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Catalysis Today
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Hydroprocessing of rapeseed pyrolysis bio-oil over NiMo/Al2 O3 catalyst

Katarzyna Pstrowska , Jerzy Walendziewski, Rafa uzny, Marek Stolarski
Wroclaw University of Technology, Faculty of Chemistry, Fuels Chemistry and Technology Division, Gdanska 7/9, 50-344 Wroclaw, Poland

a r t i c l e

i n f o

a b s t r a c t
Raw rapeseed bio-oil, bio-oil fraction boiling at the temperature over 120 C and bio-oil blend with nondesulfurized light gas oil fraction were submitted to hydrorening studies. In this experiment use of NiMo/Al2 O3 as the selected catalyst for pyrolysis oil hydrorening was tested at mild process parameter sets: temperature (260350 C), LHSV (0.52.0 h1 ) and 3 MPa hydrogen pressure. The inuence of hydrorening kinetic parameters on the physicochemical properties as well as chemical composition of the obtained products was evaluated. It was found that raw rapeseed bio-oil is a difcult raw material for a one-step upgrading with the applied process parameters. Obtained oxygen, nitrogen and sulphur removal was 70.8, 21.1 and 33.3 wt.%, respectively. Removal of low boiling bio-oil fraction and lowering of LHSV up to 0.5 h1 strongly improved hydroprocessing efciency. The HDO, HDN and HDS process efciency value of 77.3, 38.4 and 27.7 wt.% was obtained respectively. At relatively high LHSV level (2.0 h1 ), mild temperature (320 C), and 3 MPa hydrogen pressure, a satisfactory level of the blend hydrorening was achieved. Hydrorening products of bio-oil and light gas oil fraction blend fullled majority of fuel oil commercial requirements. 2013 Elsevier B.V. All rights reserved.

Article history: Received 31 January 2013 Received in revised form 16 October 2013 Accepted 23 October 2013 Available online xxx Keywords: Pyrolysis Rapeseed oil Hydrotreating Hydrodeoxygenation Upgrading

1. Introduction Thermal or catalytic cracking of agricultural biomass followed by hydroprocessing can be an alternative method for bio fuels production. Until now, recovery of energy from agricultural residues has focused on thermochemical processes such as direct combustion, gasication, and pyrolysis [15]. Simplicity of pyrolysis process and accessibility of the raw material, causes the interest in application of rapeseed for bio-oil production as a potential bio fuel or a bio fuel component. Apart from the conditions of pyrolysis process, elemental analysis of the obtained bio-oils indicates large concentration of heteroatoms (up to 45 wt.% of oxygen, up to 5 wt.% of nitrogen and to a lesser extent sulfur 0.01 to 0.2 wt.%) [35]. High oxygen content is a result of depolymerization and fragmentation of three key biomass building blocks: cellulose, hemicellulose and lignin. Sulfur and nitrogen are included in proteins which are main components of the oil in oil-seed plants. Pyrolytic oils are typical of high unsaturated hydrocarbons content (due to chemical structure of main components of biomass) and water presence, which precludes the use as fuel oil component due to bio-oils lack of thermal and chemical stability. Water in bio-oils results from the original

Corresponding author. Tel.: +48 71 320 65 92; fax: +48 71 320 65 92. E-mail address: katarzyna.pstrowska@pwr.wroc.pl (K. Pstrowska). 0920-5861/$ see front matter 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.cattod.2013.10.066

moisture in the feedstock and as a product of the dehydratation reactions occurring during biomass pyrolysis process. Raw bio-oils obtained via thermal conversion cannot be used as fuels for the internal combustion engine due to their several physical drawbacks which are the results of their chemical composition. Main properties excluding the use of bio-oils as fuels for the internal combustion engine include high viscosity, acidic nature (bio-oil has a typical pH of around 2.5 from organic acids formed by thermal degradation of biopolymers), high water and oxygen content, and incompatibility with conventional fuels [35]. Therefore, bio-oil upgrading processes are necessary. The main group of bio-oil upgrading processes takes into account physical upgrading such as solvent addition, ltration, and catalytic upgrading such as hydrotreating, zeolite cracking, and other chemical methods of upgrading, e.g. steam reforming, esterication, mild cracking [510]. Zeolite cracking [6,1113], emulsication of pyrolysis bio-oil with diesel oil [1416], and hydroning processes [6,9,1721] were found as most effective in bio-oil upgrading. Hydrodeoxygenation (HDO), which is most effective in hydroning processes, improves product stability and compatibility with conventional fuels. The efciency of kinetic parameters (temperature, hydrogen pressure, LHSV) and inuence of bio-oil water content for bio-oil HDO was widely described by Huber [4] and Elliott [6]. Catalyst activity for HDO process was also described for model compounds e.g. phenol, p-cresol [22,23] and several bio-oils from thermochemical processes [6].

