Industrial Green Chemistry

Serge Kaliaguine, Jean-Luc Dubois, Serge Kaliaguine, Jean-Luc Dubois

• Publisher: De Gruyter
• Year: 2020
• eBook ISBN: 9783110646870
• Edition: 1
• Topic: Physical Sciences
• Subtopic: Environmental Science

The editors and authors, with backgrounds in academia and industry, tie together recent and established technologies for the upcoming change to sustainable industrial chemistry. The extensive worldwide activities towards that goal are exemplified with a series of green processes. Some of these processes are already commercially applied (squalene to squalane, hydraulic fluids from vegetable oils, biosourced polycarbonates), others are ready for a large scale implementation (glycerol to acrylic acid, biosourced acrylonitrile and levulinic acid, polyamides from fatty nitriles-esters hydrogenation, butadiene from bioethanol) or are being developed (cyclic carbonates from epoxides, selective pyrolysis of biomass). This book is an indispensable source for the researchers and professionals who work for a greener chemical industry. The chapters have been arranged to guide students through the design of new processes for more sustainable chemistry, using case studies as examples.

1 Conversion of glycerol to acrylic acid

Mohammad Jaber Darabi Mahboub

Arkema Inc., King of Prussia, USA

Gregory S. Patience

École Polytechnique de Montréal, Montréal, Canada

Abstract

Acrylic acid (AA) is an extraordinary compound and serves as a monomer for adhesives and sealants, plastic additives, surface coatings and paint, absorbents in diapers and personal care products and water treatment. Annual worldwide production surpassed 5 million tons, valued of 12 $ billion, and is growing at a rate close to 5% per year. Propylene’s partial oxidation to AA is the predominant process as there is no real competitive alternative. In this gas-phase process, oxygen partially oxidizes propylene to acrolein above 300 °C, which in turn is oxidized in tandem to AA, where propylene is derived from petroleum. Society and government motivate industry and academia to develop innovative technologies to reduce the environmental footprint related to AA synthesis. A biobased feedstock is a compelling alternative to propylene to approach a carbon-neutral AA process. Glycerol, a coproduct from biodiesel from vegetable oil and animal fat, dehydrates to acrolein at 300 °C, is one such biofeedstock. However, crude glycerol contains salts of fatty acids (FA), methanol, as well as various nonglyceric organic matter that adds distillation costs. Consequently, many companies choose to combust it for its fuel value, while a few convert it to methanol or epichlorohydrin rather than refining, while larger companies react it to methanol. BioMCN produce methanol from glycerol, and Solvay and others produce epichlorhydride (ref). Furthermore (excluding AA), currently, there is insufficient market for glycerol that makes this product worthless for industry, therefore, its prices dropped from $0.43 kg⁻¹ in 2003 to $0.18 kg⁻¹ and $0.02 kg⁻¹ for refined and crude glycerol, respectively, in 2010 [1]. Here, we discuss commercial or potential processes to produce AA.

1.1 Introduction

Acrylic acid (AA) is a specialty chemical (monomer) for cosmetic materials, absorbents, plastics, rubbers and adhesives [2]. Propylene (derived from fossil fuel) is the predominant feedstock; however, greenhouse gas emissions due to hydrocarbon combustion has alarmed society and government [3, 4, 5, 6]. This preoccupation has motivated industry to substitute current technology with processes that are carbon neutral. Renewable biofeedstocks such as glycerol – a coproduct of the transesterification of vegetable oil and biodiesel derived from vegetable oil or animal fat – is an attractive alternative with the following features [7, 8, 9, 10, 11]:

1. low cost
2. commercial capacity (due to increased biodiesel production) and
3. worldwide availability

Glycerol dehydration, oxidehydration and partial oxidation processes produce value-added chemicals starting with a low-cost feedstock [12, 13, 14]. Catalysts dehydrate it to acrolein in both the liquid and the gas phase [6, 15]. Catalyst operating in the gas phase deactivate due to coke while conversion remains unacceptably low in liquid-phase chemistry to warrant commercialization [7, 12, 16, 17, 18]. In this chapter, we present industrial-scale processes to AA and emerging technology related to glycerol as a feedstock.

1.2 Glycerol and its applications

Fossil fuels are inexpensive feedstocks and dominate the market for most chemical processes, but they produce greenhouse gases (CO₂). Governments encourage academia and industry to identify technology to replace petroleum with renewable resources [19, 20]. Lignocellulosics, vegetable oils, fats and other types of biomass are potential feedstocks.

Methanol transesterifies vegetable oil and animal fat triglycerides to FA esters (biodiesel) and glycerol as a coproduct – 0.10 g/g (Figure 1.1) [21, 22]. Biodiesel capacity will increase from 22.7 million tons in 2012 to 36.9 million tons in 2020 (Figure 1.2) [4, 19].

Figure 1.1: Overall transesterification reaction scheme [21, 22].

Figure 1.2: Annual production of biodiesel [19].

The ever-increasing biodiesel production has flooded the market with glycerol. Consequently, its price has dropped because of ove...

Table of contents

• Title Page
• Copyright
• Contents
• 1 Conversion of glycerol to acrylic acid
• 2 Alternative routes to more sustainable acrylonitrile: biosourced acrylonitrile
• 3 Biobased levulinic acid production
• 4 Fatty nitrile esters hydrogenation for biosourced polyamide polymers
• 5 Ni-free hydrogenation of natural products for the personal care industry: case study, squalene hydrogenation
• 6 High-performance hydraulic fluids from vegetable oils
• 7 Biomass valorization: bioethanol upgrading to butadiene
• 8 Biosourced polycarbonates
• 9 Organic cyclic carbonates synthesis under mild conditions
• 10 Biomass selective pyrolysis, bio-oil separation and products development: challenges and opportunities for green chemistry
• Index