen at oligomerisation of vanillin occurred causing incomplete mass balance [25]. Analogously in guaiacol 100 °C oligomerisation of vanillin occurred causing incomplete mass balance [25]. Analogously in HDO the mass balance was not complete when performing HDO over Mo2 C/CNF in the temperature guaiacol HDO the mass balance was not complete when performing HDO over Mo 2C/CNF in the ◦ range of 300–375 C under 55 bar hydrogen. The highest mass balance closure of ca. 96% was obtained temperature range of 300–375 °C under 55 bar hydrogen. The highest mass balance closure of ca. 96% at 375 ◦ C [54]. It was stated [35] that in order to avoid polymerisation, stirring of the bio-oil should be was obtained at 375 °C [54]. It was stated [35] that in order to avoid polymerisation, stirring of the started during its heating. In bio-oil HDO CO2 was the main product due to the presence of carboxylic bio‐oil should be started during its heating. In bio‐oil HDO CO 2 was the main product due to the acids in the feed [35]. When comparing gaseous composition after bio-oil HDO it could be seen that presence of carboxylic acids in the feed [35]. When comparing gaseous composition after bio‐oil HDO Ru/C produced more methane from CO2 than supported Ni-catalysts, in line with 80% more hydrogen it could be seen that Ru/C produced more methane from CO 2 than supported Ni‐catalysts, in line consumption [35]. with 80% more hydrogen consumption [35]. 3.4. HDO of Simulated and Real Bio-Oils and Lignin 3.4. HDO of Simulated and Real Bio‐Oils and Lignin 3.4.1. HDO of Simulated Bio-Oils 3.4.1. HDO of Simulated Bio‐Oils Mixtures of different phenolic compounds to simulate bio-oil have been used in HDO (Figure 16, Mixtures of different phenolic compounds to simulate bio‐oil have been used in HDO Table 4) [40,62]. The main products in the HDO of simulated bio-oil containing phenol, o-cresol (Figure 16, Table 4) [40,62]. The main products in the HDO of simulated bio‐oil containing phenol, o‐ and guaiacol over Ni- and Ni-Fe/H-Beta catalysts at 300 ◦ C during 4 h under 16 bar hydrogen cresol and guaiacol over Ni‐ and Ni‐Fe/H‐Beta catalysts at 300 °C during 4 h under 16 bar hydrogen were oxygenated aromatic compounds [40]. The lowest amount of oxygenates was produced over were oxygenated aromatic compounds [40]. The lowest amount of oxygenates was produced over NiFe-H-Beta catalysts along with substantial amounts of cycloalkanes. It was also stated that water as NiFe‐H‐Beta catalysts along with substantial amounts of cycloalkanes. It was also stated that water a solvent is beneficial for HDO, whereas methanol diminished selectivity towards hydrocarbons [40]. as a solvent is beneficial for HDO, whereas methanol diminished selectivity towards hydrocarbons The proposed reaction network for HDO of this simulated bio-oil is shown in Figure 17. It contains [40]. The proposed reaction network for HDO of this simulated bio‐oil is shown in Figure 17. It in addition to hydrogenation and deoxygenation also ring contraction of 1,2-cyclohexanediol to contains in addition to hydrogenation and deoxygenation also ring contraction of 1,2‐ cyclopentanol over acidic Ni-Fe/H-Beta catalyst. In HDO of a mixture of phenol, cresol, eugenol and cyclohexanediol to cyclopentanol over acidic Ni‐Fe/H‐Beta catalyst. In HDO of a mixture of phenol, trans-anethole over Ni/SiO2 -ZrO2 at 300 ◦ C under 50 bar during 8 h it was observed that this catalyst cresol, eugenol and trans‐anethole over Ni/SiO2‐ZrO2 at 300 °C under 50 bar during 8 h it was was rather efficient towards hydrocarbons with 62% selectivity to cyclohexane at 91% conversion [62]. observed that this catalyst was rather efficient towards hydrocarbons with 62% selectivity to Gas-phase pyrolytic products contain also hydrogen, CO2 , CO and water vapours. Guaiacol HDO was cyclohexane at 91% conversion [62]. Gas‐phase pyrolytic products contain also hydrogen, CO 2, CO investigated using a co-feed of the simulated pyrolysis vapors [33]. The effect of gaseous co-feed is and water vapours. Guaiacol HDO was investigated using a co‐feed of the simulated pyrolysis discussed, however, in Section 3.5.6. vapors [33]. The effect of gaseous co‐feed is discussed, however, in Section 3.5.6.


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22 of 42

Figure 16. Conversion and selectivity to different products as a function of time on stream in HDO of Figure 16. Conversion and selectivity to different products as a function of time on stream in HDO of Figure 16. Conversion and selectivity to different products as a function of time on stream in HDO of C a mixture of m‐cresol, anisole, dimethoxybenzene and guaiacol at 280 °C under 144 kPa over Mo a mixture of m-cresol, anisole, dimethoxybenzene and guaiacol at 280 ◦ C under 144 kPa over2C Mo22C a mixture of m‐cresol, anisole, dimethoxybenzene and guaiacol at 280 °C under 144 kPa over Mo catalyst [42]. catalyst [42]. catalyst [42].

