JFUE 9863 No.

of Pages 5, Model 5G
25 November 2015

Fuel xxx (2015) xxx–xxx

1

Contents lists available at ScienceDirect

Fuel
Vol. 168, 15 March 2016, 76-80
journal homepage: www.elsevier.com/locate/fuel

4
5

3 Ethers of glycerol and ethanol as bioadditives for biodiesel

6 Bianca P. Pinto a,c, Jéssica T. de Lyra a, Júlia A.C. Nascimento b, Claudio J.A. Mota a,b,c,⇑
7 a
Universidade Federal do Rio de Janeiro, Instituto de Química, Av Athos da Silveira Ramos 149, CT Bl A, Cidade Universitária, Rio de Janeiro 21941-909, Brazil
8 b
Universidade Federal do Rio de Janeiro, Escola de Química, Av Athos da Silveira Ramos 149, CT Bl E, Cidade Universitária, Rio de Janeiro 21941-909, Brazil
9 c
INCT Energia e Ambiente, UFRJ, 21941-909 Rio de Janeiro, Brazil

10
a r t i c l e i n f o a b s t r a c t
1 4
2 2
13 Article history: The production of biofuel has increased considerably over the last years. Glycerol, a by-product of biodiesel 25
14 Received 30 July 2015 synthesis, accounts for about 10 wt% of the total mass balance in the transesterification process and has a 26
15 Received in revised form 9 November 2015 limited range of applications. The acid-catalyzed etherification of glycerol with alcohols could be an attrac- 27
16 Accepted 12 November 2015
tive solution to address the excess of glycerol. This study is focused on the etherification of glycerol with 28
17 Available online xxxx
ethanol over solid acid catalysts, such as zeolites, clays and sulfonic resins. All the catalysts produced mono, 29
di and tri-glycerol-ethers that can be used as biodiesel fuel components. Higher conversion and selectivity 30
18 Keywords:
to ethyl glyceryl ethers were obtained at 180 °C, ethanol/glycerol molar ratio of 3:1 and 4 h of reaction 31
19 Biodiesel
20 Glycerol
time, with Amberlyst-15 acid resin as catalyst. Under these reaction conditions, 96% of glycerol conversion 32
21 Ethers and 80% selectivity to the ethyl ethers were observed. Laboratory tests using a blend containing 0.5–1.0 vol 33
22 Oxygenated fuel additive % of the ethyl glyceryl ethers in biodiesel showed reduction of pour and cloud points, indicating the 34
23 potential of these ethers as bioadditives to fuels. 35
Ó 2015 Elsevier Ltd. All rights reserved. 36
37

