Preparation of biofuels with waste cooking oil by fluid catalytic cracking: The effect of catalyst performance on the products

Accepted Manuscript Preparation of biofuels with waste cooking oil by fluid catalytic cracking: The effect of catalyst performance on the products Yan Wang, Yang Cao, Jin Li PII:

S0960-1481(17)30845-5

DOI:

10.1016/j.renene.2017.08.084

Reference:

RENE 9182

To appear in:

Renewable Energy

Received Date: 10 January 2017 Revised Date:

10 August 2017

Accepted Date: 28 August 2017

Please cite this article as: Wang Y, Cao Y, Li J, Preparation of biofuels with waste cooking oil by fluid catalytic cracking: The effect of catalyst performance on the products, Renewable Energy (2017), doi: 10.1016/j.renene.2017.08.084. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT 1

Preparation of biofuels with waste cooking oil by fluid catalytic

2

cracking: the effect of catalyst performance on the products

3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

Yan Wanga , Yang Caoa,b , Jin Li a,b* a

College of Materials and Chemical Engineering, Hainan University, Ren Min Road 58#,Hainan, Haikou570228,

China State Key Laboratory of Marine Resource Utilization in South China Sea ,Hainan University, Ren Min Road

RI PT

b

58#,Hainan, Haikou570228, China

Abstract: Biofuels were produced with waste cooking oil by Fluid Catalytic Cracking (FCC). The catalytic reactions involved two catalysts of Endurance and CGP-1HN, which were characterized by Scanning Electron Microscopy (SEM), N2 Adsorption-Desorption, X-ray Diffraction (XRD) and Pyridine Fourier Transform Infrared

SC

Spectroscopy (Py-FTIR). The results indicated that the structure and properties of Endurance and CGP-1HN were similar, and the most obvious difference between them was a different content of acid sites. The Lewis and Brönsted acid contents of Endurance were 189.39 and 341.69 µmol/g, respectively, and the Lewis and Brönsted

M AN U

acid contents of CGP-1HN were 21.53 and 258.23 µmol/g, respectively. The different acid sites resulted in different distributions of products under the same reaction conditions. A higher diesel yield (32.04 wt.%) was achieved using Endurance, and a higher Liquefied Petroleum Gas(LPG) yield (42.71 wt.%) was produced using CGP-1HN. The result shows that different type acid and acid contents effect on the product distribution.The Lewis acid sites decreases the catalytic cracking depth of waste cooking oil.

Keywords: Fluid catalytic cracking; Biofuels; Waste cooking oil; catalyst acidity ;

20

1. Introduction

21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39

In recent years, the domestic demand for energy was increasing due to the fast economic development. The energy demand will increase rapidly in the next few years, and the current energy structure cannot be satisfied for the sustainable development of society, including air pollution and energy short. To solve the energy crisis, the biofuels can be used as an alternative to the conventional petroleum supply.[1-3] Utilizing biomass to make biofuels has been the focus of much research in recent years.[4-5] Biofuels required an upgrading step before it could be used as a transport fuel. Although catalytic hydrogenation could convert biofuels into liquid hydrocarbons, it consumed a lot of hydrogen.[6,7] Catalytic esterification could reduce the corrosiveness of biofuels, but it makes less contribution to improve its heating value.[8,9] Emulsification could provide a homogeneous mixture with biofuels and petrochemical diesel, but the addition of biofuels made the emulsions corrosive[10,11]. Moreover, pyrolysis technique using microwave heating offers a promising approach for the conversion of biomass or bio-oil into biofuel products with improved properties, but the complicated equipments is not suitable for the industrial production.[12-15] Comparable to the techniques mentioned above, the FCC process consumes no hydrogen and has the potential of converting biomass into biofuels compatible with existing petroleum products, with the full-fledged industrial technique.[16,17] The FCC is currently used in the petroleum and petrochemical industry to convert high molecular weight oil components to lower molecular weight ones which can be used directly or blended for use as fuel.[18] In this process, gasoline and diesel can be directly replaced with

