Deoxy-Liquefaction of Laminaria japonica to High-Quality Liquid Oil

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Deoxy-liquefaction of Laminaria japonica to highquality liquid oil over metal modified ZSM-5 catalysts Jinhua Li, Guo-Ming Wang, Cuili Gao, Xiang Lv, Zonghua Wang, and Haichao Liu Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/ef4004208 • Publication Date (Web): 12 Aug 2013 Downloaded from http://pubs.acs.org on August 19, 2013

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Deoxy-liquefaction of Laminaria japonica to high-quality liquid oil over metal modified ZSM-5 catalysts Jinhua Li*,a , Guoming Wang*,a, Cuili Gaoa, Xiang Lva, Zonghua Wanga, Haichao Liub a

College of Chemistry and Chemical Engineering and Environment, Teachers College, Qingdao

University, Qingdao 266071, China b

Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular

Engineering, Peking University, Beijing, 100871, China.

Abstract: The marine brown macroalgae, Laminaria japonica, was converted into liquid oil through deoxy-liquefaction in a stainless steel microreactor. The liquid oil was mainly composed of aromatics, phenols, alkanes and alkenes, other oxygen containing compounds and some nitrogen containing compounds. The HZSM-5 and metal modified Fe/HZSM-5 and Ni/HZSM-5 catalysts were introduced to investigate the yield, distribution and properties of the liquid oil. For all catalysts, the aromatics and long-chain alkanes increased, while those phenols and nitrogen containing species decreased, contributing to a distinct decrease in oxygen content. A maximum oil yield of 15.32±0.2% was obtained when the Ni/HZSM-5 catalyst was used. The aromatics and alkanes reached 9.15% and 22.96% respectively, and the higher heating value was up to 44.58 MJ/kg. The results suggested that L. japonica has potential as biomass feedstock for fuel and chemicals and that deoxy-liquefaction technique may be an effective way to convert macroalgae into high-quality liquid oil. Keywords: macroalgae, liquid oil, HZSM-5, deoxy-liquefaction 1. INTRODUCTION With the global depletion of fossil fuels and increasing pressure on the environment, biomass, as a renewable and carbon-neutral resource, has become an alternative energy source for the production of fuels and chemicals. Most of the earlier researches on biomass conversion focused on the production of first- and second-generation bio-fuels from food crops and lignocellulosic biomass, which led to the competition of fuel vs food and arable areas. Therefore, it is necessary to develop third generation bio-fuels based on marine algae. Macroalgae, for example, has been considered to be a very promising feedstock for producing fuels and chemicals 1

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because of their higher photosynthesis efficiency and faster growth rate compared to terrestrial biomass.1,2 Laminaria japonica, belonging to the brown algae, is easily found and has been cultured on a large-scale in coastal areas of China. It is commonly used as foods, cosmetics, fertilizers and a source of many useful industrial chemicals such as phycocolloids.3 Considered the higher content of polysaccharides and lipids possessed in L. japonica, it should also be an especially promising feedstock for bio-fuel. Bae et al.,4 for example, reported the pyrolysis of three marine macroalgae including Laminaria japonica at 500ºC to produce bio-oil with yields between 37.5% and 47.4%. Anastasakis et al.,3 however, converted the brown macroalgae (Laminaria saccharina) into bio-crude by hydrothermal liquefaction. Unexpectedly, such bio-oils obtained by pyrolysis and hydrothermal liquefaction were highly oxygenated complex mixture, which usually led to lower HHV (higher heating value) and poor combustion properties. Therefore, developing technologies that favor to reduce oxygen content is attractive from the energy perspective. Deoxy-liquefaction technique has recently been proved to be an effective method to produce high-quality liquid oils.5-7 To date, various types of biomass such as different terrestrial biomass (soybean stalk, cotton stalk, corn stalk, rice straw, wheat straw, poplar leaves, and Crofton weed)8-11 and aquatic biomass (water hyacinth)12 had been deoxy-liquefied to give liquid oils with lower oxygen contents (only about 6%) and higher heating values (more than 40 MJ/kg). The main purpose of our work is to investigate the possibility of producing liquid oil from L. japonica by deoxy-liquefaction and the influence of catalysts on the products yield, composition and distribution of the liquid oils. We introduce ZSM-5 zeolite catalysts based on the following considerations: (1) Molecular sieve catalyst of ZSM-5 might be effective on deoxygenation reactions, and simultaneously raise the selectivity of aromatic and aliphatic hydrocarbons.13-18 (2) The incorporation of metals into HZSM-5 support might bring significant changes in their acid and textural properties,19-21 which would lead to a strong influence in catalytic performance. Accordingly, the HZSM-5 and the catalysts modified with transition metal ions (Fe3+, and Ni2+) were adopted and attempted to produce high-quality liquid oil. The analyses such as elemental analysis, Fourier transform infrared (FTIR) spectroscopy, and gas chromatography-mass spectrometry (GC-MS) were carried out to evaluate the main compounds in the liquid oil with and without catalysts. 2


