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Methylation of Glycerol with Dimethyl Sulfate to Produce a New Oxygenate Additive for Diesels
Jyh-Shyong Chang, Yu-Da Lee, Lawrence Chao-Shan Chou, Tzong-Rong Ling, and Tse-Chuan Chou
Ind. Eng. Chem. Res., Just Accepted Manuscript DOI: 10.1021/ie201612t Publication Date (Web): 06 Dec 2011 Downloaded from http://pubs.acs.org on December 7, 2011

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Methylation of Glycerol with Dimethyl Sulfate to Produce a New Oxygenate Additive for Diesels

Jyh-Shyong Changa*, Yu-Da Leea, Lawrence Chao-Shan Choub, Tzong-Rong Lingc, and Tse-Chuan Choua,d

Department of Chemical Engineering, Tatung University, 40 Chungshan North Road, 3rd

Sec., Taipei, Taiwan, ROC


b

Department of Chemical Engineering, Case Western Reserve University, Cleveland, OH

44106, USA
c

Department of Chemical Engineering, I-Shou University, 1, Section 1, Hsueh-Cheng

Road, Ta-Hsu Hsiang, Kaohsiung 84008,, Taiwan, ROC


d

Department of Chemical Engineering, National Cheng Kung University, Tainan 701,

Taiwan, ROC * Author to whom correspondence should be addressed Telephone number: +886-2-1822928-6266 Fax number: +886-2-5861939 E-mail: jschang@ttu.edu.tw

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Abstract

A new oxygenate additive for diesels (bio or petroleum) was manufactured using glycerol, dimethyl sulfate (DMS), and sodium hydroxide pellets as raw materials. By feeding the dimethyl sulfate into the batch reactor containing the sodium glycerate, a semibatch mode operation enhanced the effective methylation of glycerol. A conventional stirred tank reactor that can produce large quantities of oxygenate additives under a normal atmospheric pressure operation became the main feature of the methylation process. With a 3:2 molar ratio of DMS to glycerol, a 3:1 molar ratio of sodium hydroxide to glycerol, a 0.43:1 molar ratio of water to sodium hydroxide, and a temperature of 343 K at the reaction time of 24 hours with the feeding time of DMS under 12 hours, the conversion of glycerol (93.5%) and a combined yield of GDMEs and GTME of 71.2% were achieved for a once-through operation. A product mixture of GDME (20 wt%) and GTME (80 wt%) served as a new oxygenate additive for (bio or petroleum) diesels.

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1. Introduction Oxygenates are used as additives for both gasoline and diesel. The gasoline oxygenates are added to enhance the octane rating of internal combustion engines and to reduce air pollution by ensuring a more complete fuel combustion in the engines. Meanwhile, the use of oxygenated compounds with diesel is designed to reduce harmful exhaust emissions, namely particulates, and sometimes NOx as well.1 The two main families of oxygenated additives are alcohols and ethers. Alcohols are less interesting because they have several drawbacks1,2 such as high water solubility, high Reid vapor pressure (RVP), high volatility, high latent heat of vaporization, and a low heating value. These drawbacks result in phase separation problems: clogging of the fuel flow, increase of the volatile organic compound emissions, cold startup and drivability issues, and a low heating value. By contrast, ethers, aside from retaining all the benefits of alcohols without any separation problems, give high octane numbers, enhance gasoline combustion, and reduce CO emissions.1 Oxygenate utilization, used to produce cleaner burning diesel fuels, has been noted for over fifty years. Diethylene glycol dimethyl ether (DGM) and dibutyl ether (DBE) are known as diesel cetane enhancers.1 In recent years, tert-butyl ethers of glycerol with a high content of di-ethers produced by the etherification of glycerol with isobutylene or tert-butyl alcohol using homogeneous or solid acid catalysts have been considered promising as oxygenate additives for diesel fuels.3-8 The etherification of glycerol with ethanol over solid acid catalysts can transform glycerol into monoalkyl glyceryl ethers (MAGEs). MAGEs are interesting intermediates for the production of various chemicals, among them dioxolane.9 With the objective of introducing new large-scale processes based on glycerol transformation, dioxanes and dioxolanes can be interesting targets, serving as excellent candidates to be used as co-fuels for the diesel fraction.9 The

