Bio-Based Solvents

François Jérôme, Rafael Luque

• Publisher: Wiley
• Year: 2017
• ISBN:
  9781119065449
• Edition: 1
• Topic: Physical Sciences
• Subtopic: Industrial & Technical Chemistry

A multidisciplinary overview of bio-derived solvent applications, life cycle analysis, and strategies required for industrial commercialization

This book provides the first and only comprehensive review of the state-of-the-science in bio-derived solvents. Drawing on their own pioneering work in the field, as well as an exhaustive survey of the world literature on the subject, the authors cover all the bases—from bio-derived solvent applications to life cycle analysis to strategies for industrial commercialization—for researchers and professional chemists working across a range of industries.

In the increasingly critical area of sustainable chemistry, the search for new and better green solvents has become a top priority. Thanks to their renewability, biodegradability and low toxicity, as well as their potential to promote advantageous organic reactions, green solvents offer the promise of significantly reducing the pernicious effects of chemical processes on human health and the environment.

Following an overview of the current solvents markets and the challenges and opportunities presented by bio-derived solvents, a series of dedicated chapters cover all significant classes of solvent arranged by origin and/or chemical structure. Throughout, real-world examples are used to help demonstrate the various advantages, drawbacks, and limitations of each class of solvent.

Topics covered include:

• The commercial potential of various renewably sourced solvents, such as glycerol
• The various advantages and disadvantages of bio-derived versus petroleum-based solvents
• Renewably-sourced and waste-derived solvents in the design of eco-efficient processes
• Life cycle assessment and predictive methods for bio-based solvents
• Industrial and commercial viability of bio-based solvents now and in the years ahead
• Potential and limitations of methodologies involving bio-derived solvents
• New developments and emerging trends in the field and the shape of things to come

Considering the vast potential for new and better products suggested by recent developments in this exciting field, Bio-Based Solvents will be a welcome resource among students and researchers in catalysis, organic synthesis, electrochemistry, and pharmaceuticals, as well as industrial chemists involved in manufacturing processes and formulation, and policy makers.

Chapter 1
Glycerol as Eco-Efficient Solvent for Organic Transformations

Palanisamy Ravichandiran and Yanlong Gu

School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan, China

1.1 Introduction

Organic solvents are used in the chemical and pharmaceutical industries [1]. The global demand for these solvents has reached 20 million metric tons annually [2]. Solvents are unreactive supplementary fluids that can dissolve starting materials and facilitate product separation through recrystallization or chromatographic techniques. In a reaction mixture, the solvent is involved in intermolecular interactions and performs the following: (i) stabilization of solutes, (ii) promoting the preferred equilibrium position, (iii) changing the kinetic profile of the reaction, and (iv) influencing the product selectivity [3]. Selection of appropriate solvents for organic transformations is important to develop green synthesis pathways using renewable feedstock. In the past two decades, green methodologies and solvents have gained increasing attention because of their excellent physical and chemical properties [4–6]. Green solvents should be non-flammable, biodegradable and widely available from renewable sources [7].

Biodiesel production involves simple catalytic transesterification of triglycerides under basic conditions (Figure 1.1) [8]. This process generates glycerol as a by-product (approximately 10% by weight). The amount of glycerol produced globally has reached 1.2 million tons and will continue to increase in the future because of increasing demand for biodiesel [9]. Glycerol has more than 2000 applications, and its derivatives are highly valued starting materials for the preparation of drugs, food, beverages, chemicals and synthetic materials (Figure 1.2) [10].

Figure 1.1 Reaction for biodiesel production.

Figure 1.2 Commercial consumption of glycerol (industrial sectors and volumes).

The biodiesel industries generate large amounts of glycerol as a by-product. As such, the price of glycerol is low, leading to its imbalanced supply. Currently, a significant proportion of this renewable chemical is wasted. This phenomenon has resulted in a negative feedback on the future economic viability of the biodiesel industry and adversely affects the environment because of improper disposal [11]. In this regard, the application of glycerol as a sustainable and green solvent has been investigated in a number of organic transformations (Table 1.1). Glycerol is a colourless, odourless, relatively safe, inexpensive, viscous, hydroscopic polyol, and a widely available green solvent. Glycerol acts as an active hydrogen donor in several organic reactions. Glycerol exhibits a high boiling point, polarity and non-flammability and is a suitable substitute for organic solvents, such as water, dimethylformamide (DMF) and dimethylsulfoxide (DMSO). Thus, glycerol is considered a green solvent and an important subject of research on green chemistry. This review provides new perspectives for minimizing glycerol wastes produced by biomass industries.

Table 1.1 Physical, chemical and toxicity properties of glycerol

Melting point	17.8°C
Boiling point	290°C
Viscosity (20°C)	1200 cP
Vapour pressure (20°C)	<1 mm Hg
Density (20°C)	1.26 g cm^−3
Flash point	160°C (closed cup)
Auto-ignition temperature	400°C
Critical temperature	492.2°C
Critical pressure	42.5 atm
Dielectric constant (25°C)	44.38
Dipole moment (30–50°C)	2.68 D
LD50 (oral, rat)	12600 mg kg^−1
LD50 (dermal, rabbit)	>10 000 mg kg^−1
LD50 (rat, 1 h)	570 mg m^−3

Our research group has contributed a comprehensive review on green and unconventional bio-based solvents for organic reactions [12]. However, enthusiasm for using glycerol as a green solvent for organic transformations in partic...

Table of contents

• Cover
• Title Page
• Copyright
• Table of Contents
• List of Contributors
• Series Preface
• Foreword
• Chapter 1: Glycerol as Eco-Efficient Solvent for Organic Transformations
• Chapter 2: Aromatic Bio-Based Solvents
• Chapter 3: Solvents from Waste
• Chapter 4: Deep Eutectic and Low-Melting Mixtures
• Chapter 5: Organic Carbonates: Promising Reactive Solvents for Biorefineries and Biotechnology
• Chapter 6: Life Cycle Assessment for Green Solvents
• Chapter 7: Alkylphenols as Bio-Based Solvents: Properties, Manufacture and Applications
• Index
• End User License Agreement