Novel Process Windows
Description
The first part presents the new reactor and process-related technologies, introducing the potential and benefit analysis. The core of the book details scenarios for unusual parameter sets and the new holistic and systemic approach to processing, while the final part analyses the implications for green and cost-efficient processing.
With its practical approach, this is invaluable reading for those working in the pharmaceutical, fine chemicals, fuels and oils industries.
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Dr.-Ing. habil. Norbert Kockmann, born 1966, studied mechanical engineering at Technical University of Munich and received his diploma in 1991. Dr. Kockmann was awarded his doctorate thesis in 1996 on fouling in falling film evaporators and its mitigation from The University of Bremen. In 1997, Dr. Kockmann worked as a project engineer at Messer Griesheim, Germany and was project manager for air separation units and a syngas plant. After 5 years industrial experience, he formed a research group for micro process engineering at the IMTEK Albert-Ludwig University of Freiburg, and was awarded his habilitation in 2007 on transport phenomena in micro process engineering. Since October 2007, Dr. Kockmann is senior researcher at Lonza Ltd, Visp, Switzerland and responsible for microreactor development and continuous-flow reactor technology. His fields of research comprise micro process engineering for mixing, heat transfer, fine chemistry and pharmaceutics, and micro reactor development and fabrication. Dr. Kockmann is author or co-author of more than 30 journal publications and 65 conference contributions, five book chapters, and two books. In 2009, Dr. Kockmann received the ASME award ICNMM09 Outstanding Researcher in Transport Phenomena in Microchannels.
Dana Kralisch, born in 1973, studied environmental chemistry at the Friedrich-Schiller-University (FSU), Jena, Germany. After two years consulting in environmental analytics at the Agency for Agriculture of the Federal State of Thuringia, she started to work as a research assistant at the Institute of Technical and Environmental Chemistry (FSU) in 2002. In her work she concentrated on the integration of sustainability criteria into chemical process development with a focus on micro reaction technology and ionic liquids. In 2006, she was awarded her PhD from the School of Chemical and Earth Sciences (FSU).Since 2007, she is leading the Green Process Engineering and Evaluation Research Group at the Institute of Technical and Environmental Chemistry. She is currently working on the coupling of life cycle assessment and green chemical process design in the framework of the German Novel Process Windows cluster and in the context of nanocellulose research. Dr. Kralisch is author or co-author of 13 per-reviewed publications, 4 book chapters, 27 conference contributions and two patents.
Content
Prelude - Potential for Green Chemistry and Engineering
Green Chemistry
Green Engineering
Micro- and Milli-Process Technologies
Flow Chemistry
Two Missing Links - Cross-Related
NOVEL PROCESS WINDOWS
Transport Identification - The Potential of Reaction Engineering
Chemical Reactivity in Match or Mismatch to Intensified Engineering
Chemical Intensification through Harsh Conditions - Novel Process Windows
Flash Chemistry
Process-Design Intensifiaction
CHEMICAL INTENSIFICATION
Length Scale
Time Scale
Length and Time Scale of Chemical Reactions
Temperature Intensification
Pressure Intensification
MAKING USE OF THE "FORBIDDEN" - EX-REGIME/HIGH SAFETY PROCESSING
Hazardous Reactants and Intermediates
Ex-Regime and Thermal Runaway Processing
EXPLORING NEW PATHS - NEW CHEMICAL TRANSFORMATIONS
Direct Syntheses via One Step
Direct Syntheses via Multicomponent Reactions
Multistep One-Flow Syntheses
Multistep Syntheses in One Microreactor/Chip
Multistep Syntheses in Coupled Microreactors/Chips
ACTIVATE - HIGH-T PROCESSING
Tailored High-T Microreactor Design and Fabrication
Cryogenic to Ambient - Allowing Fast Reactions to be Fast
From Reflux to Superheated - Speeding-Up Reactions
Solvent-Scope Widening by Virtue of Pressurizing Existing High-T Reactions
New Temperature Field for Product and Material Control
Energy Activation Other than Temperature - Photo, Electrochemical, Plasma
PRESS - HIGH-p PROCESSING
Tailored High-p Microreactor Design and Fabrication
High Pressure to Intensify Interfacial Transport in Gas-Liquid Reactions
Pressure as Direct Means - Activation Volume Effects and More
Pressure for Advanced Fluidic Studies - to be Used for Shaping Materials and More
COLLIDE AND SLIDE - HIGH-c AND TAILORED-SOLVENT PROCESSING
Batch Process-Based Inspirations for High-c Flow Processes
Solvent-Free or Solvent-Less Operation - "Highest-c"
Supercritical Fluids to Combine the Former Separated - Mass Transfer Boost
