*Bio-Solvents: Synthesis, Industrial Production and Applications DOI: http://dx.doi.org/10.5772/intechopen.86502*

nickel. Industrial and Engineering Chemistry Research. 2005;**44**:8535-8537. DOI: 10.1021/ie0489251

*Solvents, Ionic Liquids and Solvent Effects*

bbb.1328

Biofuels, Bioproducts and Biorefining. 2012;**6**(4):483-493. DOI: 10.1002/

[39] Wolfson A, Dlugy C, Shotland Y. Glycerol as a green solvent for high product yields and selectivities. Environmental Chemistry Letters. 2007;**5**:67-71. DOI: 10.1007/

[40] Pagliaro M, Rossi M. Aqueous Phase Reforming. The Future of Glycerol: New Uses of a Versatile Raw Material. Cambridge: Wiley-VCH; 2008. DOI:

[41] Moity L, Benazzouz A, Molinier V, Nardello-Rataj V, Elmkaddem MK, De Caro P, et al. Glycerol acetals and ketals as bio-based solvents: Positioning in Hansen and COSMO-RS spaces, volatility and stability towards hydrolysis and autoxidation. Green Chemistry. 2015;**17**(3):1779-1792. DOI:

[42] Solvay. Augeo™ SL 191 [Internet]. Available from https://www.solvay.us/ en/markets-and-products/featuredproducts/augeo.html, http://www. youliao.com.cn/Uploads/Download/ Document/tds/20398\_tds.PDF [Accessed: April 1, 2019]

[43] Ellis JE, Lenger SR. A convenient synthesis of 3,4-dimethoxy-5 hydroxybenzaldehyde. Synthetic

[44] Salehpour S, Dube MA. Towards the sustainable production of highermolecular-weight polyglycerol.

[45] Sutter M, Da Silva E, Duguet N, Raoul Y, Metay E, Lemaire M. Glycerol ether synthesis: A bench test for green chemistry concepts and technologies. Chemical Reviews. 2014;**115**(16): 8609-8651. DOI: 10.1021/cr5004002

[46] Perosa A, Tundo P. Selective hydrogenolysis of glycerol with Raney

macp.201100064

Communications. 1998;**28**(9):1517-1524. DOI: 10.1080/00397919808006854

Macromolecular Chemistry and Physics. 2011;**212**:1284-1293. DOI: 10.1002/

s10311-006-0080-z

10.1002/cssc.200800115

10.1039/c4gc02377c

[32] Grand View Research, Marketing Research and Consulting, Global Furfural Market By Application (Furfuryl Alcohol, Solvents) Expected To Reach USD 1 200.9 Million By 2020. The Global Furfural Market By Application (Furfuryl Alcohol, Solvents) Expected To Reach USD 1,200.9 Million By 2020; 2015

[33] Available from: https://ihsmarkit. com/products/furfural-chemicaleconomics-handbook.html [Accessed: March 11, 2019–March 11, 2018], https:// IhsmarkitCom/Products/Furfural-Chemical-Economics-HandbookHtml

[Accessed: March 11, 2019]

[34] Available from: https://www. bechtel.com/services/oil-gas-chemicals/ bhts/oil-processing/furfural-refining/ [Accessed: March 11, 2019], https:// WwwBechtelCom/Services/Oil-Gas-Chemicals/Bhts/Oil-Processing/Furfural-Refining/ [Accessed: March 11, 2019]

[35] Available from: http://www. furan.com/furfural\_applications\_ of\_furfural.html [Accessed: March 11, 2018], http://WwwFuranCom/ Furfural\_applications\_of\_furfuralHtml

[Accessed: March 11, 2018]

[36] World Bioenergy Association. Global Bioenergy Statistics. 2018. Available from: https://worldbioenergy.org/ uploads/181203%20WBA%20GBS%20 2018\_hq.pdf [Accessed: April 1, 2019]

[37] Pagliaro M, Rossi M. Glycerol: Properties and Production. The Future of Glycerol: New Uses of a Versatile Raw Material. Cambridge: Wiley-VCH; 2008.

DOI: 10.1002/cssc.200800115

DOI: 10.1039/c001628d

[38] Gu Y, Jerome F. Glycerol as a sustainable solvent for green chemistry. Green Chemistry. 2010;**12**:1127-1138.

**20**

[47] Bricker ML, Leonard LE, Kruse TM, Vassilakis JG, Bare SR. Methods for Converting Glycerol to Propanol. 8101807 B2; 2012

[48] Crabtree SP, Tyers DV. Hydrogenolysis of Sugar Feedstock; 2007

[49] Ji N, Zhang T, Zheng M, Wang A, Wang H, Wang X, et al. Direct catalytic conversion of cellulose into ethylene glycol using nickel-promoted tungsten carbide catalysts. Angewandte Chemie International Edition. 2008;**47**: 8510-8513. DOI: 10.1002/anie.200803233

[50] Sappi Limited. Sappi Invests in Sugar Separations and Clean-Up Technology to Strengthen its Renewable Bio-Chemicals Offering [Internet]. 2017. Available from: https://www.sappi.com/ sappi-invests-sugar-separations-andclean-technology-strengthe

[51] Ge L, Wu X, Chen J, Wu J. A new method for industrial production of 2,3-butanediol. Journal of Biomaterials and Nanobiotechnology. 2011;**2**:335-336. DOI: 10.1007/s002530000486