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2. EXPERIMENTAL SECTION 2.1. Materials. The sample of L. japonica was collected from the Qingdao coast of Yellow Sea, Shandong province, China and water washed in distilled water to remove the impurities and sea salts. The sample was sundried for 4 days and milled to 100 meshes. Then, it was dried in an oven at 50ºC for 24 h and stored in sealed containers for experiments. Ultimate analysis of the sample was carried out by using an Elemental Varian EL elemental analyzer. Moisture analysis was conducted according to ASTM E871-82 standard. The ash content was determined according to ASTM E1755-01 standard. The contents of crude protein, crude fat and carbohydrate were determined by Kjeldahl method, Soxhel-extract method and phenol-sulfuric acid method. The characteristics of the L. japonica sample on dry basis were shown in Table 1. 2.2. Catalyst Preparation and Characterization. The ZSM-5 zeolite (SiO2/Al2O3= 50) used was directly purchased from Shanghai AiBi Chemistry Preparation Co. LTD., China. ZSM-5 was calcined in air at 550ºC overnight before treatment. HZSM-5 was synthesized by using the ion-exchange method with a 1.0 M solution of NH4NO3 at 70ºC for 1h. Then, the residual was filtered, washed with deionized water, dried at 100ºC for 10h, and calcined at 550℃ overnight.13,14,22 Similarly, Ni/HZSM-5 and Fe/HZSM-5 were prepared by using the ion-exchange method with 0.5 M Ni(NO3)2 and Fe(NO3)3 solution, followed by filtration and washing.23 The remaining powder was dried in air at 100ºC for 10h, calcined at 550ºC overnight and then kept in the desiccator for the experiments. The textural characterization of the resulting catalyst samples was performed by means of nitrogen adsorption-desorption isotherms at 77K with a Tristar 3000 instrument. Before measuring, the samples were pretreated under vacuum at 300 ºC for 5h under nitrogen flow. Specific surface area was calculated by using the conventional BET method. And microporous volume was calculated by t-plot method. The catalyst samples were analyzed by different characterization methods. The acidity of the three catalysts (HZSM-5, Fe/HZSM-5 and Ni/HZSM-5) was characterized by temperature-programmed desorption of ammonia (NH3-TPD) on a FINESORB-3010 instrument using helium as carrier gas. For each test, the sample (0.02g) was loaded. The sample was pretreated in a He flow (20cm3/min) at 100 ºC for 60 min. After this, it was saturated under an ammonia stream (15cm3/min) for 30 3


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min. Subsequently, it was flushed with a He flow for 30 min to remove the physically adsorbed NH3. Finally, NH3-TPD was performed up to 600 ºC at a heating rate of 10 ºC per minute under the same flow of He (20 cm3/min). X-ray diffraction with Cu Kα radiation, carried out in an X’Pert PRO MPD diffractometer, was used to measure the crystallinity of the samples. XRD patterns were recorded within 3-70° range at a scanning rate 2θ of 2°/min. The Fourier transform infrared (FTIR) spectra were obtained using a Varian 3100 FTIR spectrometer, with samples prepared by the conventional KBr disk method. 2.3. Experimental Procedure. Similar to the methods described in the literatures,5-12 the direct liquefaction experiments were performed on the sample of 25g with 15% (wt.%) water as medium and 5% (wt.%) catalysts in a stainless steel tubular reactor with length of 100 mm and internal diameter of 20 mm. The samples were heated with the heating rate of 60 ºC/min and maintained for 20min at the final temperature of 350 ºC. The reactor was airproofed during the whole reaction. Thus the final pressure of the system ranged from 10 to 15 Mpa using different catalysts. After the reactor was cooled to room temperature, the volatile products were collected by gas collecting bags. Then, the residue was further distilled at ambient pressure, with the temperature raised gradually from room temperature to 500ºC to obtain the liquid oil that floated on the water. When distillation finished, water was separated by an injector. Finally, the solid char was removed and weighed at room temperature. The experiments were repeated for three times and the mean values were obtained. The experimental errors for deoxy-liquefaction products were lower than 4% by three duplicate runs under the same conditions. The yields of the products (liquid oil, solid char and gas) were calculated on the basis of the mass of feed according to the following equations: liquid oil (wt%) = Woil/Wfeedstock ×100%

(1)

char (wt%) = Wchar/Wfeedstock ×100%

(2)

water (wt%) = Wwater/Wfeedstock ×100%

(3)

gas (wt%) = 1-(oil + char + water)(wt%)

(4)

Where Woil is the mass of the liquid oil; Wfeedstock is the mass of algae biomass fed into the reactor; Wchar is the mass of solid residue after distillation. Wwater refers to the difference of the mass between obtained and added water. It should be noted that the yield of gaseous products was obtained by difference; therefore, the contribution of 4


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some losses was also included. 2.4. Product Analysis. The higher heating values were obtained from calculation by Dulong’s formula.24 HHV (MJ/kg) = [338.2×C wt. % +1442.8× (H wt. %-O wt. %/8)] ×0.001

(5)

Elemental analyses (C, H, and N) of the raw material and oil were performed on an Elemental Varian EL elemental analyzer from Germany. The oxygen content was calculated by difference as follows: O (wt. %)=100 - (C + H + N + ash) (wt. %)

(6)

For characterization of liquid oil, the FTIR spectra were recorded using a Varian 3100 Fourier-Transform Infrared Spectrometer from America over a range 400-4000 cm-1. The compositions of the liquid oils were analyzed by a Shimadzu gas chromatography and mass spectrometry (GC-MS) (QP2010S). The GC was fitted with a 30 m×0.25 mm×0.25 µm fused quartz capillary column and coated with TR-5MS as the stationary phase. Helium (99.999%) was used as carrier gas with a constant flow of 1.0 mL/min and split ratio was 50:1. The injector temperature was 250ºC. The oven temperature was programmed from an initial temperature of 50ºC (1min) followed by a 10ºC/min to a final temperature of 250ºC and held for 10min. After a solvent delay of 2 min, full scan mass spectra were acquired from 50 to 650 m/z with a scan rate of 0.4 s per scan. Compounds in the oils were identified by comparison with the mass spectra with the NIST (National Institute of Standards and Technology) 08 library, together with the literature data to obtain the highest likelihood of compound identification. 3. RESULTS AND DISCUSSIONS 3.1. Catalysts Characterization. The textural properties of the catalyst samples (HZSM-5 and the modified samples) were investigated by nitrogen adsorption. The values of the surface area and microporous volume were given in Table 2. The obtained data showed that the introduction of metal was accompanied by a decrease in the BET surface area and the microporous volume,25 which may be attributed to the small oxide aggregates on the external surface and a partial blockage of zeolite pores and channels. These results indicated the incorporation of metal ions into the micropore space of HZSM-5.