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etherification of glycerol with methanol to produce glycerol mono-methoxy ethers (GMMEs), di-methoxy ethers (GDMEs), and tri-methoxy ether (GTME) as a green solvent can be found in the work of Garci et al.10 3-methoxy-1,2-propanediol (CAS 623-39-2), 2-methoxy-1,3-propanediol (CAS 761-06-8) are the isomers of GMME; 1,3 or 2,3-dimethoxy-1-propanol (CAS 40453-77-8); 1,3-dimethoxy-2-propanol (CAS 623-69-8) are the isomers of GDME, and 1,2,3-trimethoxypropane (20637-49-4)) is GTME. Nevertheless, the possible oxygenate additive composed of glycerol di-methoxy ethers and tri-methoxy ether for gasoline or diesel fuels have not been developed. GMME is a promising cryoprotector in the low-temperature preservation of blood cells, bone marrow, and reinoculated cell cultures.11 The production of the mixture of GDMEs and GTME as oxygenate additive is promising,12-16 because the feedstock of methanol is much cheaper than that of isobutylene or tert-butyl alcohol and a large amount of glycerol is being produced during the transesterification of fatty acids into biodiesel. The etherification reactions addressed above are generally operated under the autogenic pressure in an autoclave. Depending on the reacting component (methanol, ethanol, isobutylene or tert-butyl alcohol) involved in the reaction with glycerol, the operating pressure ranges from several to around 100 atmospheric pressures. The requirement of an autoclave to carry out these etherification reactions of glycerol will hinder the production of a large quantity of the reacting medium, for an autoclave is normally very expensive. Hence, the methylation of glycerol with alcohol using a suitable methylation agent is deemed to be another synthetic route to produce the oxygenate additive, because the methylation reaction is typically operated under normal atmospheric pressure and thus a large quantity of the reacting medium can easily be processed in a conventional stirred tank reactor. Procedures for preparing GMMEs were addressed in the work of Koshchii11 involving preparations of sodium glycerate from equimolar amounts

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of anhydrous glycerol and powdered NaOH, followed by alkylation with alkyl halides to obtain glycerol 1-monoalkyl ethers. We performed experiments to refine the conditions for preparing the mixture of GDMEs and GTME as an oxygenate additive to gasoline or diesel. Our goal was to find the methods and conditions that would ensure the highest yield of the target products with the simpler possible procedure. For the route to GDMEs and GTME, we chose the methylation of glycerol with dimethyl sulfate (DMS) in the presence of alkali. It seemed appropriate to refine the effects of the synthesis parameters (reaction time, reaction temperature, molar ratio of sodium hydroxide to water, and DMS feeding time) on the yield and isomeric composition of the product. In the following section, the main properties of the mixture of GDMEs and GTME as a new oxygenate additive are introduced. Section 3 presents the experimental system including glycerol methylation, product separation procedure, and product analysis. Section 4 gives the main experimental results and discussion. Finally, the conclusions are presented. 2. Main Properties of the Mixture of GDMEs and GTME as a New Oxygenate Additive The laboratory of Chinese Petroleum Company (CPC) in Taiwan analyzes the collected product of GDMEs (20 wt%) and GTME (80 wt%) mixture. The product properties are being used to compare with the existing diesel cetane enhancers DGM and DBE, shown in Table 1. From the comparison, we conclude that the product mixture of GDMEs (20 wt%) and GTME (80 wt%) can serve as a new oxygenate additive for diesels (bio or petroleum). 3. The Experimental Section 3.1. Glycerol Methylation and Product Separation Procedure. The synthesis of GDMEs and GTME involved the following steps: (1) mixing glycerol with NaOH and

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H2O in the molar ratio NaOH : glycerol

= 3 : 1, NaOH : H2O =

2.35 : 1; (2) reflux

under reduced pressure (130 mm Hg) on an oil bath, with the bath temperature gradually increased to 70 for half an hour; (3) adding DMS to the resulting sodium glycerate (GONa) at 70 over a period of 5 h in the molar ratio DMS : glycerol = 3 : 2; (4) removing Na2SO4 from the reaction mixture; (5) distilling the product mixture of CH3OH, H2O, GDMEs and GTME from the bottoms at 180 o C /130 mm Hg; (6) extracting
GDMEs and GTME form the product mixture obtained in step 5 with chloroform in the volume ratio CHCl3 : product mixture = 1.5 : 1 overnight; and (7) distilling the extracted phase to remove chloroform at 90 o C /130 mm Hg to obtain the final product mixture GDMEs and GTME. The total yield of the final product mixture was 31.8 %.