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Several papers mention the use of hydroprocessing NiMo/Al2 O3 catalyst for conversion of different bio-oils, e.g. from poplar wood [6], white oak [8], pine sawdust [18]. Elliott and co-workers [6] developed a two-step hydrotreating process for the bio-oil upgrading derived from wood pyrolysis. The rst step at low temperature (270 C, 136 atm) hydrogenates the thermally unstable bio-oil compounds. The second step involves a catalytic hydrogenation at higher temperature (400 C, 136 atm). The same catalyst, a sulded Co-Mo/Al2 O3 or sulded Ni-Mo/Al2 O3 , is used for both steps. This process can produce rened oil containing less than 1 wt.% of oxygen. During this process, 2030% of carbon atoms in the bio-oil are converted into gaseous hydrocarbons, decreasing the overall bio-oil yield. For keeping their activity, commonly used catalysts such as NiMo/Al2 O3 and CoMo/Al2 O3 require sulphur compounds in the reaction space. Liquid products from rapeseed pyrolysis are characteristic by low sulphur content. Therefore there is a need for bio-oils co-rening with sulphide containing petroleum fractions such as light gas/vacuum gas oil [24] or search for new non-sulphide catalysts [25]. The addition of petroleum fraction would considerably reduce oxygen content in raw material for hydrorening process as well as acidity of bio-oil and water content would be lowered. Blend upgrading would reduce hydrogen consumption, and at the same time reduce overall cost of fuel components production from bio-sources such as pyrolytic bio-oils. The other feasible method of bio-oils upgrading is a two-step hydrorening. At the rst step, mild hydrorening process would partly remove oxygen from the bio-oil. Second step could involve hydrorening of partly deoxygenated (and properly dehydrated) oil with non-rened petroleum fractions (e.g. diesel oil fraction/light gas oil fraction). According to the authors knowledge, there are not too many papers considering comparison of hydrorening parameters between raw bio-oil, dehydrated bio-oil and hydrorening of biooil blend with petroleum fraction particularly for agricultural type bio-oils from thermochemical decomposition of the energy plants as rapeseed. The catalytic hydrorening efciency of raw rapeseed bio-oil, dewatered bio-oil fraction boiling at temperature over 120 C, and bio-oil blend with non-desulfurized light gas oil fraction were investigated. The inuence of hydrorening parameters (in temperature range of 260350 C, LHSV 0.52.0 h1 , 3 MPa hydrogen pressure) was investigated on physical properties and chemical composition of hydrorening products. The hydrorening process was operated under mild process parameters (temperature in the range of 260350 C) to prevent high conversion of the feed to gas-phase products, which reduces liquid product yield. Moreover, relatively low hydrogen pressure (3 MPa) and high LHSV (0.52.0 h1 ) was applied in order to reduce hydrorening costs.

2.2. Rapeseed pyrolysis Pyrolysis experiments were carried out at the temperature of 500 C. The applied pyrolysis reactor was a xed bed design made of heat-resisting steel. The reactor was heated externally by an electrical furnace in which temperature was measured with two thermocouples FeKo (J type). One thermocouple was placed in the central part of the reactor (inside the reactor) and second one in the wall of the furnace (space between the furnace and the reactor). In the typical experiment, 2200 g of the rapeseed material was loaded to the reactor and then the reactor temperature was increased at the steady rate of 5 C/min till desired nal temperature was reached. At this point, the experiment was held at a constant (nal) temperature for 30 min till the process was completed. Before the experiment, the reactor was purged with argon for 15 min at a ow rate of 20 l/h to remove air from the apparatus system. The gaseous pyrolysis products were owing through a water condenser, where they were condensed and cooled in a water jacket and next in a cold trap maintained at 5 C. The liquid products were separated into aqueous and oil fractions. Bio-oil fractions were additionally dried over molecular sieves 4A. The hermetically closed glass bottles containing bio-oil were stored at reduced temperature (3 to 5 C). The experimental results of pyrolysis, which were conducted at 5 C/min heating rate, and 500 C nal temperature under static atmosphere, were obtained as following: yield of biochar: 32.4 wt.%, bio-oil: 34.4 wt.%, water fraction: 17.4 wt.%, gas fraction: 15.8 wt.%.

