Handbook of Green Chemistry and Technology

by Clark, James H.; Macquarrie, Duncan J.

• ISBN13: 9780632057153
• ISBN10: 0632057157
• Edition: 1st
• Format: Hardcover
• Copyright: 2002-03-15
• Publisher: Wiley-Blackwell

Summary

Sustainable development is now accepted as a necessary goal for achieving societal, economic and environmental objectives. Within this chemistry has a vital role to play. The chemical industry is successful but traditionally success has come at a heavy cost to the environment. The challenge for chemists and others is to develop new products, processes and services that achieve societal, economic and environmental benefits. This requires an approach that reduces the materials and energy intensity of chemical processes and products; minimises the dispersion of harmful chemicals in the environment; maximises the use of renewable resources and extends the durability and recyclability of products in a way that increases industrial competitiveness as well as improve its tarnished image.

Author Biography

James Clark is Professor of Chemistry and Director of the Green Chemistry Network and former industrialist.

Duncan Macquarrie is now a Royal Society University Research Fellow at the University of York.

Table of Contents

Contributors	iii
Preface	xvii
Introduction	1	(9)
James H. Clark
Introduction	1	(9)
Chemistry-past, present and future	1	(2)
The costs of waste	3	(1)
The greening of chemistry	3	(6)
References	9	(1)
Principles of Sustainable and Green Chemistry	10	(18)
Mike Lancaster
Introduction	10	(1)
Green Chemistry and Industry	10	(2)
Waste Minimisation and Atom Economy	12	(3)
Atom economy	12	(1)
Some inherently atom economic reactions	13	(2)
Some inherently atom uneconomic reactions	15	(1)
Reduction of Materials Use	15	(5)
Catalytic solutions	16	(1)
Question the need for protection	17	(1)
Reduction of non-renewable raw material use	17	(2)
Process intensification	19	(1)
Reduction of Energy Requirement	20	(2)
Some energy efficiency improvements	21	(1)
Alternative energy sources	22	(1)
Reduction of Risk and Hazard	22	(3)
Inherently safe design	22	(3)
Alternative solvents	25	(1)
Conclusions	25	(3)
References	26	(2)
Chemistry and the Environment	28	(28)
John V. Holder
Introduction	28	(1)
Chemistry of the Atmosphere	28	(11)
Structure of the atmosphere	28	(2)
Tropospheric pollution	30	(8)
Stratospheric pollution	38	(1)
Pollution of the built environment	39	(1)
Chemistry of the Terrestrial Environment	39	(11)
The Earth's crust	39	(1)
Pollution of the land	40	(3)
Freshwaters	43	(1)
Pollution of freshwater	44	(6)
Chemistry of the Oceans	50	(4)
Chemistry of the open ocean	50	(1)
Chemistry of estuaries	51	(1)
Pollution of the oceans	52	(2)
Conclusion	54	(2)
References	54	(1)
Bibliography	55	(1)
Green Chemistry and Sustainable Development	56	(6)
Thomas E. Graedel
The Concept of Sustainability	56	(1)
Green Chemistry and Sustainability's Parameters	56	(4)
Sustainable use of chemical feedstocks	57	(1)
Sustainable use of water	58	(1)
Sustainable use of energy	59	(1)
Environmental resilience	59	(1)
A Sustainability Scenario	60	(2)
References	60	(2)
Life-cycle Assessment: a Tool for Identification of More Sustainable Products and Processes	62	(24)
Adisa Azapagic
Introduction	62	(1)
The LCA Methodology	62	(7)
Methodological framework	63	(6)
The Applications of LCA	69	(11)
Product-oriented LCA	69	(4)
Process-oriented LCA	73	(7)
Conclusions	80	(1)
Appendix	81	(5)