3.2. Product Analysis. A gas chromatograph, CHINA GC2000, which was provided
with a capillary column Varian CP9210 (l, 30 m; i.d., 0.32 mm; film thickness, 0.5 mm) under the oven temperature program from 40 to 250 o C (with a heating rate of 10 o C min-1) and at 250
o

C for 3 min, analyzed the sample of the reaction products.

0.2 l of the sample was injected manually. Each data set was obtained with an accuracy of 2.5% from an average of three independent measurements, using the internal
standard method (n-butanol, 2 wt.% in respect to the sample). Water content was measured with the Karl Fisher Titrator, MKS-500. For quantification of the reaction product, the GDMEs and GTME components were separated and used as the standards. The standard 3-methoxy-1,2-propanediol (one isomer of GMMEs) was purchased from Alfa Aesar. The way to obtain pure GDMEs and GTME components and characterization of these two standards are summarized in the Appendix. The glycerol conversion is defined as
XG = ( N Go N G ) N Go

(1)

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and the yield of glycerol ethers is defined as

YPi =

N Pi NG0

(2)

where X G is the conversion of glycerol (mol %); YPi ( Pi represents GMMEs (i=1), GDMEs (i=2), and GTME (i=3)) is the yield of different glycerol ethers (mol %); N G0 and N G are the amounts of starting glycerol (mol) and the resulting glycerol (mol), respectively; N Pi is the total amount of glycerol ethers (mol).

4. Results and Discussions


When the methylation of glycerol with DMS synthesized the glycerol ether in the presence of NaOH, the sodium glycerate reacted with DMS, and five glycerol ether isomers were potentially produced including two GMMEs (3-methoxy-1,2-propanediol and 2-methoxy-1,3-propanediol), two GDMEs (1,3-dimethoxy-2-propanol and 2,3dimethoxy-2-propanol), and one GTME (1,2,3-trimethoxypropane), as shown in Figure 117. The GDMEs and GTBE were the desired products in this reaction. While, methanol and sodium sulfate were the by-products. All the experimental data shown in the following figures were the average of duplicative experiments.

4.1. Effects of Reaction Times. To study the influence of reaction time on the glycerol
methylation reaction, experiments using the same loading velocity of DMS were implemented at 6, 12, 24, and 48 h. Minor variations in the conversion of glycerol are observed in Figure 2(a); at the reaction time of 6, 12 and 24 h, the conversion of glycerol reached 97%; but, at the reaction time of 48 h, the conversion dropped slightly to 96%. However, the reaction time influenced the yield of glycerol ethers. In the mixture of glycerol ethers, the yield of GMMEs obviously decreased from the reaction hour of 12 to 24 but the yield of GMMEs maintained at the hour of 48 (Figure 2(b)). The yield of GDMEs decreased from the reaction hour of 6 to 24 and GTME manifested the opposite

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tendency with respect to the yield of GDMEs (Figure 2(a) and 2(b)). The methylation of glycerol in this work was aimed at the combined yield of GDMEs and GTME; therefore, the target performance of the process is conspicuously treated in the figures. Figure 2 (a) shows the combined yield of GDMEs and GTME and Figure 2 (b) displays the yields of GMMEs and GDMEs at the end of the reaction stage (step (3) described in Section 3.1) and the separation stage (step (7)), respectively. The yield of GTME at the end of the reaction increased as the reaction time increased, but the combined yield of GDMEs and GTME at the end of the reaction reached the maximum (75.5%) at the time of 24 h and dropped slightly at the time of 48 h. However, the maximal combined yield of GDMEs and GTME at the end of the extraction and separation was reduced to 31.8%, because the high solubility of GDMEs in the aqueous phase of the product mixture hindered the recovery of GDMEs in the non-aqueous phase of the adopted solvent (chloroform) during the extraction and distillation. These results can be explained as follows: The glycerol methylation reaction was comprised of consecutive reversible steps: first, in the presence of aquous NaOH, glycerol transformed into sodium glycerate. Consecutive reversible reactions between sodium glycerate and DMS led to GMMEs, GDMEs, and GTME (Figure 1). The transformation of GMMEs, GDMEs and GTME was enhanced with the increase of the reaction time. However, the possible side reaction between DMS and H2O reduced the availability of DMS (Figure 1); the maximal combined yield of GDMEs and GTME occurred at 24 h rather than at 48 h. The presence of methanol in the product mixture confirmed the occurrence of this side reaction. Considering the purpose of the optimization was to obtain a high glycerol conversion and a high combined yield of GDMEs and GTME, 24 h was thus considered as a suitable reaction time in this experimental system.

