acs.energyfuels.7b01251

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Evolution of Functional Groups during Pyrolysis Oil Upgrading Filip Stankovikj, Chi Cong Tran, Serge Kaliaguine, Mariefel Valenzuela Olarte, and Manuel Garcia-Perez Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.7b01251 • Publication Date (Web): 26 Jun 2017 Downloaded from http://pubs.acs.org on July 3, 2017

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Evolution of Functional Groups during Pyrolysis Oil Upgrading Filip Stankovikj1, Chi-Cong Tran3, Serge Kaliaguine3, Mariefel V. Olarte4, Manuel Garcia-Perez1* 1Department

of Biological Systems Engineering, Washington State University, Pullman, WA 99164-6120, United States

2Center

for NMR Spectroscopy, PO Box 644630, Washington State University, Pullman, WA 99164–4630, United States 3 4

Department of Chemical Engineering, Laval University, Québec, Canada

Pacific Northwest National Laboratory, Richland, WA 99354, United States

(Submitted to Energy and Fuel)

Abstract: In this paper, we examine the evolution of functional groups (carbonyl, carboxyl, phenol, and hydroxyl) during hydrotreatment at 100–200 °C of two typical wood derived pyrolysis oils from BTG and Amaron in a batch reactor over Ru/C catalyst for 4h. An aqueous and an oily phase were obtained. The content of functional groups in both phases were analyzed by GC/MS, 31P-NMR, 1H-NMR, elemental analysis, KF titration, carbonyl groups by Faix, Folin – Ciocalteu method and UV-Fluorescence. The consumption of hydrogen was between 0.007 and 0.016 g/g oil, and 0.001-0.020 g of CH4/g of oil, 0.005-0.016 g of CO2/g oil and 0.03-0.10 g H2O/g oil were formed. The content of carbonyl, hydroxyl, and carboxyl groups in the volatile GC-MS detectable fraction decreased (80, 65, and ~70% respectively), while their behavior in the total oil and hence in the non-volatile fraction was more complex. The carbonyl groups initially decreased having minimum at ~125-150°C and then increased, while the hydroxyl groups had reversed trend. This might be explained by initial hydrogenation of the carbonyl groups to form hydroxyls, followed by continued dehydration reactions at higher temperatures that may increase their content. The

31

P-NMR was on the limit of its sensitivity for the

carboxylic groups to precisely detect changes in the non-volatile fraction, however the more precise titration method showed that the concentration of carboxylic groups in the non-volatile

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fraction remains constant with increased hydrotreatment temperature. The UV-Fluorescence results show that repolymerization increases with temperature. ATR-FTIR method coupled with deconvolution of the region between 1490 and 1850 cm-1 showed to be a good tool for following the changes in carbonyl groups and phenols of the stabilized pyrolysis oils. The deconvolution of the IR bands around 1050 and 1260 cm-1 correlated very well with the changes in the 31P-NMR silent O groups (likely ethers). Most of the H2O formation could be explained from the significant reduction of these silent O groups (from 12% in the fresh oils, to 6 to 2% in the stabilized oils) most probably belonging to ethers.

Keywords: fast pyrolysis, characterization, stabilization, hydrotreating, hydrogenation, functional groups.

*Corresponding author: Manuel Garcia-Perez Associate Professor Biological Systems Engineering Department, Washington State University e-mail: [email protected] Phone number: 509-335-7758

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1.

