Improvement of diesel lubricity by chemically modified tung oil-based

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Improvement of diesel lubricity by chemically modified tung oil-based fatty acid esters as additives Zengshe Liu, Jing Li, Gerhard Knothe, Brajendra K. Sharma, and Jianchun Jiang Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.9b00854 • Publication Date (Web): 03 May 2019 Downloaded from http://pubs.acs.org on May 6, 2019

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Improvement of diesel lubricity by chemically modified tung oil-based fatty

2

acid esters as additives§

3 4

Zengshe Liua,*, Jing Lia,b, Gerhard Knothea, Brajendra K. Sharmac and Jiangchung Jiangb

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aBio-Oils

7

Research Service, U.S. Department of Agriculture, 1815 N. University Street, Peoria, Illinois

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61604, USA

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bInstitute

Research Unit, National Center for Agricultural Utilization Research, Agricultural

of Chemical Industry of Forestry Products, CAF, Nanjing, Jiangsu 210042, China

10

cIllinois

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Hazelwood Drive, Champaign, Illinois 61820, USA

Sustainable Technology Center, University of Illinois at Urbana-Champaign, 1

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*Corresponding author: Zengshe Liu, Tel.: + 1 309-681-6104; Fax: 309-681-6524

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E-mail address: [email protected]

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Keywords: Tung oil; Maleation; Esterification; Ultra-low-sulfur diesel (ULSD); Lubrication

17

additives

18 19

§

20

providing specific information and does not imply recommendation or endorsement by the U.S.

21

Department of Agriculture. USDA is an equal opportunity provider and employer.

Mention of trade names or commercial products in this publication is solely for the purpose of

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ABSTRACT

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Diesel fuel lubricity has been a concern of diesel fuel injection equipment manufacturers for many

27

years. The problem has drawn attention because of the reduction in lubricity associated with the

28

extreme hydrogenation needed to reach the low sulfur levels required in modern diesel fuels. Ultra-

29

low-sulfur diesel (ULSD) fuels require higher concentrations of additives or blending with other

30

materials of sufficient lubricity, thereby increasing the cost. Here we communicate the synthesis

31

of tung oil based fatty acid methyl ester (eleostearic acid methyl ester, EAME) and the maleation

32

compound (EAME/MA) by reacting with maleic anhydride (MA) via the Diels–Alder reaction.

33

The EAME/MA reacts with short chain alcohols, such as methanol and butanol, by opening the

34

cyclic anhydride to form esters, i.e., EAME/MA/ME and EAME/MA/BU. The EAMA/MA/ME

35

and EAME/MA/BU compounds effectively enhanced the lubricity of ULSD. The lubricity of

36

ULSD at low additive levels (500-1000 ppm) of those two compounds resulted in great

37

improvement in the high-frequency reciprocating rig (HFRR) lubricity tests. For instance, by

38

adding low additive levels of 500 ppm to the ULSD fuel, sufficient lubricity was induced and the

39

wear scar and friction of ULSD was reduced by 40% and 46-47%, respectively. The additive

40

concentrations were 20 and 40 times lower than blending ULSD with biodiesel at 1-2% (w/w).

41

Further, by adding EAME/MA/BU at a level of 1000ppm into other kinds of petrodiesel, such as

42

0150H GP1 Base Oil and 166 POA, wear scar values were reduced by 25% and 26%, respectively.

43


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1. Introduction

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The use of ultra-low-sulfur diesel (ULSD) fuels, as required by regulations in the United

46

States, Europe, and elsewhere, has led to the failure of diesel engine parts such as fuel injectors

47

and pumps because they are lubricated by the fuel itself.1-10 The poor lubricity of ULSD requires

48

additives or blending with another material of sufficient lubricity to regain lubricity.1-11 Blending

49

with another fuel such as biodiesel increases the cost since the recent price of biodiesel is > $4/gal

50

compared to < $3/gal for petrodiesel (in most locations in the United States, 2014, data from U.S.