Figure 17. Proposed reaction scheme for the HDO of simulated bio‐oil containing guaiacol, phenol and o‐cresol as feedstock over Ni‐H‐Beta catalyst. Notations: DDO: direct deoxygenation, HYD: hydrogenation, DMO: demethoxylation, DME: demethylation, AL: alkylation and DHY: dehydration Figure 17. Proposed reaction scheme for the HDO of simulated bio-oil containing guaiacol, Figure 17. Proposed reaction scheme for the HDO of simulated bio‐oil containing guaiacol, phenol [40].

phenol and o-cresol as feedstock over Ni-H-Beta catalyst. Notations: DDO: deoxygenation, direct deoxygenation, and o‐cresol as feedstock over Ni‐H‐Beta catalyst. Notations: DDO: direct HYD: HYD: hydrogenation, DMO: demethoxylation, DME: demethylation, AL: alkylation and DHY: hydrogenation, DMO: demethoxylation, DME: demethylation, AL: alkylation and DHY: dehydration dehydration [40]. [40].


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3.4.2. HDO of Real Bio-Oil HDO of real bio-oils [4,30,35,62] have been investigated in several publications. Bio-oil derived from yellow poplar via fast pyrolysis was hydrodeoxygenatied at 300 ◦ C in ethanol at 30 bar hydrogen [4]. The lowest O/C content was obtained with Pt/C catalyst [4]. HDO of the bio-oil prepared via fast pyrolysis of Miscanthus sinensis at 350 ◦ C and 30 bar over noble metals supported on carbon, in supercritical ethanol [30] showed deoxygenation of the heavy oil fraction of the bio-oil to 78% with the heating value of the product 27.8 MJ/kg. It is also important to note that such unstable compounds, as acids, furfural, vanillin and levoglucosan were converted to esters, ketones and saturated phenols [30]. Macromolecular products in that work were also characterized [28]. The results showed that the carbon content in the polymer increased and at the same time oxygen content decreased indicating lower amounts of phenolic and hydroxyl and methoxy groups. It was also observed that after prolonged reaction times the amount of methoxy groups decreased while phenol groups remained constant indicating that dehydroxylation of the phenol groups was not feasible under these reaction conditions [28]. On the other hand, when the bio-oil was hydrodeoxygenated over Pd/C catalyst at different temperatures varying from 250 ◦ C to 350 ◦ C phenolics started to polymerize [28]. In addition to Pt/C also Ni/SBA-15 was rather active in HDO of bio-oil giving ca. 55% deoxygenation in 1 h [4]. The main reactions occurring during HDO of bio-oil over the latter catalyst were guaiacol and 4-propylsyringol. In this case stability of the deoxygenated bio-oil was improved, since acetic acid, levoglucosan and furfural were totally converted. Gas phase products contained methane, CO, ethane and propane. The produced heavy oil fraction contained only 9.3% water with the heating value of 22.8 MJ/kg [4]. HDO of a real lignin derived bio-oil was successfully carried out over Ni/SiO2 -ZrO2 catalyst at ◦ 300 C under 50 bar hydrogen resulting in formation of 63% of cyclic hydrocarbons, out of which 8% were aromatics. In addition it was stated that most of the identified products, were cyclic hydrocarbons, such as cyclohexane, toluene and xylene exhibiting suitable vapor pressures and carbon number to be used in gasoline [62]. 3.4.3. HDO of Lignin Soda lignin HDO was investigated over various Ni/SiO2 catalysts impregnated with Ni2 P and also with CuMgAlOx [3]. The best results were obtained using a mixture of catalysts comprising Ni/SiO2 containing Ni2 P together with CuMgAlOx. At 340 ◦ C under 20 bar of hydrogen for HDO in ethanol of oxygen removal 84% was achieved with the aromatic lignin monomer yield of 51% and relatively low ring hydrogenation [3]. It was stated that the role of CuMgAlOx was to generate hydrogen during lignin ethanolysis [19] which in turn activates the reduced and passivated Ni2 P/SiO2 catalyst [78]. Complete conversion of organosolv lignin was obtained during its HDO with Ni-BEA at 320 ◦ C under 20 bar hydrogen [2]. The hydrocarbon selectivity of 70% was reported, while the amount of water and the solid residue were 21% and 4%, respectively. The reaction network includes disruption of phenolic compounds of lignin from ether linkages. Thereafter ring hydrogenation followed by deoxygenation occur over Ni-catalyst with slow hydrogenolysis. It was also concluded that at lower temperatures oligomers are formed via recombination of phenolic compounds. 3.5. Catalyst Deactivation, Regeneration and Reuse during HDO of Phenolic Compounds Catalyst deactivation and continuous HDO have been intensively investigated for phenolic compounds [31,33,42,49,50,57]. Catalyst stability, activity as a function of time-onstream [31,33,36,39,42,43,47,48,58,59,61], reuse [30,54,56–58,63], regeneration [34,36], origin of the catalyst deactivation [30], chemical composition of coke [31], thermogravimetrical analysis of the spent catalysts [62], modelling of deactivation [33] are also very important from the industrial point of view. Since the real bio-oils contain in addition to lignin derived compounds also water [59], acetic acid