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The acidity of the parent HZSM-5 and the metal modified ZSM-5 catalysts was determined by NH3-TPD, and the results were given in Figure 1. The TPD curve of the parent HZSM-5 presented a major peak at around 230ºC, which can be reasonably ascribed to weaker non-framework Lewis acid sites. This curve also showed a small shoulder at about 360ºC attributed to the stronger acid sites related to Brønsted acid sites on Si-O-Al groups.13,20,26,27 With the addition of Fe3+ and Ni2+, the intensity of the low desorption temperature peak was increased and the intensity of the high desorption temperature peak was decreased although the maximum temperature were kept unchanged. This suggested a distinct increase in the weaker Lewis acid sites,13 which may be attributed to the creation of Lewis acid sites of Fe(OH)2+ and Ni(OH)+.13,27 While the introduced Fe and Ni species suppressed the acidity of stronger acid sites over HZSM-5. A possible explanation is that the Brønsted acid protons were substituted by Fe3+ and Ni2+, leading to the decline of Brønsted acidity.13,28 The total amount of ammonia desorption was listed in Table 2, which represented the total sum of the weaker and stronger acid sites. The XRD patterns of the parent HZSM-5 and the metal modified ZSM-5 catalysts were shown in Figure 2. Obviously, all samples exhibited the typical diffraction pattern corresponding to the MFI structure (2θ=6.18, 10.06, 20.22, 23.42, 26.76). Therefore, the Fe and Ni ion-exchange procedure seems not to affect the sample crystallinity20. Meanwhile, the characteristic responses of metal oxides were not observed in the XRD patterns, suggesting that the metal ions were well dispersed over the zeolite or existed in the form of small metal oxide clusters that do not show XRD diffraction25. As shown in Figure 3, the FTIR spectra of the parent and metal modified HZSM-5 catalysts are comparable and show typical peaks. The weak bands at 3745 cm-1 are attributed to isolated and terminal silanol groups. The bands near 3490 cm-1 are characteristic of the hydroxyl groups connected to extra framework aluminum species and H-O-H stretching vibration of adsorbed water molecules. The framework absorption region is in the 1400-400 cm-1 range and the typical peaks include the absorption bands at about 1100, 790, 550, and 450 cm-1.25,29 The band observed at 550 6


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arises from the double 5-ring external linkage peak. While, the band at 450 cm-1 is assigned to the structure-intensive T-O bending modes for tetrahedral TO4 units (T=Si or Al).30 For all catalysts, comparison of the positions and intensities of the absorption bands revealed a small decrease for Fe/HZSM-5 and a small increase for Ni/HZSM-5 in the intensity of the bands corresponding to the vibrations between the tetrahedral.29 This suggested that almost no loss of crystallinity occurred in the zeolite samples after metal modifying, which was also in agreement with the XRD results. The weak absorptions near 960 cm-1 in the spectra of Fe/HZSM-5 and Ni/HZSM-5 are ascribable to the stretching vibration of polarized SiOδ--Mxδ+ or Mx=O (M=Fe, Ni). This might prove the incorporation of metals into the framework of the zeolite. 3.2. Effects of Catalysts on the Product Yield. To better estimate the deoxy-liquefaction performance of L. japonica, the catalysts including HZSM-5, Fe/HZSM-5 and Ni/HZSM-5 were individually introduced into the system at 350ºC. As shown in Figure 4, the liquid oil yield was 8.54±0.3% without catalyst, while these values can reach 10.42±0.3%, 13.28±0.4% and 15.32±0.2% when HZSM-5, Fe/HZSM-5 and Ni/HZSM-5 were present. Similarly, the gas yield was increased to 27.23±0.3%, 31.35±0.7% and 37.20±0.5% respectively, higher than 23.48±0.7% observed in the absence of catalyst. By contrast, the char yield had a declining trend as 43.85±1.1% without catalyst and decreased to 35.57±0.6%, 33.19±1.7% and minimum value of 28.95±1.0% in the presence of HZSM-5, Fe/HZSM-5 and Ni/HZSM-5 catalysts, respectively. Different from the yield trend of oil, gas and char, the water yield without catalyst was 24.13±0.8% and increased to 26.19±1.2% with HZSM-5, and then decreased to 22.18±0.7% and 18.53±0.4% with Fe/HZSM-5 and Ni/HZSM-5. These results suggested that all the catalysts had significant catalytic effects on the L. japonica conversion, and can increase the liquid oil yield. Similar phenomenon was also reported in the hydrothermal liquefaction of the microalgae Nannochloropsis sp with zeolite catalyst.1 3.3. Properties of the Liquid Oils. The main characteristics of the liquid oils obtained from L. japonica with and without catalysts were shown in Table 3. Interestingly, the liquid oils obtained from L. japonica were all carbon-rich fuels with low oxygen and nitrogen content, whether the HZSM-5, Fe/HZSM-5 and Ni/HZSM-5

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catalysts were used or not. The empirical formulae of the liquid oils were CH1.62O0.055N0.049,