DOING MORE BY COMBINING - PROCESS INTEGRATION
Integration of Reaction and Cooling/Heating, Separation, or Other
Integration of Process Control and Sensing
Thermal Integration on a Process Level
Integration of Units on Racks, Backbones, Frames, Interfaces, or Similar Level
Fully Intensified/Flow Process Development
DOING THE SAME WITH LESS - PROCESS SIMPLIFICATION
Omitting the Use of a Catalyst
Simplifying Separation
IMPLICATIONS OF NPW TO GREEN AND COST EFFICIENT PROCESSING
Introduction
Knowledge-Based Design of Future Chemistry - Coupling the Implementation of NPW with Evaluation and Decision Support Tools
Evaluation Methods
Evaluation of the NPW Concept Impact on Sustainability
Future Environmental and Economic Sustainability Evaluation in the Context of Flow-Chemistry under NPW Conditions
FROM MILLIGRAMS TO KILOGRAMS - SCALE-UP IN MODULAR FLOW REACTORS
Reactor Types
Scale-Up Parameters
Numbering-Up
Single-Channel Operation
Methodology for Continuous-Flow Process Development
Conclusions
EVOLUTION OF NOVEL PROCESS WINDOWS
Multifaceted Novel Process Windows: Evolution
High-p,T Commerical Flow Chemistry Equipment
Funding Agency Initiatives
SCIENTIFIC DISSEMINATION OF NOVEL PROCESS WINDOWS
Literature Share for Chemical Intensification
Literature Share for Process-Design Intensification
OUTLOOK
Process Automation
Means of Activation Other than High-Temperature, High-Pressure, High-Concentration, and High-Solvent
Index
1
From Green Chemistry to Green Engineering - Fostered by Novel Process Windows Explored in Micro-Process Engineering/Flow Chemistry
1.1 Prelude - Potential for Green Chemistry and Engineering
Green Chemistry is since about 20 years an approach which is meanwhile quite established in chemical research and education [1]. Experts predict a fast-paced growth of the market for Green Chemistry-type processing, from $2.8 billion in 2011 to $98.5 billion in 2020 (Pike Research study [2]). Finally - yet probably not before the next 20 years - experts expect this to eliminate the need for Green Chemistry as an own approach, since it will be identical to the chemistry in the future. Anastas and Kirchhoff [3] bring this to the point in "Origins, Current Status, and Future Challenges of Green Chemistry" as follows.
The revolution of one day becomes the new orthodoxy of the next.
Green Engineering followed somewhat later and just recently came out the shadow of "its big brother." The implementation of that idea in the chemical industry proceeds now steadily, yet for reasons of complexity of the chemical processes, unavoidably at a slow rate. Today, only 10% of the current process technologies employed on industrial scale can be considered environmentally benign. It is estimated that another 25% could be made so. That leaves room for exploring and discovering the residual 65% of industrial process technology and to render them sustainable [4].
That means that there is still a considerable need to improve the enabling technologies which render chemical synthesis and chemical processes green. Under the umbrella of process intensification, microreaction technology and flow chemistry are prime enablers on the reactor and process side (see later in this chapter for citations). They help to improve current Green Chemistry approaches and in addition even give opportunities to develop new Green Chemistry concepts, which are not possible with conventional equipment. On top of that, micro- and milli-continuous processing provides a more straightforward way to upscale new green ideas. Seeing the last paragraph and the achieved 10% penetration, this is obviously still an open issue.
In continuation of the above given aphorism, this book shall open a window from Green Chemistry to Green Engineering as follows.
The revolution in the chemical laboratory needs to stimulate and bridge to the sustainability evolution on the full-production scale. [5]
1.2 Green Chemistry
Driven by political as well as societal demands, sustainability aspects gain increasing importance in all areas of human beings. Chemical production of compounds, for example, textiles, construction, ingredients in food and cosmetics, packaging, pharmaceuticals, and so on, covers more or less all aspects of human needs. The resulting extensive impact on our environment and consumption of depletable resources distinctly demands for the most efficient use of raw materials and energy. Pollution has to be prevented or at least minimized at the source to avoid end-of-pipe treatments.
New concepts have to come off with significant benefits, for example, in yield, selectivity, heat management, waste reduction, to become an environmentally benign alternative to the state of the art. Also, the environmental burdens of any reaction component, auxiliaries, and energies, obtained during upstream processes, as well as all downstream processes involved have to be taken into account.