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or furfural [56] as well several catalyst poisons, such as chlorine, potassium and sulphur containing compounds [47], it is very important not only to investigate HDO of model compounds but also the real feed [30] using different approaches, such as a single component feed, co-feed studies, real bio-oil [30], simulated bio-oil [40], adsorption studies [48,79] as well as continuous operation [33,36,39,42,43,48]. 3.5.1. Catalyst Reuse in HDO of Model Compounds and Bio-Oils Reuse of the catalysts in HDO of phenolic compounds has been intensively investigated [49,54,56,57,62]. Mo2 C/CNF catalyst was reused in guaiacol HDO at 350 ◦ C under 55 bar after rinsing it with diethyl ether [54]. The results were very promising showing that in three consecutive experiments more than 99% conversion was achieved. On the other hand, W2 C/CNF gave lower activity exhibiting only 48% conversion after three consecutive experiments. Mo2 C/CNF catalyst suffered from irreversible coking during three consecutive HDO experiments of guaiacol at 300 ◦ C under 40 bar [56]. The reuse of Ni/SiO2 -ZrO2 was investigated in guaiacol HDO at 300 ◦ C under 50 bar hydrogen [62]. The results showed that in four consecutive experiments the conversion decreased as follows: 100%, 91%, 90% and 87% indicating minor catalyst deactivation. The use of Pt/C is favorable in HDO of phenolic compounds in order to avoid coke formation [57]. Successful recycling was demonstrated in 4-propylphenol HDO over Pt on active carbon giving more than 99% yield of propylcyclohexane in three consecutive experiments at 280 ◦ C under 40 bar hydrogen [57]. The results revealed also that no sintering occurred. Recycling of noble metal supported catalysts in guaiacol HDO was done in three consecutive experiments, with catalyst washing with acetone and reduction at 200 ◦ C in between. The results showed minor deactivation of Ru/C and Pd/silica alumina [49]. It was confirmed that especially in HDO of eugenol the catalyst was poisoned by strongly adsorbed products causing also a brownish colour of the product. In bio-oil HDO over noble metal catalysts supported on active carbon at 300 ◦ C under 30 bar hydrogen, the catalyst deactivation was intensive during reuse [30]. It was also concluded that Ru/C deactivated mainly via fouling and blocking of active sites, whereas activity loss of Pt/C was attributed to extensive char deposition on the catalyst surface. 3.5.2. Time-on Stream Behavior in HDO of Model Compounds Time-on-stream behavior during HDO of cresol over MoO3 catalyst at 320 ◦ C at atmospheric pressure showed catalyst deactivation. When the catalyst was regenerated at 400 ◦ C via calcination, its original activity was restored, however, after each 24 h a repeated regeneration was required [36]. Promising results have been obtained in HDO of phenyl acetate over Pt/Al2 O3 at 325 ◦ C under 5 bar hydrogen. After 25 h time-on-stream a stable period of 40 h with constant activity followed [61]. Phenol formation was rapid from phenyl acetate, whereas the consecutive benzene formation was rather slow. Only minor catalyst deactivation was also observed in HDO of m-cresol, anisole, dimethoxybenzene and guaiacol mixture at 280 ◦ C under 1.5 bar pressure over Mo2 C catalyst giving mostly toluene and benzene as products (Figure 18) [42]. On the other hand, the most rapid deactivation of Mo2 C/ZrO2 as a function of time on stream was observed in HDO of guaiacol at 350 ◦ C under 60 bar hydrogen, followed by anisole and phenol showing clearly that compounds bearing two oxygen atoms caused the most intensive deactivation (Figure 18) [39]. Prominent catalyst deactivation observed in guaiacol HDO can partially be explained by a strongly bound phenate mode of guaiacol by double anchoring to the catalyst surface covering a large part of active sites [80]. Catalyst deactivation occurred also in HDO of anisole and guaiacol over Pt-Sn/CNF/Inconel as a funbction of time on stream (Figure 19) [48]. In addition, in the HDO of anisole, less water is formed than, for example, in phenol HDO. At higher temperature catalyst stability is improved in the presence of smaller amounts of adsorbed water. Catalyst deactivation in guaiacol HDO was also more intensive than in HDO of anisole over Pt-Sn/CNF catalyst at 400 ◦ C under atmospheric pressure (Figure 20) i.e., conditions favoring deactivation [48]. Guaiacol is overall more reactive than anisole at 400 ◦ C, thus more prominent catalyst