[52] Archer Daniels Midland Company. Fuels and Industrials Catalogue, ADM Solvents [Internet]. 2019. p. 16. Available from: https://assets.adm.com/ Products-And-Services/Industrials/ ADM-Fuels-and-Industrials-Catalog. pdf [Accessed: April 6, 2019]

[53] Gonnzalez YM, Thiebaud-roux YMG, De Caro P, Lacaze-Dufaure C. Fatty acid methyl esters as biosolvents of epoxy resins: A physicochemical study. Journal of Solution Chemistry. 2007;**36**:437-446. DOI: 10.1007/s10953-007-9126-5

[54] Hu J, Gu Y, Guan Z, Li J, Mo W, Li T, et al. An efficient palladium catalyst system for the oxidative carbonylation of glycerol to glycerol carbonate. ChemSusChem. 2011;**4**:1767-1772. DOI: 10.1002/cssc.201100337

[55] Aresta M, Dibenedetto A, Nocito F, Pastore C. A study on the carboxylation of glycerol to glycerol carbonate with carbon dioxide: The role of the catalyst, solvent and reaction conditions. Journal of Molecular Catalysis A: Chemical. 2006;**257**:149-153. DOI: 10.1016/j. molcata.2006.05.021

[56] Ochoa-Gomez RJ, Gomez-Jimenez-Abersturi O, Ramirez-Lopez C, Belsue M. A brief review on industrial alternatives for the manufacturing of glycerol carbonate, a green chemical. Organic Process Research and Development. 2012;**16**:389-399. DOI: 10.1021/op200369v

[57] Sonnati MO, Amigoni S, De Givenchy EPT, Darmanin T, Choulet O, Guittard F. Glycerol carbonate as a versatile building block for tomorrow: Synthesis, reactivity, properties and applications. Green Chemistry. 2013;**15**(2005):283-306. DOI: 10.1039/ c2gc36525a

[58] Clarke CJ, Tu WC, Levers O, Bröhl A, Hallett JP. Green and sustainable solvents in chemical processes. Chemical Reviews. 2018;**118**(2):747-800. DOI: 10.1021/acs.chemrev.7b00571

[59] Amenuvor G, Makhubela BCE, Darkwa J. Efficient solvent-free hydrogenation of levulinic acid to γ-valerolactone by pyrazolylphosphite and pyrazolylphosphinite ruthenium(II) complexes. ACS Sustainable Chemistry & Engineering. 2016;**4**:6010-6018. DOI: 10.1021/ acssuschemeng.6b01281

[60] Amenuvor G, Darkwa J, Makhubela BCE. Homogeneous polymetallic ruthenium(ii)^zinc(ii) complexes: Robust catalysts for the efficient hydrogenation of levulinic acid to

γ-valerolactone. Catalysis Science and Technology. 2018;**8**(9):2370-2380. DOI: 10.1039/c8cy00265g

[61] Zhang Z. Synthesis of γ-valerolactone from carbohydrates and its applications. ChemSusChem. 2016;**9**(2):156-171. DOI: 10.1002/ cssc.201501089

[62] Zhang L, Yu H, Wang P, Li Y. Production of furfural from xylose, xylan and corncob in gammavalerolactone using FeCl3·6H2O as catalyst. Bioresource Technology. 2014;**151**:355-360. DOI: 10.1016/j. biortech.2013.10.099

[63] Dougan L, Tych KM, Hughes ML. Article Type a Single Molecule Approach to Investigate the Role of Hydrogen Bond Strength on Protein Mechanical Compliance and Unfolding History2014. pp. 8-10. DOI: 10.1039/b000000x

[64] Ismalaj E, Strappaveccia G, Ballerini E, Elisei F, Piermatti O, Gelman D, et al. γ-Valerolactone as a Renewable Dipolar Aprotic Solvent Deriving from Biomass Degradation for the Hiyama Reaction2014. DOI: 10.1021/sc5004727

[65] Strappaveccia G, Ismalaj E, Petrucci C, Lanari D, Marrocchi A, Drees M, et al. A biomass-derived safe medium to replace toxic dipolar solvents and access cleaner heck coupling reactions. Green Chemistry. 2015;**17**(1):365-372. DOI: 10.1039/c4gc01677g

[66] Camp JE. Bio-available solvent cyrene: Synthesis, derivatization, and applications. ChemSusChem. 2018;**11**(18):3048-3055. DOI: 10.1002/ cssc.201801420

[67] Zhou L, Lie Y, Briers H, Fan J, Remón J, Nyström J, et al. Natural product recovery from bilberry (*Vaccinium myrtillus* L.) presscake via microwave hydrolysis. ACS Sustainable Chemistry & Engineering. 2018;**6**(3):3676-3685. DOI: 10.1021/ acssuschemeng.7b03999

[68] Zhuang G, Bai J, Wang X, Leng S, Zhong X, Wang J, et al. Role of pretreatment with acid and base on the distribution of the products obtained via lignocellulosic biomass pyrolysis. RSC Advances. 2015;**5**(32):24984-24989. DOI: 10.1039/c4ra15426f

[69] Lu Q, Wang TP, Wang XH, Dong CQ, Zhang ZB, Ye XN. Selective production of levoglucosenone from catalytic fast pyrolysis of biomass mechanically mixed with solid phosphoric acid catalysts. BioEnergy Research. 2015;**8**(3):1263-1274. DOI: 10.1007/s12155-015-9581-6