51

Energy Information Administration). Improvement of lubricity by blending with biodiesel

52

typically requires at least 1% (10000 ppm), or even 2% (20000 ppm), of such fuel. Therefore,

53

economically it is better to enhance the lubricity of ULSD by using additives at low additive levels.

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There is currently a need for efficient additives with relatively low cost for ULSD fuels. Renewable

55

biobased lubricant and biodegradable nanolubricant are gaining growing attention as a means

56

against fossil fuel dependence and towards greener forms of energy resource. Zainala et al and

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Darminesh et al have reviewed the recent development of these areas.12,13

58

In the past a few years, we have worked on development of tung oil-based materials.14-16

59

Here, we report the synthesis of new compounds based on the eleostearic acid obtained from tung

60

oil because of its three conjugated double bonds with more active reactivity. Another reason to

61

select tung oil as starting material is that tung oil is non-edible oil, therefore, there isn’t an issue

62

with food-fuel debate. These new compounds can serve as lubricity-improving additives for

63

ULSD. Thus, as shown in Scheme 1, eleostearic acid methyl ester (EAME) from tung oil gave

64

EAME/MA via a Diels-Alder reaction with maleic anhydride (MA) and subsequent esterification

65

of the MA moiety with a short-chain alcohol, methanol or butanol, gave the compounds termed


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EAME/MA/ME and EAME/MA/BU. The lubricity of neat ULSD and other petrodiesel fuels

67

additized with EAME/MA/ME and EAME/MA/BU were evaluated using the HFRR lubricity test.

68

The high-frequency reciprocating rig (HFRR) (ASTM D-6079, ISO 12156) lubricity tester

69

has been used for lubricity tests because the HFRR method is more user-friendly than other tests

70

and can be pressurized to study the lubricity of fuels.17 The HFRR test is a ball-on-disk method.

71

The wear scar is an average of the major and minor axes of an elliptical contact area. The maximum

72

wear scar on the ball is 460 μm (60 °C) as described in the European petrodiesel standard EN 590,

73

and 520 μm (60 °C) as described in the American petrodiesel standard ASTM D-975. These

74

standards are used to indicate fuels with sufficient lubricity for practical use in a diesel engine,

75

whereas fuels generating wear scars above those limits may or may not be acceptable.

76

2.

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2.1 Materials

Materials and methods

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Tung oil was purchased from Alnor Oil Company, Inc. (Valley Stream, NY, USA). It had a

79

yellow color and a specific gravity of 0.935–0.940 at 25 °C. Maleic anhydride (MA) and p-

80

toluenesulfonic acid monohydrate (PTS), sodium methoxide solution (25% w/w in methanol) were

81

obtained from Sigma-Aldrich Inc. (St. Louis, MO, USA). Tung oil fatty acid esters (EAME) were

82

prepared using a transesterification process reported to convert a vegetable oil into biodiesel,18 also

83

reported in section 2.2. Polyalphaolefin (PAO-6) (Durasyn 166) was received from Ineos

84

Oligomers (League City, TX, USA) with specific gravity, 0.828 g/mL (ASTM D 4052); kinematic

85

viscosity at 40 and 100 °C, 31.13 and 5.91 cSt, respectively (ASTM D 445); pour point, −66 °C

86

(ASTM D 97). Hydrotreated heavy paraffinic mineral oil (Kendex 0150H), a Group I base oil, was

87

obtained from American Refining Group (Bradford, PA, USA) with specific gravity, 0.864 g/mL


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(ASTM D 4052); kinematic viscosity at 40 and 100 °C, 27 and 5.2 cSt, respectively (ASTM D

89

445); pour point, < −9 °C (ASTM D 97); sulfur content, < 300 ppm, ASTM D 5183).