AC C

EP

TE D

19

*

Corresponding author: Tel: +0086 15607608499; E-mail: [email protected] 1

ACCEPTED MANUSCRIPT biofuels which have little oxygen. In the case of catalytic cracking to prepare biofuels, Tian et al[19] determined that oils and fats can either be used along or co-feed with vacuum gas oil as FCC feed, which can produce a high yield of liquefied petroleum gas (LPG), which include C2-C4 olefins, by two-stage riser fluid catalytic cracking. Tamunaidu et al[20] observed the effect of the reaction temperature, catalyst/palm oil ratio and residence time on the conversion of palm oil. The optimum reaction conditions included a reaction temperature of 450 oC, a residence time of 20 s and catalyst/palm oil ratio of 5 g·g-1. Dupain et al[21] researched the effect of the reaction time and temperature using vegetable oil as the feedstock. The triglycerides were predominately converted to fatty acids via radical cracking reactions within 50 ms at 485-585 oC. Due to a lower aromaticity, the serial cracking reactions to produce lower olefins are much better, and the oxygen from the fatty acids is predominantly evolved as H2O, CO2 or CO. Other studies have reported similar results.[22-24] In addition, by contrast with petroleum-based fuels, the high cost of biofuels (approximately 70–85% of the total biofuel) arises from the cost of the feedstock may be the barrier for biofuels producing in industry.[25] For this reason other alternative routes are being explored which have the potential to lower the overall production cost. The research result of Lam et al[26] showed that the fruit wastes can be a suitable feedstock for pyrolysis conversion into bio-oil, bio-gas, and bio-char for further use as potentially useful products such as fuel, chemical feedstock, or catalyst support. Furthermore, palm oil[27], jatropha oil[28], and vegetable oil[29] as the feedstock for preparing biofuels have been researched extensively. Comparable to the raw materials above, using waste cooking oil as the feedstock for biofuels preparing can decrease the production cost, so that the price of the production has a competition with the petrochemical fuels. Meanwhile waste cooking oils are well-known hazardous substances due to the presence of degraded additives and undesired substances that could bring about adverse impacts to human health and the environment. The production of waste cooking oil has been increasing each year throughout the world. For instance, China generated approximately 5 million tons/year of waste cooking oil.[30] The rational utilization of waste cooking oil can both solve the environment and energy issues. However, the selection of a suitable catalyst for FCC process preparing biofuels is a critical factor defining the FCC product yield and quality as well as the operating cycle time of the process in renewable energy industry. Bezergianni et al[31] involved the process of selecting a suitable hydroprocessing catalyst for the conversion of waste cooking oil into biofuels. Three commercial hydroprocessing catalysts were employed and their activity was investigated for a range of temperatures. Meanwhile, there are several FCC catalysts using in petroleum industry could be used for FCC process preparing biofuels.

74 75 76 77 78

In this work, two commercial FCC catalysts were employed to prepare biofuels, using waste cooking oil as feedstock via the FCC process. The structure and property of the catalysts were analyzed to investigate the mechanism of catalytic cracking. According to the product solutions, the suitable catalyst was selected, which could be applied for biofuels preparing in petroleum refining industry.

79

2. Experimental

80

2.1. Materials

81

AC C

EP

TE D

M AN U

SC

RI PT

40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73

CGP-1HN and Endurance catalysts were taken from Hainan Refining & Chemical Co., Ltd.

2

ACCEPTED MANUSCRIPT The waste cooking oil was taken from the kitchen waste disposal plant, and was directly used as feedstock of FCC for preparing biofuels. As the compose of the waste cooking oil is mixed, the waste cooking oil was transformed into fatty acid methyl esters by transesterification, and the products were analyzed by GC-MS. The fatty acid composition of this feed is shown in Fig.1 .

SC

RI PT

82 83 84 85

87 88

M AN U

86

Fig. 1 Composition of the methyl-esterified waste cooking oil

2.2. Catalyst characterization

The morphologies of the catalysts were characterized using a Scanning Electron Microscope (SEM) (S-3000N). The Brunauer-Emmett-Teller (BET) surface area and pore volume were measured by N2 Adsorption-Desorption at 77 K using a Beckman Coulter SA3100 instrument. The X-Ray Diffraction (XRD) patterns of the catalysts were recorded on a Bruker D8 Advance X-Ray Diffractometer at 40 kV and 30 mA with Cu Kα as the radiation source. The acidities of the catalysts were characterized using IR spectra from pyridine adsorbed and Infrared Spectroscopy on a Bruker-IFS113 V type Fourier Transform Infrared (FT-IR) spectrometer. The microactivity of the catalysts were evaluated in a fixed bed reactor after pretreatment at 800 oC with 100% steam for 10 hours. The Loss On Ignition (LOI) of the catalysts was evaluated to determine their high temperature ability. The catalyst was dried at 105 oC and then ignited at 800 oC, and the weight difference was calculated. The chemical content (i.e., the content of Na2O and Al2O3) in the catalysts was determined using a flame atomic spectrophotometer.