Definition of environmental impacts	81	(2)
References	83	(3)
Industrial Processes using Solid Acid Catalysts	86	(34)
Mark A. Harmer
Introduction	86	(1)
Concepts in Acidity and Solid Acid Catalysts	87	(3)
Industrial Applications of Solid Acid Catalysts	90	(18)
Zeolite-based solid acid catalysts	90	(8)
Heteropolyacid-based solid acid catalysts	98	(4)
Sulfated zirconia	102	(2)
Ion-exchange resins	104	(3)
Acidic and pillared clays	107	(1)
Some Recent Developments in Catalytic Materials and Processes	108	(9)
The 'Kvaerner Process' and esterification chemistry	108	(1)
Nafion®/silica nanocomposites	109	(5)
Haldor-Topsoe alkylation process to high-octane fuels	114	(1)
Mobil-Badger cumene process	115	(1)
Isodewaxing process (Chevron)	116	(1)
Summary	117	(3)
Acknowledgements	117	(1)
References	117	(3)
Micelle-templated Silicas as Catalysts in Green Chemistry	120	(30)
Duncan Macquarrie
Introduction	120	(1)
Structured Mesoporous Materials	120	(5)
Synthesis of micelle-templated materials	120	(3)
Post-functionalisation of micelle-templated materials	123	(1)
Direct preparation of organically modified micelle-templated silicas	123	(2)
Catalytic Applications	125	(21)
Fundamental activity of micelle-templated silicas and aluminosilicas	125	(1)
Micelle-templated materials with enhanced acidity	126	(2)
Oxidation catalysis	128	(11)
Base catalysis (other than oxidations)	139	(5)
Enantioselective catalysis	144	(2)
Conclusion	146	(4)
References	147	(3)
Polymer-supported Reagents	150	(38)
Georges Gelbard
Introduction	150	(2)
A breakthrough in organic synthetic methods or a fancy for doing things differently?	150	(1)
Polymeric tools for organic synthesis	150	(1)
What is really possible and what is still expected	151	(1)
Making Functional Polymers	152	(7)
General schemes	152	(1)
Required properties	153	(1)
Copolymerisation with usual monomers	153	(1)
Polystyrenes	154	(1)
Spacers	155	(1)
Polyacrylates	156	(2)
Polyvinylpyridines	158	(1)
Polybenzimidazoles	158	(1)
Polyphosphazenes	158	(1)
Chlorofluoropolymers	158	(1)
Syntheses with Polymer-supported Reagents	159	(24)
Acid chlorides and anhydrides	161	(1)
Alcohols	161	(2)
Aldehydes and ketones	163	(4)
Amides and lactams	167	(1)
Amines	168	(2)
Azides	170	(1)
Azo dyes	170	(1)
Bromo-, chloro- and iodoaromatics	170	(2)
Carbodiimides	172	(1)
Epoxides	172	(1)
Esters and lactones	173	(1)
Ethers	174	(1)
Fluoro derivatives	175	(1)
Halides and dehalogenation reactions	176	(2)
Halohydrins	178	(1)
Isoxazolidines	178	(2)
Nitriles	180	(1)
Sulfoxides	181	(1)
Thiocyanates and ureas	181	(1)
Thiiranes, thiols and disulfides	181	(2)
Wittig and Wittig-related reactions	183	(1)
Conclusion	183	(5)
References	183	(5)
Biocatalysis	188	(18)
Herbert L. Holland
Introduction	188	(1)
Chemical Production by Biocatalysis	188	(9)
Bulk chemicals	188	(2)
Pharmaceuticals	190	(1)
Flavour and fragrance compounds	191	(1)
Carbohydrates	192	(2)
Enantiomerically pure synthons	194	(1)
Polymers	195	(2)
Green Biocatalytic Processes	197	(5)
Biocatalysis in supercritical CO2	198	(1)
Biocatalysis in waste treatment	198	(4)
Biodesulfurisation	202	(1)
Conclusions	202	(4)
References	203	(3)
Recent Advances in Phase-transfer Catalysis	206	(52)
Yoel Sasson
Gadi Rothenberg
Introduction	206	(1)
Progress in Classical PTC Reactions	207	(11)
Nucleophilic aliphatic and aromatic substitutions	207	(1)
Phase-transfer catalysis elimination and isomerisation reactions	208	(3)