2.3. Hydroprocessing Three series of pyrolytic bio-oil hydroprocessing experiments were carried out. The reactor feed was composed of raw material: rst series raw bio-oil, second series dewatered bio-oil fraction boiling over 120 C, third series 20% (v/v) of raw bio-oil and 80% (v/v) non-rened light gas oil fraction mixture. The experiments were performed in the laboratory scale continuous ow apparatus previously described by Walendziewski et al. [24]. The applied series parameters are presented in Table 1. A commercial hydrocracking NiMo/Al2 O3 catalyst was used in this research. 50 cm3 of the catalyst was packed into the reactor tube (total reactor volume 300 cm3 ). The catalyst was activated by sulphiding process (3 MPa of H2 , temperature 320 C, LHSV = 2 h1 , sulphiding time 12 h) with diethyl sulde, S(C2 H5 )2 solution in diesel fuel. Fig. 1 presents the schematic view of hydrorening continuous ow apparatus.

2.4. Bio-oil and hydrorening products analyses 2. Experimental 2.1. Material The rapeseed grain samples (Brassica napus L.) were taken from the city of Malczewo located in the west region of Poland. Samples were used as received (average particle size 2 mm). Rapeseed grain is rich in carbon (64.8 wt.%), hydrogen (10.1 wt.%), and oxygen (21.6 wt.%). Nitrogen and sulphur contents in the feed attained values 3.2 wt.% and 0.3 wt.%, respectively. Approximate analysis indicated high volatile matter content (90.2 wt.%), high heat of combustion value (24.8 MJ/kg) and 3.6 wt.% of ash content. Oil content in the material was determined as 40.3 wt.% with hexane extraction method (EN ISO 734-1:2006). - products density at 15 C was determined using aerometer, according to EN ISO 3675, EN ISO 12185, - fractional composition, according to EN ISO 3405, - bromine number, respectively olen content calculation was determined with potentiometer titration according to ASTM D1159-07, - kinematical viscosity at 20 and 40 C was determined using Ubbelohde viscometer, according to EN ISO 3104, - freezing point according to ASTM D238606, - heat of combustion according to ASTM D4809, - water content according to ASTM D6304-7. The following analyses of the obtained products were carried out according to the suitable standards:

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K. Pstrowska et al. / Catalysis Today xxx (2013) xxxxxx 3 Series/exp. no. I/1 I/2 I/3 I/4 II/1 II/2 II/3 III/1 III/2 III/3 Temp., [o C] 260 290 320 350 350 350 350 260 290 320 Hydrogen pressure, [MPa] 3 3 3 3 3 3 3 3 3 3 LHSV, [h1 ] 2.0 2.0 2.0 2.0 0.5 1.0 2.0 2.0 2.0 2.0

Table 1 Hydroprocessing parameters. Feed Raw rapeseed pyrolysis bio-oil

Rapeseed pyrolysis bio-oil fraction boiling over 120 C

20% (v/v) raw rapeseed pyrolysis bio-oil and 80% (v/v) light gas oil fraction blend

Elemental analysis of raw materials and obtained hydrorening products were carried out using the CHNS EA 1110 CE Instruments analyzer. Sulfur content was measured with Varian-ICP-AES Liberty 220 analyzer, and oxygen content was calculated from the difference. NMR Bruker DRX 300 spectrometer with a 5 mm broad band probe was used to record the 1 H NMR and 13 C NMR. The 1 H NMR spectra of the oils (200 l of bio-oils were mixed with 300 l CDCl3 ) was obtained at H frequency of 300.12 MHz, measured in range of 3.838 to 16.137 ppm (16 scans, delay: 1 s acquisition time: 5.46 s). The 13 C spectra, at C frequency of 75.45 MHz, was measured in the range of 10 to 230 ppm (1024 scans, delay: 30 s, acquisition time: 3.62 s). The percentage of protons and carbon atoms in different groups were determined according to the method proposed by Mullen et al. [26] using spectra of equimolar solution (1:1:1:1) of 1-hexene, isooctane, m-cresol and 4-methyl-2-pentanone. Differences in relaxation time of the obtained spectra were corrected using the standard mixture correlations.

3. Results and discussion 3.1. Raw rapeseed bio-oil hydroprocessing Table 2 presents results of bio-oil hydroprocessing over NiMo/Al2 O3 , at constant LHSV (2.0 h1 ) and 3 MPa hydrogen pressure. For the series I, the bed temperature in range of 260350 C was the variable parameter (Table 1). Raw bio-oil from rapeseed pyrolysis contains large amount of water (9.5 wt.%), difcult to remove with physical methods. Elemental composition indicates low hydrogen content (10.6 wt.%), high oxygen (9.45 wt.%) and nitrogen (3.07 wt.%) content. Up to the temperature of 330 C distilled 70% (v/v) of the bio-oil. Further heating of the product in the course of distillation results in thermal decomposition. Rapeseed pyrolysis oil is also characterized by high olen content (58.8 vol.%). Primary properties of the raw material for hydrorening process are listed in Table 2. Proton NMR points 4.4% of heteroaromatic protons and 65.5% of alkanes

Fig. 1. Schematic view of hydrorening apparatus [24]. (1) Gasmeter, (2) pump, (3) feed tank, (4) reactor, (5) temperature controllers, (6) water cooler, (7) pressure gasliquid separator, (8) atmospheric separator.