101 102 103 104

2.3. GC-MS analysis

105 106 107 108 109 110 111

2.4. Production of biofuel

AC C

EP

TE D

89 90 91 92 93 94 95 96 97 98 99 100

With the HP-INNOWAX (30m ×0.25mm×0.25µm) capillary column, the temperature was increased to 90 oC within 2 mins, temperature up to 240 oC at 6 oC/min, and retained 18mins. Where the inlet temperature is 250 oC and FID 302 oC.

The reaction of waste cooking oil was performed on a stationary fluid catalytic cracking unit with the CGP-1HN and Endurance catalysts, respectively. The conditions of reaction are 1atm, 450 oC, and a weight hourly space velocity (WHSV) of 17.84 h-1 and 18.04 h-1, respectively. In addition, the catalyst/oil ratio was 3.36 and 3.33, respectively. The stationary Fluid Catalytic Cracking process is shown in Fig. 2. The procedures for production of biofuel from FCC are as follows: 3

ACCEPTED MANUSCRIPT (1) The fresh catalyst aging was carried out in an aging reactor. (2) The aged catalyst was charged into the reactor, introducing nitrogen and heating. (3) When heated to the reaction temperature, pumped the feed oil. (4) After completion of the reaction, water vapor was introduced and the product was isolated. (5) Pass the air for catalyst regeneration.

SC

RI PT

112 113 114 115 116 117

119

M AN U

118

Fig. 2 The stationary FCC process of catalytic conversion with waste cooking oil

120

3. Results and discussion 3.1. Catalytic cracking reaction of waste cooking oil

123 124 125

The liquid products of FCC with waste cooking oil were used simulated distillation method to separate and get the biofuels. The conversion and the yield were calculated by the equations as follows:

TE D

121 122

126

Total liquid yield = Gasoline+ Diesel+ Liquefied Petroleum Gas(LPG

127

Conversion (wt. %) = [(waste cooking oil (g) – residue oil (g))/ waste cooking oil (g)]*100%

EP

129 130 131 132 133 134 135 136 137 138 139 140 141 142 143

Yield (wt.%) = [weight of product (g)/ waste cooking oil (g)]*100%

(2)

(3)

The mass data of gasoline, diesel, and LPG were came from the simulated distillation experiment, and the yields of biofuels were calculated following Eqs. (1)-(3). The residue oil is heavy oil and the major biofuel products prepared with the Endurance and CGP-1HN catalysts were showed in Fig.3. Based on the calculation, the conversion of feedstock using CGP-1HN and Endurance catalysts were 96.36 wt.% and 91.07 wt.%, respectively. According to these results, both of the catalysts have a higher conversion, more than 90 wt.%. Moreover, the two catalysts also produced a higher yield, and the total yields of CGP-1HN and Endurance were 98.55 wt.% and 97.96 wt.%. Separately, the total liquid yields of the two catalysts was 88.2 wt.%( CGP-1HN) and 82.89 wt.%( Endurance). By contrast of the specific products of the two catalysts, it is different. Both of the catalysts had a low yieds of coke and heavy oil, which indicated the coke selectivity of the two catalysts was low, and both of these catalysts did a deeper cracking reaction. In addition, the yield of LPG in the product with CGP-1HN was high, gasoline had the same condaton, but the yield of diesel was low. In the products with Endurance, the yields of diesel and gasoline were high, yield of LPG was low. Based on the specific composition of the product, the two catalysts exhibited good catalytic activities. The results indicated that CGP-1HN had a

AC C

128

(1)

4

ACCEPTED MANUSCRIPT 144 145 146

stronger cracking ability than Endurance. Therefore, CGP-1HN preferentially produced a light oil fraction (LPG and gasoline). The reason for the catalysts producing different products is discussed based on the analyses of their properties and structure.