CH1.68O0.048N0.029,

CH1.71O0.046N0.038

and

CH1.8O0.034N0.036,

respectively. The H/C and O/C molar ratios were in the range of 1.62-1.80 and 0.034-0.055, almost comparable to conventional petroleum (1.77 and 0.01). The oxygen content was 5.85% without catalyst, while these values decreased to 5.18%, 4.97% and 3.74% when HZSM-5, Fe/HZSM-5 and Ni/HZSM-5 were used. Obviously, the present oxygen contents were much lower than those found in the bio-oils obtained from E. prolifera31 (22.45%) by hydrothermal liquefaction and U. pinnatifida (29.8%), L. japonica (12.9%) and P. tenera (17.3%) by pyrolysis method.30 This indicated that the deoxy-liquefaction technique could provide more effective method to remove the oxygen from the feedstock. Accordingly, the HHV of the four oils were determined as 41.02, 42.70, 43.32 and 44.58 MJ/kg, respectively. The low oxygen contents and high HHV of the liquid oils suggest that L. japonica is a promising marine algae feedstock for production of liquid oil via deoxy-liquefaction. 3.4. GC-MS Analysis of the Liquid Oils. The identifications of the components in four liquid oils were analyzed by GC-MS. For each liquid oils, more than 90 organic species were observed, among which the compounds with relative peak area more than 0.3% were selected and their molecular formula, relative peak area and retention time were listed in Table 4. The major compounds in each liquid oils were comparable (Figure 5), and classified as aromatics, phenols, alkanes and alkenes, some nitrogen containing compounds, as well as some other oxygen containing compounds including alcohols, aldehydes etc. Interestingly, compounds such as acids, ketones, furan and esters, which abounded in the bio-oils from other macroalgae,3,4,31,32 were found non-existent or with trace amount in the present oils from L. japonica. The alkanes found in the liquid oil obtained without any catalyst were featured straight long-chain alkanes with carbon distribution range of C13-C20, and the total relative peak area was about 16.97%. When the HZSM-5, Fe/HZSM-5 and Ni/HZSM-5 catalysts were added, however, the carbon distribution of the long-chain alkanes spanned from C12 to C21, and the amount of alkanes reached 20.62%, 18.92% and 22.86%, respectively. In addition, alkenes such as 1-pentadecene, 1-hexadecene

8


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and 1-eicosene, which may be generated from the conversion of unsaturated fatty acids in algal cells, were simultaneously observed. Aromatics in the liquid oils can be classified into monocyclic aromatic hydrocarbons and polycyclic aromatic hydrocarbons (PAHs) with two rings. Monocyclic aromatics, such as toluene, ethyl-benzene and xylene, were identified in both the absence and presence of catalysts. The PAHs, however, were mainly characterized as dimethyl-naphthalene and observed only when the catalysts were used. The relative peak area of aromatics in liquid oils catalyzed by HZSM-5, Fe/HZSM-5 and Ni/HZSM-5 were 5.86%, 7.43% and 9.15%, higher than that in the case without catalyst (4.29%). The increase of aromatics content may be due to the increase in availability of active sites in ZSM-5 catalyst after incorporation of metals into the HZSM-5 support, which was suitable for the synthesis of aromatic hydrocarbons. During the liquefaction, the acidity of the catalysts was responsible for alkylation, isomerization, cyclization and aromatization reactions.17 In detail, the dehydrogenation reaction during aromatization mainly took place at the weaker Lewis acid sites of the HZSM-5 catalyst. When metal was introduced into the zeolite, the dehydrogenation activity of the catalysts was greatly increased. So the amount of aromatics was raised with the increase of weaker acid sites of the catalysts as Fe and Ni were loaded. As many as 10 kinds of phenolic compounds were found in the liquid oils, almost all of which contained methyl-, dimethyl-, trimethyl- and ethyl- groups. This is quite different from those found in the oils from algae by pyrolysis and hydrothermal liquefaction methods,4,31 in which the phenolic products usually featured methoxy groups, such as 2-methoxy-phenol, 4-ethyl-2-methoxy-phenol and 4-methoxy-phenol, etc. This indicated that deoxy-liquefaction reaction was favorable for the demethoxylation of aromatic rings. Distinct from the increase of alkanes and aromatics, the amount of phenols underwent a noticeable decrease when the catalysts were introduced. The relative peak area of phenols in liquid oil was 32.48% in the absence of catalyst, significantly higher than that in other three oils with HZSM-5 (26.76%), Fe/HZSM-5 (24.67%) and Ni/HZSM-5 (22.95%) catalysts. This suggested that the metal modified HZSM-5 catalysts were effective in the selective deoxygenation, which was consistent with the conclusions drawn by many researchers.13,17,22,33,34 The phenols were thought to be derived from the secondary catalytic cracking of some lignin-like compounds by breaking the C-O and C-C bonds, 9