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deactivation in HDO of guaiacol compared to anisole is mainly seen from the product distribution. Catalysts 2017, 7, x FOR PEER REVIEW 25 of 42 For anisole, the main product was benzene, whereas it was anisole for HDO of guaiacol. 60

50

Conversion (%)

"OH" 40

"-OCH3"

30

20

"-OH + -OCH3"

10

0 0

2

4

6

8

Time on stream (h)

◦C

Figure 18. Conversion of guaiacol, anisole and phenol in their single feed HDO at 350 under 60 bar Figure 18. Conversion of guaiacol, anisole and phenol in their single feed HDO at 350 °C under 60 bar inin a down flow trickle bed reactor adapted from [39]. Notation: ( ) phenol, ) anisole and (o) guaiacol. a down flow trickle bed reactor adapted from [39]. Notation: (●) (phenol, (■) anisole and (o)

guaiacol.

Figure 19. Continuous hydrodeoxygenation of (a) anisole and (b) guaiacol at 400 ◦ C under atmospheric pressure over Pt-Sn/CNF/Inconel catalyst [48].

Figure 19. Continuous hydrodeoxygenation of (a) anisole and (b) guaiacol at 400 °C under atmospheric pressure over Pt‐Sn/CNF/Inconel catalyst [48].



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calcination

80

Conversion (C-mol%)

31 of 40

regenerated

60

calcination

40

20

0 0

5

10

15

20

25

30

35

40

45

TOS (h)

50

Figure 20. Figure 20. Conversion of m‐cresol as a function of time on stream at 320 °C under 1 bar over MoO Conversion of m-cresol as a function of time on stream at 320 ◦ C under 1 bar over MoO3 3 catalyst. Regeneration of the catalyst was performed at 400 °C in oxygen for 3 h adapted from [36]. catalyst. Regeneration of the catalyst was performed at 400 ◦ C in oxygen for 3 h adapted from [36]. Catalyst regeneration has also been investigated in continuous operation [36]. Typically, the catalyst is calcined in air at 400 °C in order to avoid sintering of metal‐like particles, as it was the case Catalyst regeneration has also been investigated in continuous operation [36]. Typically, the catalyst in HDO of m‐cresol at 320 °C under atmospheric pressure over MoO 3 (Figure 21) [36]. The results is calcined in air at 400 ◦ C in order to avoid sintering of metal-like particles, as it was the case in HDO showed clearly that already after 24 h TOS the catalyst activity declined from 50% conversion to 28% ◦ of m-cresol at 320 C under atmospheric pressure over MoO3 (Figure 21) [36]. The results showed conversion and the intermittent calcination was required in order to keep the catalyst activity high clearly thatenough. already after 24 h TOS the catalyst activity declined from 50% conversion to 28% conversion and the intermittent calcination was Catalysts 2017, 7, x FOR PEER REVIEW required in order to keep the catalyst activity high enough. 27 of 42

Conversion/Selectivity (%)

100

50

0 0

2

4

Reaction time (h)

6

Figure 21. Results from HDO of guaiacol over Mo2C/CNF catalyst at 350 °C under 55 bar hydrogen. Figure 21. Results from HDO of guaiacol over Mo2 C/CNF catalyst at 350 ◦ C under 55 bar hydrogen. Symbols: mass balance (■), conversion (●), phenol (o) and cresol (□) adapted from reference [54]. Symbols: mass balance (), conversion ( ), phenol (o) and cresol () adapted from reference [54].

3.5.3. Catalyst Selection in HDO of Phenolic Compounds Precious metal catalysts have some advantages during HDO of phenolic compounds being highly active at low pressures and temperatures and enabling use of smaller reactors and other economic benefits [61]. Metal‐like carbides have also shown activity in HDO of phenolic compounds [56]. For nitride and carbide catalysts, neutral carbon and zirconia are preferred as supports in direct deoxygenation of guaiacol [46]. Hydrophobic carbons are also efficient supports for bio‐oil HDO [78] deactivating only slightly in the presence of water during bio‐oil HDO [55]. Hydrothermal stability of the catalysts is important during HDO of lignin derived phenolic


