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Introduction

The emerging area of green chemistry envisages the minimum use of hazardous chemicals as far as possible.

Main Goal

The main goal of MAPSYN is the development of a multifaceted strategy and a net of collaborations for a rational application of alternative energy sources to selected end user chemistries and an optimal scaling up of innovative protocols born in the laboratory scale prototypes.

Applications

The application of novel process conditions beyond usual conditions to suited chemical reactions, these can help to improve process performance and can open new ways for chemical transformation.

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Background

The MAPSYN project has been granted funding from the European Union Seventh Framework Programme (Grant Number: 309376) to investigate chemical process intensification, specifically: “Highly efficient chemical syntheses using alternative energy forms”. The information provided below has been produced by members of the MAPSYN consortium to highlight the advantages of process intensification and give background information on the state-of-the-art to encourage the further development and implementation of these technologies.

The main focus of the MAPSYN project is use of alternative energy sources and the use of flow chemistry and these topics are the main areas covered by the information below.For copyright reasons, it is not possible to provide the referenced articles for download from the MAPSYN website, but the reference and DOI descriptor are given to enable quick access to publisher’s website.

What is Process Intensification?

Process intensification can mean many things to many different people. For the scope of the MAPSYN project, we are considering process intensification in the area of chemical synthesis/manufacture. In its simplest form, process intensification is “getting more from less”, specifically obtaining higher output/throughput of a chemical process with the same or lower input (raw materials, energy, time, reactor volume).

Process intensification is not one single technology, rather is it a collection of technologies, equipment and methodologies applied together to result in a significantly more efficient chemical synthesis. In a review article from 2009 (Ind. Eng. Chem. Res. 2009, 48, 2465, DOI: 10.1021/ie801501y), Van Gerven and Stankiewicz defined 4 basic principles and domains to intensify a chemical process: spatial, thermodynamic, functional and temporal.

Process intensification is complementary to the “12 Principles of Green Chemistry” (http://www.acs.org/content/acs/en/greenchemistry/what-is-green-chemistry/principles/12-principles-of-green-chemistry.html)

developed by Paul Anastas and John Warner, which outlines an early conception of what would make a greener chemical, process, or product.

General Process Intensification (PI) Information

Many reviews have been published on process intensification and it does not make sense to duplicate all the information included there. Listed below are some general references to review articles and also information on other websites.

Review Article: Process Intensification: Transforming Chemical Engineering (Stankiewicz and Moulijn, Chemical Engineering Progress, 2000, 22)

Additional information can be found in two books dedicated to process intensification:

Process Intensification: Engineering for Efficiency, Sustainability and Flexibility, 2nd edition, D. Reay, C. Ramshaw and A. Harvey (eds.) (Butterworth-Heinemann, 2013)

Process Intensification Green Chemistry, K. Boodhoo and A. Harvey (eds.) (Wiley, 2013)

Presentation on Process Intensification (ENKI Innovation)

(http://www.enki2.com/images/PI_Fine_Chem_Adv_Materials_jan07.pdf)

Review Article: Novel Process Windows for Enabling, Accelerating, and

Uplifting Flow Chemistry (Hessel et al, ChemSusChem 2013, 6, 746, DOI: 10.1002/cssc.201200766)

There has also been a review article written by MAPSYN consortium members on the specific MAPSYN technologies under investigation: plasma, microwave and ultrasound in the areas of nitrogen fixation and hydrogenation. (Hessel et al, Chemical Engineering and Processing 71 (2013) 19, DOI: 10.1016/j.cep.2013.02.002). A related review article, also summarising the use of alternative energy sources has been published by Nasir Baig and Varma (Chem. Soc. Rev., 2012, 41, 1559, DOI: 10.1039/c1cs15204a)

In the section below, further information about specific technologies is summarised and links provided to presentations prepared by MAPSYN consortium members and also other journal articles and websites.

Flow Chemistry and Micro-reactor technology

Flow chemistry has been in use for decades in the chemical industry for the continuous synthesis of target molecules. More recently in the area of process intensification, the use of micro-reactors is becoming more prevalent, not just for the synthesis of small quantities of material, but also on an industrial scale with many parallel flow reactions. Just some of the advantages are improved mixing; faster heating and cooling, defined and controllable residence time and safe use of extreme reaction conditions or hazardous reagents.

MAPSYN partner, Fraunhofer-IMM, has been at the forefront of micro-reactor development and have prepared a presentation highlighting the capabilities and successes of micro-reactors.

(Fraunhofer-MicroReactor.pdf)

Another MAPSYN partner, DSM, has been using microreactors including 3D-metal-printed ones on a lab scale and through its joint venture DPx has production scale reactors capable of producing up to 800 tonnes/year under c-GMP conditions.

(DSM-FlowChem.pdf)

A recent article has been published by a DSM scientist on the industrialisation of flow chemistry (DSM-ChimicaOggi.pdf) which is available to be download here with kind permission of the publisher, Chimia Oggi (www.teknoscienze.com/pages/co-archive.aspx)

In addition, MAPSYN partner Syrris/Blacktrace is a manufacturer of a wide variety of flow chemistry modules including control systems. In addition to information on their Asia and Africa research and development systems (http://syrris.com/flow-products), they also have a huge database of flow chemistry examples in process chemistry as well as discovery/medicinal chemistry and other applications (http://syrris.com/applications).