90 91

2.2 Preparation of EAME from tung oil

92

Eleostearic acid and methyl ester were prepared and purified in accordance with

93

reference.16,18 Typically, in a three-neck round-bottom flask fitted with reflux condenser,

94

thermometer and addition port, was added 50 g tung oil and 12 ml methanol. The solution was

95

stirred at 60 °C and 2.78 ml sodium methoxide (25 % w/w in methanol solution) was added, and

96

then allowed to react for 1 h. After cooling to room temperature, 50 ml hexane was added. In a

97

separatory funnel, the reaction was allowed to separate and remove the lower methanol and

98

glycerol layer. The methyl esters were washed with deionized water (DI) three times, or until pH

99

was near neutral. The solution was dried over magnesium sulfate, then filtered and a rotary

100

evaporator was used to remove the hexane and any remaining methanol. The product was termed

101

EAME with yield about 90% (repeatable).

102 103

2.3 Preparation of EAME/MA and esterification with methanol and butanol

104

In the first step, EAME (9.0 g, 30.8mmol) and MA (3.17 g, 32.4 mmol) were placed in a

105

250 mL round-bottom flask equipped with a silicone oil bath and a magnetic stirrer. The mixture

106

was bubbled with N2 for 5 min at room temperature, and then stirred at 150 ℃ for 2 h in N2

107

atmosphere to give a clear, dark yellow and viscous liquid (EAME/MA). In the second step, PTS

108

(180 mg, 2 % w/w to EAME/MA) and methanol (10.0 mL, 247.4 mmol, i.e. molar ratio methanol

109

to EAME/MA 8:1) were added into the reactor. The reaction mixture was stirred and heated to

110

reflux for 3 h, and then excess methanol and produced water were removed through vacuum-rotary


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evaporation procedure. 10.0 mL fresh methanol was added, and the same operation repeated twice.

112

Eventually the final product, methylated EAME/MA, was obtained through neutralization, water

113

wash, separation and vacuum drying. The product was termed EAME/MA/ME. The

114

EAME/MA/BU was prepared in the same procedure using butanol instead of methanol.

115 116

2.3 Lubricity determination

117

Lubricity determinations were performed at 60 °C (controlled to 1 °C), according to the

118

standard method ASTM D-6079,19 with an HFRR lubricity tester obtained from PCS Instruments

119

(London, England) via Lazar Scientific (Granger, IN). Controlling the humidity to 30-50% is

120

necessary for the HFRR test to give reproducible results20 which was accomplished here,

121

according to the standard19 with a potassium carbonate bath (50% humidity). In addition to the

122

usual wear scar data of the HFRR ball, we report the friction data (which involves the coefficient

123

of friction21 and film data (which involves the electrical resistance21 recorded by the software)

124

during the experiments.

125 126

3.

Results and Discussion

127

3.1 Characterization of EAMA/MA/ME and EAMA/MA/BU

128

Chemically modified tung oil fatty acid methyl ester (EAME), the maleation product,

129

EAMA/MA and the esterification products, EAME/MAME and EAMA/MA/BU, were

130

characterized by FT-IR, 1H NMR, and 13C NMR, spectra as shown in Figs. 1, 2, and 3, respectively.

131

In the FT-IR spectra of Figure 1, the EAME/MA, the strong peak observed at 1055 cm-1

132

was assigned to the double bond C-H bending of MA. The strong band at 993 cm-1 can be attributed

133

to the conjugated double bonds of tung oil and EAME, but this band shows a weak absorption of


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EAME/MA and EAME/MA/esters (such as methyl ester and butyl ester in the bio-lubricant) due

135

to the maleation reaction. The typical anhydride C=O stretching of MA was found at 1849 and

136

1776 cm-1 for EAME/MA, but these two peaks almost disappeared after esterification, with the

137

ester C=O stretching peak at 1720 cm-1 becoming strong as seen in EAME/MA/ester spectra. All starting materials and final products were also examined by 1H NMR (Figure 2) and

138 139

13C

NMR (Figure 3). No peak existed at 7.1 ppm in the 1H NMR spectrum of the EAMA/MA,