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accompanied with the hydrogen proton. This cracking may take place at the acid sites of the catalysts, especially at the Brønsted acid sites.17 As described in the previous section, the introduction of metal decreased the stronger Brønsted acid sites of the HZSM-5 catalysts. Thus, the amount of phenols decreased with the introduction of Fe and Ni to the HZSM-5. On the other hand, the metals could activate the catalytic deoxygenation behavior of the HZSM-5 catalysts by promoting dehydration, decarbonylation and decarboxylation.17 In addition, some nitrogen containing compounds such as 1H-indole, 2-methyl-, 2,3,4-Trimethylpyrrole and hexadecanenitrile etc., were also detected and mainly derived from the decomposition of protein.31 As observed in previous studies on algae,3,31 a relatively high nitrogen (protein) content of algal feedstock usually resulted in a high nitrogen content of oils, though the addition of metal modified HZSM-5 catalysts could decrease the proportion of nitrogen containing compounds to some extent. Therefore, the denitrogenation upgrading was necessary for further use of such oil as a fuel. 4. CONCLUSIONS In this paper, the macroalgae L. japonica can be converted to the liquid oil with low oxygen content (40MJ/kg) by deoxy-liquefaction. Effects of HZSM-5 and metal modified catalysts such as Fe/HZSM-5 and Ni/HZSM-5 on the product yield and distribution were investigated. The influence of catalysts on the products showed that all the catalysts could increase the liquid oil yield and the contents of aromatics and long-chain alkanes. Simultaneously, they decreased considerable amounts of the phenols, other oxygen and nitrogen containing species, thus resulting in the increase of the heating values of the liquid oil. The HHV of the oils were 42.70, 43.32 and 44.58 MJ/kg respectively, when HZSM-5, Fe/HZSM-5 and Ni/HZSM-5 catalysts were added. The results indicated that suitable catalysts were helpful to improve the yield and quality of the liquid oil from deoxy-liquefaction of L. japonica feedstock. And this oil can also be used as a raw material in upgrading, separation and distillation processes to obtain useful fuels such as gasoline, diesel oil or some valuable chemicals.

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AUTHOR INFORMATION Corresponding Author *

Tel:

+86-0532-85955529.

Fax:

+86-0532-85955529.

E-mail:

[email protected] (J.H.L.).

ACKNOWLEDGEMENTS This study was supported by National Natural Science Foundation of China (No. 20901043), the Natural Science Fund of Shandong Province (No. ZR2009FQ022 and No. ZR2009BM018), Beijing National Laboratory for Molecular Sciences (BNLMS), Project of Shandong Province Higher Educational Science and Technology Program (No. J13LD18) and Taishan Scholar Program. REFERENCES (1) Duan, P. G.; Savage, P. E. Hydrothermal liquefaction of a microalga with hetorogeneous catalysts. Ind. Eng. Chem. Res. 2011, 50, 52-61. (2) Li, D. M.; Chen, L. M.; Zhao, J. S.; Zhang, X. W.; Wang, Q. Y.; Wang, H. X.; Ye, N. H. Evaluation of the pyrolytic and kinetic characteristics of Enteromorpha prolifera as a source of renewable bio-fuel from the Yellow Sea of China. Chem. Eng. Res. Des. 2010, 88, 647-652. (3) Anastasakis, K.; Ross, A. B. Hydrothermal liquefaction of the brown macro-alga Laminaria Saccharina: effect of reaction conditions on product distribution and composition. Bioresour. Technol. 2011, 102, 4876-4883. (4) Bae, Y. J.; Ryu, C.; Jeon, J. K.; Park, J.; Suh, D. J.; Suh, Y. W.; Chang, D.; Park, Y. K. The characteristics of bio-oil produced from the pyrolysis of three marine macroalgae. Bioresour. Technol. 2011, 102, 3512-3520. (5) Lu, W. P.; Yang, F.; Wang, C.; Yang, Z. Y. Comparison of high-caloric fuel (HCF) from four different raw materials by deoxy-liquefaction. Energy Fuels 2010, 24, 6633-6643. (6) Li, J. H.; Wu, L. B.; Yang, Z. Y. Analysis and upgrading of bio-petroleum from biomass by direct deoxy-liquefaction. J. Anal. Appl. Pyrol. 2008, 81, 199-204. (7) Guo, S. P.; Wu, L. B.; Wang, C.; Li, J. H.; Yang, Z. Y. Direct conversion of 11


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sunflower shells to alkanes and aromatic compounds. Energy Fuels 2008, 22, 3517–3522. (8) Wang, C.; Pan, J. X.; Li, J. H.; Yang, Z. Y. Comparative studies of products produced from four different biomass samples via deoxy-liquefaction. Bioresour. Technol. 2008, 99, 1778-1786. (9) Li, J. H.; Wang, C.; Yang, Z. Y. Production and separation of phenols from biomass-derived bio-petroleum, J. Anal. Appl. Pyrol. 2010, 89, 218-222. (10) Wu, L. B.; Guo, S. P.; Wang, C.; Yang, Z. Y. Direct deoxy-liquefaction of poplar leaves to biopetroleum with two kinds of catalysts. Ind. Eng. Chem. Res. 2008, 47, 9248-9255. (11) Yu, J. Y.; Wang, C.; Wang, Y. P.; Yang, Z. Y. Deoxy-liquefaction products obtained from Crofton weed at different temperatures, J. Anal. Appl. Pyrol. 2011, 92, 68-75. (12) Lu, W. P.; Wang, C.; Yang, Z. Y. The preparation of high caloric fuel (HCF) from water hyacinth by deoxy-liquefaction. Bioresour. Technol. 2009, 100, 6451-6456. (13) Fanchiang, W. L.; Lin, Y. C. Catalytic fast pyrolysis of furfural over H-ZSM-5 and Zn/H-ZSM-5 catalysts. Appl. Catal., A 2012, 419-420, 102-110. (14) Foster, A. J.; Jae, J.; Cheng, Y. T.; Huber, G. W.; Lobo, R. F. Optimizing the aromatic yield and distribution from catalytic fast pyrolysis of biomass over ZSM-5. Appl. Catal., A 2012, 423-424, 154-161. (15) Bulushev, D. A.; Ross, J. R. H. Catalysis for conversion of biomass to fuels via pyrolysis and gasification: A review. Catal. Today 2011, 171, 1-13. (16) Mihalcik, D. J.; Mullen, C. A.; Boateng, A. A. Screening acidic zeolites for catalytic fast pyrolysis of biomass and its components. J. Anal. Appl. Pyrol. 2011, 92, 224-232. (17) Pattiya, A.; Titiloye, J. O.; Bridgwater, A. V. Fast pyrolysis of cassava rhizome in the presence of catalysts. J. Anal. Appl. Pyrol. 2008, 81, 72-79. (18) Chen, Y. G.; Yang, F.; Wu, L. B.; Wang, C.; Yang, Z. Y. Co-deoxy-liquefaction of biomass and vegetable oil to hydrocarbon oil: influence of temperature, residence 12