Introduction

The discovery of crude oils and the development of refining technologies in the 19th century together with the invention of the automobile opened the door for the commercialization of hydrocarbon liquid fuels that have driven world economic growth and improved living standards for more than a century.1,2 Publicly available data on petroleum reserves is often contradictory,3 however, we are getting close to the conventional oil peak,4–6 which is reflected in the gradually increasing oil extraction costs.3,6,7 Hence, addressing the growing energy demand in the world would be difficult without introducing renewable fuels into the energy mix (consumption projected to increase to 815 quadrillions Btu at 2040).8 The global warming associated with the release of green-house gases due to fossil fuels combustion, and the instability of supply from the middle east countries are also sources of considerable concern.9–11 To tackle these energy issues, and the political and environmental concerns related to the use of fossil fuels, it is imperative to develop alternative, renewable and economical sources for fuels and chemicals. Plant biomass is our most sensible renewable source for the production of carbon based fuels and chemicals.12–16 Fast pyrolysis is one of the most important routes for the production of bio-based fuels and chemicals.14,15,17–20 Small lignocellulosic particles are heated rapidly in absence of air (in the range of 450-550 °C) to produce vapors that are rapidly removed from the reactor space (residence time of vapors < 2s) and quenched to produce crude pyrolysis oil. Yields of oil over 65 wt. % are typically achieved with fast pyrolysis.21,22 However, the high oxygen content, poor stability and high acidity prevent pyrolysis oils from being directly used as petroleum refinery feedstocks.18,23 Hence, catalytic hydro-processing involving the removal of heteroatoms, hydrocracking, and saturation of unsaturated bonds has been developed, and today this approach represents the most viable pathway for the conversion of highly oxygenated bio-oils to hydrocarbon fuels.18,24,25 Pyrolysis bio-oil is a complex organic mixture containing more than 300 oxygenated compounds26 such as aldehydes, ketones, and phenolic groups, which can react with each other in condensation or polymerization reactions leading to formation of high molecular weight compounds and coke at high temperatures.23,27–30 These undesirable reactions are the main reason for the deactivation of catalysts and reactor plugging during bio-oil hydrotreatment. Water insoluble phenolic fraction has been traditionally identified as a culprit for coking,31,32 3 ACS Paragon Plus Environment

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however, recent studies show that the water soluble high molecular weight fraction, which is commonly present in higher concentration, has even higher impact on the coke formation.33–35 Therefore, to carry out the hydrocracking and deoxygenation at high temperatures, it is critical to stabilize

the

pyrolysis

oils

by

converting

these

reactive

compounds

into

stable

molecules.18,25,28,30,36 Deeper understanding of bio-oil hydrotreatment reactions has been limited by the availability of standardized analytical techniques,37 and the limitations on the analytical tools used to characterize the heavy fraction of these oils. Table 1summarizes some of the most recent bio-oil hydrotreatment studies reported in the literature and the analytical techniques used for the characterization of hydrotreated oils. A review on analytical techniques used for characterization of pyrolysis oils can be found elsewhere.38,39 Very few of the studies reported in Table 1 examined the changes in the chemical composition of the aqueous phase.40–44 None of them has studied separately the changes of the composition of the volatile GC/MS detectable and the heavy oligomeric fractions, especially in terms of functional groups. It is only recently that the changes of some of the functional groups, solely in the whole oil, have been studied and reported for a continuous flow system under stabilization conditions (120 and 160°C over Ru/TiO2).30 In this paper we are expanding the understanding of bio-oil behavior during hydrotreatment by using a tandem of analytical techniques that allowed us to study in detail not only the oily, but also the aqueous phase.45,46 For the first time we will study separately the evolution of functional groups in the volatile GC/MS detectable fraction and the heavy oligomeric fraction of the stabilized oil.


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Table 1. Review of bio-oil hydrotreatment studies Hydrotreatment conditions Feedstock: pine wood fluidized bed 480°C Batch autoclave 19-20 MPa First step: Ru/C at 250 or 300°C with reaction time of 2 h. Second step: Ni-Mo/Al2O3 at 375 or 400°C with reaction time of 2 or 4 h. Feedstock: mallee wood in a grinding pyrolyser operated at 450 °C Batch autoclave 10 MPa Presulphided NiMo/Al2O3 and CoMo/Al2O3 at 150–300°C with reaction time of 3h Feedstock: softwood forest residues and pine wood pyrolysis Plug flow 10.3 MPa Ru/TiO2 at 120 to 160°C LHSV 0.4 h-1 Feedstock: pine pyrolysis oil Plug flow 8.4 MPa Pretreatment: Ru/C at 80°C or 140°C LHSV 0.5 h-1 Two-stage reactor: Ru/C at 140-200°C and XMo/Al2O3 at 385-405°C LHSV 0.1 h-1 Feedstock: WS of pine wood pyrolysis oil Plug flow 5-10 MPa Pt/C, Ru/C at 75-275°C LHSV 0.75-6.0 h-1 Feedstock: heavy phenolic fraction SF1&SF248 Two stage reactor: Pd/C, followed by Re/C at 350 °C P: 10.5 MPa, LHSV: 0.5 Two stage reactor: Ru/C at 140 °C and Pd/C at 370 °C, P: 12.1 MPa, LHSV: 0.2, 0.1 Single stage reactor: sulfided CoMo/Al2O3 at 400 °C, P: 10.4,12.5 MPa, LHSV: 0.5, 0.2 Feedstock: Mountain-pine-beetle-killed wood and hog fuel from a saw mill Two stage plug flow 13.8 MPa First stage: Ru/C sulfide at 170°C LHSV 0.19 h-1 Second stage: CoMo/Al2O3 at 405°C LHSV 0.18 h-1 Feedstock: mallee woody biomass 500°C fluidized bed Batch autoclave 10 MPa Pd/C at 150-300°C 3-12h Pre-esterification with MeOH 70-170°C Feedstock: oak fast-pyrolysis oil Semi-batch reactor 7-17MPa Sulfided Ni−Mo/Al2O3, Pd/C(activated), Pd/char, Pt/char, Ru/char: stabilization (150280°C), deoxygenation (340-400°C), 1h Feedstock: mallee woody biomass 500°C Batch autoclave 10 MPa Pd/C 150-300°C 1-12h