38
39
40 1. Introduction Etherification of glycerol is one of the promising processes for 60
the production of oxygenated fuel additives [17]. It can also be a 61
41 The first chemical industrial application of glycerol was devel- good alternative for the glycerol produced from biodiesel [4,18]. 62
42 oped by Alfred Nobel, who reported in 1860 the use of nitroglyc- Glycerol has three hydrophilic hydroxyl groups, that are responsi- 63
43 erin to produce dynamite. Glycerol is a component of all natural ble for its solubility in water and hygroscopic nature [19,20]. It also 64
44 fats and oils in the form of fatty acid esters, and an important inter- has a high viscosity and boiling point and it is miscible with polar 65
45 mediate in the metabolism of living organisms. It is the most substances and immiscible with hydrocarbons and other nonpolar 66
46 important byproduct of the oleochemistry industry and it can also substances. Therefore, it cannot be directly added to fuels, but 67
47 be produced through fermentation of sugars and chemical synthe- must be transformed into other chemicals to reduce the polarity 68
48 sis from propylene [1,2]. and viscosity. 69
49 Glycerol is the main coproduct of biodiesel production by the The use of glycerol ethers can reduce the emissions, mainly par- 70
50 transesterification of oils and fats with methanol [3]. For each ticulate matters, carbon monoxide and carbonyl compounds in 71
51 90 m3 of biodiesel produced from transesterification, approxi- exhaust gases [21]. They can decrease the cloud point of diesel fuel 72
52 mately 10 m3 of glycerol are generated [4]. The world production when combined with biodiesel [22]. Appropriate ratio of glycerol 73
53 of glycerol is rising significantly, leading to lower market prices, ether, alcohol and gasoline could reduce the vapor pressure to 74
54 which makes glycerol a particularly attractive molecule for the the desired level and reduce fuel consumption [23]. The presence 75
55 synthesis of many products, such as surfactants [5,6], emulsifiers of glycerol ethers could help lowering the gel temperature of fuels, 76
56 [7], solvents, humectants, lubricants and cosmetics [8]. A potential which leads to viscosity reduction. The presence of hydroxyl 77
57 and promising application of glycerol derivatives is the automotive groups could also lower the NOx emission [24]. 78
58 sector. Glycerol acetals [2,11–16] and glycerol ethers have been A limitation on the use of fat acid methyl esters, the biodiesel, in 79
59 identified as valuable fuel additives. many engines is the cloud point. For petroleum-derived diesel 80
fuels, the cloud point is around 16 °C, but for biodiesel the cloud 81
point can be around 0 °C. The addition of ethers, such as glycerol 82
⇑ Corresponding author at: Universidade Federal do Rio de Janeiro, Instituto de ethers, decrease the cloud point of diesel fuels [25]. 83
Química, Av Athos da Silveira Ramos 149, CT Bl A, Cidade Universitária, Rio de A number of studies on the preparation of glycerol ethers, using 84
Janeiro 21941-909, Brazil.
different catalytic systems, have been reported. Klepáčová and 85
E-mail address: cmota@iq.ufrj.br (C.J.A. Mota).

http://dx.doi.org/10.1016/j.fuel.2015.11.052
0016-2361/Ó 2015 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Pinto BP et al. Ethers of glycerol and ethanol as bioadditives for biodiesel. Fuel (2015), http://dx.doi.org/10.1016/j.
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2 B.P. Pinto et al. / Fuel xxx (2015) xxx–xxx