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K. Pstrowska et al. / Catalysis Today xxx (2013) xxxxxx Raw material Sample no. I/1 I/2 290 3 2.0 94.2 0.910 80.20 12.20 2.66 0.17 4.77 1.83 83 104 305 335 335 80 9.0 45.6 42.5 13.5 1 40.2 I/3 320 3 2.0 92.3 0.907 80.80 13.10 2.42 0.12 3.56 1.94 87 105 288 326 327 90 10.4 41.2 16.8 6.2 6 39.9 I/4 350 3 2.0 91.0 0.893 80.75 13.36 2.95 0.12 2.82 1.83 76 98 290 323 323 80 1.0 44.9 12.9 7.6 5 39.0

Table 2 Raw bio-oil and hydrorening products properties.

Temperature, [ C] Hydrogen pressure, [MPa] LHSV, [h1 ] Liquid product yield, [wt.%] Density at 15 C, [g/cm3 ] Elemental composition, [wt.%] C H N S Oa Atomic ratio H/C Distillation IBP, [ C] 10%, [ C] 50%, [ C] 80%, [ C] EBP, [ C] % Distilled fraction Water content, [wt.%] Olen content, [vol.%] Viscosity at 20 C, [cSt] 40 C, [cSt] Freezing point, [ C] Heat of combustion, [MJ/kg]
a

260 3 2.0 0.914 76.70 10.60 3.07 0.18 9.45 1.66 85 94 300 331 70 9.5 58.8 30.3 15.7 13 35.4 94.6 0.910 77.30 11.40 3.00 0.18 8.12 1.77 83 105 311 330 78 11.0 45.1 60.8 17.2 10 39.1

Calculated by difference.

Table 3 Percentage composition of hydrogen based on 1 H NMR analysis raw rapeseed bio-oil and hydroprocessing raw bio-oil product Series I experiment. Chemical shift, ppm Proton assignments Raw material % 0.51.5 1.53.0 3.04.4 4.46.0 6.08.5 9.510.0 Alkanes Aliphatics- to unsaturated or heteroatom Alcohols, methylene-dibenzene, ethers Methoxy, carbohydrates (Hetero-) aromatics Aldehydes, carboxylic acids 65.5 25.9 0.1 4.1 4.4 76.4 19.7 1.3 2.6 I/3

type protons (Table 3). 13 CNMR studies point 16.5% of carbon atoms in aromatic and olen structures. Within the molecule chain,CH2 represents the majority of all carbon present in bio-oil structure (63.1% Table 4) which conrms 1 HNMR calculations pointing the saturated hydrocarbons as the dominant state in the bio-oil structure. In order to use rened bio-oils as internal combustion engine fuels or fuel oils a considerable percentage of oxygen and nitrogen must be removed. It is also necessary to reduce the unsaturated hydrocarbons content and improve physical properties of the product. Increase in process temperature causes higher gas production, at the same time reduces liquid product yields and leads to the H/C ratio increase which is caused mainly by oxygen removal

and partly by olens and aromatics hydrogenation. Hydrorening products distillation prole was improved up to 90% (v/v) of I/3 product distillation at the temperature of 327 C (Table 2). The slight decrease in high olens content together with process temperature (58.841.2 vol.% I/3 Table 2) certies unsaturated hydrocarbons presence and their resistance to the applied process parameters. This was conrmed by 1 HNMR and 13 CNMR spectra analysis (Figs. 2 and 3). Hydrogenation of unsaturated hydrocarbons (16.5 13.2% I/3 Table 4) causes increase in alkanes type carbon content (65.5 76.4% I/3 Table 3) which is the reason for the improvement in hydrorening products physical properties. Products characteristic modication was conrmed by viscosity and freezing point determination. Freezing point temperature rises

Table 4 Results of calculation of percentage content of carbon based on 13 C NMR analysis of Series I experiment. Chemical shift [ppm] Carbon assignments Raw material % 015 1520 2030 3055 5595 95165 165180 180215 Peripheral CH3 -olens Peripheral, CH3 -aliphatics Inside chain CH2 Chain branching CH2 Alcohols, ethers, phenolic-, methoxys-, carbohydrates Aromatics, olens Esters, carboxylic acids Ketones, aldehydes 16.8 63.1 3.6 16.5 22.0 58.3 6.5 13.2 I/3

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Fig. 2.