[70] Wang Z, Zhang Y, Liao B, Guo QX, Sui XW. Preparation of levoglucosenone through sulfuric acid promoted pyrolysis of bagasse at low temperature. Bioresource Technology. 2011;**103**(1):466-469. DOI: 10.1016/j. biortech.2011.10.010

[71] Halpern Y, Riffer R, Briodo A. Levoglucosenone. Journal of Organic Chemistry. 1973;**38**(2):204-209

[72] Sarotti AM, Spanevello RA, Suárez AG. An efficient microwave-assisted green transformation of cellulose into levoglucosenone. Advantages of the use of an experimental design approach. Green Chemistry. 2007;**9**(10):1137-1140. DOI: 10.1039/ b703690f

[73] Zhang H, Meng X, Liu C, Wang Y, Xiao R. Selective low-temperature pyrolysis of microcrystalline cellulose to produce levoglucosan and levoglucosenone in a fixed bed reactor. Fuel Processing Technology. 2017;**167**(August):484-490. DOI: 10.1016/j.fuproc.2017.08.007

[74] Available from: https:// ilbioeconomista.com/2018/02/19/ an-interview-with-tony-duncan-ceo-

**23**

*Bio-Solvents: Synthesis, Industrial Production and Applications*

2013;**5**(5):428-432. DOI: 10.1038/

[81] Simakova IL, Murzin DY. Transformation of bio-derived acids into fuel-like alkanes via ketonic decarboxylation and hydrodeoxygenation: Design of multifunctional catalyst, kinetic and mechanistic aspects. Journal of Energy Chemistry. 2016;**25**(2):208-224. DOI:

10.1016/j.jechem.2016.01.004

Lu GZ, Wang YQ. Pd/NbOPO4 multifunctional catalyst for the direct production of liquid alkanes from aldol adducts of furans. Angewandte Chemie International Edition. 2014;**53**(37): 9755-9760. DOI: 10.1002/anie.201403440

[82] Xia QN, Cuan Q, Liu XH, Gong XQ,

[83] Song HJ, Deng J, Cui MS, Li XL, Liu XX, Zhu R, et al. Alkanes from bioderived furans by using metal triflates and palladium-catalyzed hydrodeoxygenation of cyclic ethers. ChemSusChem. 2015;**8**(24):4250-4255.

[84] Li Z, Lepore AW, Salazar MF, Foo GS, Davison BH, Wu Z, et al. Selective conversion of bio-derived ethanol to renewable BTX over Ga-ZSM-5. Green Chemistry. 2017;**19**(18):4344-4352.

DOI: 10.1002/cssc.201500907

DOI: 10.1039/c7gc01188a

[Accessed: March 26, 2019]

cs300011a

[85] Available from: http://www. anellotech.com/technology.BTX.pdf

[86] Williams CL, Chang CC, Do P, Nikbin N, Caratzoulas S, Vlachos DG, et al. Cycloaddition of biomass-derived furans for catalytic production of renewable p-xylene. ACS Catalysis. 2012;**2**(6):935-939. DOI: 10.1021/

[87] Tanzi CD, Vian MA, Ginies C, Elmaataoui M, Chemat F. Terpenes as green solvents for extraction of oil from microalgae. Molecules.

nchem.1609

*DOI: http://dx.doi.org/10.5772/intechopen.86502*

circa-group-the-most-innovativebioeconomy-ceo-2017/; https:// IlbioeconomistaCom/2018/02/19/ an-Interview-with-Tony-Duncan-Ceocirca-Group-the-Most-Innovative-Bioeconomy-Ceo-2017/ [Accessed: 2018]

[75] Krishna SH, McClelland DJ, Rashke QA, Dumesic JA, Huber GW. Hydrogenation of levoglucosenone to renewable chemicals. Green Chemistry. 2017;**19**(5):1278-1285. DOI: 10.1039/

[76] Kudo S, Goto N, Sperry J, Norinaga K, Hayashi JI. Production

dihydrolevoglucosenone by catalytic reforming of volatiles from cellulose pyrolysis using supported ionic liquid phase. ACS Sustainable Chemistry & Engineering. 2017;**5**(1):1132-1140. DOI: 10.1021/acssuschemeng.6b02463

Dihydrolevoglucosenone (Cyrene) as a bio-based alternative for dipolar aprotic solvents. Chemical Communications. 2014;**50**(68):9650-9652. DOI: 10.1039/

[78] Zhang J, White GB, Ryan MD, Hunt AJ, Katz MJ. Dihydrolevoglucosenone (Cyrene) as a green alternative to N,Ndimethylformamide (DMF) in MOF synthesis. ACS Sustainable Chemistry & Engineering. 2016;**4**(12):7186-7192. DOI: 10.1021/acssuschemeng.6b02115

[79] Wilson KL, Murray J, Jamieson C, Watson AJB. Cyrene as a bio-based solvent for HATU mediated amide coupling. Organic and Biomolecular Chemistry. 2018;**16**(16):2851-2854. DOI:

[80] Sutton AD, Waldie FD, Wu R, Schlaf M, Pete'Silks LA, Gordon JC. The hydrodeoxygenation of bioderived furans into alkanes. Nature Chemistry.