86 collaborators studied the etherification of glycerol with isobutene glycerol and ethanol to form ethers may lead to a fuel additive 152
87 or tert-butanol over Amberlyst resins and zeolites H-Y and H- 100% derived from renewable sources. This work also aims to study 153
88 Beta [26]. They reported that zeolites H-Y and H-Beta provided these ethers as bioadditives to improve fuel properties, by testing 154
89 lower selectivity than ion-exchange resins; in addition, water for- blends of the ethers with biodiesel. 155
90 mation, in the case of using tert-butyl alcohol (TBA) as reagent, has
91 an inhibition effect on glycerol etherification. The highest yield 2. Material and methods 156
92 with Amberlyst-15 and Amberlyst-35 (88%) were obtained at
93 60 °C when isobutene was used as the etherification agent. Glycerol and ethanol were analytical grades. The K-10 Montmo- 157
94 Karinen and Krause reported that the tert-butyl glyceryl ethers rillonite and Amberlyst-15 acid resin were obtained from Sigma– 158
95 obtained have octane number suitable for gasoline component Aldrich. Zeolites H-ZSM-5 and H-Beta were purchased from Zeo- 159
96 [27]. Mota and collaborators reported the etherification of glycerol lyst. Tallow biodiesel was kindly provided by Instituto Virtual 160
97 with benzyl alcohol using heterogeneous acid catalysts [28]. Internacional de Mudanças Globais (Ivig), Coppe UFRJ. The soybean 161
98 Jérôme and collaborators studied the direct etherification of glyc- biodiesel was prepared in the laboratory by traditional transester- 162
99 erol with alkyl alcohols, olefins and dibenzyl ethers catalyzed by ification with sodium hydroxide and methanol. 163
100 acid-functionalized silica, allowing the first catalytic access to The acid strength distribution of the catalysts was measured by 164
101 valuable monoalkyl glycerol ethers [1]. temperature-programmed desorption (TPD) of n-butylamine, 165
102 Pariente and collaborators reported different types of acidic using a thermo gravimetric equipment. About 25 mg of the catalyst 166
103 heterogeneous catalysts, including sulfonic resins, zeolites and were initially pretreated in a straight glass reactor, under flowing 167
104 grafted silicas for the synthesis of mono-ethers of glycerol using helium (40 mL min 1), at the temperatures shown in Table 1. The 168
105 ethanol. With the Amberlyst resin, monoethyl glyceryl ethers were temperature was then set to 150 °C and the flow of helium 169
106 selectively produced up to a glycerol conversion of 40% at a tem- (10 mL min 1) was driven to a saturator containing n-butylamine 170
107 perature of 160 °C. The best results were found at 200 °C, using at room temperature. The flow of the amine was passed over the 171
108 grafted silica (68% glycerol conversion with a 75% selectivity to catalyst for 10 min. Then, the excess of the amine was desorbed 172
109 mono and 25% selectivity to di-ethyl ether). Silicon-rich zeolites by passing a flow of helium (20 mL min 1) over the catalyst bed 173
110 (Si/Al = 25) also presented good activities, with glycerol conversion for an additional 20 min period. The solid was then carefully placed 174
111 of 57% and selectivity of 75% and 25% to mono and di-ethyl glyceryl in the thermo gravimetric equipment (Shimadzu TGA-51) and the 175
112 ethers, respectively [29]. TPD profile was taken following the weight loss up to 450 °C, under 176
113 Yuan and collaborators have reported the etherification of glyc- flowing nitrogen gas. 177
114 erol with bioethanol over tungstophosphoric acid (HPW) to syn- Surface area was determined by nitrogen adsorption/desorption 178
115 thesize glycerol ethers. Bulk HPW and SiO2-supported HPW isotherms using a Micromeritics Tristar 2000 equipment. Before 179
116 catalysts exhibited the highest activity among the tested catalysts, analysis, all the samples were outgassed at 300 °C under vacuum 180
117 with 97% of glycerol conversion at 160 °C, ethanol/glycerol molar for 24 h. The areas were calculated according to the BET equation. 181
118 ratio of 6:1 and 20 h. The selectivity to mono ether (62%) decreased The catalysts were pre-treated for 30 min (Table 1), just previ- 182