H NMR spectra of raw material and hydroprocessing product Series I.

from 13 C (raw bio-oil) up to 1 C. for the product obtained at the hydrorening temperature of 290 C. Increase in process temperature slightly lowers the freezing point temperature up to 6 C (I/3) and 5 C (I/4 Table 2). The initial increase in freezing point temperature observed at the hydrorening temperature of 290 C is a result of increase in alkanes content, which freeze in higher temperatures. The increase in the parafns content is caused by olens hydrogenation. Successively lowering the freezing point temperature in higher hydrorening temperature was caused by isomerization of alkanes formed in lower temperatures. The higher content of i-alkanes is advantageous from the fuel-use point of view because it improves low-temperature properties of the product. The highest oxygen removal was observed at the temperature of 350 C 70.1%. Incomplete hydrogenolysis of oxygen compounds may be caused by the presence of less reactive aromatic oxygen compounds e.g. phenols where C O bonding is more durable (dissociation energy at the level of 422468 kJ/mol) than in aliphatic compounds (339385 kJ/mol). The obtained results indicate that the remained oxygen in the structure of hydrorening products is mainly aromatic type, e.g. phenol. Additionally, nitrogen compounds and H2 O presence cause lowering of HDO efciency [9]. With the increase in hydrorening temperature, the degree of desulfurization increases. Maximum hydrogenolysis of sulphur

compounds was observed at the level of 33.3% up to the value 0.12 wt.% (I/3, I/4). Unsatisfactory level of HDS processes may be caused by many factors, e.g. too low LHSV (too short contact time of the feed with the catalyst material), too low hydrogen pressure (the degree of desulfurization increases with the partial pressure of hydrogen increase), high nitrogen and oxygen content (ammonia and water, products of nitrogen and oxygen containing compounds hydrogenolysis in larger concentrations are poison of acid centres of NiMo catalyst). The rate of nitrogen compounds hydrogenation reactions is lower than the rate of hydrogenolysis of the sulphur compounds. Applied catalyst and process parameters do not promote satisfactorily HDN processes (Table 2). Maximum nitrogen removal was observed at 320 C with 21.1% efciency. Such low degree of nitrogen removal implies hydrogenation of aliphatic or aromatic nitrogen-containing compounds in which nitrogen is present in the substituent. Aliphatic and aromatic nitrogen compounds, in which nitrogen is present in the substituent (e.g. amines, nitriles) are much easier to remove than heterocyclic nitrogen compounds and aromatics in which nitrogen is embedded in the ring. At that point it is highly possible that the majority of nitrogen compounds present in the bio-oil structure are heterocyclic type or aromatics, in which nitrogen is embedded in the ring.

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Fig. 3.

13

C NMR spectra of raw material and hydroprocessing product Series I experiment.

Table 5 Hydrorening of raw rapeseed pyrolysis bio-oil fraction boiling over 120 C properties of the raw material and hydrorening products. Raw material Sample no. II/1 Temperature, [ C] Hydrogen pressure, [MPa] LHSV, [h1 ] Liquid product yield, [wt.%] Density at 15 C, [g/cm3 ] Elemental composition, [wt.%] C H N S Oa Atomic ratio H/C Distillation IBP, [ C] 10%, [ C] 50%, [ C] 80%, [ C] EBP, [ C] % Distilled fraction Water content, [wt.%] Olen content, [vol.%] Viscosity at 20 C, [cSt] 40 C, [cSt] Freezing point, [ C] Heat of combustion, [MJ/kg]
a

II/2 350 3 1.0 91.8 0.860 83.20 13.10 2.03 0.14 1.53 1.89 78 113 284 304 75 0.7 36.0 8.7 5.4 1 41.2

II/3 350 3 2.0 91.1 0.847 78.39 12.10 2.91 0.17 6.43 1.85 93 170 320 342 70 1.0 36.8 18.4 9.4 2 41.3

350 3 0.5 0.894 78.40 11.89 3.10 0.18 6.43 1.82 120 202 273 281 60 2.1 55.6 66.5 27.3 10 40.5 95.7 0.865 83.20 13.30 1.91 0.13 1.46 1.92 83 189 292 316 316 80 1.5 34.8 7.1 4.9 1 43.1

Calculated by difference.

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K. Pstrowska et al. / Catalysis Today xxx (2013) xxxxxx 7 Proton assignments Raw material % II/1

Table 6 Percentage composition of hydrogen based on 1 H NMR analysis hydroprocessing of Series II experiment. Chemical shift [ppm]

0.51.5 1.53.0 3.04.4 4.46.0 6.08.5 9.510.0

Alkanes Aliphatics- to unsaturated or heteroatom Alcohols, methylene -dibenzene, ethers Methoxy, carbohydrates (Hetero-) aromatics Aldehydes, carboxylic acids

68.9 23.1 0.1 4.2 3.7

75.1 18.6 4.1 2.2

Table 7 Results of calculation of percentage content of carbon based on 13 C NMR analysis of Series II experiment. Chemical shift [ppm] Carbon assignments Raw material % 015 1520 2030 3055 5595 95165 165180 180215 Peripheral CH3 -olens Peripheral, CH3 -aliphatics Inside chain CH2 Chain branching CH2 Alcohols, ethers, phenolic-, methoxys-, carbohydrates Aromatics, olens Esters, carboxylic acids Ketones, aldehydes 18.2 3.0 57.3 3.6 17.9 23.9 56.9 6.6 0.1 12.5 II/1

Fig. 4.