100 90

98.55

content（ wt%）

70 60 50

82.89

88.20 40 30

Coke Residue Oil Diesel Gasoline LPG Dry Gas

SC

20 10 0

Fig. 3 The FCC of waste cooking oil over CGP-1HN and Endurance

148

3.2. Property and structure characterization of CGP-1HN and Endurance

EP

TE D

3.2.1. Structure characterization of the catalysts The SEM images of the CGP-1HN and Endurance catalysts are shown in Fig.4(A-L). The SEM micrographs of the CGP-1HN (Fig.4 A-D) and Endurance (Fig.4 I-L) indicated a ball-like structure. Many micropores on the surface are observed, reaction material can come into the catalysts by channel. Many tiny particles on the surface of the Endurance catalyst (Fig.4.I-L) were observed. The presence of these tiny particles resulted in a further improvement in the volumetric surface area. In addition, the active center increased, and the activity of the catalyst was enhanced. The results in Fig.4 (E-H) indicated that CGP-1HN had a well-developed and uniformly distributed pore structure on the inside with a high specific surface area, which is advantageous for the reaction. Therefore, CGP-1HN had better active center distribution and excellent catalytic activity. By comparing these two catalysts at the same magnification, the particle size of CGP-1HN was larger than that of Endurance.

AC C

149 150 151 152 153 154 155 156 157 158 159 160 161

Endurance

M AN U

CGP-1HN

147

RI PT

97.96

80

5

M AN U

SC

RI PT

ACCEPTED MANUSCRIPT

162

Fig. 4 SEM micrographs of the prepared CGP-1HN and Endurance samples under different conditions

164

(A-D: CGP-1HN was amplified for 0.5k, 1k, 2k and 5k times; E-H: broken CGP-1HN was amplified for 0.5k, 1k,

165

2k and 5k times; I-L: Endurance was amplified for 0.5k, 1k, 2k and 5k times.)

166 167 168 169 170

The specific surface area, pore volume and BJH pore size of Endurance and CGP-1HN are listed in Table 1. The specific surface area of Endurance and CGP-1HN are 265.3 m2/g and 253.5 m2/g, the pore volumes are 0.334 cm3/g and 0.303 cm3/g, and the BJH pore size are 2.4nm and 2.5nm, respectively. The specific surface area, pore volume and BJH pore size of the two catalysts are similar.

EP

AC C

171

TE D

163

Table 1 Specific surface area and pore volume data for the samples SBET (m2/g)

Pore volume (cm3/g)

BJH pore size (nm)

Endurance

265.3

0.334

2.4

CGP-1HN

253.5

0.303

2.5

172 173 174 175 176 177 178

The N2 adsorption/desorption isotherm data for the Endurance and CGP-1HN catalysts are shown in Fig.5. The isotherms show that the two catalysts exhibite a hysteresis loop at P/P0 = 0.4 to 0.95, confirming the presence of a non-uniform pore system that was slit shaped with pores inside the micropores resulting in the H4 hysteresis loop. The isotherms for the Endurance and CGP-1HN catalysts exhibited a type I hysteresis, which indicates that the interior pore was primarily a micropore. A large adsorption was observed at a high relative pressure for CGP-1HN 6

ACCEPTED MANUSCRIPT 179

due to N2 adsorption in the interparticle voids. The isotherms of the two catalysts were similar.

CGP-1HN Endurance

250

150

100

50

0 0.0

0.1

0.2

0.3

0.4

180

0.7

0.8

0.9

1.0

SC

182 183 184 185 186

0.6

Fig. 5.N2 adsorption/desorption isotherms of Endurance and CGP-1HN

Fig.6 shows the XRD patterns of the CGP-1HN and Endurance catalysts. The two catalysts exhibited similar patterns. The main peaks that appeared in the XRD patterns were assigned to the formation of an orthorhombic structure (JCPDS: 39-1380) in the two catalysts, which is the characteristic pattern of Y zeolites. Therefore, the main composition of CGP-1HN and Endurance consisted of Y zeolites with a faujasite crystal structure.

M AN U

181

0.5

P/Po

RI PT

Volume（ cc/g）

200

EP

Intensity(a.u.)