119 with the increased conversion of glycerol, whereas the selectivity ously to the reaction. The number of acid sites was kept constant 183
120 toward di (28%) and tri ether (10%) increased [30]. (1.5 mmol), varying the amount of catalyst loaded. After cooling 184
121 Frusteri and collaborators investigated the heterogeneous cat- to room temperature 10 g (109 mmol) of glycerol and the appro- 185
122 alytic etherification of glycerol with tert-butyl alcohol in the pres- priate molar amount of ethanol were introduced in a 100 mL Parr 186
123 ence of solid acid catalysts. An increase in reaction temperature reactor loaded with the catalyst. The system was previously purged 187
124 favors the formation of di-substituted ethers. Steric hindrance with N2 to remove the air, and the experiments were performed 188
125 and water prevent the formation of the tri-substituted ether. Water under inert atmosphere, with glycerol:ethanol molar ratio varying 189
126 removal was necessary to achieve higher yields of the ethers [31]. from 1:3 to 1:6. The reaction was conducted at 180 °C and kept at 190
127 The etherification with tertiary alcohols occurs through a this temperature for 4 or 8 h under autogenic pressure (5–30 bar). 191
128 SN1-type reaction, involving the formation of a tertiary carbocation. At the end, the system was cooled down to room temperature, the 192
129 On the other hand, for ethanol and other primary alcohols, the catalyst separated by filtration and the liquid phase analyzed by 193
130 mechanism is typically a SN2 reaction, involving the nucleophilic gas chromatograph (Agilent 6850) coupled to a mass quadrupole 194
131 attack of glycerol, to the protonated ethanol, with concomitant loss spectrometer (Agilent 5973), operating in electron impact ioniza- 195
132 of water. tion (70 eV), using a methyl-phenyl-silicone column. Analyses 196
133 Melero and collaborators studied the best conditions to maxi- were carried out with the temperature program increasing from 197
134 mize glycerol conversion. At 200 °C, ethanol/glycerol molar ratio 80 to 220 °C (with a slope of 10 °C/min). Blank experiments, with- 198
135 of 15:1 and catalyst loading of 19 wt%, they obtained 74% of glyc- out adding catalyst, were also carried out for comparison purposes. 199
136 erol conversion and 42% yield to ethyl ethers after 4 h of reaction The glycerol ethers were also produced at higher scale, using a 200
137 [32]. 2 L autoclave. No separation of the MEG, DEG and TEG was 201
138 Frusteri and collaborators produced ethers of glycerol through attempted in this case. 202
139 the reaction with isobutene over spherical silica supported Hyflon The glycerol ether mixtures were blended with soybean and 203
140 as catalysts. They obtained yields to di and tri-ethers higher than palm biodiesel in 0.5 and 1 vol%. The mixtures were subjected 204
141 that obtained with Amberlyst-15 commercial catalyst. Engine to tests of cloud point (ASTM D 2500) [34] and pour point 205
142 tests, using a blend containing 10 vol% of the glycerol ether mix- (ASTM D 97) [35]. 206
143 ture, confirmed the positive role as additives to reduce emissions
144 of particulates and unburned hydrocarbons, with significant 3. Results and discussion 207
145 improvement of diesel combustion efficiency [33].
146 The purpose of this work is to study the production of ethyl The main physical and chemical properties of the catalysts are 208
147 glyceryl ethers from the acid-catalyzed reaction of glycerol with reported in Table 1. The areas varies from 54 to 564 m2 g 1. Zeolite 209
148 ethanol, to obtain bioadditives with high oxygen content Beta showed the highest BET area, but its acidity was 1.4 mmol g 1. 210
149 (Scheme 1) that could improve fuel properties. Ethanol is a renew- On the other hand, the Amberlyst-15 acid resin catalyst showed 211
150 able compound, produced mainly from the fermentation of sugars the lowest surface area and the highest acidity among the catalysts 212
151 and commonly used as bioadditive in gasoline. The combination of tested. 213