H NMR spectra of raw material and hydroprocessing product Series II experiment.

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Fig. 5.

13

C NMR spectra of raw material and hydroprocessing product Series II experiment.

Moderate hydrorening transformation of raw rapeseed derived bio-oil was obtained in series I of the experiment. Unsatisfactory level of hydrorening process may be caused by many factors, e.g. raw material water content (catalyst deactivation), presence of the water fraction forming in the rening process (catalyst deactivation), too low hydrogen pressure or too high LHSV. In order to improve efciency of HDO and HDN processes as well as saturation of olen hydrocarbons, LHSV in the range of 0.52.0 h1 was lowered. Additionally, in order to remove water and low boiling fraction, raw materials vacuum distillation up to 120 C was applied. 3.2. Hydroprocessing of dewatered bio-oil fraction boiling over 120 C Series II of rapeseed pyrolysis bio-oil hydrorening was performed with dewatered bio-oil fraction boiling at temperature over 120 C. Removal of the low-boiling fraction was performed under vacuum to avoid bio-oil components polymerization process. Variable parameter of the series II was the liquid hour space velocity (LHSV) in range of 0.52.0 h1 (Table 1). The strongly polar character of the bio-oils excludes complete water removal. Vacuum distillation up to 120 C leads to the biooil raw material containing 2.1 wt.% of water (Table 5). High level

of water removal strongly inuenced bio-oil primary properties as density (decrease up to 0.894 g/cm3 at 15 C) and elemental composition (C 78.40 wt.%, H 11.89 wt.% Table 5). Moreover, water content reduction improved the heat of combustion value of the material from 35.4 (raw material of series I Table 2) up to 40.5 MJ/kg (raw material of series II Table 5). In comparison to raw bio-oil, low-boiling fraction removal impairs distillation prole. Up to the temperature of 280 C distils 60 (v/v)% of the product. Further heating results in thermal decomposition which certies the end of atmospheric distillation process. Reduction of the bio-oil distillation capability is caused by concentration of heavy hydrocarbons and heteroatom compounds. Aromatic and olen carbons content in dewatered rapeseed bio-oil fraction boiling over 120 C attained 17.9% level (Table 7) while (hetero-) aromatic protons concentration attained 3.7% level (Table 6). Inside chain CH2 is a majority of all carbons present in bio-oil structure (57.3% Table 7) which conrms 1 HNMR calculations pointing saturated hydrocarbon protons as dominant in the bio-oil structure (68.9% Table 6). The primary properties of the products obtained in the process are more diversied than in series I. The characteristic of properties is presented in Table 5. Lowering LHSV up to 0.5 h1 reduces olens content in greater extent than in case of series I, although the olen content remains on high level (from 55.6 in the raw

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K. Pstrowska et al. / Catalysis Today xxx (2013) xxxxxx 9 Light gas oil fraction Raw material Sample no. III/1 III/2 290 3 2.0 96.9 0.855 84.93 14.50 0.43 0.01 0.13 2.05 96 233 291 317 326 90 1.4 9.3 6.65 3.42 14 44.2 III/3 320 3 2.0 95.7 0.850 85.00 14.60 0.28 0.01 0.11 2.06 86 241 291 305 335 90 1.0 7.0 4.91 3.43 14 44.2

Table 8 Hydrorening of 20% (v/v) rapeseed pyrolysis bio-oil and 80% (v/v) light gas oil fraction blend properties of the raw material and hydrorening products.

Temperature, [ C] Hydrogen pressure, [MPa] LHSV, [h1 ] Liquid product yield, [wt.%] Density at 15 C, [g/cm3 ] Elemental composition, [wt.%] C H N S Oa Atomic ratio H/C Distillation IBP, [ C] 10%, [ C] 50%, [ C] 80%, [ C] EBP, [ C] % Distilled fraction Water content, [wt.%] Olen content, [vol.%] Viscosity at 20 C, [cSt] 40 C, [cSt] Freezing point, [ C] Heat of combustion, [MJ/kg]
a

260 3 2.0 0.858 0.866 83.50 10.61 0.77 0.10 5.02 1.52 88 98 242 263 65 1.9 11.5 6.04 4.66 9 43.3 97.4 0.860 85.00 14.40 0.46 0.01 0.13 2.03 90 209 285 307 312 90 1.5 10.0 6.07 4.09 11 44.8

0.10 n/a 231 261 289 310 336 99 n/a 0.4 4.82 3.45 n/a 44.7

Calculated by difference.