10.1039/c8ob00653a

of levoglucosenone and

[77] Sherwood J, De Bruyn M, Constantinou A, Moity L, McElroy CR, Farmer TJ, et al.

c6gc03028a

c4cc04133j

*Bio-Solvents: Synthesis, Industrial Production and Applications DOI: http://dx.doi.org/10.5772/intechopen.86502*

circa-group-the-most-innovativebioeconomy-ceo-2017/; https:// IlbioeconomistaCom/2018/02/19/ an-Interview-with-Tony-Duncan-Ceocirca-Group-the-Most-Innovative-Bioeconomy-Ceo-2017/ [Accessed: 2018]

*Solvents, Ionic Liquids and Solvent Effects*

10.1039/c8cy00265g

cssc.201501089

biortech.2013.10.099

10.1021/sc5004727

10.1039/c4gc01677g

cssc.201801420

[61] Zhang Z. Synthesis of

γ-valerolactone. Catalysis Science and Technology. 2018;**8**(9):2370-2380. DOI: 2018;**6**(3):3676-3685. DOI: 10.1021/

[68] Zhuang G, Bai J, Wang X, Leng S, Zhong X, Wang J, et al. Role of pretreatment with acid and base on the distribution of the products obtained via lignocellulosic biomass pyrolysis. RSC Advances. 2015;**5**(32):24984-24989.

[69] Lu Q, Wang TP, Wang XH, Dong CQ, Zhang ZB, Ye XN. Selective production of levoglucosenone from catalytic fast pyrolysis of biomass mechanically mixed with solid phosphoric acid catalysts. BioEnergy Research. 2015;**8**(3):1263-1274. DOI:

acssuschemeng.7b03999

DOI: 10.1039/c4ra15426f

10.1007/s12155-015-9581-6

biortech.2011.10.010

b703690f

[70] Wang Z, Zhang Y, Liao B, Guo QX, Sui XW. Preparation of levoglucosenone through sulfuric acid promoted pyrolysis of bagasse at low temperature. Bioresource Technology. 2011;**103**(1):466-469. DOI: 10.1016/j.

[71] Halpern Y, Riffer R, Briodo A. Levoglucosenone. Journal of Organic Chemistry. 1973;**38**(2):204-209

[72] Sarotti AM, Spanevello RA, Suárez AG. An efficient microwave-assisted green transformation of cellulose into levoglucosenone. Advantages of the use of an experimental design approach. Green Chemistry. 2007;**9**(10):1137-1140. DOI: 10.1039/

[73] Zhang H, Meng X, Liu C, Wang Y, Xiao R. Selective low-temperature

pyrolysis of microcrystalline cellulose to produce levoglucosan and levoglucosenone in a fixed bed reactor. Fuel Processing Technology. 2017;**167**(August):484-490. DOI: 10.1016/j.fuproc.2017.08.007

[74] Available from: https:// ilbioeconomista.com/2018/02/19/ an-interview-with-tony-duncan-ceo-

γ-valerolactone from carbohydrates and its applications. ChemSusChem. 2016;**9**(2):156-171. DOI: 10.1002/

[62] Zhang L, Yu H, Wang P, Li Y. Production of furfural from xylose, xylan and corncob in gammavalerolactone using FeCl3·6H2O as catalyst. Bioresource Technology. 2014;**151**:355-360. DOI: 10.1016/j.

[63] Dougan L, Tych KM, Hughes ML. Article Type a Single Molecule Approach to Investigate the Role of Hydrogen Bond Strength on Protein Mechanical Compliance and Unfolding History2014. pp. 8-10. DOI: 10.1039/b000000x

[64] Ismalaj E, Strappaveccia G, Ballerini E, Elisei F, Piermatti O, Gelman D, et al. γ-Valerolactone as a Renewable Dipolar Aprotic Solvent Deriving from Biomass Degradation for the Hiyama Reaction2014. DOI:

[65] Strappaveccia G, Ismalaj E, Petrucci C, Lanari D, Marrocchi A, Drees M, et al. A biomass-derived safe medium to replace toxic dipolar solvents and access cleaner heck coupling reactions. Green Chemistry. 2015;**17**(1):365-372. DOI:

[66] Camp JE. Bio-available solvent cyrene: Synthesis, derivatization, and applications. ChemSusChem. 2018;**11**(18):3048-3055. DOI: 10.1002/

[67] Zhou L, Lie Y, Briers H, Fan J, Remón J, Nyström J, et al. Natural product recovery from bilberry (*Vaccinium myrtillus* L.) presscake via microwave hydrolysis. ACS

Sustainable Chemistry & Engineering.

**22**

[75] Krishna SH, McClelland DJ, Rashke QA, Dumesic JA, Huber GW. Hydrogenation of levoglucosenone to renewable chemicals. Green Chemistry. 2017;**19**(5):1278-1285. DOI: 10.1039/ c6gc03028a

[76] Kudo S, Goto N, Sperry J, Norinaga K, Hayashi JI. Production of levoglucosenone and dihydrolevoglucosenone by catalytic reforming of volatiles from cellulose pyrolysis using supported ionic liquid phase. ACS Sustainable Chemistry & Engineering. 2017;**5**(1):1132-1140. DOI: 10.1021/acssuschemeng.6b02463

[77] Sherwood J, De Bruyn M, Constantinou A, Moity L, McElroy CR, Farmer TJ, et al. Dihydrolevoglucosenone (Cyrene) as a bio-based alternative for dipolar aprotic solvents. Chemical Communications. 2014;**50**(68):9650-9652. DOI: 10.1039/ c4cc04133j

[78] Zhang J, White GB, Ryan MD, Hunt AJ, Katz MJ. Dihydrolevoglucosenone (Cyrene) as a green alternative to N,Ndimethylformamide (DMF) in MOF synthesis. ACS Sustainable Chemistry & Engineering. 2016;**4**(12):7186-7192. DOI: 10.1021/acssuschemeng.6b02115

[79] Wilson KL, Murray J, Jamieson C, Watson AJB. Cyrene as a bio-based solvent for HATU mediated amide coupling. Organic and Biomolecular Chemistry. 2018;**16**(16):2851-2854. DOI: 10.1039/c8ob00653a

[80] Sutton AD, Waldie FD, Wu R, Schlaf M, Pete'Silks LA, Gordon JC. The hydrodeoxygenation of bioderived furans into alkanes. Nature Chemistry.

