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Sustainable Production of ACrylic acId from reNewable waste Glycerol

Lead Research Organisation: University of Manchester
Department Name: Chem Eng and Analytical Science

Abstract

Acrylic acid is an essential bulk chemical commodity used for the production of resins, coatings, adhesives, textile, detergents and other consumer products. It is currently manufactured on the commercial using fossil fuel-based routes, in particular from the oxidation of propylene, the latter being a major product of the naphtha and oil cracking process. The global market of acrylic acid is currently growing of 3-5% annually and the UK is responsible of consuming > 25 ktons/y with no local production capacity thus totally relying on imports from EU and Asia. On the other hand, glycerol is an abundant and cheap feedstock with yearly production of 58 tons/y between UK and Ireland.

In order to reach the much sought-after goal of a carbon neutral society, the chemical industry must evolve and shift the focus on new and sustainable routes that are still able to meet current demands of key chemicals, such as acrylic acid, but with significant reduction of detrimental effects on the environment.

In this context, the main goal of the SPACING project is the demonstration and scale-up of a new process for acrylic acid manufacturing using waste glycerol.

This project comprises three interlinked work packages (WPs):

- WP1 will involve the design, testing and characterisation of new bi-functional catalytic materials, stability test and kinetic studies, including the scale-up to 200 grams for the subsequent tests.

- WP2 will focus on the development and testing of the new integrated fluidised membrane reactor. Both new experimental demonstration and long-term testing under different reactive conditions will be carried out including the benchmark and comparison of different reactor configurations. The experimental results will be used to validate the reactor model. The knowledge gained both from the experimental and numerical activities will be used as guidance for future pilot-scale demonstration of the technology.

- In WP3, the SPACING process will be integrated into the acrylic acid process including feedstock pre-treatment and downstream product separation and refining. The techno-economic and environment performance of the process will be compared with commercial state-of-the-art technologies for acrylic acid manufacturing.

Publications

10 25 50

 
Description The current project investigates the feasibility of producing acrylic acid from glycerol, a renewable feedstock that can be obtained as a by-product of biodiesel production. The comprehensive approach combines experimental catalyst screening studies, the operation of an innovative membrane reactor, and complementary modelling efforts to identify optimal reaction conditions. To date, the following key findings have been obtained:

1 - Fluidized Bed Membrane Reactor Design: Our team has designed and developed a fluidized bed membrane reactor. Investigation into integrating a membrane reactor into the design is underway to enhance process efficiency further. Additionally, advanced 1D and 2D simulations using software like C++ and COMSOL have been used to develop models for optimising temperature, feed composition, and pressure in the reaction processes being investigated. Preliminary simulations show the possibility to achieve high glycerol conversion and selectivity for acrolein and acrylic acid. The initial work has been presented in several international conferences. A paper on this topic has recently been submitted.

2- Catalyst and Process Development: There has been a significant progress and achievements in optimal catalyst design and synthesis for the direct conversion of glycerol to acrylic acid. In particular, we successfully synthesized a bifunctional catalysts for the direct conversion of glycerol to acrylic acid, which is one of the main goals of the project. The catalyst was tested on a fixed-bed reactor (TRL 2 - 3) and showed excellent yield to acrylic acid with very good stability. The results have been summarised in a high standard research paper that has been submitted and is now under review. We are now working on the scale-up of this process on a larger scale reactor.