TE D

Endurance CGP-1HN

188

20

30

40

50

2θ(degree)

AC C

10

187

Fig. 6 XRD patterns of the prepared CGP-1HN and Endurance catalysts

189

3.2.2. Performance of the catalysts

190 191 192 193 194 195 196 197 198

In general, the types of acid sites (i.e., Brönsted or Lewis) were determined using infrared adsorption experiments with basic probe molecules, such as pyridine[12]. Fig.7 shows the Py–FTIR spectra for the Endurance and CGP-IHN catalysts degassed at 200 oC (total acid) and 350 oC (strong acid). The absorption peaks that appeared at 1450 and 1540 cm−1 were due to Lewis (L) and Brönsted (B) acid sites, respectively[13]. Table 2 shows the acid strength distribution of the two catalysts, which was quantitatively calculated from the FTIR results of pyridine adsorption at 200 o C and 350 oC. As shown in Fig.7, the absorption peaks of the Endurance catalyst, which are located at 1450 and 1540 cm-1, are more intense at 200 oC and 350 oC due to the corresponding L acid sites and B acid sites. In addition, the absorption spectra for CGP-1HN contained a band at 7

ACCEPTED MANUSCRIPT located 1450 cm-1, which indicated that CGP-1HN contained few L acid sites. As shown in Table 2, the total number (at 200 oC) of B and L acid sites in the Endurance catalyst is more than that in CGP-1HN. In particular, the number of total L acid sites in CGP-1HN was obviously less than that in Endurance, which contained barely any L acid sites.

L

L+B

B 350

1400

1450

1500

1550

1600

203

350

CGP-1HN

200

CGP-1HN

1650

1700

M AN U

Wavelength(cm-1)

Endurance

SC

Asorption

200

Endurance

RI PT

199 200 201 202

204

Fig. 7.IR spectra of pyridine adsorption on the Endurance and CGP-1HN catalysts at 200 oC and 350 oC

205

Table 2 The acid amount of L and B about CGP-1HN and Endurance µmol/g

200 oC

Brönsted

CGP-1HN

21.53

Endurance

189.39

206

350 oC

Lewis

TE D

Lewis

total

strong

(weak acid)

Brönsted

Lewis

Brönsted

258.23

16.60

218.72

4.928

39.51

341.69

135.88

269.57

53.50

72.12

Table 3 shows the microreactivity, LOI and chemical composition of the CGP-1HN and Endurance catalysts. The microreactivity and LOI of the Endurance and CGP-1HN catalysts are close. The loss of mass is mainly form crystal water of two catalysts. In addition, both catalysts have higher microreactivity. In Table 3, the content of SiO2 can be calculated in both of catalysts with the content of Na2O and Al2O3, and the SiO2 content in the Endurance and CGP-1HN catalysts was 64.72 wt.% and 57.59 wt.%, respectively. According to these data, n (SiO2)/ n (Al2O3) of Endurance and CGP-1HN was 3.12 and 2.31, respectively. The number of L acid sites decreased as the content of Al2O3 increased.

215

Table 3 Microreactivity, LOI and chemical composition of CGP-1HN and Endurance

AC C

EP

207 208 209 210 211 212 213 214

Chemical composition Catalyst

Microreactivity (%)

LOI

% Na2O (%)

%

Endurance

83.27

7.78

0.11

35.17

CGP-1HN

81.42

8.04

0.10

42.31

216 217

Al2O3

3.3. Analysis of the catalytic mechanism 8

ACCEPTED MANUSCRIPT The reaction of FCC is followed by the carbonium ion mechanism with waste cooking oil. The catalytic cracking reaction mechanism involves the double bond obtaining H+ in the center of the B acid site or alkanes releasing H- in the center of the L acid site to form a classic carbocation. This carbonium ion could undergo beta C-C fracture, hydrogen transfer, isomerization and aromatization.

223 224 225 226 227 228 229

The results in Table 2 indicate that L and B acid sites are both present in the Endurance catalyst. The acid sites in the CGP-1HN catalyst primarily consisted of B acid sites. The Fig.3, shows that the cracking depth of Endurance is less than CGP-1HN, because the yields of LPG and gasoline with CGP-1HN are higher. The percent of conversion and the total yield of products with Endurance are higher, because the L and B acid sites of Endurance have the synergistic effect in the cracking reaction, L acid sites of Endurance decrease the catalytic cracking depth of waste cooking oil.