4.2. Effects of Reaction Temperatures. To study the influence of the reaction

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temperature on the glycerol methylation reaction, experiments were conducted at 323, 343, 363, and 383 K. As shown in Figure 3(a), the conversion of glycerol increased with the increase of temperature from 50 o C to 110 o C but showed little conversion at 323 K; by contrast, a near complete conversion of glycerol (97%) was obtained at 343 K after 24 h. Nevertheless, the results showed that the conversion exhibited a decrease from temperature 70 to 90 o C and also at 110 o C . As is also shown in Figure 3(b), the yield of GMMEs increased from 50 o C to 110 o C ; that of GDMEs increased from 50 o C to 70 o C and then dropped at 90 o C and increased at 110 o C ; that of GTME increased from 50 o C to 70 o C and then fell from 70 o C to 110 o C (Figure 3(a) and 3(b)). In Figure 3(a), the combined yield of GDMEs and GTME reached the maximum (75.5%) at the end of the reaction and at the end of the extraction and separation dropped to 31.8% at 70 o C . In general, a comparatively higher temperature normally initiates a higher reaction rate. Because a higher temperature could enhance the back-reactions 1, 3, an 5 shown in Figure 1, which would lead to an decrease in the formations of GTME as shown in Figure 3(a) and 3(b). In the mean time, the reaction between DMS and H2O is an undesired side reaction that also depends on reaction time and temperature. Higher reaction temperature would promote this side reaction which would consume a large amount of DMS and might influence the glycerol conversion and yield of GTME. Based on these considerations, 70 o C was chosen as the optimizing temperature.

4.3. Effect of Molar Ratio of Water to Sodium Hydroxide. From the proposed overall
reaction network for the methylation of glycerol (Figure 1), water is a detrimental factor to the production of the ethers due to the reversible reactions 1, 3, 5, and 7 shown in Figure 1. However, enough initial loading of water could dissolve sodium hydroxide pellets properly and facilitate the mixing of the dissolved sodium hydroxide with the rest of reactants. Therefore, the effect of the H2O to NaOH molar ratio on the methylation

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reaction was studied using four different ratios in the range from 0 (anhydrous) to 2.78. As shown in Figure 4(a), the glycerol reached a constant conversion (97 0.5 %) and the yield of GDMEs and GTME in the glycerol ether mixture decreased with an increase in the molar ratio from 0.43 to 2.78. With a further decrease in the molar ratio from 0.43 to 0 (anhydrous), the reaction ceases to occur, because anhydrous glycerol cannot dissolve any sodium hydroxide pellet. The yield of GTME decreased at the end of the reaction as the molar ratio of H2O to NaOH increased, and the combined yield of GDMEs and GTME reached the maximum (75.5%) at the end of the reaction under the molar ratio of 0.43 (Figure 4(a) and 4(b)). However, the maximal combined yield of GDMEs and GTME at the end of extraction and separation reduced to 31.8%, because the high solubility of GDMEs in the aqueous phase of the product mixture reduced the recovery of GDMEs in the non-aqueous phase of the adopted solvent (chloroform) during extraction and distillation. Basing on these considerations, the molar ratio of H2O to NaOH (0.43) was chosen as the optimizing initial water loading.