Base-promoted C, N, O and S alkylation and arylation reactions	211	(4)
Alkylations (C, N, O and S) in alycyclic and heterocyclic syntheses	215	(3)
Inverse PTC	218	(2)
Three Liquid Phases and Triphase Catalysis	220	(2)
Asymmetric PTC	222	(5)
Phase-transfer Catalysis in Polymerisation Processes	227	(3)
Applications of PTC in Analytical Chemistry	230	(1)
Phase Transfer Combined with Metal Catalysis	230	(9)
Phase transfer in homogeneous transition metal catalysis	230	(3)
Catalysis by onium-salt-stabilised transition metal nanoclusters	233	(1)
Phase transfer in heterogeneous catalysis	234	(5)
Phase-transfer catalysis activation of metallic and non-metallic reagents	239	(1)
Hydrogen Peroxide and Other PTC Oxidations and Halogenations	239	(4)
Hydrogen peroxide and alkyl hydroperoxide oxidations	239	(2)
Other oxidising agents	241	(2)
Supercritical and Ionic Liquid PTC	243	(2)
New Experimental Tools and Modelling Techniques in PTC Research	245	(13)
References	246	(12)
Hydrogen Peroxide in Waste Minimisation-Current and Potential Contributions	258	(48)
William R. Sanderson
Introduction	258	(3)
Factors in the introduction of new technology	258	(1)
Scope of this chapter	258	(1)
Manufacture of hydrogen peroxide	259	(1)
Uses of hydrogen peroxide	259	(2)
Peroxygen Systems and their Reactivity	261	(7)
Effect of acids and bases	261	(1)
Oxygen species	262	(1)
Peracids and organic activation	263	(2)
Catalytic activation	265	(3)
State of Progress on Main Catalytic Systems	268	(8)
Redox metal and oxo-metal complexes	268	(2)
Peroxo-metal systems	270	(2)
Polyoxometallates and heteropolyanions	272	(1)
Zeolitic and smectitic materials	273	(3)
Enzymes	276	(1)
Developments in Catalysed Oxidations for Chemical Synthesis	276	(18)
Oxidations at carbon	277	(11)
Oxidations at nitrogen	288	(3)
Oxidations at sulfur	291	(2)
Halogenations	293	(1)
Developments in Catalysed Oxidations for Effluent Treatment	294	(12)
Catalysed H2O2 systems	294	(1)
Advanced oxidation processes (AOPs)	295	(1)
Treatment of refractory effluents	296	(1)
Gaseous effluent treatment	297	(1)
Soil remediation	297	(1)
References	297	(9)
Waste Minimisation in Pharmaceutical Process Development: Principles, Practice and Challenges	306	(15)
Tony Y. Zhang
Introduction	306	(4)
Focus of Process Chemistry	310	(4)
Safety	310	(1)
Increasing complexity	311	(1)
Means of purification	311	(1)
Choice of starting material	311	(1)
Yields	311	(1)
Number and order of steps	312	(1)
Robustness	312	(1)
Solvents	312	(2)
Reagents	314	(1)
Reaction temperature	314	(1)
Heavy metals	314	(1)
Endurance	314	(1)
Example 1	314	(3)
Example 2	317	(2)
Conclusion	319	(2)
References	319	(2)
Green Catalysts for Industry	321	(17)
Keith Martin
Introduction	321	(1)
Supported Reagents	322	(1)
Envirocats™	322	(1)
Envirocat EPZ10	322	(1)
Envirocat EPZG	322	(1)
Envirocat EPZE	323	(1)
Envirocat EPIC	323	(1)
Envirocat EPAD	323	(1)
Advantages of Envirocats	323	(1)
Friedel-Crafts reactions	323	(1)
Esterifications	323	(1)
Oxidations	324	(1)
Activation of Envirocats	324	(1)
General Methods for Using Envirocats	325	(1)
Catalyst concentration	325	(1)
Reaction temperature	325	(1)
Commercial Applications of Envirocats	325	(4)
Benzoylations	325	(1)
Acylations	325	(1)
Benzylations	326	(1)
Olefin alkylation	326	(1)
Aromatic bromination	327	(1)
Sulfonylation	327	(1)
Esterifications	328	(1)
Aerobic oxidations	328	(1)
Other Applications of Envirocat Catalysts	329	(3)
Envirocat EPZG	330	(1)
Envirocat EPIC	331	(1)