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3.5.3. Catalyst Selection in HDO of Phenolic Compounds Precious metal catalysts have some advantages during HDO of phenolic compounds being highly active at low pressures and temperatures and enabling use of smaller reactors and other economic benefits [61]. Metal-like carbides have also shown activity in HDO of phenolic compounds [56]. For nitride and carbide catalysts, neutral carbon and zirconia are preferred as supports in direct deoxygenation of guaiacol [46]. Hydrophobic carbons are also efficient supports for bio-oil HDO [78] deactivating only slightly in the presence of water during bio-oil HDO [55]. Hydrothermal stability of the catalysts is important during HDO of lignin derived phenolic compounds. It is known that ZrO2 exhibits hydrothermal stability, whereas alumina is unstable in the presence of water under hydrothermal conditions [81]. Nitrides have been more stable against sulfides in HDO of guaiacol in a continuous operation [58]. Transition metal carbides, nitrides and phosphides require demanding preparation conditions and exhibit poor stability in HDO of phenolic compounds [37]. Performing HDO at higher temperature enhances stability of MoO3 /ZrO2 due to lower amounts of water adsorbed on the catalyst surface [39]. 3.5.4. Coking during HDO of Model Compounds Possible reasons for catalyst deactivation during HDO of phenolic compounds are coking [34] and poisoning [47], in addition to a loss of active sites. In some cases minor sintering has been observed [31]. In guaiacol HDO over Pt/C slight catalyst deactivation occurred at 325 ◦ C [31]. Coking can be explained by ring condensation favored by low pressure and high temperature [82], whereas aromatic hydrogenation is favored at lower temperature using high hydrogen pressure. Condensed ring products are more strongly adsorbed on the catalyst surface and can be desorbed only at higher temperatures [83]. Co-MCM-41 was used for HDO of guaiacol resulting in a quite rapid catalyst deactivation occurred at 400 ◦ C under atmospheric conditions [34], as these conditions promoted extensive coking. Coking during HDO is typically favored over catalysts having acidic supports, while for less acidic supports, such as zirconia and activated carbon, the catalysts retain their activity longer [58]. More intensive coking during HDO of guaiacol at 300 ◦ C was observed for Ru/C compared to Pt/C [31]. Catalyst coking has been also investigated in HDO of guaiacol and anisole [50]. Confirming that reactant nature has an effect on coking in particular more coke has been formed from guaiacol than anisole on Ni-based catalysts at relatively high temperatures, between 350–400 ◦ C [50]. Coke formation was confirmed in guaiacol HDO at 400 ◦ C under atmospheric pressure over Co/Al-MCM-41 catalyst by TGA [34]. Furthermore, it was stated that the catalyst regeneration at 450 ◦ C was not able to release all coke. From TEM images it was found that coke is located on both on acidic sites and close to Co-particles [34] leading to conclusion that coke formation depends not only on acidity, but also on the presence of metal sites [34]. Analysis of coke deposited on the spent catalyst used in HDO of guaiacol at 300 ◦ C under atmospheric pressure was performed using thermogravimetry and GC-MS [31]. The TGA results revealed that more coke was desorbed from Ru/C compared to Pt/C. Furthermore, linked ring structures such as biphenyl, aromatic compounds, e.g., benzene, and condensed rings including naphthalene and 1-methylnaphtalene were found after extraction of adsorbed species by dichloromethane not being present in the liquid product. It was additionally concluded that there was no sintering of Ru/C under HDO conditions, while minor sintering of Pt/C was observed. 3.5.5. Deactivation Due to Strong Adsorption on the Catalyst Surface Deactivation studies of different supports, such as alumina and silica have been performed by adsorption of different model molecules (phenol, anisole, guaiacol) on these supports and desorbing them at different temperatures [79]. Based on IR-studies interaction mechanisms of these molecules at higher temperatures have been proposed. The results revealed that anisole is demethylated at