2013;**5**(5):428-432. DOI: 10.1038/ nchem.1609

[81] Simakova IL, Murzin DY. Transformation of bio-derived acids into fuel-like alkanes via ketonic decarboxylation and hydrodeoxygenation: Design of multifunctional catalyst, kinetic and mechanistic aspects. Journal of Energy Chemistry. 2016;**25**(2):208-224. DOI: 10.1016/j.jechem.2016.01.004

[82] Xia QN, Cuan Q, Liu XH, Gong XQ, Lu GZ, Wang YQ. Pd/NbOPO4 multifunctional catalyst for the direct production of liquid alkanes from aldol adducts of furans. Angewandte Chemie International Edition. 2014;**53**(37): 9755-9760. DOI: 10.1002/anie.201403440

[83] Song HJ, Deng J, Cui MS, Li XL, Liu XX, Zhu R, et al. Alkanes from bioderived furans by using metal triflates and palladium-catalyzed hydrodeoxygenation of cyclic ethers. ChemSusChem. 2015;**8**(24):4250-4255. DOI: 10.1002/cssc.201500907

[84] Li Z, Lepore AW, Salazar MF, Foo GS, Davison BH, Wu Z, et al. Selective conversion of bio-derived ethanol to renewable BTX over Ga-ZSM-5. Green Chemistry. 2017;**19**(18):4344-4352. DOI: 10.1039/c7gc01188a

[85] Available from: http://www. anellotech.com/technology.BTX.pdf [Accessed: March 26, 2019]

[86] Williams CL, Chang CC, Do P, Nikbin N, Caratzoulas S, Vlachos DG, et al. Cycloaddition of biomass-derived furans for catalytic production of renewable p-xylene. ACS Catalysis. 2012;**2**(6):935-939. DOI: 10.1021/ cs300011a

[87] Tanzi CD, Vian MA, Ginies C, Elmaataoui M, Chemat F. Terpenes as green solvents for extraction of oil from microalgae. Molecules.

2012;**17**(7):8196-8205. DOI: 10.3390/ molecules17078196

[88] John I, Muthukumar K, Arunagiri A. A review on the potential of citrus waste for D-limonene, pectin, and bioethanol production. International Journal of Green Energy. 2017;**14**(7):599-612. DOI: 10.1080/15435075.2017.1307753

[89] Martin-Luengo MA, Yates M, Rojo ES, Huerta Arribas D, Aguilar D, Ruiz Hitzky E. Sustainable p-cymene and hydrogen from limonene. Applied Catalysis A: General. 2010;**387**(1-2):141-146. DOI: 10.1016/j. apcata.2010.08.016

[90] Deepthi Priya K, Petkar M, Chowdary GV. Bio-production of aroma compounds from alpha pinene by novel strains. International Journal of Biological Sciences and Applications. 2015;**2**(2):15-19

[91] Antonucci V, Coleman J, Ferry JB, Johnson N, Mathe M, Scott JP, et al. Toxicological assessment of 2-methyltetrahydrofuran and cyclopentyl methyl ether in support of their use in pharmaceutical chemical process development. Organic Process Research and Development. 2011;**15**(4):939-941. DOI: 10.1021/ op100303c

[92] Zhu YL, Xiang HW, Li YW, Jiao H, Wu GS, Zhong B, et al. A new strategy for the efficient synthesis of 2-methylfuran and γ-butyrolactone. New Journal of Chemistry. 2003;**27**(2):208-210. DOI: 10.1039/ b208849p

[93] Teng BT, Zhu YL, Li Y, Xiang HW, Zheng HY, Zhao GW, et al. Effects of calcination temperature on performance of Cu–Zn–Al catalyst for synthesizing γ-butyrolactone and 2-methylfuran through the coupling of dehydrogenation and hydrogenation. Catalysis Communications.

2004;**5**(9):505-510. DOI: 10.1016/j. catcom.2004.06.005

[94] Brown Ripin DH, Vetelino M. 2-Methyltetrahydrofuran as an alternative to dichloromethane in 2-phase reactions. Synlett. 2003;**34**(15):2353. DOI: 10.1055/s-2003-42091

[95] Funel JA, Schmidt G, Abele S. Design and Scale-Up of Diels À Alder Reactions for the Practical Synthesis of 5-Phenylbicyclo [2.2.2]oct-5-en-2 one2011. pp. 1420-1427

[96] Wilkes JS. A short history of ionic liquids—From molten salts to neoteric solvents. Green Chemistry. 2002;**4**: 73-80. DOI: 10.1039/b110838g

[97] Plechkova NV, Seddon KR. Applications of ionic liquids in the chemical industry. Chemical Society Reviews. 2008;**37**:123-150. DOI: 10.1039/b006677j

[98] Sheldon RA. Green solvents for sustainable organic synthesis: State of the art. Green Chemistry. 2005;**7**:267-278. DOI: 10.1039/b418069k