Envirocat EPZ10	332	(1)
The Second Generation of Envirocats	332	(3)
Envirocat EPA10	333	(1)
Envirocat EPCS	334	(1)
Future Envirocats	335	(1)
Conclusions	335	(3)
References	336	(2)
Green Chemistry in Practice	338	(28)
Joseph J. Bozell
Introduction	338	(1)
What is the Impact of Green Process Technology on the Chemical Industry?	338	(2)
Overview	340	(1)
Catalysis	341	(11)
Examples of heterogeneous catalysis in practice	341	(3)
Examples of homogeneous catalysis in practice	344	(8)
Renewables as Chemical Feedstocks and Biocatalysis	352	(9)
The case for renewables	353	(2)
Examples of the use of renewable feedstocks for the production of chemicals	355	(1)
Bioproduction of chemicals in industry	356	(5)
Conclusions	361	(5)
References	362	(4)
Process Intensification for Green Chemistry	366	(6)
Roshan Jachuck
Introduction	366	(1)
Relevance to Green Chemistry	366	(2)
Spinning Disc Reactor	368	(1)
Microreactors	369	(1)
Intensified Cross-corrugated Multifunctional Membrane	370	(1)
Conclusions	371	(1)
References	371	(1)
Sonochemistry	372	(25)
Timothy J. Mason
P. Cintas
Introduction	372	(4)
Sonochemistry	372	(1)
Power ultrasound	373	(1)
Apparatus available for sonochemistry	374	(2)
Sonochemistry in Chemical Synthesis	376	(11)
The nature of sonochemical reactions	377	(8)
Ultrasonic preparation of micro- and nanostructured materials	385	(2)
Ultrasound in Electrochemistry: Sonoelectrochemistry	387	(1)
Electroplating	388	(1)
Electrosynthesis	388	(1)
Ultrasound in Environmental Protection and Waste Control	388	(4)
Chemical decontamination	389	(2)
Biological decontamination	391	(1)
Enhanced Extraction of Raw Materials from Plants	392	(1)
Large-scale Sonochemistry	392	(1)
Batch systems	392	(1)
Flow systems	392	(1)
Conclusions	393	(4)
References	393	(4)
Applications of Microwaves for Environmentally Benign Organic Chemistry	397	(19)
Christopher R. Strauss
Background	397	(1)
Properties of Microwaves	397	(1)
Influence of Microwave Heating on Chemical Reactions	397	(1)
Rate Studies and Investigations into 'Microwave Effects'	398	(1)
Approaches to Microwave-assisted Organic Chemistry	399	(4)
Solvent-free methods	400	(1)
Methods with solvents	401	(2)
Advantages of the Pressurised Microwave Systems	403	(4)
Elevated temperature	403	(1)
Rapid heating, cooling and ease of use for high-temperature reactions	404	(2)
Control of heating	406	(1)
Exothermic reactions, differential heating and viscous reaction mixtures	406	(1)
Reaction vessels	406	(1)
Reactions with a distillation step	407	(1)
Flexible operation	407	(1)
High-temperature Water as a Medium or Solvent for Microwave-assisted Organic Synthesis	407	(3)
Reactions in high-temperature water	408	(2)
Reactions in aqueous acid and base	410	(1)
Limiting salt formation	410	(1)
Avoiding solvent extraction through resin-based adsorption processes	410	(1)
Metal-catalysed Processes	410	(1)
Enzymatic Processes	411	(1)
Deuteration and Tritiation	412	(1)
Tandem Technologies	412	(1)
Conclusion	412	(4)
References	413	(3)
Photochemistry	416	(17)
Ian X. Dunkin
Photons as Clean Reagents	416	(5)
Reduced usage of reagents	416	(1)
Lower reaction temperatures	416	(1)
Control of selectivity	417	(3)
Photochemical reactions for industry	420	(1)
General Problems with Photochemical Processes	421	(2)
Specialized photochemical reactors and process technology	421	(1)
Window fouling	422	(1)
The cost of photons	422	(1)
The Light Ahead	423	(3)
Photochemical reactors	423	(2)
