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Evaluation of Alternative Reaction Pathways

Chapters 7 and 8

David T. Allen
Department of Chemical Engineering
University of Texas at Austin
Modified by Robert Hesketh,
Rowan University
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University of Texas at Austin Michigan Technological University

Reaction pathways. • atom efficiency raw materials. 8 conversions. Detailed design • Process integration Tier 3 10. Flowsheet systhesis. 11 methods • multimedia environmental fate modeling • relative risk assessment 2 University of Texas at Austin Michigan Technological University . Release estimation. Tier 2 8. solvents 2. 9 specific process units optimum choice of defined • mass separating agents • process units • processing conditions 3. Module 3: Hierarchical design process for pollution prevention Design Stage P2 Tools Environmental Book Evaluation Chapter 1. • Green Chemistry Tier 1 7. and yields.

Module 3: Green Chemistry .Ch 7  Guiding principles for reactions » Simplicity » Safety » High yield and selectivity » High energy and atom efficiency » Use of renewable resources » Recyclable reagents and raw materials 3 University of Texas at Austin Michigan Technological University .

Module 3: Feedstocks and solvents  Important considerations » Human / ecosystem health properties – Bioaccumulative? – Persistent? – Toxic? – Global warming. Smog formation? – Flammable or otherwise hazardous? – Renewable or non renewable resource? » Life cycle environmental burdens? . Ozone depletion.Ch 13. 14 4 University of Texas at Austin Michigan Technological University .

Module 3: Alternative choices: raw materials Benzene • fossil fuel source • carcinogenic Glucose • renewable source • non-toxic 5 University of Texas at Austin Michigan Technological University .

Module 3: Alternative choices: Solvents Supercritical CO2 Non-toxic. renewable sources Selectivity enhancement with SC CO2 Water as alternative solvent (as a co-solvent with an alcohol) Reaction rate enhancements 6 University of Texas at Austin Michigan Technological University . non-flammable.

Module 3: Synthesis pathways Reaction Type Waste Generation Potential Addition Reaction • completely incorporate starting Isobutylene + methanol  methyl tert-butyl ether material into product C4H8 + CH3OH  (C4H9)-O-CH3 Substitution Reaction • stoichiometric amounts of Phenol + ammonia  analine + water waste are generated C6H5-OH+ NH3  C6H5-NH2 + H2O Elimination Reaction • stoichiometric amounts of Ethylbenzene  styrene + hydrogen waste are generated C6H5-C2H5  C6H5-C2H3 + H2 7 University of Texas at Austin Michigan Technological University .

8% • Oxygen .100% Mass Efficiency (Basis 1 mole of product) C6H5-OH+ NH3  C6H5-NH2 + H2O Mass in Product = (6 C) (12) + (7 H) x (1) + (0 O) x 16) + (1 N) x (14) = 93 grams Mass in Reactants = (6 C) (12) + (9 H) x (1) + (1 O) x 16) + (1 N) x (14) = 111 grams Mass Efficiency = 93/111 x 100 = 83.the fraction of starting material incorporated into the desired product - C6H5-OH+ NH3  C6H5-NH2 + H2O • Carbon . Module 3: Atom and Mass Efficiency: magnitude of improvements possible Atom Efficiency .8% 8 University of Texas at Austin Michigan Technological University .0/1 x 100 = 0% • Nitrogen .100% • Hydrogen .7/9 x 100 = 77.

search a database for alternatives • Designing Safer Chemicals .alternative solvents / uses .information on chemical classes • Green Solvents/Reaction Conditions . Module 3: Software exploration Green Chemistry Expert System TOPIC AREAS • Green Synthetic Reactions .solvent properties 9 University of Texas at Austin Michigan Technological University .

Module 3: Software demonstration Green Chemistry Expert System search Green Synthetic Reactions for adipic acid references 10 University of Texas at Austin Michigan Technological University .