Table 9 Percentage composition of hydrogen based on 1 H NMR analysis hydroprocessing of Series III experiment. Chemical shift [ppm] Proton assignments Raw material % 0.51.5 1.53.0 3.04.4 4.46.0 6.08.5 9.510.0 Alkanes Aliphatics- to Usaturated or heteroatom Alcohols, methylene -dibenzene, ethers Methoxy, carbohydrates (hetero-) aromatics Aldehydes, carboxylic acids 64.8 26.7 2.8 5.7 78.5 18.6 2.9 III/3

material of series II to 34.8 vol.% product II/1), which makes it unacceptable for use of obtained product as a liquid fuel. Reduction in the value of LHSV up to 0.5 h1 effects in freezing point temperature increase up to +1 C. It is caused by a higher freezing point temperature of saturated hydrocarbons compared to olens. As a result of partial olens hydrogenation and heteroatom compounds hydrogenolysis, also signicant viscosity reduction was observed (Table 5). It is evident that unsaturated hydrocarbons are resistant to the applied process parameters (Table 1) which was conrmed by NMR spectra (Figs. 45). Partial unsaturated hydrocarbons hydrogenation (17.512.5% II/1 Table 7) causes increase in alkane protons content (68.975.1% II/1 Table 6) which is the

main reason for improvement in hydrorening products physical properties. In case of II/1 product, the maximum oxygen removal was observed at 77.3% level. Lowering the LHSV up to 0.5 h1 (II/1 product) additionally intensies HDN processes up to 38.4% level. Applied parameters of series II led to the less polar products than in case of raw rapeseed hydrorening products. It was possible with application of physical methods to remove water from the products up to the content 0.71.5 wt.%. The removal of low-boiling rapeseed pyrolysis bio-oil fraction meaningfully improved biooils properties as the raw material for mild hydrorening process. Hydrorening products, particularly sample II/1 obtained at 0.5 h1

Table 10 Results of calculation of percentage content of carbon based on 13 C NMR analysis of Series III experiment. Chemical shift [ppm] Carbon assignments Raw material % 015 1520 2030 3055 5595 95165 165180 180215 Peripheral CH3 -olens Peripheral, CH3 -aliphatics Inside chain CH2 Chain branching CH2 Alcohols, ethers, phenolic-, methoxys-, carbohydrates Aromatics, olens Esters, carboxylic acids Ketones, aldehydes 13.8 7.3 20.0 44.6 14.3 21.8 9.3 37.1 20.7 11.1 III/3

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Fig. 6.

H NMR spectra of raw material and hydroprocessing product Series III experiment.

LHSV is characterized by 77.3% HDO, 38.4% of HDN, 27.7% of HDS, increase of H/C ratio up to 1.92 and 43.1 MJ/kg heat of combustion value, points right selection of hydrorening parameters. Still nitrogen (1.91 wt.%) and sulphur (0.13 wt.%) content remains at the high level, which limits direct use of the product as a fuel. As in case of series I, unsatisfactory level of HDS and HDN may be caused by presence of heteroatom compounds resistant to the applied process parameters, e.g. for nitrogen -heterocyclic type or aromatics, in which nitrogen is embedded in the ring, or thiophene type sulphur compounds. Potentially, at the proper selection of share, hydrorening product II/1 could be used as a fuel oil component in a mixture with a suitable petroleum fraction. 3.3. Hydrorening of rapeseed pyrolysis bio-oil and non-desulfurized light gas oil fraction blend Series III raw material was 20% (v/v) of raw bio-oil from rapeseed pyrolysis and 80% (v/v) of non-rened light gas oil petroleum fraction containing blend (Table 8). The blended material for hydrorening process was characterized by the lowest water content of all employed raw materials (1.9 wt.% Table 8). Benecial elemental composition (H/C ratio 1.52, oxygen content 5.02 wt.%, nitrogen content 0.77 wt.%) and relatively low olens