Light sources	425	(1)
Conclusions	426	(1)
The Basics of Photochemistry	427	(6)
Light and energy	427	(1)
Absorption of light by molecules	428	(2)
Excited-state processes	430	(1)
Acknowledgements	431	(1)
References	431	(2)
Electrochemistry and Sustainability	433	(33)
K. Scott
Introduction	433	(1)
Green Electrochemistry	433	(1)
Electrochemistry Fundamentals	434	(8)
Electrode potential, kinetics and mass transport	435	(4)
Electrochemical cells	439	(3)
Electrochemistry and Energy Sustainability	442	(5)
Fuel cells	443	(4)
Electrochemical Synthesis	447	(6)
Metal salt preparation	448	(1)
In situ generation of reagents	448	(1)
Influence of counter-electrode	449	(1)
Paired synthesis	449	(1)
Organic electrosynthesis	450	(3)
Electrochemical Waste Minimisation	453	(13)
Recovery and recycling of metal ions	454	(3)
Cell technology and applications	457	(1)
Integration of electrodeposition with other separations	458	(1)
Electrochemical ion exchange	459	(1)
Electrochemical membrane processes	459	(2)
Electrohydrolysis	461	(3)
References	464	(2)
Fuel Cells: a Clean Energy Technology for the Future	466	(16)
Brian Grievson
Introduction	466	(1)
Fuel Cell Electrochemistry	466	(2)
Fuel Cell Technology	468	(8)
Alkaline fuel cell	469	(1)
Solid polymer fuel cell	470	(1)
Phosphoric acid fuel cell	471	(1)
Molten carbonate fuel cell	472	(1)
Solid oxide fuel cell	473	(3)
Fuel Cell Applications	476	(3)
General economics	476	(1)
Transport applications	477	(1)
Stationary power generation applications	478	(1)
Battery replacement applications	479	(1)
The Future of Fuel Cells	479	(3)
References	480	(2)
Supercritical Carbon Dioxide as an Environmentally Benign Reaction Medium for Chemical Synthesis	482	(20)
Nathalie Tanchoux
Walter Leitner
Introduction	482	(1)
Phase Behaviour and Solubility in Supercritical Reaction Mixtures	483	(2)
Supercritical CO2 as a Replacement for Organic Solvents	485	(2)
Use of Supercritical CO2 for Safer Processes	487	(3)
Improvement of Process Performance	490	(5)
Process intensification	490	(3)
Improvement of changes in stereoselectivity	493	(2)
Enhanced catalyst lifetime	495	(1)
Use of Supercritical CO2 for Product Separation and Catalyst Recycling	495	(3)
Multiphase processes using supercritical CO2 as a reaction and separation phase	495	(1)
Single-phase reactions with subsequent separation using supercritical CO2 as the reaction and separation phase	496	(2)
Simultaneous Use of Supercritical CO2 as Reaction Medium and Reagent	498	(1)
Conclusion	499	(3)
References	500	(2)
Chemistry in Fluorous Biphasic Systems	502	(22)
Jozsef Rabai
Zoltan Szlavik
Istvan T. Horvath
Introduction	502	(1)
The Fluorous Biphase Concept	502	(1)
Fluorous Solvents	503	(1)
Synthesis of Fluorous Compounds	504	(4)
Fluorous Extraction	508	(1)
Fluorous Synthesis	509	(1)
Fluorous Reagents	510	(5)
Fluorous Tags	515	(5)
Fluorous Biphasic Catalysis	520	(1)
Relationship between Fluorous and Supercritical Carbon Dioxide Media	520	(1)
Economical Feasibility of Fluorous Biphasic Chemistry	520	(4)
References	521	(3)
Extraction of Natural Products with Superheated Water	524	(8)
A. A. Clifford
Introduction	524	(1)
Properties of Superheated Water	524	(2)
Extraction of Materials Other Than Natural Products	526	(1)
Chromatography with Superheated Water	526	(1)
Extraction of Rosemary	526	(1)
Extraction of Other Plant Materials	527	(1)
Process Development	528	(1)
Extraction with Reaction	529	(3)
References	531	(1)
Index	532