230

4. Conclusion

231 232 233 234 235 236 237 238

The yield of the diesel is higher with the catalyst of Endurance. For the catalyst of CGP-1HN, the yields of LPG and gasoline are higher, and both catalysts show higher microreactivity. The Endurance and CGP-1HN catalysts have nearly the same surface morphology and inner structure. The main difference between the two catalysts is the acid amount. The Endurance catalyst contained both L and B acid sites, and the CGP-1HN catalysts primarily consisted of B acid sites with few L acid sites, which cause different product distribution. These insights into the relationships between the catalysts and production can provide guidance for the designing or selecting of a catalyst for the biofuel products by FCC in the future.

239 240 241 242

Acknowledgements

SC

M AN U

TE D

This work was supported by the Key Project of Hainan Province (ZDXM2015116) and the Hainan Natural Science Foundation of China (20152028).

Reference

EP

[1] G.W. Huber, S. Iborra, A. Corma, Synthesis of transportation fuels from biomass: chemistry, catalysts, and engineering, Chem Rev. 106(2006)4044-4098. [2] S.N. Naik, V.V. Goud, P.K. Rout, A.K. Dalai, Production of first and second generation biofuels: A comprehensive review, Renew Sust Energ Rev.14 (2010)578-597.

AC C

243 244 245 246 247 248 249 250 251 252 253 254 255 256 257 258 259

RI PT

218 219 220 221 222

[3] R.E. Sims, W. Mabee, J.N. Saddler, M. Taylor, An overview of second generation biofuel technologies, Bioresour Technol. 101(2010)1570-1580. [4] R.A. Candeia, M.C.D. Silva, J.R. Carvalho Filho, M.G.A. Brasilino, T.C. Bicudo, I.M.G. Santos,et al, Influence of soybean biodiesel content on basic properties of biodiesel–diesel blends, Fuel. 88(2009)738-743. [5] Hill J, Nelson E, Tilman D, et al. Environmental, economic, and energetic costs and benefits of biodiesel and ethanol biofuels[J]. Proceedings of the National Academy of sciences, 2006, 103(30): 11206-11210. [6] D.C. Elliott, Historical developments in hydroprocessing biooils, Energy Fuels. 21(2007)1792-1815 [7] D.C.Elliott, T.R.Hart, G.G.Neuenschwander, L.J.Rotness, A.H.Zacher, Catalytic hydroprocessing of biomass fast pyrolysis bio-oil to produce hydrocarbon products. Environ Prog Sustain Energy.28(2009)441-449. [8] Y.L.Gu, Z.G.Guo, L.J.Zhu, G.H.Xu, S.R.Wang, Experimental research on catalytic esterification of bio-oil volatile fraction, Asia-Pacific power and energy engineering conference. DOI:101109/APPEEC20105448436, 2010

9

ACCEPTED MANUSCRIPT [9] J.Peng, P.Chen, H.Lou, X.M.Zheng, Upgrading of Bio-oil over aluminum silicate in supercritical ethanol, Energy Fuels.22( 2008)3489-3492 [10] X.X.Jiang, N.Ellis, Upgrading bio-oil through emulsification with biodiesel: thermal stability. Energy Fuels. 24(2010)2699-2706. [11] M.Ikura, M.Stanciulescu, E.Hogan, Emulsification of pyrolysis derived bio-oil in diesel fuel, Biomass Bioenergy, 24(2003)221-232. [12] S.S.Lam, W.A.W.Mahari, A.Jusoh, et al, Pyrolysis using microwave absorbents as reaction bed: An improved

147(2017)263-272.

RI PT

approach to transform used frying oil into biofuel product with desirable propertie, Journal of Cleaner Production.

[13] S.S.Lam, W.A.W.Mahari, C.K.Cheng, et al, Recovery of diesel-like fuel from waste palm oil by pyrolysis using a microwave heated bed of activated carbon, Energy. 115(2016)791-799.

[14] W. A.W.Mahari, N.F.Zainuddin, W.M.N.Wan Nik, et al, Pyrolysis recovery of waste shipping oil using

SC

microwave heating, Energies. 9(2016)780.

