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: marco.ranocchiari@psi.chtel: +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