[99] Hulsbosch J, De Vos DE, Binnemans K, Ameloot R. Biobased ionic liquids: Solvents for a green processing industry? ACS Sustainable Chemistry & Engineering. 2016;**4**:2917-2931. DOI: 10.1021/acssuschemeng.6b00553

[100] Jha AK, Jain N. Synthesis of glucose-tagged triazolium ionic liquids and their application as solvent and ligand for copper (I) catalyzed amination. Tetrahedron Letters. 2013;**54**(35):4738-4741. DOI: 10.1016/j. tetlet.2013.06.114

[101] Poletti L, Chiappe C, Lay L, Pieraccini D, Russo G. Glucose-derived ionic liquids: Exploring low-cost sources for novel chiral solvents. Green Chemistry. 2007;**9**:337-341. DOI: 10.1039/b615650a

**25**

*Bio-Solvents: Synthesis, Industrial Production and Applications*

[109] Calvo FG, María F, Monteagudo J. Green and bio-based solvents. Topics in Current Chemistry. 2018;**376**(18):1-40. DOI: 10.1007/s41061-018-0191-6

[110] Abbott AP, Capper G, Davies DL, Munro HL, Rasheed RK. Preparation of novel, moisture-stable, Lewis-acidic ionic liquids containing quaternary ammonium salts with functional side chains. Chemical Communications. 2001;**1**(19):2010-2011. DOI: 10.1039/

[111] Zeisel SH. A brief history of choline. Annals of Nutrition and Metabolism. 2012;**61**:254-258. DOI:

[112] Abbott AP, Capper G, Davies DL, Rasheed RK, Tambyrajah V. Novel solvent properties of choline chloride/urea mixtures. Chemical Communications. 2003;**1**(1):70-71

[113] Singh B, Lobo H, Shankarling G. Selective N-alkylation of aromatic primary amines catalyzed by biocatalyst or deep eutectic solvent.

Catalysis Letters. 2011;**141**:178-182. DOI:

substituted 1-aminoanthra-9,10-quinone

[115] Pawar PM, Jarag KJ, Shankarling GS. Environmentally benign and energy efficient methodology for condensation: An interesting facet to the classical Perkin reaction. Green Chemistry. 2011;**13**:2130-2134. DOI: 10.1039/

[116] Shahbaz K, Mjalli FS, Hashim MA, ALNashef IM. Using deep eutectic solvents for the removal of glycerol from palm oil-based biodiesel. Journal of

10.1007/s10562-010-0479-9

[114] Phadtare SB, Shankarling GS. Halogenation reactions in biodegradable

solvent: Efficient bromination of

in deep eutectic solvent (choline chloride: Urea). Green Chemistry. 2010;**12**:458-462. DOI: 10.1039/b923589b

c0gc00712a

b106357j

10.1159/000343120

*DOI: http://dx.doi.org/10.5772/intechopen.86502*

[102] Handy ST, Okello M, Dickenson G. Solvents from biorenewable sources: Ionic liquids based on fructose. Organic Letters. 2003;**5**(14):2513-2515. DOI:

[103] Chiappe C, Marra A, Mele A. Synthesis and applications of ionic liquids derived from natural sugars. In: Rauter AP, Vogel P, Queneau Y, editors. Carbohydrates and Sustainable Development II—A Mine for Functional

Molecules and Materials. Berlin:

[104] Ferraz R, Branco C, Marrucho IM, Rebelo PN, Nunes M, Prud C. Development of novel ionic liquids based on ampicillin. Medicinal Chemistry Communications. 2012;**3**:494-497. DOI: 10.1039/

[105] Wasserscheid P, Bolm C. Synthesis and properties of ionic liquids derived from the 'chiral pool'. Chemical Communications. 2002;**1**(3):200-201.

[106] Heckel T, Winkel A, Wilhelm R. Chiral ionic liquids based on nicotine for the chiral recognition of carboxylic acids. Tetrahedron: Asymmetry. 2013;**24**(18):1127-1133. DOI: 10.1016/j.

[107] Parmentier D, Metz SJ, Kroon MC. Tetraalkylammonium oleate and linoleate based ionic liquids: Promising extractants for metal salts. Green Chemistry. 2013;**15**:205-209. DOI:

[108] Kwan ML, Mirjafari A, Mccabe JR, Brien RAO, Essi DF, Baum L, et al. Synthesis and thermophysical

Cyclopropyl moieties versus olefins as Tm-reducing elements in lipidinspired ionic liquids. Tetrahedron Letters. 2013;**54**(1):12-14. DOI: 10.1016/j.tetlet.2012.09.101

properties of ionic liquids:

DOI: 10.1007/128\_2010\_47

c2md00269h

DOI: 10.1039/B109493A

tetasy.2013.07.021

10.1039/c2gc36458a

Springer-Verlag Berlin Heidelberg; 2010.

10.1021/ol034778b

*Bio-Solvents: Synthesis, Industrial Production and Applications DOI: http://dx.doi.org/10.5772/intechopen.86502*

[102] Handy ST, Okello M, Dickenson G. Solvents from biorenewable sources: Ionic liquids based on fructose. Organic Letters. 2003;**5**(14):2513-2515. DOI: 10.1021/ol034778b

*Solvents, Ionic Liquids and Solvent Effects*

2012;**17**(7):8196-8205. DOI: 10.3390/

2004;**5**(9):505-510. DOI: 10.1016/j.