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higher temperature, whereas guaiacol is bound via two oxygen atoms on Al-sites. The amounts of adsorbed species on SiO2 were much lower than those recorded for Al2 O3 in the case of phenol and anisole. Even if for guaiacol adsorption quantitative data were not achieved, it was concluded that its interaction with supports was clearly stronger than for phenol and anisole. Strong adsorption of reactants or other molecules during eugenol hydrodeoxygenation has been proposed to cause catalyst deactivation [49]. In eugenol HDO incomplete carbon balance at 250 ◦ C under 30 bar hydrogen in hexadecane over noble metal catalysts supported was ascribed strong adsorption of the products on the catalyst surface [49]. Adsorption strength of guaiacol and anisole was investigated using pulse experiments at 400 ◦ C by adsorbing these molecules on Pt-Sn/CNF catalyst [48]. It was confirmed that guaiacol is more strongly adsorbed than anisole. Furthermore, it was also stated that guaiacol and its HDO-product, catechol with two oxygen atoms, are more strongly adsorbed on the catalyst surface than their single functionalized counterparts, e.g., anisole and phenol [48]. 3.5.6. Poisons in Bio-Oil Causing Catalyst Deactivation Hydrodeoxygenation (HDO) is an important treatment method for bio-oils which have low stability and heating value as described above. Due to a complex structure of bio-oil and presence of possible catalyst poisons [47] and water, its HDO is, however, demanding. Bio-oils stemming from hemicellulose and cellulose contain also acetic acid and furfural, which have been used as co-feed in HDO of guaiacol [56]. Co-feed including also H2 O, CO2 and O2 has been used in HDO of guaiacol [33,59]. The effect of several poisons, such as chlorine, sulfur and potassium was investigated in HDO of guaiacol and 1-octanol over Ni/ZrO2 catalyst in a trickle bed reactor at 250 ◦ C under 100 bar hydrogen [47]. In these experiments, the catalyst was deactivated with 1-octanethiol, 1-chlorooctane, KCl or KNO3 . When using potassium salts a stoichiometric amount of salt compared to nickel was used. The results revealed that with sulfur present in the catalyst, the latter retained its activity during more than 4 h which was followed by a dramatic activity drop almost to zero. Effect of chlorine poisoning was more rapid decreasing the catalyst activity immediately after the start of the chlorine feed. On the other hand, a potassium poisoned catalyst exhibited high activity in guaiacol conversion, even if its deoxygenation activities towards guaiacol were 3% and 18% for respectively KCl and KNO3 in comparison with the not poisoned catalyst displaying 66% deoxygenation degree of guaiacol. It was also noteworthy that chlorine and potassium poisoning was reversible and chloride was found in the liquid product. Sulfur poisoning inhibited both hydrogenation of the aromatic ring in guaiacol as well as subsequent deoxygenation reactions over Ni/ZrO2 catalyst at 250 ◦ C under 100 bar hydrogen, whereas potassium poisoned mainly deoxygenation sites. Chlorine poisoning decreased both hydrogenation and deoxygenation activity of Ni/ZrO2 catalyst. The presence of acetic acid and furfural was investigated in HDO of guaiacol over Mo2 C/CNF catalyst in dodecane at 300 ◦ C under 40 bar hydrogen [56]. The results showed that both acetic acid and furfural were converted to a large extent, whereas guaiacol conversion was only 6% after 4 h. The main products were phenol and catechol, while without furfural and acetic acid catechol formation was much lower. Catalyst stability was investigated during HDO of m-cresol with Mo2 C using co-feeds of H2 O, CO2 and O2 [59]. The results revealed that especially toluene formation rate was retarded with adsorption of oxygen on metal like sites catalyzing HDO reaction. In the gas phase HDO of m-cresol-anisole, dimethoxybenzene and guaiacol mixture the experimental observations could be correlated with the bond dissociation energies showing that the most prominent products were toluene and benzene at 280 ◦ C over Mo2 C catalysts. This catalyst was completely inactive for hydrogenation of the products. It was stated [59] that CO and water, which are typically present in pyrolysis vapor, inhibit hydrogenation of the aromatic ring. Co-feeding CO and CO2 has been also investigated in HDO of guaiacol [33]. Direct hydrodeoxygenation of phenolic compounds was achieved over Mo2 C catalyst without ring


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hydrogenation which was also confirmed by co-feed of water and CO. In guaiacol HDO in the presence of CO, CO2 and water over Fe/SiO2 catalyst at 400 ◦ C under atmospheric pressure inhibition of guaiacol transformations to cresol was observed (Figure 22) [33]. In the vapor-phase anisole HDO, benzene was formed with high selectivity over metal-like carbides, Mo2 C and W2 C [43,44]. It was, however, observed that with co-fed CO formation of benzene during anisole HDO was suppressed over Mo2 C catalyst at 133 ◦ C under atmospheric pressure [43]. Analogously in the presence of Catalysts 2017, 7, x FOR PEER REVIEW CO-co-feeding during anisole HDO at 150 ◦ C over Mo2 C under atmospheric pressure benzene31 of 42 formation was suppressed and completely recovered after CO-co-feed was stopped [44]. Pt/C is active for water gas shift reaction forming carbon dioxide during HDO [84]. 2.0x10-6

1

k (kmol/s.kgcat)

1.5x10-6

1.0x10-6

5.0x10-7

2 3 4

0.0 0

50

100

150

200

Time on stream (min) Figure 22. Decrease of the kinetic constants as a function of time on stream in the HDO of guaiacol at 400 ◦ C under 1 bar over Fe/SiO2 adapted from ref. [33]. The reaction mixture Figure 22. Decrease of the kinetic constants as a function of time on stream in the HDO of guaiacol at contained also 50% H2 , 5% CO2 , 2.5% CO and 2.5% H2 O. Notation: (1) guaiacol to products, 400 °C under 1 bar over Fe/SiO 2 adapted from ref. [33]. The reaction mixture contained also 50% H 2, 6 e−4.61·10−3 x , (2) guaiacol to cresol, line fitting : y = 4.93·10−7 e−7.29·10−3 x , line fitting: = 2, 2.85 ·10−CO 5% CO 2.5% and 2.5% H2O. Notation: (1) guaiacol to products, line fitting: 2.85 ∙ −3 x . ∙ . ∙ to toluene, line fitting: (3) phenol fitting: y = 1.37line fitting: ·10−7 e−4.85· 10 4.93 , and (4) cresol 10 to benzene, , line 2 guaiacol to cresol, ∙ 10 , − 3 −8 e−5.03·10 x . . ∙ y = 2.813·10 phenol to benzene, line fitting: 1.37 ∙ 10

and 4 cresol to toluene, line fitting:

2.81 ∙ 10

.