Analytical techniques used for products characterization GC-MS, GPC, elemental analysis (CHS), TGA, synchronous UV fluorescence, water content (KF)

Reference Kadarwati, et al. 201634

GC-MS, elemental analysis (CHN), TGA, synchronous UV fluorescence, water content (KF)

Kadarwati, et al. 201647

13

Wang et al. 201630

C NMR, elemental composition (CHNO), inorganic material (ICP-OES), water content (KF), viscosity and density (Stabinger apparatus), carbonyl groups by Faix titration, acids and phenols titration (CAN/TAN) 13 C-NMR, elemental analysis (CHN-O-S), ICPOES, water content (KF), total acid number (TAN), viscosity, carbonyl titration

Olarte et al. 201628

GC–MS, sugar/alcohols and levoglucosan (HPLC), total organic carbon (TOC)

Sanna et al. 201541

GC-MS, volatile components by simulated distillation, elemental analysis (CHN), metal content (ICP-OES), water content (KF), filterable solids, total acid number, viscosity and density (Stabinger apparatus)

Elliott et al 201549

GC×GC−TOFMS, volatile components by simulated distillation, elemental analysis (CHNOS), metal content (ICP-AES), water content (KF), total acid number

Zacher al.50

et

TGA, synchronous UV fluorescence

Li et 201451;

al.

GC-MS, 13C-NMR carboxylic acid number (CAN), elemental analysis (CHNS), proximate analysis, water content (KF), qualitative miscibility, carbonyl group by oxime titration

French et. al. 201452

GC-MS, FTIR, water content (KF)

Gunawan et al. 201353


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Table 1. Review of bio-oil hydrotreatment studies (Continuation…) Hydrotreatment conditions Feedstock: mallee woody biomass 500°C fluidized bed Plug flow 5-15 MPa Pd/C at 175-300°C LHSV 0.1 - 1.0 h-1 Feedstock: pine wood pyrolysis oil Batch autoclave 10 MPa NiCu/Al2O3 (various Ni/Cu ratios) at 150 1 h, followed by 3 h at 350°C Feedstock: pine wood pyrolysis oil Batch autoclave 20 MPa Ni–Cu (various supports: CeO2–ZrO2, ZrO2, SiO2, TiO2, rice husk carbon, and Sibunite) at 150°C for 1h followed at 350°C for 3h Feedstock: pine wood pyrolysis oil Batch autoclave 20 MPa Mono- and bimetallic metal catalysts based on Rh, Pt, Pd on ZrO2 at 350°C 4 h Feedstock: forest residues pyrolysis oil Batch autoclave 12 MPa – 19 MPa Ru/C at 80-310°C for 10-60 min Feedstock: forestry residues pyrolysis oil Plug flow 15-30Mpa Ru/C up to 400°C, WHSV 5-10 kg h−1 kg−1 cat Feedstock: beech wood pyrolysis oil Batch autoclave 10 and 20 MPa Ru/C, Ru/TiO2, Ru/Al2O3, Pt/C, and Pd/C compared with sulfided NiMo/Al2O3 and CoMo/Al2O3 at 250 and 350°C 4h Feedstock: pine wood pyrolysis oil Plug flow 7.5-15 MPa 2 stage, Ru/C and CoMo/Al2O3 at 170 or 250 to 400°C LHSV 0.19 h-1 Feedstock: mixed wood, corn stover, oak, poplar Plug flow 14 MPa Pd/C at 310 and 375°C and LHSV 0.18 and 1.12 h-1, followed by CoMo/Al2O3 at 400°C 0.4 LHSV

2.