Please cite this article in press as: Pinto BP et al. Ethers of glycerol and ethanol as bioadditives for biodiesel. Fuel (2015), http://dx.doi.org/10.1016/j.
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B.P. Pinto et al. / Fuel xxx (2015) xxx–xxx 3

Scheme 1. Etherification of glycerol with ethanol using solids acids.

Table 1
Physical and chemical properties of the catalysts.

Catalyst Area Aciditya Catalyst Activation Si/Al

(m2 g1) (mmol g 1
) loadingb (g) temperaturec (°C)
K-10 260 0.70 2.1 150 1.5
H-ZSM-5 408 0.80 1.9 550 40
H-Beta 564 1.40 1.1 550 19
Amberlyst-15 53 4.7 0.32 120 –
a
Measured from n-butylamine adsorption at 150 °C.
b
To achieve 1.5 mmol of acid sites in each experiment.
c
Rate = 10 °C min 1; time in activation temperature = 2 h.

214 It can be seen that Amberlyst-15 acid resin presents the highest
215 conversion among all solid acid catalysts tested, also showing the
216 highest selectivity to di and tri-ethyl glyceryl ethers. It is interest-
217 ing to notice that the glycerol conversion is around 90% after 4 h
218 (molar ratio 1:3) of reaction time, indicating the high activity of Fig. 1. XRD patterns of new and used resin samples.
219 the acid resin catalyst for etherification. This also explains the
220 highest selectivity to di- ethyl glyceryl ethers and tri-ethyl glyceryl The K-10 clay presented a conversion of 70% after 8 h (molar 228
221 ethers, because they are formed through consecutive etherification ratio 1:3) of reaction time, but the selectivity to di and tri-ethyl 229
222 reactions. In fact, acid exchange resins are effective catalysts for glyceryl ethers was lower when compared with Amberlyst-15. 230
223 etherification [26,29,32]. The di-ethyl glyceryl ethers were produced with 14% selectivity, 231
224 It is worth mentioning that we were not able to separate or indicating that a second and third etherification of glycerol is 232
225 identify the two different mono and di-ethyl glyceryl ethers slower in K-10 clay than in Amberlyst-15. 233
226 formed by reaction on the primary and secondary hydroxyl group The HZSM-5 zeolite presented a conversion of 61% after 8 h 234
227 of glycerol. (molar ratio 1:3) of reaction time. The main product formed was 235
the mono-ethyl glyceryl ethers with a selectivity of 94%. The di 236
and tri-ethyl glyceryl ethers were also produced, but with a selec- 237
Table 2 tivity of 4% and 2%. 238
Etherification of glycerol with ethanol over different solid acid catalysts (reaction The results can be explained by the acidity of the materials, 239
temperature = 180 °C).
because the TPD of n-butylamine indicated that the zeolites have 240
Entry Catalyst Molar Time Conversion Selectivity (%) higher acid strength than K-10. 241
ratio (h) (%) The low conversion and selectivity to the di and tri ethyl glyc- 242
Mono Di Tri
eryl ethers observed on HZSM-5 might be partly explained in terms 243
1 No catalyst 1:6 8 0 0 0 0
2 K-10 1:3 4 54 82 11 7 of diffusion and steric constraint problems. It is evident that di and 244
3 K-10 1:3 8 70 79 14 7 tri-ethyl glyceryl ethers are space demanding and their formation 245
4 K-10 1:6 4 59 72 18 10 and diffusion inside the zeolite pores would be difficult, explaining 246
5 K-10 1:6 8 58 74 17 9 the poor selectivity to these products on the zeolite catalysts. 247
6 H-ZSM-5 1:3 4 56 91 5 4
7 H-ZSM-5 1:3 8 61 94 4 2
Nevertheless, the HZSM-5 zeolite has a high Si/Al ratio, being 248

8 H-ZSM-5 1:6 4 39 96 3 1 hydrophobic, allowing the desorption of the water molecules from 249
9 H-ZSM-5 1:6 8 40 95 3 2 the channels and probably preserving the acidity of the sites. 250
10 H-Beta 1:3 4 85 74 15 11 The etherification of glycerol with ethanol proceeds in the pres- 251
11 H-Beta 1:3 8 92 71 17 12
ence of an acid catalyst and can generate up to five different com- 252
12 H-Beta 1:6 4 59 85 8 7
13 H-Beta 1:6 8 89 75 14 10 pounds: mono-ethyl glyceryl ethers (MEG), di-ethyl glyceryl ethers 253
14 Amberlyst-15 1:3 4 90 87 5 8 (DEG) and tri-ethyl glyceryl ether (TEG) (Scheme 1). The MEG and 254
15 Amberlyst-15 1:3 8 96 65 19 16 DEG can include isomers, depending upon the etherification posi- 255
16 Amberlyst-15 1:6 4 95 79 12 9 tion within the glycerol molecule. The etherification of glycerol 256
17 Amberlyst-15 1:6 8 89 87 7 5
with ethanol over different heterogeneous catalysts was carried 257

Please cite this article in press as: Pinto BP et al. Ethers of glycerol and ethanol as bioadditives for biodiesel. Fuel (2015), http://dx.doi.org/10.1016/j.
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99,6
99

98

97

96

95

94

93
%T
92

91

90

89

88

87

86,0
4000,0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 650,0
cm-1

Fig. 2. Infrared spectra of new and used resin samples. (------) before reaction (------) 1st reaction (- - - - - -) 2nd reaction.