4.4. Effects of the Feeding Time of Dimethyl Sulfate. The feeding time of DMS is one
of the important factors influencing the reaction rate, for this highly exothermic reaction favors a semibatch operation. Therefore, the effect of the feeding time of DMS on the glycerol methylation reaction was investigated with various feeding time intervals of DMS in the range from 1 to 23 h. A short feeding time means a high feed rate. As

shown in Figure 5(a), the conversion of glycerol climbed with the increasing feeding time at the hour of 1 and 5; then it dropped and maintained at 93.5% from hour 12 to hour 23. The highest conversion was obtained when the feeding time of DMS was hour 5. The combined yield of GDMEs and GTME reached 75.5% at the end of reaction and dropped to 31.8% at the end of the extraction and separation reduced under the feeding time of DMS (5 h) as depicted in Figure 5 (a). However, a higher combined yield of GDMEs and

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GTME (34.5 %) at the end of the extraction and separation reduced under the feeding time of DMS (12 h) can be observed. Under this feeding time of DMS (12 h), more GTME was produced than that operated under 5 h feeding time and more GDMEs and GTME were extracted and separated as depicted in Figure 5 (a). For the lowest feed rate of DMS (the feeding time 23 h), the side reaction (reaction 7 depicted in Figure 1) reduced the availability of DMS. The results of the reactions characterized by low yield of GTME are shown in Figure 5(a). Therefore, the optimizing feeding time of DMS for this experimental system was found to be 12 h. Figure 5(b) displays the yield variations of GMMEs and GDMEs over the DMS feeding time. For the lowest feed rate of DMS (the feeding time 23 h), the highest yield of GMMEs results in the low yield of GDMEs and GTME (Figure (a)).

5. Conclusions
The methylation of glycerol with DMS in the presence of alkali under an optimizing condition produces the product mixture of GDMEs (20 wt%) and GTME (80 wt%). This mixture serves as a new possible oxygenate additive for diesels (bio or petroleum). The properties of this new oxygenate additive for diesels are comparable to those of DGM and DBE. A normal atmospheric pressure operation of the methylation of glycerol with dimethyl sulfate is the main feature that large quantities of oxygenate additive can easily be manufactured in a conventional stirred tank reactor. The conversion of glycerol (93.5%) and the combined yield of GDMEs and GTME (71.2%) were obtained using a 3:2 molar ratio of dimethyl sulfate to glycerol, a 3:1 molar ratio of sodium hydroxide to glycerol, a 0.43:1 molar ratio of water to sodium hydroxide, and a temperature of 343 K under the reaction time of 24 h with the feeding time of dimethyl sulfate under 12 h. The maximal combined yield of GDMEs and GTME at the end of the extraction and separation fell to 34.5% for a once-through operation. The

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recycle of GMMEs and GDMEs could further improve the yield of the final products.

Acknowledgments
Financial support from the National Science Council (Grant NSC

98-3114-E-036-001) is gratefully acknowledged.

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Appendix: Preparation and Identification of the Standards for GDMEs and GTME
A preparation of the standards for GDMEs and GTME involved the following steps: (1) Mix the final product mixture obtained in Section 3.1 with CHCl3 and H2O in the volume ratio CHCl3 : product mixture = 1 : 1 and H2O : product mixture = 2 : 1; (2) Separate the aqueous phase and non-aqueous phase first, and then identify whether the components of GDMEs still exist in the non-aqueous phase using GC analysis. If the non-aqueous phase still contains GDMEs, remove the aqueous phase and go back to step (1); (3) Distill the non-aqueous phase containing CHCl3 and GTME to obtain pure GTME from the bottoms at 110 o C /130 mm Hg; (4) Distill the collected aqueous phase containing H2O and GDMEs to obtain pure GDMEs from the bottoms at 100 o C /130 mm Hg. The corresponding GC analyses of the final reaction mixture of the purified GTME and GDMEs are presented in Figures A1-A3. The standard GMMEs was purchased from Alfa Aesar and its GC analysis is shown in Figure A4.

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Caption of Table Table 1. Comparison of Main Properties of the New Oxygenate Additive with the Existing Additives Caption of Figures Figure 1. The proposed overall reaction network for the production of GMMEs, GDMEs
and GTME from glycerol and DMS.

Figure 2. The influence of the reaction time on (a) the conversion X G and the combined
yield of Yf, GDMEs and Yf, GTME . Reaction conditions: reaction temperature, 343 K; H2O/NaOH molar ratio, 0.43; feeding time of DMS, 5 hr and (b) the yields of the desired products at the end of reaction ( YGMMEs and YGDMEs ) and at the end of extraction and separation ( Yf, GMMEs and Yf, GDMEs ) (glycerol, 0.435 mole; DMS/glycerol molar ratio, 1.5; NaOH/glycerol molar ratio, 3).