[94] Brown Ripin DH, Vetelino M. 2-Methyltetrahydrofuran as an alternative to dichloromethane in 2-phase reactions. Synlett. 2003;**34**(15):2353. DOI: 10.1055/s-2003-42091

[95] Funel JA, Schmidt G, Abele S. Design and Scale-Up of Diels À Alder Reactions for the Practical Synthesis of 5-Phenylbicyclo [2.2.2]oct-5-en-2-

[96] Wilkes JS. A short history of ionic liquids—From molten salts to neoteric solvents. Green Chemistry. 2002;**4**: 73-80. DOI: 10.1039/b110838g

[97] Plechkova NV, Seddon KR. Applications of ionic liquids in the chemical industry. Chemical Society Reviews. 2008;**37**:123-150. DOI:

[98] Sheldon RA. Green solvents for sustainable organic synthesis: State of the art. Green Chemistry. 2005;**7**:267-278.

[99] Hulsbosch J, De Vos DE, Binnemans K, Ameloot R. Biobased ionic liquids: Solvents for a green processing industry? ACS Sustainable Chemistry & Engineering. 2016;**4**:2917-2931. DOI: 10.1021/acssuschemeng.6b00553

[100] Jha AK, Jain N. Synthesis of glucose-tagged triazolium ionic liquids and their application as solvent and ligand for copper (I) catalyzed amination. Tetrahedron Letters. 2013;**54**(35):4738-4741. DOI: 10.1016/j.

[101] Poletti L, Chiappe C, Lay L, Pieraccini D, Russo G. Glucose-derived ionic liquids: Exploring low-cost sources for novel chiral solvents. Green Chemistry. 2007;**9**:337-341. DOI:

one2011. pp. 1420-1427

10.1039/b006677j

DOI: 10.1039/b418069k

tetlet.2013.06.114

10.1039/b615650a

catcom.2004.06.005

[88] John I, Muthukumar K, Arunagiri A. A review on the potential of citrus waste for D-limonene, pectin, and bioethanol production. International Journal of Green Energy. 2017;**14**(7):599-612. DOI: 10.1080/15435075.2017.1307753

[89] Martin-Luengo MA, Yates M, Rojo ES, Huerta Arribas D, Aguilar D, Ruiz Hitzky E. Sustainable p-cymene and hydrogen from limonene. Applied Catalysis A: General.

2010;**387**(1-2):141-146. DOI: 10.1016/j.

Chowdary GV. Bio-production of aroma compounds from alpha pinene by novel strains. International Journal of Biological Sciences and Applications.

[91] Antonucci V, Coleman J, Ferry JB,

[92] Zhu YL, Xiang HW, Li YW, Jiao H, Wu GS, Zhong B, et al. A new strategy for the efficient synthesis of 2-methylfuran and γ-butyrolactone.

New Journal of Chemistry. 2003;**27**(2):208-210. DOI: 10.1039/

Catalysis Communications.

[93] Teng BT, Zhu YL, Li Y, Xiang HW, Zheng HY, Zhao GW, et al. Effects of calcination temperature on performance of Cu–Zn–Al catalyst for synthesizing γ-butyrolactone and 2-methylfuran through the coupling of dehydrogenation and hydrogenation.

Johnson N, Mathe M, Scott JP, et al. Toxicological assessment of 2-methyltetrahydrofuran and cyclopentyl methyl ether in support of their use in pharmaceutical chemical process development. Organic Process Research and Development. 2011;**15**(4):939-941. DOI: 10.1021/

[90] Deepthi Priya K, Petkar M,

molecules17078196

apcata.2010.08.016

2015;**2**(2):15-19

op100303c

b208849p

**24**

[103] Chiappe C, Marra A, Mele A. Synthesis and applications of ionic liquids derived from natural sugars. In: Rauter AP, Vogel P, Queneau Y, editors. Carbohydrates and Sustainable Development II—A Mine for Functional Molecules and Materials. Berlin: Springer-Verlag Berlin Heidelberg; 2010. DOI: 10.1007/128\_2010\_47

[104] Ferraz R, Branco C, Marrucho IM, Rebelo PN, Nunes M, Prud C. Development of novel ionic liquids based on ampicillin. Medicinal Chemistry Communications. 2012;**3**:494-497. DOI: 10.1039/ c2md00269h

[105] Wasserscheid P, Bolm C. Synthesis and properties of ionic liquids derived from the 'chiral pool'. Chemical Communications. 2002;**1**(3):200-201. DOI: 10.1039/B109493A

[106] Heckel T, Winkel A, Wilhelm R. Chiral ionic liquids based on nicotine for the chiral recognition of carboxylic acids. Tetrahedron: Asymmetry. 2013;**24**(18):1127-1133. DOI: 10.1016/j. tetasy.2013.07.021

[107] Parmentier D, Metz SJ, Kroon MC. Tetraalkylammonium oleate and linoleate based ionic liquids: Promising extractants for metal salts. Green Chemistry. 2013;**15**:205-209. DOI: 10.1039/c2gc36458a

[108] Kwan ML, Mirjafari A, Mccabe JR, Brien RAO, Essi DF, Baum L, et al. Synthesis and thermophysical properties of ionic liquids: Cyclopropyl moieties versus olefins as Tm-reducing elements in lipidinspired ionic liquids. Tetrahedron Letters. 2013;**54**(1):12-14. DOI: 10.1016/j.tetlet.2012.09.101

[109] Calvo FG, María F, Monteagudo J. Green and bio-based solvents. Topics in Current Chemistry. 2018;**376**(18):1-40. DOI: 10.1007/s41061-018-0191-6