content (11.5 vol.%) indicate the blend material type suitable for mild hydrorening process. Increase in temperature causes signicant improvement of hydrorening products properties. Products distill up to 90% (v/v) at the temperature range of 312 (III/1) 335 C (III/3 Table 8). Elemental composition indicates high H/C ratio up to 2.06 (III/3). Hydrodeoxygenaton at the hydrorening temperature of 320 C reached value of 97.8%. Similarly, high hydrodesulphurization and hydrodenitrication levels, 90.0% and 63.6% respectively, were also obtained. Intensication of hydrogenolysis in case of HDO, HDN and HDS in series III was caused mainly by the dilution of large amount of heteroatom compounds containing bio-oil with low heteroatoms containing light gas oil petroleum fraction (oxygen and nitrogen). High hydrogenolysis level of oxygen and sulphur containing compounds is a result of diminished content of nitrogen containing compounds. Nitrogen compounds in larger concentrations and ammonia, product of their hydrogenolysis, are poison of acid centres of nickel-molybdenum catalyst and lower its hydrogenation activity. Therefore a low level of desulfurization in hydrorening processes of raw bio-oil and dewatered bio-oil (Tables 2 and 5) in comparison to hydrorening of gas oil and low nitrogen containing feed was observed (Table 8). The signicant increase in H/C ratio (up to 2.06 at the hydrorening temperature of 320 C)

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Fig. 7.

13

C NMR spectra of raw material and hydroprocessing product Series III experiment.

is presumably also a result of the increased catalyst activity and aromatic hydrogenation degree because diminishing of olen content in series III was rather small (Tables 8 and 10). This observation is conrmed by decrease in the freezing point (from 9 to 14 C, Table 8). In case of dewatered bio-oil hydrorening process, quite the opposed phenomenon was observed. Freezing point of the hydrorened products increased (from 10 to +1, Table 5), as a result of hydrogenation of olens, that have lower freezing point in comparison with the parafns with the same length of carbon chain. The product heat of combustion was high and averaged at 44.2 MJ/kg. The NMR spectra (Figs. 67) indicates 14% increase in alkane type protons content, decrease in heteroaromatic protons content up to 2.9%, and total decomposition of methoxy, and carbohydrate derivatives (III/3 Table 9). The application of the blend consisting of 20% (v/v) of rapeseed bio-oil and 80% (v/v) of light gas oil petroleum fraction considerably improves mild hydrorening process effects. It is connected with the lowest concentration of heterocompounds, such as nitrogen and oxygen containing compounds. At relatively high LHSV level (2.0 h1 ), low temperature and hydrogen pressure, satisfactory level of hydrorening was achieved. Hydrorening product of series III fulls the majority of light fuel oil requirements. The main disadvantage of hydrorening of bio-oils from rapeseed pyrolysis is huge quantity of hydrogen consumption for oxygen and nitrogen removal as well as double bond hydrogenation. It results in rather high costs of hydrorening process. Oxygen content in fuel oils is not detrimental. However, hydrorening process is accompanied by parallel hydrogenolysis of oxygen, nitrogen

and sulphur containing compounds, and hydrogenation of double bonds. Therefore it would be protable to apply more selective catalyst which the main feature would be mild hydrogenation, denitrogenation and desulphurization properties. 4. Conclusions One-step hydrorening of raw bio-oils from rapeseed grain biomass pyrolysis does not result in satisfactory rening level. The obtained low quality products cannot be used as fuel oils or their components. Maximum HDO, HDN and HDS processes efciency, at 70.1, 21.1% and 33.3% level were obtained respectively. Unsatisfactory level of hydrorening process is caused by high water as well as olenes and heteroatoms content in the rened bio-oils. Removal of low-boiling fractions and part of water meaningfully improved bio-oils properties as the raw material for mild hydrorening process. The obtained products, particularly samples obtained at low LHSV (0.5 h1 ) are characterized by relatively high HDO level (77.3%), 38.4% of HDN, 27.7% of HDS, increase in H/C ratio up to 1.92, and 43.1 MJ/kg heat of combustion value. These results conrm proper choice of conception of rening process. Potentially, rening product obtained from raw dewatered bio-oil fraction at process parameters (350 C, 0.5 h1 , 3 MPa of H2 ) could be used as a fuel oil component (2040 wt.%) in a mixture with a suitable petroleum fraction. The application of the blend consisting of 20% (v/v) of rapeseed bio-oil and 80% (v/v) of light gas oil petroleum fraction considerably improves hydrorening process results. It is connected with

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the relatively low concentration of nitrogen and oxygen containing organic heterocompounds in gas oil fraction. At a relatively high LHSV level (2.0 h1 ), low temperature (320 C), and hydrogen pressure (3 MPa), hydrorening products full majority of light commercial fuel oil requirements. It is necessary to underline that because bio-oils contain high quantity of olenes as well as oxygen, nitrogen and sulphur compounds, applying hydrorening processes consume large quantity of hydrogen. This results in production cost increase of nal product. Acknowledgements This work was supported by Polish Ministry of Science and Higher Education, Project number N N205 278835. The authors would like to thank Pawe Dabrowski MSc, from NMR Laboratory Wroclaw University of Technology, for his support in NMR analysis. References
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