Figure 3.

The influence of the reaction temperature on (a) the conversion X G and the

combined yield of Yf, GDMEs and Yf, GTME . Reaction conditions: reaction time, 24 hr; H2O/NaOH molar ratio, 0.43; feeding time of DMS, 5 hr and (b) the yields of the desired products at the end of reaction ( YGMMEs and YGDMEs ) and at the end of extraction and separation ( Yf, GMMEs and Yf, GDMEs ) (glycerol, 0.435 mole; DMS/glycerol molar ratio, 1.5;

NaOH/glycerol molar ratio, 3).

Figure 4. The influence of the molar ratio of H2O/NaOH on (a) the conversion X G and
the combined yield of Yf, GDMEs and Yf, GTME . Reaction conditions: reaction time, 24 h; reaction temperature, 343 K; feeding time of DMS, 5 hr and (b) the yields of the desired products at the end of reaction ( YGMMEs and YGDMEs ) and at the end of extraction and separation ( Yf, GMMEs and Yf, GDMEs ) (glycerol, 0.435 mole; DMS/glycerol molar ratio, 1.5;

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NaOH/glycerol molar ratio, 3).

Figure 5. The influence of the DMS feeding time on (a) the conversion X G and the
combined yield of Yf, GDMEs and Yf, GTME . Reaction conditions: reaction time, 24 h; reaction temperature, 343 K; H2O/NaOH molar ratio, 0.43 and (b) the yields of the desired products at the end of reaction ( YGMMEs and YGDMEs ) and at the end of extraction and separation ( Yf, GMMEs and Yf, GDMEs ) (glycerol, 0.435 mole; DMS/glycerol molar ratio, 1.5; NaOH/glycerol molar ratio, 3).

Figure A1. Exemplary GC chromatographic analysis. 1-methanol; 2-n-butanol; 3-1,2,3-trimethoxypropane; 4-1,3-dimethoxy-2-propanol; 5-2,3-dimethoxy-1-propanol; 6-3-methoxy-1,2-propanediol; 7-2-methoxy-1,3-propanediol; 8-glycerol. Figure A2. Exemplary GC chromatographic analysis. 1-1,2,3-trimethoxypropane. Figure A3. Exemplary GC chromatographic analysis. 1-1,2,3-trimethoxypropane; 2-1,3-dimethoxy-2-propanol; 3-2,3-dimethoxy-1-propanol. Figure A4. Exemplary GC chromatographic analysis. 1-1,3-dimethoxy-2-propanol; 2-2,3-dimethoxy-1-propanol; 3-3-methoxy-1,2-propanediol.

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Table 1. Comparison of Main Properties of the New Oxygenate Additive with the Existing Additives

Oxygenates of this work* GDMEs CAS No. Chemical formula Chemical structure 623-69-8 40453-77-8 GTME 20637-49-4

Existing Oxygenates1 DGM 11-96-6 C6H14O3 (CH3OCH2CH2)2O DBE 142-96-1 C8H18O (C4H9)2O

Molecular weight, kg/kmol Normal boiling point, K Density, kg/m3 Heat of combustion, J/kg Flash point, K Lower flammability limit, %vol Autoignition temperature, K Cetane number Lower heating value, kJ/g

C5H12O3 C5H12O3 C6H14O3 (CH3OCH2)2CHOH CH3OCH2CH(OCH3)CH2OH (CH3OCH2)2CHOCH3 120 120 134 442 453 421 968 -2.74107 322 1.47 58 25.12

134 435 937 -2.52107 343 1.2 112 24.5

130.2 414 764 -3.80107 298 1.5 467 91-100 -

*: The oxygenates mixtures are composed of GDMEs (20 wt%) and GTME (80 wt%)

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Figure 1. The proposed overall reaction network for the production of GMMEs, GDMEs and GTME from glycerol and DMS.17

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(a)
100
XG

Conversion and yield (%)

YGDMEs+GTME

80

Yf,GDMEs+GTME

60

40

20

(b)

0 0 60
YGMMEs

12

24

48

50

Yf,GMMEs YGDMEs Yf,GDMEs

40

Yield (%)

30

20

10

Time (h)
0 0 6 12 24 48

Time (h)

20
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Figure 2. The influence of the reaction time on (a) the conversion X G and the
combined yield of Yf, GDMEs and Yf, GTME . Reaction conditions: reaction temperature, 343 K; H2O/NaOH molar ratio, 0.43; feeding time of DMS, 5 hr and (b) the yields of the desired products at the end of reaction ( YGMMEs and YGDMEs ) and at the end of extraction and separation ( Yf, GMMEs and Yf, GDMEs ) (glycerol, 0.435 mole; DMS/glycerol molar ratio, 1.5; NaOH/glycerol molar ratio, 3).

