529-0192-00L Jeroen A. van Bokhoven, Marco Ranocchiari · 2020-03-12 · Green Chemistry uses...
Transcript of 529-0192-00L Jeroen A. van Bokhoven, Marco Ranocchiari · 2020-03-12 · Green Chemistry uses...
Industrial Chemistry529-0192-00L
Jeroen A. van Bokhoven, Marco Ranocchiari
Contact Info
Dr. Marco Ranocchiari
Laboratory for Catalysis and Sustainable Chemistry (LSK)OSUA/2045232 Villigen PSISwitzerland
email: [email protected]: +41 (0)56 310 58 43
Fr. 10.45 – 11.30 HCI J 4
Learning Material and Books
Script/Slideshttp://www.vanbokhoven.ethz.ch/education/
Book 1H.-J. Arpe, Industrial Organic Chemistry, Wyley-VCH, 5th Edition
Book 2G. P. Chiusoli, P. M. Maitlis, Metal-catalysis in Industrial Organic Processes, RSC Publishing, 2008
The Exam30 min Oral Exam
The GOALS
Understanding where the most important chemicals come from
Understanding and discussing reaction mechanisms of some industrial processes
Understanding and discussing reactor design of some industrial processes
Understanding how industrial processes are developed
The goal of the chemical industry
To be competitive on the market
Introduction of new process Constant improvement of existing processes
The industrial chemical sectorsRefinery Commodity Fine-
chemicalsPharmaceuticals
Process intensive
Scale ~4000 Mt/a
Crude oil Natural gas
Coal
10-100 Mt/a 0.01-10 kt/a
R&D investments 1% 2-5% 5-7% 15%
R&D focus Process improvements
Mechanisms and catalyst development
Fast synthesis Formulation & drug discovery
Examples of products
Gas fuels, paraffins, gasoline, naphtha
kerosene, diesel fuel
ethylene, methanol, polymers,
styrene, acetic acid
Pure chemicals for
pharma, agrochemical applications
Formulated drugs for
pharma and agrochemical
sectors
Selection of the right processThe importance of feedstockAn example: Acetic acidMethod 1: CH2=CH2 + 1/2 O2 → CH3CHO CH3CHO + 1/2 O2 → CH3COOHMethod 2: CH3-CH2-CH2-CH3 + O2 → 2 CH3COOH + other productsMethod 3: CO + 2 H2 → CH3OH CH3OH + CO → CH3COOH
Available feedstocksOil, natural gas are feedstocks for 95% of organicscoal, biomass are becoming a valuable alternative
Thermodynamic feasibilityGenerally ΔG >40 kJ/molDrive equilibrium to the desired directionΔH has fundamental role: reactions with ΔH > 0 requires energy from outside in reactions with ΔH < 0, energy needs to be removed to avoid runaway reactions
Reactions need to be fast
Preferred: Cheaper and more available feedstock
The importance of catalysisA Catalyst opens a new reaction pathway:
The equilibrium position is determined by by thermodynamic parameters of the reaction and NOT by the presence of the catalyst (ΔG0 < 0 → K > 1).
Synthesis of ammonia 3/2 H2 + 1/2 N2 NH3
• "detonator of the population explosion"
• produces 450 million tonnes of nitrogen fertilizer per year
Without Catalyst
With Catalyst
ΔH
Reaction coordinate
Homogeneous catalysisExample: Metathesis of olefins
Heterogeneous catalysisExample: Ethylene hydrogenation
Atom economy
Atom economy (atom efficiency) is the conversion efficiency of a chemical process in terms of all atoms
involved and the desired products produced.
E-factor
The E-factor is defined by the ratio of the mass of waste per mass of product
Sustainable chemistryGreen Chemistry
Everyone’s Doing It! The 12 Principles of Green Chemistry
A framework for designing or improving materials, products, processes and systems.
1. Prevent Waste 2. Atom Economy 3. Less Hazardous Synthesis 4. Design Benign Chemicals 5. Benign Solvents & Auxiliaries 6. Design for Energy Efficiency 7. Use of Renewable Feedstocks 8. Reduce Derivatives 9. Catalysis (vs. Stoichiometric) 10. Design for Degradation 11. Real-Time Analysis for Pollution Prevention 12. Inherently Benign Chemistry for Accident Prevention
*Anastas, P. T.; Warner, J. C. Green Chemistry: Theory and Practice, Oxford University Press: New York, 1998, p.30. By permission of Oxford University Press.
www.acs.org/greenchemistry
A New Kind of Chemistry
Green Chemistry is based on a set of principles that when used in the design, development and implementation of chemical products and processes, enables scientists to protect and benefit the economy, people and the planet. Green Chemistry uses renewable, biodegradable materials which do not persist in the environment. Green Chemistry is using catalysis and biocatalysis to improve efficiency and conduct reactions at low or ambient temperatures. Green Chemistry is a proven systems approach. Green Chemistry reduces the use and generation of hazardous substances. Green Chemistry offers a strategic path way to build a sustainable future.
© 2014 ACS Green Chemistry Institute® To catalyze and enable the implementation of green chemistry
and engineering throughout the global chemical enterprise
Homogeneous catalysis and transition metal complexeshttp://www.vanbokhoven.ethz.ch/education/APPENDIX 1. G. P. Chiusoli, P. M. Maitlis, Metal-catalysis in Industrial Organic Processes, RSC Publishing, 2008.
Heterogeneous catalysis and surfacesAPPENDIX 2. G. P. Chiusoli, P. M. Maitlis, Metal-catalysis in Industrial Organic Processes, RSC Publishing, 2008.
The basics of catalysis