All this has stimulated an on-going and total rethinking how to change the elemental pathways of chemical synthesis design, which has become a large movement and created an own scientific filed and society known as Green Chemistry. While processes in the past were guided by economic, technical, and safety criteria, it is now becoming increasingly obvious and a to-do-must to have considered environmental criteria from the very beginning of the process development - which is the creative intuition of the organic chemist how to conceptually approach synthetic chemistry.
1.2.1 12 Principles in Green Chemistry
In one sentence, Green Chemistry was defined as follows [2].
Green chemistry is the utilization of a set of principles that reduces or eliminates the use or generation of hazardous substances in the design, manufacture, and application of chemical products.
In kind of tabellaric goal definition, Green Chemistry was defined as follows [1b, p. 30].
- Prevention
- Atom economy
- Less hazardous chemical syntheses
- Designing safer chemicals
- Safer solvents and auxiliaries
- Design for energy efficiency
- Use of renewable feedstocks
- Reduce derivatives
- Catalysis
- Design for degradation
- Real-time analysis for pollution prevention
- Inherently safer chemistry for accident prevention.
Essentially, one can reduce that to three major incentives which are to optimize the type of feedstock, its efficiency in conversion, and the safety while doing so (derived from own thoughts and [2]).
- Feedstock: A shift to renewable (non-petroleum) feedstocks
- Efficiency: (i) make maximal use of starting materials (reactants) and minimize waste; (ii) minimize solvent load; and (iii) minimize energy efficiency
- Safety: have maximal process safety and minimize toxicity (to human).
Ideally, supposed-to-be nongreen reagents just vanish from the chemical protocol by using a new chemical route such as given for GSK (Glaxo-Smith-Kline)'s green Friedel-Crafts alkylations [6]. Manifold applications have been demonstrated with respect to modern synthetic strategies, alternative solvents, renewable resources, catalysis, and environmental-friendly enzymatic catalysis in flow [1c-e, 7].
1.3 Green Engineering
1.3.1 10 Key Research Areas in Green Engineering
In 2005, the American Chemical Society (ACS) Green Chemistry Institute (GCI) and global pharmaceutical companies established the ACS GCI Pharmaceutical Round-table to motivate for integration of Green Chemistry and Engineering into the pharmaceutical industry [8]. This Roundtable developed a list of key research areas in green chemistry in 2007. In 2010, the Roundtable companies have identified a list of the key green engineering research areas that is intended to be the required companion of the first list. The companies involved were Boehringer Ingelheim Pharmaceuticals, Pfizer, Eli Lilly, GlaxoSmithKline, Dutch State Mines/De Staats Mijnen (DSM), Johnson & Johnson, AstraZeneca, and Merck (US).
Ten key green engineering research areas were ranked in relevance (see Table 1.1). The issues 6-10 match with what is understood under process-design intensification in this book - (6) life-cycle analysis, (7) integration of chemistry and engineering, (8) scale-up, (9) process energy intensity, and (10) mass and energy integration. The key areas 1-5 in Table 1.1 refer partly to chemical intensification.
Table 1.1 Ten prime green engineering research areas as identified by ACS GCI Pharmaceutical Round Table (reproduced with permission)
Rank Main key areas Sub-areas/aspects 1 Continuous processing Primary, secondary, Semi-continuous, and so on 2 Bioprocesses Biotechnology, fermentation, biocatalysis, GMOs 3 Separation and reaction technologies Membranes, crystallizations, and so on 4 Solvent selection, recycle, and optimization Property modeling, volume optimization, recycling technologies, in process recycle, regulatory aspects, and so on 5 Process intensification Technology, process, hybrid systems, and so on 6 Integration of life cycle assessment (LCA) Life cycle thinking, total cost assessment, carbon/eco-foot printing, social LCA, stream lines tools 7 Integration of chemistry and engineering Business strategy, links with education, and so on 8 Scale-up aspects Mass and energy transfer, kinetics, and others 9 Process energy intensity Baseline for pharmaceuticals, estimation, energy optimization 10 Mass and energy integration Process integration, process synthesis, combined heat and power, and so onAdapted with permission from [8]. Copyright 2012 American Chemical Society.
1.3.2 12 Principles in Chemical Product Design
A product-design view is provided by the 12 Principles of Green Engineering which were proposed by Anastas and Zimmerman [9]. Sustainability is here approached in a hierarchical crossover between the molecular, product, process, and system levels.
- Inherent rather than circumstantial
Designs of chemical processes shall be so much efficient and nonhazardous as possible. Example is a process to synthesize organic solvents from sugars, which has replaced many more hazardous solvents such as methylene chloride (Argonne National Laboratory). The very low energy input, high efficiency, elimination of...