140

indicating that no unreacted MA was left after purification. New bands appeared around 3.5 ppm,

141

which represent the protons at the structures where MA attached onto EAME. Secondly, the bands

142

at 5.3–6.4 ppm, which correspond to the protons on the conjugated triene structures of EAME,

143

decreased significantly due to the maleation reaction between MA and the C=C bonds on the

144

EAME chain. In the

145

which represent the connection between MA and the EAME chain. The peaks at 126-136 ppm

146

denoting the C=C bonds on EAME chains also decreased significantly. Finally, two peaks at

147

around 172–174 ppm, which denote the carbonyl carbons on the attached anhydride groups,

148

appeared at EAME/MA esters but disappeared at EAMA/MA esters, i.e., (EAME/MA/ME and

149

EAME/MA/BU) because of esterification. All results indicate that MA grafted onto EAME

150

effectively and esterification products were confirmed.

13C

NMR spectrum (Figure 3), new band signals appeared at 44-48 ppm,

151 152

3.2 Lubricity

153

Lubricity was assessed using the ASTM D-6079 (HFRR) method at 60 °C. Table 1 gives

154

the wear scar values of the ULSD and ULSD with additives. Lubricity, as determined per the

155

HFRR test, can be evaluated using the lubricity specification in the petrodiesel standard ASTM

156

D975. The low-lubricity ULSD used here exhibits poor lubricity in the neat form (Table 1) with


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wear scar values of 550 μm and 530 μm with two runs (standard error with ± 2%) . The neat

158

samples of EAME/MA/ME and EAME/MA/BU in Table 1 showed excellent lubricity, as

159

demonstrated by the low wear scar values, about 100 μm and 200 μm, respectively. These results

160

prompted us to prepare samples in which, initially, 100 ppm, 500 ppm and 1000 ppm of

161

EAME/MA/ME and EAME/MA/BU were added to the low-lubricity ULSD fuel. The effect of the

162

lubricity additives in ULSD is clearly visible. Both samples clearly perform extremely well.

163

Adding the samples at 500 ppm appears to induce sufficient lubricity to low-lubricity ULSD fuel.

164

The additives reduced the wear scar values of ULSD by 40%. There appears to be little to no

165

advantage in applying at a 1000 ppm level. On the other hand, for friction data, the 1000 ppm level

166

performs a little better than the 500 ppm level, as it was reduced by 46% and 47%, respectively.

167

The results are in accordance with the report that vegetable oils have excellent lubricity.22 This is

168

because polar ester groups in vegetable oils are able to adhere to metal surfaces and, therefore,

169

possess good boundary lubrication properties. Here, the EAMA/ME and EAME/MA/BU also are

170

fatty acid with short chain esters.

171

Lubricity for the other two diesel fuels, PAO-6 and Kendex 0150H with EAME/MA/ME

172

and EAME/MA/BU as additives were also tested. The HFRR results are shown in Table 2. With

173

1000 ppm of EAME-MA-BU, the wear scar values are reduced 25% and 26% for 0150H GP1

174

Base Oil and 166 POA, respectively. However, the EAME-MA-ME reduced wear scar 11.0% and

175

29.0% for 0150H GP1 Base Oil and 166 POA, respectively. The EAME-MA-ME responded better

176

for 166 POA than for 150H GP1 Base Oil.

177

The present results not only show that EAME/MA/ME and EAME/MA/BU have excellent

178

lubricity, as demonstrated by very low wear scar values, but, as additives, both effectively reduced

179

the wear scar values of ULSD and other diesel fuels.


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4.

Conclusions

182

(a) Tung oil-based methyl ester EAME and maleation compound of EAME, i.e., EAME/MA

183

were synthesized by the transesterification of tung oil with methanol and by reacting with

184

maleic anhydride via the Diels–Alder reaction. The formed cyclic anhydrides have been

185

successfully reacted with short chain alcohols, methanol and butanol, to form the esters,

186

i.e., EAME/MA/ME and EAME/MA/BU.