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(a)

100

Conversion and yield (%)

80

XG
YGDMEs+GTME Yf,GDMEs+GTME

60

40

20

0 50 70 90 110
YGMMEs Yf,GMMEs YGDMEs Yf,GMMEs

(b)

50

40

Yield (%)

30

20

10

0 50 70 90 110

Temperature ( C)

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Figure 3.

The influence of the reaction temperature on (a) the conversion X G and

the combined yield of Yf, GDMEs and Yf, GTME . Reaction conditions: reaction time, 24 hr; H2O/NaOH molar ratio, 0.43; feeding time of DMS, 5 hr and (b) the yields of the desired products at the end of reaction ( YGMMEs and YGDMEs ) and at the end of extraction and separation ( Yf, GMMEs and Yf, GDMEs ) (glycerol, 0.435 mole;

DMS/glycerol molar ratio, 1.5; NaOH/glycerol molar ratio, 3).

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(a)

100

XG

Conversion and yield (%)

80

YGDMEs+GTME Yf,GDMEs+GTME

60

40

20

(b)

0
50

0.43

0.74

2.78

YGMMEs Yf,GMMEs
40

YGDMEs Yf,GDMEs

Yield (%)

30

20

10

0 0 0.43 0.74 2.78

H2O/NaOH molar ratio (mol/mol)

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Figure 4. The influence of the molar ratio of H2O/NaOH on (a) the conversion
X G and the combined yield of Yf, GDMEs and Yf, GTME . Reaction conditions: reaction
time, 24 h; reaction temperature, 343 K; feeding time of DMS, 5 hr and (b) the yields of the desired products at the end of reaction ( YGMMEs and YGDMEs ) and at the end of extraction and separation ( Yf, GMMEs and Yf, GDMEs ) (glycerol, 0.435 mole;

DMS/glycerol molar ratio, 1.5; NaOH/glycerol molar ratio, 3).

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(a)

100

XG
80

YGDMEs+GTME
Yf,GDMEs+GTME

Conversion and yield (%)

60

40

20

0 1 5 12 23

(b)

50
YGMMEs Yf,GMMEs YGDMEs Yf,GDMEs

40

Yield (%)

30

20

10

0 1 5 12 23

DMS feeding time (h)

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Figure 5. The influence of the DMS feeding time on (a) the conversion X G and the
combined yield of Yf, GDMEs and Yf, GTME . Reaction conditions: reaction time, 24 h; reaction temperature, 343 K; H2O/NaOH molar ratio, 0.43 and (b) the yields of the desired products at the end of reaction ( YGMMEs and YGDMEs ) and at the end of extraction and separation ( Yf, GMMEs and Yf, GDMEs ) (glycerol, 0.435 mole; DMS/glycerol molar ratio, 1.5; NaOH/glycerol molar ratio, 3).

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FID response (mv)

Time (min)

Figure A1. Exemplary GC chromatographic analysis. 1-methanol; 2-n-butanol; 3-1,2,3-trimethoxypropane; 4-1,3-dimethoxy-2-propanol; 5-2,3-dimethoxy-1-propanol; 6-3-methoxy-1,2-propanediol; 7-2-methoxy-1,3-propanediol; 8-glycerol.

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FID response (mv)

Time (min)

Figure A2. Exemplary GC chromatographic analysis. 1-1,2,3-trimethoxypropane.

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FID response (mv)

Time (min)

Figure A3. Exemplary GC chromatographic analysis. 1-1,2,3-trimethoxypropane; 2-1,3-dimethoxy-2-propanol; 3-2,3-dimethoxy-1-propanol.

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FID response (mv)

Time (min)

Figure A4. Exemplary GC chromatographic analysis. 1-1,3-dimethoxy-2-propanol; 2-2,3-dimethoxy-1-propanol; 3-3-methoxy-1,2-propanediol.

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