∙

.

3.5.7. Carbon Balance during HDO of Model Compounds 4. Conclusions Mass balance in HDO of phenolic model compounds has often been reported to be below Hydrodeoxygenation of guaiacol bio‐oils, lignin has been intensively 100% [25,31,54]. One example is HDO and overtheir Mo2model C/CNFcompounds and W2 C/CNF catalysts (Figureinvestigated in the recent years. The main findings in this area are summarized in the current work. 12) [54], where the authors also stated that the mass balance increased with increasing reaction ◦ C under Several Amodel molecules have been closure used in above HDO 90% of bio‐oil including single, double or triple temperature. relatively high mass balance was achieved at 375 55 bar oxygenated phenolic compounds. Several reaction networks based on kinetic results have hydrogen [54]. Analogously to the work of Jongerius et al., mass balances vary in the range of 70–98% been proposed for guaiacol HDO. main catalysts parameters affecting activity and out product in guaiacol HDOespecially at 300 ◦ C under 40 bar using MoThe (Figure 21). It also pointed 2 C/CNF distribution are temperature and pressure, type of a catalytically active metal, nature of the support that the mass balances contained only the liquid phase and coke from the catalyst surface omitting and its acidity. [56]. Two main coking pathways during HDO are either ring followed by the gaseous products Clearly [56] and release of products into the hydrogenation gas phase decrease the deoxygenation at high pressure and temperature below 300 °C, as well as deoxygenation at elevated mass balance calculated on the basis of the liquid phase products. In HDO of guaiacol the highest carbontemperatures, when hydrogenation is thermodynamically suppressed. recovery in the liquid phase over noble metals supported on carbon was ca. 70% obtained The degree of deoxygenation is important in order to increase the energy density and heating at 300 ◦ C [31]. Especially the ring opening reaction at high temperatures leads to formation of more value of the products. Typically, guaiacol is deoxygenated at elevated temperatures or under very high pressures at temperatures below 350 °C affording HDO yields between 60–80%. One exception in guaiacol HDO is Ni/SiO2‐ZrO2 giving 97% cyclohexane at 300 °C under 50 bar. In addition to cyclohexane, also cyclopentanone is formed, especially over Pt. These results can be explained theoretically at a DFT level, confirming the reactivity of phenolic compounds decreases with an


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gaseous products [18]. On the other hand, total carbon yields varied in the range of 95–98% in the HDO of different phenolic compounds at 300–350 ◦ C over MoO3 catalyst under atmospheric pressure [36]. Solid products are also formed during HDO of phenolic compounds and lignin [2,25,62]. Polymerization, occurring especially for vanillin, is intensive, decreasing the carbon balance [25], for example, in vanillin HDO at 100 ◦ C under 30 bar hydrogen over Mo2 C/AC catalyst. As a result mass balances in the range of 65–70% were reported. It was concluded by Zhang et al. [62] that the mass losses are caused by formation of coke and polymers as well as formation of volatile gaseous products. In addition large amounts of char were formed being in the range of 9–19% in the HDO of pyrolysis oil over Ni-supported catalysts at 300 ◦ C under 30 bar hydrogen [4]. Noteworthy is that formation of a solid residue in lignin HDO decreased with increasing reaction temperature indicating that at higher temperature unwanted reactions of phenolic products are retarded [2]. Formation of gaseous products is typically enhanced at higher temperatures [31,34], while at lower temperatures less gases were formed [43]. For example, in the temperature range of 147–247 ◦ C no gaseous C2–C5 products were observed in vapor phase HDO of anisole on Mo2 C and the main product was benzene formed by C-O bond cleavage [43]. In addition, low gas generation during HDO was observed at 250 ◦ C under 80 bar hydrogen over various Ni catalysts [35]. At elevated temperature, 350 ◦ C, both char and gas formation from HDO of miscanthus bio-oil was enhanced when HDO was performed over Pd/C catalyst under 30 bar of hydrogen [28]. Under these conditions char and gas yields vary in the ranges of 16% and 19–36%, respectively depending on the reaction time in the range of 30–60 min [28]. The liquid yields, composed of light and heavy oil fractions were the highest, above 80%, when HDO of bio-oil was performed over Pd/C catalyst between 250–300 ◦ C [28]. Formation of gaseous products depends also on the type of active metal in the catalyst [31]. For noble metal catalysts the amounts of gaseous products formed during guaiacol HDO increased in the following order: Pd/C < Ru/C < Rh/C < Pt/C [31]. A substantial amount of gaseous products, 50%, was formed in HDO of guaiacol at 400 ◦ C under atmospheric pressure over NiCo-Al-MCM-41 catalysts [34]. Methane formation was very extensive during HDO of guaiacol over Co/Al-MCM-41 at 400 ◦ C under atmospheric pressure and it increased with increasing ratio of catalyst weight to feed rate [34]. The gas phase product amount was was the highest with Ni/Al-MCM-41, being 78%, whereas it was the lowest (30%) for Co-MCM-41 [34]. The main gaseous product yield in the HDO of bio-oil over supported Ni-catalysts at 300 ◦ C under 30 bar hydrogen was CO being in the range of 88–95% from the gaseous products, followed by methane varying in the range of 2–7.1% [4]. It was also possible to obtain a few % of propane, ethyne and ethane [4]. Only minor amounts of methane were formed over supported Ni-catalysts in the HDO of guaiacol under 7.9 bar hydrogen in the temperature range of 350–450 ◦ C, whereas coking was rather high under these conditions over Ni-catalysts being in the range of 3–8 wt % from the total products [50]. Analogously, in the HDO of pyrolysis bio-oil from yellow polar over Ni supported catalysts at 300 ◦ C under 30 bar of hydrogen, formation of gaseous products was significant over Ni supported catalysts varying in the range of 6.6–27% depending on the support type [4]. On the other hand, low methanation degree was achieved over MoO3 /ZrO2 at 320 ◦ C under atmospheric pressure in anisole HDO showing clearly its carbon efficiency [51]. 3.5.8. Modelling of Deactivation for HDO of Model Compounds Modelling of deactivation along with kinetic modelling was performed [33] for HDO of guaiacol over Fe/SiO2 catalyst [33]. When the rate constants were plotted against time on stream it was noticed that the decrease of rate constants occurred similarly for HDO of phenol to benzene and cresol to toluene, whereas in guaiacol transalkylation to cresol the decline of the rate constant was more rapid (Figure 22) [33]. Thus, it was concluded that inhibition of guaiacol to cresol transformations may happen on different sites compared to HDO reactions.