V.02-. N2O.from cyclohexanol/cyclohexanone Cu (.1%) 92-96% Yield of Adipic Acid hazardous global warming • Carbon .100% ozone depletion • Oxygen . N2) V (. Adipic Acid.493 11 University of Texas at Austin Michigan Technological University . 466 .7% Davis and Kemp.10/18 x 100 = 55. Module 3: Adipic Acid Synthesis Traditional vs. 1991.6% • Nitrogen .5%) C6H12O+ 2 HNO3 + 2 H2O C6H10O4 + (NO. in Kirk-Othmer Encyclopedia of Chemical Technology.0% Product Mass = (6 C)(12) + (10 H)(1) + (4 O)(16) = 146 g Reactant Mass = (6 C)(12) + (18 H)(1) + (9 O)(16) + (2 N)(14) = 262 g Mass Efficiency = 146/262 x 100 = 55. NO2.1-.4% • Hydrogen . New Traditional Route . 1.4/9 x 100 = 44.

from cyclohexene Na2WO4•2H2O (1%) C6H10 + 4 H2O2 C6H10O4 + 4 H2O [CH3(n-C8H17) 3N]HSO4 (1%) 90% Yield of Adipic Acid • Carbon . Science. 11 Sept. 1646 .6% Product Mass = (6 C)(12) + (10 H)(1) + (4 O)(16) = 146 g Reactant Mass = (6 C)(12) + (18 H)(1) + (8 O)(16) = 218 g Mass Efficiency = 146/218 x 100 = 67% Sato.100% • Oxygen . V. A “green” route to adipic acid:…. et al.10/18 x 100 = 55.4/8 x 100 = 50% • Hydrogen . New New Route . 281. 1998.1647 12 University of Texas at Austin Michigan Technological University . Module 3: Adipic Acid Synthesis Traditional vs.

Mass Efficiency Benzene Route (Hedley et al.6% (4)(12) + 3. 8) V2O5 2 C6H6 + 9 O2 2 C4H2O3 + H2O + 4 CO2 (air) MoO3 95% Yield of Maleic Anhydride from Benzene in Fixed Bed Reactor 2(4)(12) + 3(2)(16) + 2(2)(1) Mass Efficiency = (100) = 44.5(2)(16) + (10)(1) Felthouse et al. 893 . “Maleic Anhydride. 1975. 15.. in Kirk-Othmer Encyclopedia of Chemical Technology. Module 3: Maleic Anhydride Synthesis Benzene vs Butane . .”. V. 1991..5 O2 C4H2O0 + 4 H2O (air) 60% Yield of Maleic Anhydride from Butane in Fixed Bed Reactor (4)(12) + (3)(16) + (2)(1) Mass Efficiency = (100) = 57.4% 2(6)(12) + 9(2)(16) + 2(6)(1) Butane Route (VO)2P2O5 C4H10 + 3.928 13 University of Texas at Austin Michigan Technological University . reference in ch.

.0 Maleic Anhydride 1. Texas Liquid (Butane 6/22/00) 3 Threshold Limit Value.530 0.html and www.html 5 ChemFate Database .00 0. 1981. Module 3: Maleic Anhydride Synthesis Benzene vs Butane .25 ---.19 0. www.141 800 ---.acgih. 1.epa. Wiley Interscience.22 0.gov/ngispgm3/iris/subst/index.Summary Table Chapter 8 Stoichiometry 1 $/lb 2 TLV 3 TW 4 Persistence 5 log Material BCF 5 Air Water (d) (d) Benzene Process Benzene [71-43-2] -1.184 10 100 10 10 1.org 4 Toxicity Weight.7 7x10-4 ---- Butane Process Butane [106-97-8] -1.epa. Conf. 1.com. www.25 ---.7 7x10-4 ---- 1 Rudd et al. ACGIH . ---- Maleic Anhydride 1.gov/opptintr/env_ind/index. 7. Indust.00 0. EFDB menu item 14 University of Texas at Austin Michigan Technological University . Inc..25 ---.www. Hyg. “Petroleum Technology Assessment”.esc.530 0. New York 2 Chemical Marketing Reporter (Benzene and MA 6/12/00). of Gov.syrres.Amer.

22)(1 / 800) + (1.0)(1 / .25) = 4.12 Butane Route TLV Index = (1.19)(1 / 10) + (1. Module 3: Maleic Anhydride Synthesis Benzene vs Butane .00 Where i is the overall stoichiometric coefficient of reactant or product i 15 University of Texas at Austin Michigan Technological University .0)(1 / .25) = 4.Tier 1 Assessment (TLV Index) Environmental Index (non .carcinogenic) = |  i i |  (TLVi )1 Benzene Route TLV Index = (1.

0)(0) = 119 Butane Route EPA Index = (1.19)(100) + (1.Tier 1 Assessment EPA Index Environmental Index (carcinogenic) = |  |  (Maximum toxicity weight) i i i Benzene Route EPA Index = (1.0)(0) = 0 16 University of Texas at Austin Michigan Technological University .22)(0) + (1. Module 3: Maleic Anhydride Synthesis Benzene vs Butane .