Analytical techniques used for products characterization TGA, synchronous UV fluorescence, water content (KF), GC-MS

GPC, organic acids capillary electrophoresis (CE), TGA, elemental analysis (CHNSO), metal content (ICP-OES), water content (KF), solubility test GPC, TGA, elemental analysis (CHNSO), water content (KF), solubility test

Elemental analysis (CHNSO), water content (KF), oil phase: 1H-NMR, 13C-NMR, GPC, TGA, metal content (ICP-OES), aqueous phase: organic acids capillary electrophoresis (CE) GPC, elemental analysis CHN, water content (KF), coking tendency of the upgraded oils was measured by MCRT GC-MS, elemental composition (CHN-S), water content (KF), solvent fractionation, carbohydrates by BRIX 1 GC-MS, 2D-GC, H-NMR, elemental composition (CHN), water content (KF), flashpoint, viscosity, higher heating value (HHV)

Reference Chaiwat et al. 201354

Ardiyanti et al. 201255



De Miguel Mercader et al. 201142,58 Venderbosch et al. 201059 Wildschut et al. 200960

Simulated distillation CHNO-S, ICP-OES, water content (KF), total acid number TAN, density

Elliott et al. 200961

GC-MS, elemental composition CHN, water content (KF), density, viscosity, density, viscosity, total acid number (TAN)

Elliott et al. 200962

Material and Methods

2.1. Pyrolysis oils Two biomass pyrolysis oils produced by two distinct technologies were used for our studies. BTG-BTL bio-oil from the Biomass Technology Group was produced from pine wood using a rotating cone reactor (http://www.btg-btl.com/). Briefly, the average particle size was 3 mm, the average reactor temperature 510°C, gas residence time < 2s, and condensation temperature: 40°C (one step condensation). Amaron Energy bio-oil (http://www.amaronenergy.com/) was produced 6 ACS Paragon Plus Environment

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from Arbor Pellets in rotating drum reactor (6”/15.2 cm pipe, heated length 48”/122 cm, temperature 450°C, 18 rpm). The particle size used was 6.4 mm (1/4”), approximate reactor residence times for the solid particles was 5 min, and for the gas/vapor products 2 s. A two stage condenser was used to trap the condensable gases, where the first stage temperature was held at 88°C (this fraction is used for analysis), and the second stage temperature was held at 37°C. These oils were thoroughly characterized and their chemical makeup is given elsewhere.45 2.2. Reactor setup and hydrotreatment experiments The hydrotreatment experiments were carried out in a stirred autoclave (PARR Instrument Company, USA: 4576A-FG-SS-230-VS.25-5000-SC-4848-SVM2) with total volume of 250 mL, designed for maximum pressure and temperature of 34 MPa (5000 psi) and 500°C. The catalyst used was Ru/C with metal loading of 5 wt. % (Alfa Aesar #11748). The Ru/C catalyst has a particle size of ~14 µm and BET surface area is 810±11 m2/g. Before each bio-oil stabilization run, the catalyst was reduced in a tube furnace at 350°C for 4h under H2 flow of 100ml/min, and cooled down under Ar for 1h before it was transferred into the reaction vessel.


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Figure 1. Scheme of the hydrotreatment unit used in this study. In a typical experiment, 100 g of raw bio-oil were loaded with 5 g Ru/C into the reactor vessel (see Figure 1). After closing the autoclave, hydrogen was flushed for 15 min to evacuate air. Leak test with pressurized H2 was performed at 18 MPa (2600 psi) for 1h (acceptable leaks 125-150°C), more water is produced than functional groups converted (Table 9). Interestingly, the portion of H2 used for reduction of functional groups drops from 60 to 44% as the stabilization temperature increases. In other words, the rate of H2 consumption is significantly higher than the rate of functional groups reduction (Table 9). According to literature, H2 at low temperatures is mainly utilized to 35 ACS Paragon Plus Environment