3- Life Cycle Assessments (LCAs): We conducted LCAs to evaluate different aspects of chemical production in the glycerol to acrylic acid processes. One study focused on purifying glycerol, the main by-product of biodiesel production. Findings, published in the Journal of Cleaner Production (Elsevier), revealed significant impacts of waste and raw materials on the carbon footprint and other environmental indicators in the purification process. Additionally, it was also found that processes using petrochemically-produced glycerol for producing acrylic acid had higher global warming impacts due to more energy-intensive processes; however using purified crude glycerol from the biodiesel industry reduced significantly the environmental impacts of acrylic acid production, hence making the glycerol to acrylic acid route much more appealing. One paper has recently been published in the Journal of Cleaner Production (Elsevier). Another study, now published in Green Chemistry (RSC) examined different process routes for producing acrylic acid from glycerol and propylene. Our results showed that the use of purified crude glycerol from the biodiesel industry results in a considerable reduction of the environmental impact relative to traditional processes based on propylene or novel approached that use epichlorohydrin-derived glycerol as the feedstocks. This shows that there are tangible environmental benefits in pursuing novel chemical processes based on bio-derived glycerol. More recently, we completed follow-up work on techno-economic assessment of biodiesel-derived crude glycerol purification processes, which has been accepted for publication in RSC sustainability with excellent reviews. This work provides crucial insights for decision-making in the growing biodiesel industry, emphasizing the need for balancing economic viability with sustainability and adaptability in glycerol purification technologies.
Exploitation Route This sustainable conversion of glycerol into acrylic acid has multifaceted outcomes and can provide a process approach that can be extended to a variety of other chemicals and other renewable feedstocks. The development of a membrane-based reactor to convert bioderived feedstocks has the potential to improve sustainability in the chemical industry both in terms of raw materials and reactor technologies and can provide an integrated approach that combines reaction and separation into a single unit, hence avoid the use of downstream separation processes. This approach could be adapted by biorefineries and could be used for cases whereby reaction products such as hydrogen and water are produced, which is the case for many industrially relevant reactions.
Sectors Chemicals

Energy

Environment

Manufacturing

including Industrial Biotechology

 
Description We were recently contacted by a company involved in the acrylate business, namely, the Columbia Holding. The company became aware of our research work after reading some of our latest research publications related to the project. We had some initial meetings discussing some potential collaboration focused on project commercialisation, in particular transformation of crude glycerol to acrylic acid. Discussion is ongoing.
First Year Of Impact 2022
Sector Chemicals,Manufacturing, including Industrial Biotechology
Impact Types Economic

 
Description Collaboration with the Department of Chemistry at the University of Ferrara (Italy) 
Organisation University of Ferrara
Country Italy 
Sector Academic/University 
PI Contribution We have contributed to unravel important physico-chemical properties of hierarchical catalytic materials used for understanding the role of humin formation in conversion of biomass-derived chemicals
Collaborator Contribution Providing new expertise in making hierarchical catalytic materials for synthesis of value-added chemicals from bio-mass derived feedstocks.
Impact https://pubs.acs.org/doi/full/10.1021/acsami.3c04613
Start Year 2023
 
Description Collaboration with the Department of Chemistry at the University of Sheffield (UK) 
Organisation University of Sheffield
Country United Kingdom 
Sector Academic/University 
PI Contribution We have used our in-house expertise on analytical tool to design and develop optimised reaction systems for conversion of glucose to fructose using zeolite catalysts, which are relevant to the project
Collaborator Contribution Providing expertise on synthesis of zeolites. Such expertise has been exploited to produce catalytic materials used in the project.
Impact https://www.sciencedirect.com/science/article/pii/S0021951723002671 https://www.sciencedirect.com/science/article/pii/S0926860X22002125
Start Year 2022
 
Description Collaboration with the Department of Industrial Chemistry at the University of Bologna (Italy) 
Organisation University of Bologna
Country Italy 
Sector Academic/University 
PI Contribution We have been working on zirconia and gold-based catalysts for the sustainable production of value-added chemicals from biomass-derived feedstcoks. We have made a significant contribution is using methods developed in the project to study surfaces of heterogeneous catalysts in order to rationalise chemical reactivity of different zirconia phases and type of catalytic nanoparticles used for the reaction.
Collaborator Contribution The collaborator provided us useful knowledge for developing catalytic materials to be used in our project.
Impact https://www.sciencedirect.com/science/article/pii/S0021951723004220 https://pubs.rsc.org/en/content/articlelanding/2023/gc/d2gc04418h
Start Year 2023
 
Description Collaboration with the Eindhoven University of Technology 
Organisation Eindhoven University of Technology
Country Netherlands 
Sector Academic/University 
PI Contribution Our team has generated new ideas in order to exploit the membrane know-how developed by the collaborator in new technologies, in our case catalytic reactors from glycerol conversion.
Collaborator Contribution A new collaboration with the Department of Chemical Engineering of the Eindhoven University of Technology has been established. Our collaborator will provide use with membranes to be integrated in catalytic reactors and will help with reaction modelling. The University will also host some of the team members for a secondment.
Impact The collaborator is going to host one of our team member to provide training and know-how on reactor membrane technologies
Start Year 2022