because the competitive self-etherification of ethanol affording 272

Table 3
Reutilization of catalyst Amberlyst-15 and H-Beta. diethyl ether (DEE), which could be observed in all reaction. Nev- 273
ertheless, quantification of DEE was not carried out due to its high 274
Run Amberlyst-15 H-Beta
volatility. The main product of glycerol etherification with ethanol 275
Conversion (%) in all catalysts studied was MEG, with selectivity varying from 72% 276
1 96 92 to 95% depending on the catalyst and reaction conditions. 277
2 89 83 An analysis of reusability was performed with Amberlyst-15 278
3 84 79
and H-Beta catalysts. Table 3 depicts the results of three consecu- 279
tive catalytic runs performed with the catalysts, at a fixed reaction 280
time of 8 h, 180 °C and molar ratio of glycerol/ethanol 1:3. After 281

Table 4 each experiment, the catalyst was separated from the reaction 282
Cloud point (CP) and pour point (PP) of the mixtures of B100 and ethyl glyceryl ethers. medium by centrifugation, washed and dried at 120 °C for 2 h. In 283
both cases there was a small reduction of the glycerol conversion, 284
Fuel Ethers (vol%) CP (°C) PP (°C)
indicating some deactivation of the catalysts, specially from the 285
Soybean B100 – 0 5
first to the second run. This may be due to coke deposition, spe- 286
Soybean B100 + ethers 0.5 2 10
Soybean B100 + ethers 1.0 1 6 cially in the case of zeolite HBeta or leaching of the active site in 287
Tallow B100 – 19 13 the case of the Amberlyst-15. XRD analysis of the acid resin, before 288
Tallow B100 + ethers 0.5 15 12 and after the tests, did not show significant changes in the struc- 289
Tallow B100 + ethers 1.0 16 10
ture (Fig. 1), indicating that the Amberlyst-15 acid resin was not 290
significantly destroyed at the conditions used to produce the glyc- 291
erol ethers, as one might have been anticipated due to the 292
258 out at 180 °C, and the results are summarized in Table 2. No con- restricted thermal stability of this catalyst. Fig. 2 shows the infra- 293
259 version was observed without catalyst (entry 1). In general, red spectra of the resin before and after the runs, indicating that 294
260 Amberlyst-15 showed the best catalytic activity compared with no appreciable loss of the sulfonic group was observed. 295
261 the other catalysts. This finding is similar to previous reported The glycerol ethers mixture was blended with soybean and tal- 296
262 studies of glycerol etherification with ethanol [29,32], which low biodiesel. Table 4 shows the results of cloud and pour points 297
263 showed that sulfonic acid-based heterogeneous catalysts pre- for the mixtures of ethyl glyceryl ethers with B100 (soybean and 298
264 sented the highest conversions. This can also be explained by the tallow), at different proportions. The glycerol ethers mixture used 299
265 higher acid strength of Amberlyst acid resins compared with zeo- was obtained from the reaction of glycerol with ethanol using 300
266 lites and clays [36]. The highest glycerol conversion (96%) was Amberlyst-15 as catalyst (entry 15 in Table 2 – 65% MEG, 19% 301
267 observed over this catalyst, with a molar ratio of glycerol to etha- DEG and 16% TEG). 302
268 nol of 1:3 and 8 h of reaction time (entry 15). Higher molar ratio of The limit of 1 vol% for the glycerol ethers in the biodiesel fuel 303
269 ethanol to glycerol does not necessary lead to higher conversion. was chosen to avoid significant alterations of other biodiesel 304
270 For instance, when K-10 was used as catalyst, the increase in molar specifications. The results clearly indicate that the ethyl glyceryl 305
271 ratio leads to a decrease in conversion (entries 2 and 4). This is ethers decrease the cloud point of the fatty acid methyl esters. The 306

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Please cite this article in press as: Pinto BP et al. Ethers of glycerol and ethanol as bioadditives for biodiesel. Fuel (2015), http://dx.doi.org/10.1016/j.
fuel.2015.11.052