187

(b) The synthesized EAME/MA/ME and EAME/MA/BU compounds were characterized by

188

FT-IR and NMR spectroscopies to confirm the MA attached to EAME and structures of

189

methanol and butanol esterification of MA cyclic anhydride.

190

(c) EAMA/MA/ME and EAME/MA/BU at low additive level significantly improved the

191

lubricity of ULSD. Adding 500 ppm to low-lubricity of ULSD decreased the wear scar and

192

friction in the HFRR test by 40 to 47%, respectively. The additive concentrations are 20

193

and 40 times lower than blending of ULSD with biodiesel at 1-2% (w/w).

194 195

(d) EAME/MA/BU at low additive level of 1000 ppm into 0150H GP1 Base Oil and 166 POA would reduce wear scar by 25% and 26%, respectively.

196 197 198 199

Acknowledgments The authors thank Mr. Kevin R. Steidley and Daniel A. Knetzer for technical support.

200


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Knothe, G.; Dunn, R. O. Biofuels Derived from Vegetable Oils and fats. In: Gunstone FD, Hamilton RJ, editors. Oleochemical Manufacture and Applications. Sheffield UK: Sheffield Academic Press; 2001, p. 106-163. Standard Test Method for Evaluating Lubricity of Diesel Fuels by the HighFrequency Reciprocating Rig (HFRR), ASTM D-6079-99, 1999 ASTM Annual Book of Standards, American Society for Testing and Materials, West Conshohocken, PA. Nikanjam, M.; Burk, E. Diesel Fuel Lubricity Additive Study. SAE Tech. Pap. Ser. 1994, 942014. Crockett, R. M.; Derendinger, M. P.; Hug, P. L.; Roos, S. Wear and Electrical Resistance on Diesel lubricated Surfaces Undergoing Reciprocating Sliding. Tribol Lett. 2004, 16, 187-194. Erhan, S. Z.; Sharma, B. K.; Perez, J. M. Oxidation and Low Temperature Stability of Vegetable Oil-based Lubricants. Ind. Crop Prod. 2006, 24, 292–299.

256 257 258 259 260 261 262 263 264 265 266 267 268 269 270 271 272 273 274 275 276 277 278 279 280 281 282 283 284 285 286


289

290

291

292


***Reduction 47%

**Reduction 46%

*Reduction 40%

EAME-MA-BU Neat

EAME-MA-ME Neat

EAME-MA-BU 1000 ppm

EAME-MA-BU 500 ppm

EAME-MA-BU 100 ppm

EAME-MA-ME 1000 ppm

EAME-MA-ME 500 ppm

EAME-MA-ME 100 ppm

Avg. 550 530 487 520 278 360* 325 329 482 522 316 289* 266 290 91 108 205 193

Disc X 540 585 535 564 321 407 400 389 514 546 372 318 312 372 80 85 296 270

Disc Y 1318 1272 1264 1295 1117 1167 1110 1125 1231 1255 1130 1112 1053 1081 1082 968 1022 1010

Results Film % 9 10 14 16 83 68 74 77 12 12 71 87 89 86 97 93 79 87 Friction 0.448 0.408 0.373 0.353 0.343 0.255 0.233 0.232** 0.382 0.405 0.242 0.219 0.231 0.220*** 0.065 0.066 0.135 0.125

287 288

Sample ID ULSD neat

Wear Scars (μm) Ball X Ball Y 557 542 559 500 515 458 555 485 279 277 390 330 371 278 377 281 513 451 559 484 348 283 321 257 304 227 337 242 98 83 116 99 252 157 243 142

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

HFRR (60oC)

Page 13 of 18 Energy & Fuels

12

Table 1 High-frequency reciprocating rig (HFRR) data of petrodiesel and with additives.