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time, and catalyst. Bioresour. Technol. 2011, 102, 1933-1941. (19) French, R.; Czernik, S. Catalytic pyrolysis of biomass for biofuels production. Fuel Process. Technol. 2010, 91, 25-32. (20) Botas, J. A.; Serrano, D. P.; García, A.; Vicente, J.; Ramos, R. Catalytic conversion of rapeseed oil into raw chemicals and fuels over Ni- and Mo-modified nanocrystalline ZSM-5 zeolite. Catal. Today 2012, 195, 59-70. (21) Nowińska, K.; Wąclaw, A.; Izbińska, A. Propane oxyhydrogenation over transition metal modified zeolite ZSM-5. Appl. Catal. A 2003, 243, 225-236. (22) Thangalazhy-Gopakumar, S.; Adhikari, S.; Chattanathan, S. A.; Gupta, R. B. Catalytic pyrolysis of green algae for hydrocarbon production using HZSM-5 catalyst. Bioresour. Technol. 2012, 118, 150-157. (23) Valkaj, K. M.; Katovic, A.; Zrnčević, S. Investigation of the catalytic wet peroxide oxidation of phenol over different types of Cu/ZSM-5 catalyst. J. Hazard. Mater. 2007, 144, 663-667. (24) Scholze, B.; Meier, D. Characterization of the water-insoluble fraction from pyrolysis oil (pyrolytic lignin). Part I: PY-GC/MS, FTIR, and functional groups. J. Anal. Appl. Pyrol. 2001, 60, 41-54. (25) Ayari, F.; Mhamdi, M.; Debecker, D. P.; Gaigneaux, E. M.; Alvarez-Rodriguez, J.; Guerrero-Ruiz, A.; Delahy, G.; Ghorbel, A. Effect of the chromium precursor nature on the physicochemical and catalytic properties of Cr-ZSM-5 catalysts: Application to the ammoxidation of ethylene. J. Mol. Catal. A: Chem. 2011, 339, 8-16. (26) Rodríguez-González, L.; Hermes, F.; Bertmer, M.; Rodríguez-Castellón, E.; Jiménez-López, A.; Simon, U. The acid properties of H-ZSM-5 as studied by NH3-TPD and 27Al-MAS-NMR spectroscopy. Appl. Catal., A 2007, 328, 174-182. (27) Long, X.; Zhang, Q. J.; Liu, Z. T.; Qi, P.; Lu, J.; Liu, Z. W. Magnesia modified H-ZSM-5 as an efficient acidic catalyst for steam reforming of dimethyl ether. Appl. Catal., B 2013, 134-135, 381-388. (28) Iwasaki, M.; Yamazaki, K.; Banno, K.; Shinjoh, H. Characterization of Fe/ZSM-5 DeNOx catalysts prepared by different methods: Relationships between

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active Fe sites and NH3-SCR performance. J. Catal. 2008, 260, 205-216. (29) Rajasekhar Pullabhotla, V. S. R.; Jonnalagadda, S. B. Scope of metal loaded microporous ZSM-5 zeolites in the “catazone” process of n-hexadecane at moderate conditions. Ind. Eng. Chem. Res. 2009, 48, 9097-9105. (30) Tao, Y.; Kanoh, H.; Kaneko, K. Uniform mesopore-donated zeolite Y using carbon aerogel templating. J. Phys. Chem. B 2003, 107, 10974-10976. (31) Zhou, D.; Zhang, L.; Zhang, S. C.; Fu, H. B.; Chen, J. M.; Hydrothermal liquefaction of macroalgae Enteromorpha prolifera to bio-oil. Energy Fuels 2010, 24, 4054-4061. (32) Li, D. M; Chen, L. M.; Xu, D.; Zhang, X. W.; Ye, N. H.; Chen, F. J.; Chen, S. L. Preparation and characteristics of bio-oil from the marine brown alga Sargassum patens C. Agardh. Bioresour. Technol. 2012, 104, 737-742. (33) Murata, K.; Somwongsa, P.; Larpkiattaworn, S.; Liu, Y. Y.; Inaba, M.; Takahara, I. Analyses of liquid products from catalytic pyrolysis of jatropha seed cake. Energy Fuels 2011, 25, 5429-5437. (34) Samolada, M. C.; Papafotica, A.; Vasalos, I. A.; Catalyst evaluation for catalytic biomass pyrolysis. Energy Fuels 2000, 14, 1161-1167.

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Energy & Fuels

Figure captions: Figure 1. NH3-TPD profiles of the parent and metal modified HZSM-5 catalysts Figure 2. XRD patterns of parent and metal modified HZSM-5 catalysts. Figure 3. FTIR spectra of parent and metal modified HZSM-5 catalysts. Figure 4. Effect of catalysts on the product yields. Figure 5. Effect of catalysts on the compositions of the liquid oils

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Energy & Fuels

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Table 1. Main Characteristics of L. japonica Ultimate analysis

L. japonica

Carbon (%)

34.86

Hydrogen (%)

4.41

Oxygen (%)

34.44

Nitrogen (%)

2.13

H/C molar ratio

1.52

O/C molar ratio

0.74

Empirical formula

CH1.52O0.74N0.05

HHV (MJ kg-1)

11.94

Crude protein (%)

8.83

Crude fat (%)