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saturate double bonds, aldehydes, ketones, and aromatic rings.83,87 If H2 was used for saturation of the aromatic rings, a dramatic reduction in phenols would have been observed (Table 6). On the other hand, there is a linear correlation between H2 consumed and the water produced, while the conversion of the measured functional groups is poorly correlated with the produced water in the system. Having in mind the oxygen unaccounted for in the functional groups (that may be assigned to the silent esters or ethers, see Table 8), which drops with increasing stabilization temperature, we may speculate that this H2 goes towards breaking of these ester or ether bonds. Furthermore, at the lower stabilization temperature, the amount of hydrogen used for functional groups reduction is lower than the amount of hydrogen in additional water formed (Table 9). As the temperature increases this proportion is inverted (>125-150°C in Table 9), and we observe higher water formation. This may implicate that at lower reaction temperatures the aldehydes and ketones react predominantly with the water, alcohols and phenolics in the oil, reactions catalyzed by the present acids,88 and form hydrates, hemiacetals, hemiketals, acetals, ketals,23 while beyond 125-150°C the catalyst increases its activity towards direct hydrogenation. Looking at the oil through these numbers, the competition between hydrogenation, dehydration, and agglomeration becomes obvious. Similar values for consumption of H2 were reported in literature 0.002-0.019 g H2/g oil,30,58,59,62 however there are also publications that reported higher H2 consumption (0.021-0.070 g H2/g oil), commonly related to continuous flow reactors and higher processing temperatures.24,52,61,87,89,90

4.

Conclusions

The behavior of functional groups in two typical wood derived pyrolysis oils under characteristic stabilization conditions (hydrogenation in the range 100-200°C) over Ru/C catalyst in a batch reactor was studied. Typical phase separation was observed, and the yields of the bottom and aqueous phase for one of the oils showed reverse trends than the other. The hydrogen consumption and the levels of deoxygenation were within the ranges reported in literature, with no surprises that the hydrogenation in the total system was more dominant than the deoxygenation. Water formation increased from 3 to 10% as the temperature increased, and we may speculate that this was predominantly resulting from condensation/oligomerization reactions instead of typical deoxygenation. Moreover, most of the O reduced was within the

31

P-NMR

silent oxygen (esters and ethers), the content of which was reduced from 6 to 2%. This correlates 36 ACS Paragon Plus Environment

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well with the additional water produced. Of all the functional groups followed we observed a drastic decrease in hydroxyl groups that may result from dehydration, or a growth of oligomerization products in the bottom phase, which was clearly observable from the UV fluorescence results. The phenols were partially removed, which may be interpreted as some of them being included in the polymeric structure, while a smaller portion got hydrogenated. The amount of carboxylic acids decreased in the volatile fraction with increasing temperature, and this is what one would expect in the total oil; the 31P-NMR was on the limit of its sensitivity for carboxylic groups to detect changes in the non-volatile fraction, however the more reliable titration method showed that the non-volatile carboxylic acid groups were recalcitrant to the stabilization conditions. We observe the condensation reactions intensify at ~125°C, hence introduction of agents in form of direct hydrogen donors or a catalyst that could also promote cracking and prevent oligomerization at these low temperatures would be beneficial for stabilization of these pyrolysis oils. The FTIR results demonstrated that this analytical technique coupled with the deconvolution of the carbonyl region between 1490 and 1850 cm-1 can be a powerful tool for analyzing hydrotreated bio-oils.

Supporting Information. Detailed GC-MS results. Dependence of reactor pressure on time and stabilization temperature. UV fluorescence. FTIR. 1H-NMR results. Gas analysis.

Acknowledgements The author wants to thank the International Fulbright S&T program for providing scholarship, Marie Swita, Dr. Teresa Lemmon, Dr. Sarah Burton and Dr. Asanga Padmaperuma at the Chemical and Biological Process Development group at PNNL for providing training and analytical support, and Jonathan Lomber within the Analytical Chemistry Service Center at Biological Systems Engineering Department for providing instrumentation and technical support. The WSU NMR Center equipment was supported by NIH grants RR0631401 and RR12948, NSF grants CHE-9115282 and DBI-9604689 and the Murdock Charitable Trust. Dr. GarciaPerez is very thankful for the financial support provided by the US National Science Foundation (CBET-1434073, CAREER CBET-1150430). This project was also partially funded by the USDA/NIFA through Hatch Projects # WNP00701. Financial support of the U.S. Department of 37 ACS Paragon Plus Environment

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Energy - Office of Energy Efficiency and Renewable Energy/ Bioenergy Technologies Office under contract number DE-AC06-76RLO-1830 with Battelle is also acknowledged. Dr Kaliaguine also thanks the BioFuelNet network and the Québec Ministry of Economy, Science and Innovation (MESI) for financial support.


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