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4. Conclusions Hydrodeoxygenation of bio-oils, lignin and their model compounds has been intensively investigated in the recent years. The main findings in this area are summarized in the current work. Several model molecules have been used in HDO of bio-oil including single, double or triple oxygenated phenolic compounds. Several reaction networks based on kinetic results have been proposed especially for guaiacol HDO. The main parameters affecting activity and product distribution are temperature and pressure, type of a catalytically active metal, nature of the support and its acidity. Two main pathways during HDO are either ring hydrogenation followed by deoxygenation at high pressure and temperature below 300 ◦ C, as well as deoxygenation at elevated temperatures, when hydrogenation is thermodynamically suppressed. The degree of deoxygenation is important in order to increase the energy density and heating value of the products. Typically, guaiacol is deoxygenated at elevated temperatures or under very high pressures at temperatures below 350 ◦ C affording HDO yields between 60–80%. One exception in guaiacol HDO is Ni/SiO2 -ZrO2 giving 97% cyclohexane at 300 ◦ C under 50 bar. In addition to cyclohexane, also cyclopentanone is formed, especially over Pt. These results can be explained theoretically at a DFT level, confirming the reactivity of phenolic compounds decreases with an increasing number of oxygen atoms. Moreover, thermodynamically the hydroxyl group connected to benzene is more difficult to cleave compared to a methoxy group. HDO of real bio-oils was also successfully demonstrated over various Ni-and Pd-supported catalysts. Unstable compounds, such as furfural, acetic acid and levoglucosan were also transformed to more stable ketones and esters. In addition, high HDO activity was obtained for lignin itself, especially over Ni/H-BEA catalyst. Catalyst deactivation studies revealed that main reason for catalytic activity decline during HDO of phenolic compounds is coking in addition to reactant polymerization. Interestingly higher mass balance closures exceeding 90% for guaiacol at 375 ◦ C could be achieved at very high temperatures, due to suppression of oxygen compounds, such as phenol over Mo2 C/CNF. Catalyst poisoning was systematically investigated showing irreversible bulk poisoning of the catalyst with sulphur, whereas chlorine poisoning was reversible. Hydrothermal stability of the catalyst is of crucial importance and suitable candidates are active carbon and ZrO2 , whereas alumina and metal carbides exhibit lower stability under catalytically relevant conditions. The HDO of phenolic compounds is challenging and requires optimization of different parameters, such as temperature, pressure and the catalyst per se in order to maximize the liquid product yield and produce desired compounds with high enough heating value and RON number. In addition, further research efforts are still needed to diminish hydrogen consumption and provide high carbon efficiency. Author Contributions: P.M-A designed the review, collected references and wrote the first draft. D.Yu.M. revised the text and contributed to the final paper. Conflicts of Interest: The authors declare no conflict of interest.

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