1.07

Carbonhydrate (%)

25.53

Moisture (%)

12.75

Ash (%)

24.76

16


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Energy & Fuels

Table 2. The Main Characteristic of the Parent and Metal Modified HZSM-5 Catalysts Sample

Surface area (m2/g)

Microporous (cm3/g)

HZSM-5 Fe/HZSM-5 Ni/HZSM-5

368 321 306

0.137 0.116 0.108

volume

Total ammonia acidity (mmol/g) 0.373 0.384 0.401

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Page 18 of 26

Table 3. Properties of the Liquid Oils Obtained With and Without Catalysts Ultimate analysis

Without catalyst

HZSM-5

Fe/HZSM-5

Ni/HZSM-5

C (%)

78.98

80.78

81.25

81.63

H (%)

10.65

11.31

11.60

12.23

O (%)

5.85

5.18

4.97

3.74

N (%)

4.53

2.71

3.57

3.40

Empirical formula

CH1.62O0.055N0.049

CH1.68O0.048N0.029

CH1.71O0.046N0.038

CH1.8O0.034N0.036

H/C molar ratio

1.62

1.68

1.71

1.80

O/C molar ratio

0.055

0.048

0.046

0.034

HHV (MJ kg−1)

41.02

42.70

43.32

44.58

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Energy & Fuels

Table 4. Identification of Compounds in the Liquid Oils Obtained from L. japonica With and Without Catalysts RT