[15] S.S.Lam, R.K.Liew, A.Jusoh, C.T.Chong, F.N.Ani, H.A.Chase,Progress in waste oil to sustainable energy, with emphasis on pyrolysis techniques, Renewable and Sustainable Energy Reviews. 53(2016)741-753. [16] J.D.Adjaye, N.N.Bakhshi, Production of hydrocarbons by catalytic upgrading of a fast pyrolysis bio-oil. Part I:

M AN U

Conversion over various catalysts, Fuel Processing Technology. 45(1995)161-183.

[17] A.Aho, N.Kumar, A.V.Lashkul, et al, Catalytic upgrading of woody biomass derived pyrolysis vapours over iron modified zeolites in a dual-fluidized bed reactor, Fuel. 89(2010)1992-2000.

[18] J.M.Thomas,W.J.Thomas,J.R.Anderson,et al,Principles and Practice of Heterogeneous Catalysis, Angewandte Chemie-English Edition.36(1997)2689-2689.

[19] H.Tian, C.Li, C.Yang, H.Shan, Alternative Processing Technology for Converting Vegetable Oils and Animal Fats to Clean Fuels and Light Olefins, Chin J Chem Eng. 16(2008)394-400.

TE D

[20] P.Tamunaidu, S.Bhatia, Catalytic cracking of palm oil for the production of biofuels: Optimization studies, Bioresour Technol. 98(2007)3591-3601.

[21] X.Dupain,D.J.Costa,C.J.Schaverien,M.Makkee,J.A.Moulijn, Cracking of a rapeseed vegetable oil under realistic FCC conditions, Appl Catal B-Environ. 72(2007)44-61. 22] T.L.Chew, S.Bhatia, Catalytic processes towards the production of biofuels in a palm oil and oil palm

EP

biomass-based biorefinery, Bioresour Technol. 99(2008)7911-7922. [23] V.P.Doronin, O.V.Potapenko, P.V.Lipin, T.P.Sorokina, Catalytic cracking of vegetable oils and vacuum gas oil. Fuel. 106(2013)757-765.

[24] R.O.Idem, S.P.R.Katikaneni, N.N.Bakhshi, Catalytic conversion of canola oil to fuels and chemicals: roles of

AC C

260 261 262 263 264 265 266 267 268 269 270 271 272 273 274 275 276 277 278 279 280 281 282 283 284 285 286 287 288 289 290 291 292 293 294 295 296 297 298 299 300 301 302 303

catalyst acidity, basicity and shape selectivity on product distribution, Fuel Process Technol. 51(1997)101-125. [25] J.Connemann, J.Fischer, Biodiesel in Europe, biodiesel processing technologies. In: Proceedings of the international liquid biofuels congress, Brazil,1998. [26] S.S.Lam, R.K.Liew, X.Y.Lim, et al, Fruit waste as feedstock for recovery by pyrolysis technique, International Biodeterioration & Biodegradation. 113(2016) 325-333. [27] O.Y.Sang, Biofuel production from catalytic cracking of palm oil, Energy Sources. 25(2003) 859-869. [28] J.C.Juan, D.A.Kartika, T.Y.Wu, et al, Biodiesel production from jatropha oil by catalytic and non-catalytic approaches: an overview, Bioresource Technology. 102(2011)452-460. [29] A.Demirbaş, Biodiesel fuels from vegetable oils via catalytic and non-catalytic supercritical alcohol transesterifications and other methods: a survey, Energy conversion and Management. 44(2003)2093-2109. [30] G.Chen, C.Liu, W.Ma, X.Zhang, Y.Li, B.Yan, et al, Co-pyrolysis of corn cob and waste cooking oil in a fixed bed, Bioresour Technol. 166(2014)500-507.

10

ACCEPTED MANUSCRIPT [31] S.Bezergianni, A.Kalogianni, A.Dimitriadis, Catalyst evaluation for waste cooking oil hydroprocessing, Fuel 93(2012) 638-41. [32] H.G.Barth, S.T.Sun, R.M.Nickol.Particle size analysis, Anal Chem. 59(1987)142R-162R. [33] E.P.Parry, An infrared study of pyridine adsorbed on acidic solids. Characterization of surface acidity,

EP

TE D

M AN U

SC

RI PT

J Catal. 2(1963) 371-379.

AC C

304 305 306 307 308

11