206 271 263 287 263 176 172

257 305 317 339 327 261 286

220

282

297 131

256 125

274 267

317 259

286 259

330 316

288 277

230 253

264 301

314 319

217 255

298 304

290 281 280

272 259

309 308

320 312 313

299 293 291

293 284 269

304 301 313

ACS Paragon Plus Environment 229 (26%)

285

1027

93

68 94

64 69

90 52

58 91

47 59

42 42 64

86

80 92

61 76

89 72

82 81

77 75

64 63 72

Results Film %

0.194

0.216 0.193

0.215 0.216

0.189 0.231

0.226 0.198

0.246 0.224

0.256 0.261 0.217

0.196

0.211 0.195

0.221 0.205

0.194 0.212

0.197 0.204

0.203 0.205

0.215 0.213 0.211

Friction

High-frequency reciprocating rig (HFRR) data of polyalphaolefin (PAO-6) and Kendex 0150H and with additives.

1102 1025

1079 1130

1036 1093

1098 1039

1110 1095

1099 1092 1108

1044

1073 1025

1124 1135

1095 1094

1053 1089

1089 1099

103 1108 1096

Disc Y

294 295

322 254

270 328

299 269

303 262

295 303

281 294 262

301

270 299

303 319

266 276

321 284

302 331

275 288 296

Disc X

Table 2

295 219 (redu.)

290 313

232 (29%) 288

307 195 (redu.)

301 298

305 297 297

251 (25%)

265 196 (redu.)

308 288

247 (11%) 277

258 280 (redu.)

291 284

Avg.

293

.***Reduction 47%

Durasyn 166 POA +100 ppm EAME-MAME Durasyn 166 POA +500 ppm EAME-MAME Durasyn 166 POA +1000 ppm EAME-MAME Durasyn 166 POA +100 ppm EAME-MABU Durasyn 166 POA +500 ppm EAME-MABU Durasyn 166 POA +1000 ppm EAME-MABU

Durasyn 166 POA - neat

0150H GP1 Base Oil +100 ppm EAME-MAME 0150H GP1 Base Oil +500 ppm EAME-MAME 0150H GP1 Base Oil +1000 ppm EAME-MAME 0150H GP1 Base Oil +100 ppm EAME-MABU 0150H GP1 Base Oil +500 ppm EAME-MABU 0150H GP1 Base Oil +1000 ppm EAME-MABU

Sample ID 0150H GP1 Base Oil neat

Wear Scars (µ) Ball X Ball Y

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

HFRR (60°C)

Energy & Fuels Page 14 of 18

13

Page 15 of 18 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

Energy & Fuels

14 296 297 298 299

Scheme 1. The synthesis route of EAME/MA and its esters.

300 301 302 303 R

R

+

O

O

O

Diels-Alder Reaction

R Alkyl alcohol O

Maleic anhydride

O R' O R' O

FAME

304

R = Methylester

R' = CH3 , or CH3CH2CH2 CH2

305


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

Page 16 of 18

15 306 307

Figure 1. FT-IR spectra of tung oil, EAME, EAME/MA and its ester.

308 309


Page 17 of 18 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

Energy & Fuels

16 310 311

Figure 2. 1H NMR spectra of AME, EAME/MA, EAME/MA/ME and EAME/MA/BU.

Tung-oil-EAME-001

EAME-MA

Tung-oil-EAME-MA-But

Tung-oil-EAME-MA-ME

312 313

7.0

6.5

6.0

5.5

5.0

4.5

4.0

3.5 PPM

3.0

2.5

314


2.0

1.5

1.0

0.5

0.0

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

Page 18 of 18

17 315

Figure 3.

13C

NMR spectra of EAME, EAME/MA, EAME/MA/ME and EAME/MA/BU.

Tung-oil-EAME

EAME-MA Tung-oil-EAME-MA-But

Tung-oil-EAME-MA-ME

316 317 318

180

170

160

150

140

130

120

110

100

90 PPM

80

70


60

50

40

30

20

10

0

Improvement of diesel lubricity by chemically modified tung oil-based

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