[110] Abbott AP, Capper G, Davies DL, Munro HL, Rasheed RK. Preparation of novel, moisture-stable, Lewis-acidic ionic liquids containing quaternary ammonium salts with functional side chains. Chemical Communications. 2001;**1**(19):2010-2011. DOI: 10.1039/ b106357j

[111] Zeisel SH. A brief history of choline. Annals of Nutrition and Metabolism. 2012;**61**:254-258. DOI: 10.1159/000343120

[112] Abbott AP, Capper G, Davies DL, Rasheed RK, Tambyrajah V. Novel solvent properties of choline chloride/urea mixtures. Chemical Communications. 2003;**1**(1):70-71

[113] Singh B, Lobo H, Shankarling G. Selective N-alkylation of aromatic primary amines catalyzed by biocatalyst or deep eutectic solvent. Catalysis Letters. 2011;**141**:178-182. DOI: 10.1007/s10562-010-0479-9

[114] Phadtare SB, Shankarling GS. Halogenation reactions in biodegradable solvent: Efficient bromination of substituted 1-aminoanthra-9,10-quinone in deep eutectic solvent (choline chloride: Urea). Green Chemistry. 2010;**12**:458-462. DOI: 10.1039/b923589b

[115] Pawar PM, Jarag KJ, Shankarling GS. Environmentally benign and energy efficient methodology for condensation: An interesting facet to the classical Perkin reaction. Green Chemistry. 2011;**13**:2130-2134. DOI: 10.1039/ c0gc00712a

[116] Shahbaz K, Mjalli FS, Hashim MA, ALNashef IM. Using deep eutectic solvents for the removal of glycerol from palm oil-based biodiesel. Journal of

Applied Sciences. 2010;**10**(24):3349-3354. DOI: 10.3923/jas.2010.3349.3354

[117] Shahbaz K, Mjalli FS, Hashim MA, Alnashef IM. Eutectic solvents for the removal of residual palm oilbased biodiesel catalyst. Separation and Purification Technology. 2011;**81**(2):216-222. DOI: 10.1016/j. seppur.2011.07.032

[118] Ho KC, Shahbaz K, Mjalli FS. Removal of glycerol from palm oil-based biodiesel using new ionic liquids analogues. Journal of Engineering Science and Technology. 2015;**10**(1):98-111

[119] Maugeri Z, Domı P. Novel cholinechloride-based deep-eutectic-solvents with renewable hydrogen bond donors: Levulinic acid and sugar-based polyols. RSC Advances. 2012;**2**:421-425. DOI: 10.1039/c1ra00630d

[120] Francisco M, Van Den Bruinhorst A, Kroon MC. New natural and renewable low transition temperature mixtures (LTTMs ): Screening as solvents for lignocellulosic biomass processing. Green Chemistry. 2012;**14**:2153-2157. DOI: 10.1039/ c2gc35660k

[121] Ge X, Gu C, Wang X, Jiangping T. Deep eutectic solvents (DESs)-derived advanced functional materials for energy and environmental applications: Challenges, opportunities, and future vision. Journal of Materials Chemistry A: Materials for Energy and Sustainability. 2017;**5**:8209-8229. DOI: 10.1039/C7TA01659J

**27**

**Chapter 2**

**Abstract**

occupational health

**1. Introduction**

contaminated water or food.

Per- and Trichloroethylene Air

*Fatma Omrane, Imed Gargouri and Moncef Khadhraoui*

and can lead to many adverse health effects up to several types of cancers.

**Keywords:** air monitoring, trichloroethylene, perchloroethylene, exposure assessment,

In the modern world, synthetic chemicals are a big part of the human life. Among these products, the organic solvents represent a group of diverse chemical substances with a generally high volatility and solubilization ability that allow their use in broad range of applications. In this respect, there are about a thousand different solvents involving a hundred common uses, especially in industrial sectors. Depending on their properties, these organic solvents can be used as degreasers (cleaning textiles and metals), additives and thinners (paints, varnishes, inks, glues, and pesticides), strippers (removal of organic products), and even purifiers (perfumes) [1]. Nevertheless, all these solvents have negative impacts on human health and the environment in case of noncaution. The health effects are variable depending on the solvent and the exposure duration and intensity [1]. Due to their volatility, humans can be typically exposed by the three routes: (i) inhalation; (ii) dermal contact, whatever the state of the skin; and (iii) ingestion through accidental absorption or

City of Sfax (Tunisia)

Monitoring in Dry Cleaners in the

The use of chlorinated solvents in dry cleaning poses risks to human health. The occupational health exposure assessment to these volatile chemicals is conducted through quantification of airborne concentrations inside the facilities. Indeed, the lack of such measurements in Tunisia pushed us to conduct the study. After identifying dry cleaners in Sfax city, we conducted door-to-door canvassing in 47 facilities. Then, the levels of perchloroethylene (PCE) and trichloroethylene (TCE) in the indoor air are measured in two sampling positions: fixed and individual. The pollutants are adsorbed with charcoal sorbent tubes where their amounts correspond to given air volumes that are suctioned through the pump. It is later used to calculate their mean concentrations. These solvents are desorbed using carbon disulfide and analyzed by gas chromatography—flame ionization detection. After the analytical validation of the protocol, 19 air samples were quantified. The measured concentrations of TCE are close to the occupational exposure limit value in almost all facilities, whereas the PCE concentrations are about half of the OELV. The overall results showed that the working environment in dry cleaning in Sfax city are concerning