3.50

Compounds

Formula

Toluene

C7H8

Area (%) WCa

HCb

FHc

2.03

1.68

1.84

1.97

e

NHd

4.98

1H-Pyrrole, 3-methyl-

C5H7N

-

0.36

0.32

0.30

5.94

Ethylbenzene

C8H10

1.81

1.66

1.7

1.83

6.88

Styrene

C8H8

0.45

0.78

0.75

0.72

6.91

Ethanone, 1-(2-furanyl)-

C6H6O2

-

0.94

1.04

0.82

7.42

1H-Pyrrole, 2,4-dimethyl-

C6H9N

0.56

0.73

0.69

0.54

7.71

Cyclooctane

C8H16

-

0.34

0.36

0.47

8.43

Benzene, 1,2,3-trimethyl-

C9H12

-

0.36

0.39

0.41

9.00

Phenol

C6H6O

1.21

1.02

0.89

1.16

9.20

Pyrazine, 2-ethyl-6-methyl-

C7H10N2

1.55

0.92

0.68

0.63

9.35

Benzene, 1,3,5-trimethyl-

C9H12

-

0.37

0.41

0.58

9.42

1H-Pyrrole, 2-ethyl-4-methyl-

C7H11N

0.7

-

-

-

9.60

1-Decene

C10H20

-

-

0.36

-

9.67

2,3,4-Trimethylpyrrole

C7H11N

1.47

1.22

1.18

1.04

9.84


C6H9N

0.53

-

-

-

9.89

Cyclohexene, 1,2-dimethyl-

C8H14

1.27

1.07

1.03

0.86

10.27

3-Methyl-cis-3a,4,7,7a-tetrahydroindan

C10H16

-

-

0.31

-

10.49

2-Cyclopenten-1-one, 2,3,4-trimethyl-

C8H12O

0.87

0.67

0.53

10.50

2,4-Heptadiene, 2,6-dimethyl-

C9H16

-

-

-

0.36

10.53

Phenol, 2-methyl-

C7H8O

1.08

1.37

1.42

1.07

10.67

Benzene, butyl-

C10H14

-

0.34

-

0.46

10.96

Phenol, 3-methyl-

C7H8O

2.35

-

-

-

10.97

trans-Chrysanthemal

C10H16O

-

-

0.97

-

10.98

1H-Pyrrole, 4-ethyl-2,3-dimethyl-

C8H13N

-

1.28

-

1.19

11.05

Benzene, 1-ethoxy-2-methyl-

C9H12O

1.13

2.14

1.8

1.57

11.23


C8H13N

2.32

1.53

0.84

0.83

11.31


C8H13N

0.85

0.83

0.93

0.57

11.42

Phenol, 2,6-dimethyl-

C8H10O

0.74

0.97

0.9

0.93

11.57

1-Dodecene

C12H24

-

0.46

-

-

11.58

1-Undecene

C11H22

-

-

0.38

0.41

11.74

Cyclohexane, (1-methylethylidene)-

C9H16

0.46

-

-

-

11.79

Undecane

C11H24

-

0.81

-

0.95

11.82

Phenol, 3-amino-4-methyl-

C7H9NO

1.6

-

-

0.9

11.85

Phenol, 2,3-dimethyl-, acetate

C10H12O2

-

-

0.87

-

11.92

Benzene, 1,2,3,4-tetramethyl-

C10H14

-

-

0.35

0.44

12.07

Phenol, 3-ethyl-

C8H10O

0.96

1.45

-

1.2

12.16


C6H9N

0.68

-

-

-

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12.23


C8H10O

1.58

1.08

0.67

-

12.26

Naphthalene, 1,2-dihydro-

C10H10

-

-

-

1.37

12.32

Benzeneamine, 3-ethyl-4-hydroxy-

C8H11NO

1.44

-

-

-

12.34


C8H10O

-

4.02

3.56

-

12.42

3,9-Epoxy-p-mentha-1,8(10)-diene

C10H14O

0.6

0.65

0.42

0.42

12.63

1H-Pyrrole, 3,4-diethyl-2-methyl-

C9H15N

2.36

1.81

1.08

-

12.65


C8H10O

-

-

-

0.85

12.68


C8H13N

1.79

-

-

-

12.77

Phenol, 2-ethyl-5-methyl-

C9H12O

2.86

1.3

1.15

1.27

12.91

1H-Pyrrole, 2-ethyl-3,4,5-trimethyl-

C9H15N

2.6

1.73

1.47

1.24

12.97


C8H10O

0.74

-

-

1.05

13.11

Phenol, 2,3,5-trimethyl-

C9H12O

1.49

0.5

0.34

0.33

13.27

1-Tridecene

C13H26

1.46

0.65

-

0.54

13.38

3,7,7-Trimethylbicyclo[4.1.0]heptan-3-ol

C10H18O

-

-

0.35

-

13.45

Tridecane

C13H28

1.22

1.3

1.2

1.64

13.53


C9H12O

2.77

3.13

2.65

2.14

13.68

Phenol, 4-ethyl-3-methyl-

C9H12O

2.71

1.51

1.55

1.34

13.78

Phenol, 3-(ethylamino)-4-methyl-

C9H13NO

2.36

1.42

1.45

1.08

13.83


C9H13NO

1.7

-

-

-

13.93

Phenol, 4-methylamino, ethyl

C9H13NO

2.23

1.48

1.23

1.03

14.01

Phenol, 4-(1-methylpropyl)-

C10H14O

1.08

1.16

-

0.63

14.10

m-Ethylaminophenol

C8H11NO

-

-

2.68

1.88

14.12


C9H12O

0.77

1.29

-

-

14.26

2,4,6-Octatriene, 2,6-dimethyl-

C10H16

-

1.44

-

-

14.32

Indole

C8H7N

-

0.48

0.51

0.44

14.33

Phenol, 4-amino-2-isopropyl-5-methyl-

C10H15NO

1.19

-

-

1.62

14.48

Phenol, 2-methyl-5-(1-methylethyl)-

C10H14O

0.87

0.56

-

-

14.62

Phenol, 3-(diethylamino)-

C10H15NO

4.01

-

1.43

-

14.72


C9H13NO

-

-

1.11

-

14.79

Benzene, 2-methoxy-1,3,5-trimethyl-

C10H14O

3.07

-

-

-

14.82

1-Tetradecene

C14H28

-

1.29

1.91

1.24

14.95

Tetradecane

C14H30

1.55

1.62

1.45

2.22

15.00


C9H12O

0.81

0.78

-

-

15.48

Phenol, 4-(dimethylamino)-3,5-dimethyl-

C10H15NO

-

-

2.19

-

15.62

1H-Indole, 3-methyl-

C9H9N

1.73

1.61

1.8

1.48

15.77

Pyrrolidine, 1-(1-cyclohepten-1-yl)-

C11H19N

1.87

-

-

-

15.90

Phenol, 2,3,5,6-tetramethyl-

C10H14O

0.57

-

-

-

15.92

Phenol, 3-(diethylamino)-

C10H15NO

-

-

-

0.89

15.97

Naphthalene, 1,3-dimethyl-

C12H12

-

0.31

0.39

0.42

16.07

2,3-Dimethyl-5-n-propylpyrazine

C9H14N2

0.75

-

0.64

-

16.18

1-Pentadecene

C15H30

1.07

1.06

1.64

0.97

16.33

Pentadecane

C15H32

2.03

2.17

1.96

2.82

16.49

7-Benzofuranol, 2,3-dihydro-2,2-dimethyl-

C10H12O2

1.77

1.36

-

-

16.72

Benzeneamine, 3-ethyl-4-hydroxy-

C8H11NO

-

1.16

0.99

0.8

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Energy & Fuels

17.01

1H-Indole, 2,3-dimethyl-

C10H11N

0.9

0.93

1.39

1.19

17.26

Benzene, hexamethyl-

C12H18

-

-

-

1.8

17.48

1-Hexadecene

C16H32

0.83

0.75

1.16

0.81

17.62

Hexadecane

C16H34

2.08

2.55

2.15

3.08

17.87

1H-Indole, 5,6,7-trimethyl-

C11H13N

0.87

0.98

1.37

1.22

18.71

1-Heptadecene

C17H34

-

0.63

0.54

0.55

18.82

Heptadecane

C17H36

0.97

0.97

0.86

1.03

19.43

Octadecane

C18H38

-

0.34

-

0.58

19.56

Tetradecanenitrile

C14H27N

0.69

1.01

0.63

1.29

19.76

2-Pentadecanone, 6,10,14-trimethyl-

C18H36O

0.66

0.69

0.62

0.6

19.85

1-Nonadecene

C19H38

0.48

0.86

0.77

0.37

19.97

Nonadecane

C19H40

1.79

1.46

1.27

1.67

20.95

3-Eicosene, (E)-

C20H40

-

0.41

0.32

0.47

21.05

Eicosane

C20H42

1.32

0.6

0.47

0.96

21.20

Heneicosane

C21H44

0.95

0.52

0.44

0.87

21.53

Cycloeicosane

C20H40

0.59

1.43

1.16

0.51

21.77

Hexadecanenitrile

C16H31N

0.89

0.98

0.68

1.1

21.91

2-Heptadecanone

C17H34O

0.62

0.56

0.58

0.51

22.08

Heneicosane

C21H44

0.54

0.6

0.39

0.56

a

WC = Without catalyst; b HC = HZSM-5; c FH = Fe/HZSM-5; d NH = Ni/HZSM-5;

detected

21


e

“-”: Not

Energy & Fuels

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

Figure 1.

22


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Energy & Fuels

Figure 2.

23


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Figure 3.

24


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Energy & Fuels

Figure 4.

25


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Figure 5.

26


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Deoxy-Liquefaction of Laminaria japonica to High-Quality Liquid Oil

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