For further reading, the following articles will be of interest:

Flow chemistry using milli- and microstructured reactors—From conventional to novel process windows (Illg et al, Bioorganic & Medicinal Chemistry, 2010, 18, 3707, DOI: 10.1016/j.bmc.2010.03.073)

Development of Microstructured Reactors to Enable Organic Synthesis Rather than Subduing Chemistry (Hessel et al, Current Organic Chemistry, 2005, 9, 765, DOI: 10.2174/1385272053764953)

Continuous-Flow Technology-A Tool for the Safe Manufacturing of Active Pharmaceutical Ingredients (Gutmann et al, Angew. Chem. Int. Ed. 2015, 54, 6688, DOI: 10.1002/anie.201409318)

Flow Chemistry: Recent Developments in the Synthesis of Pharmaceutical Products (Porta et al, Org. Process Res. Dev. 2016, 20, 2, DOI: 10.1021/acs.oprd.5b00325)

Heterogeneous Catalytic Hydrogenation Reactions in Continuous-Flow Reactors (Irfan et al, ChemSusChem 2011, 4, 300, DOI: 10.1002/cssc.201000354)

The Use of Gases in Flow Synthesis (Mallia and Baxendale, Org. Process Res. Dev. 2016, 20, 327, DOI: 10.1021/acs.oprd.5b00222)

For an even more wide-ranging overview, consult the book series: “Micro Process Engineering - A Comprehensive Handbook”, V. Hessel, A. Renken, J.C. Schouten, J. Yoshida (Eds.), WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, 2009

Microwaves

Microwave technology has been widely applied in the chemical industry. In addition to the known selective heating effects of microwaves in chemical synthesis, microwave irradiation has been use in separations, distillations, crystallisations and regeneration of adsorbents. A good overview of the use of microwaves in many fields is:

A helicopter view of microwave application to chemical processes: reactions, separations, and equipment concepts (Stefanidis et al, Rev Chem Eng, 2014, 30, 233, DOI: 10.1515/revce-2013-0033)

For the use of microwaves in chemical synthesis and especially flow chemistry, MAPSYN partner C-Tech have prepared an overview presentation. (CTech-MW.pdf)

There have been many discussions on the exact role and effect of microwaves in chemical synthesis. These discussions and many applications have been summarised in a number of recent review articles, a selection are listed below:

Controlled Microwave Heating in Modern Organic Synthesis (Kappe, Angew. Chem. Int. Ed. 2004, 43, 6250, DOI: 10.1002/anie.200400655)

Microwave dielectric heating in synthetic organic chemistry (Kappe, Chem. Soc. Rev., 2008, 37, 1127, DOI: 10.1039/b803001b)

Microwave Effects in Organic Synthesis: Myth or Reality? (Kappe et al, Angew. Chem. Int. Ed. 2013, 52, 1088, DOI: 10.1002/anie.201204103)

On the existence of and mechanism for microwave specific reaction rate enhancement (Dudley et al, Chem. Sci., 2015, 6, 2144, DOI: 10.1039/c4sc03372h)

In addition, further information on the effect of microwaves on reductions and also on the preparation of catalysts for reduction can be found in the following review article:

Effects of Ultrasound and Microwaves on Selective Reduction: Catalyst Preparation and Reactions (Wu et al, ChemCatChem 2014, 6, 2762, DOI: 10.1002/cctc.201402221)

Plasma

Information about the improvements that can be realised through the use of plasma in nitrogen fixation have been provided by MAPSYN partner TU/e. As energy consumption is one of the key driving forces in the improvement of the nitrogen fixation process, there is a huge potential for non-conventional energy sources to provide a financial and environmental benefit. (TUe-Plasma.pdf).

In addition, a review of plasma nitrogen fixation has been published:

Plasma N2-fixation: 1900–2014 (Patil et al, Catalysis Today, 256 (2015) 49, DOI: 10.1016/j.cattod.2015.05.005)

For an example of using Life Cycle Assessment to calculate the environmental impact of a plasma process, see:

Life Cycle Assessment of Nitrogen Fixation Process Assisted by Plasma Technology and Incorporating Renewable Energy (Anastasopoulou et al, Industrial & Engineering Chemistry Research, 2016 in press, DOI:10.1021/acs.iecr.6b00145)

Ultrasound

Ultrasound is a technology that has applications in many fields. In the areas of chemistry and process intensification, the mechanical effects of ultrasound can be significant. The mechanisms of action and acceleration that take place under ultrasound irradiation can be significantly different to other processes, resulting in enhanced or different selectivity and reactivity pathways. Two good introductory reviews have recently been published:

On the mechanochemical activation by ultrasound (Cravotto et al, Chem. Soc. Rev., 2013, 42, 7521, DOI: 10.1039/c2cs35456j)

Merging microfluidics and sonochemistry: towards greener and more efficient micro-sono-reactors (Fernandez Rivas et al,  Chem. Commun., 2012, 48, 10935. DOI: 10.1039/c2cc33920j)

A presentation on the modelling of flow reactors and the use of ultrasound has been prepared by MAPSYN partner Alicante University (Alicante-US2.pdf). Further information on acoustic modelling can be found in the following articles:

Guidelines for the design of efficient sono–microreactors, (F.J. Navarro–Brull et al, Green Processing and Synthesis, 2014, 3, 311, DOI: 10.1515/gps-2014-0052)

Simulation of the spatial distribution of the acoustic pressure in sonochemical reactors with numerical methods: A review, (I. Tudela et al, Ultrasonics Sonochemistry , 2014, 21, 909. DOI: 10.1016/j.ultsonch.2013.11.012)

Further information on acoustic modelling can be found in the following articles:

For specific application in the field of hydrogenation (which is a topic for the MAPSYN project), see the following review article:

Effects of Ultrasound and Microwaves on Selective Reduction: Catalyst Preparation and Reactions (Wu et al, ChemCatChem 2014, 6, 2762, DOI: 10.1002/cctc.201402221)

For further reading, the following book will be of interest:

Production of Biofuels and Chemicals with Ultrasound, Fang, Zhen, Smith, Jr., Richard L., Qi, Xinhua (Eds.) (Springer 2014)