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629 Acid/Base Catalysis 154–157

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629 Acid/Base Catalysis 154–157 629 Index a – – Horvath–Kawazoe (HK) method acid/base catalysis 154–157 525–526 – bimolecular, acid catalyzed reaction 155 – Nonlocal Density Functional Theory – bimolecular, base catalyzed reaction 156 (NL–DFT) 530–532 – Brønsted–Lowry theory 155 – physical adsorption 514–516 – RNA hydrolysis catalyzed by enzyme – theoretical description of adsorption RNase-A 157 519–523 acids 132–143, See also solid acids and bases ––BETtheoryofadsorption 521 Acinetobacter calcoaceticus 181 – – Langmuir isotherm 519–521 activated carbon supports 439 – – standard isotherms 522–523 activation, catalyst 58–64 – – t-method 522–523 – induction periods as catalyst activation – xenon porosimetry 533–534 ® 59–60 Aerosil process 435 active sites 269–273 alcohols activity of catalyst, in homogeneous catalysis – carbonylations of 245–247 54–58 – synthesis 176–177 acylases 185–186, 256 aldolases 190–193 adaptive chemistry methods 370 alkene metathesis 402–406 adiabatic reactor 569 altered surface reactivity 38–39 adsorption entropy 27–30 alumina (Al2O3) and other oxides adsorption methods for porous materials 436–438 characterization 514–534 amidases 185–186 – adsorption isotherms 517–518 amidases catalyzed reactions 256 – application of adsorption methods amino acid dehydrogenases (AADHs) 518–519 177, 253 – Barret–Joyner–Halada (BJH) method amino acids synthesis 177–178 529–530 6-aminopenicillanic acid (6-APA) 256 – classification of porous materials 517 7-aminocephalosporanic acid (7-ACA) 256 – mercury porosimetry 533 ammonia synthesis 114–119, 289–299 – mesoporous materials characterization – activation energies 116 527–532 – based on natural gas 290 – – capillary condensation 527 – catalysis 292–295 – – Kelvin equation 528–529 – composition dependence 114–119 – microporous materials characterization – mechanism of reaction 114 524–526 – process optimization 295 – – Dubinin–Astakhov methods 524–525 – structure sensitivity 114–119 – – Dubinin–Radushkevich (DR) methods – technology development 291–292 emkin 524–525 kinetic expression 118 Catalysis: From Principles to Applications, First Edition. Edited by Matthias Beller, Albert Renken, and Rutger van Santen. © 2012 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2012 by Wiley-VCH Verlag GmbH & Co. KGaA. 630 Index ammonia synthesis (contd.) Boltzmann constant 34 – Temkin Pyzhev kinetics 292 Braunauer, Emmett, and Teller (BET) theory – ultra-high-vacuum techniques 292 6, 521 Anderson–Schulz–Flory curve 313 Brønsted acid/base catalysis 132–143, 154, ansa-zirconocene-based olefin polymerization See also acid/base catalysis catalysis 271–272, 275 Brønsted–Evans–Polanyi (BEP) relationship anti-lock and key model 28, 167 14, 22 apparent activation energy 69 Brønsted–Lowry theory 155 aqueous ammonium heptamolybdate Brunauer classification 518 (AHM) 425 Brunauer, Deming, Deming, and Teller Arrhenius law 49, 69 (BDDT) 517 Arrhenius number 85 Burkholderia plantarii 254 Arthrobacter globiformis 255 Butler–Volmer setting 382 aryl halides, carbonylations of 245–247 butylbranching mechanism 329 aryl–X derivatives, carbonylation of 246 asymmetric synthesis 174–175 c atom utilization 17 Candida cylindracea 254 atomic force microscopy (AFM) 494 Carberry number 83, 85 carbon materials 438–440 b carbonylation reactions 234–247 Baeyer–Villiger oxidation 179 – of alcohols and aryl halides 245–247 – Baeyer-Villiger Monooxygenases – – aryl–X derivatives 246 (BVMOs) 180–181 – – Ibuprofen 246 – enzyme-catalyzed, mechanism 182 – – lazabemide 247 ‘band gap’ 218 – – Rhodium-catalyzed carbonylation of Barret–Joyner–Halada (BJH) method methanol 245 529–530 – hydroformylation 235–239 bases 132–143, See also solid acids – of olefins and alkynes 239–244 and bases – – 1,3-butadiene 243 basicity and nucleophilicity, relation – – palladium-catalyzed carbonylation 242 between 154 5-carboxyfluorescein diacetate (C-FDA) batchwise-operated stirred-tank reactors 506–507 (BSTR) 578–579 catalytic partial oxidation (CPOX) 357 Bayer process 436 catalytic reactor engineering 563–624, See bimolecular catalytic reactions 76–77 also fluid–solid reactors; ideal reactor biocatalysis 171–194, 250–259, See also modeling/heat management; microreaction hydrolases; lyases; oxidoreductases engineering; residence time distribution – applications 253–257 (RTD); single-phase reactors – best route, choosing 250–253 – fixed-bed reactors 574 – – enzymatic routes 251–252 – fluid–fluid reactors 571–573 – biocatalysis cycle 173 – liquid–liquid–gas system 573 – case studies 257–259 – principles 67–108 – – lipitor building blocks synthesis – – formal kinetics of catalytic reactions 257–259 68–77, See also individual entry – development 172 – – homogenous catalysis in biphasic – reaction strategy choice 174–175 fluid/fluid systems 103–108 – – kinetic resolution or asymmetric – – mass and heat transfer effects 77–103, synthesis 174–175 See also individual entry – reaction systems, choice 175–176, – slurry–suspension reactors 574–575 250–259 – structured catalysts for multiphase reactions biotransformations 171 575 biphasic fluid/fluid systems, homogenous – three-phase gas–liquid–solid systems catalysis in 103–108 573–575 Bodenstein number 596–597, 607 – types 564–575 Index 631 catalytic selective oxidation 341–363 Coherent Anti-Stokes Raman Spectroscopy – complexity/issues of 354, 356–358 (CARS) 502 – consolidated technologies 341–363 combinatorial approaches in solid catalysts – in continuous development of development 453 more-sustainable industrial technologies – for optimal catalytic performance 453–456 355–356 compensation effect 44–46 – development of industrial process, – exocyclic methylation reaction 45 challenges 353–355 – pairing reaction 45 – directions for innovation 361–363 complex reaction 73 – dream oxidations 359–361 consecutive first-order reactions 82 – fundamentals 341–363 consecutive reactions 92 – main features 341–353 constant selectivity relationship 159 – for organic compounds synthesis in constrained geometry catalysts 279 petrochemical industry 342–352 Continuously Operated Ideal Stirred Tank – – oxidation process PHASE reactor Reactors (CSTR) 580–581 342–353 – space time in 583 C–C bond cleavage 126–132 continuously stirred tank reactors (CSTRs) chain growth 314–315 546–547 chain walking 279 continuous-phase contacting 616–618 chemocatalysis, equivalence of 30–32 – falling-film contactors 617 Chilton–Colburn analogy 84, 100 Corynebacterium glutamicum 253 clariant process 247 coupling of catalytic reaction 42 crystalline catalysts design 222–223 classical chlorohydrin route 18 cumylhydroperoxide (CHP) 362 ‘classical’ guidelines for catalyst testing cycle, catalytic 20–27 536–557 – appropriate laboratory reactor, selecting d 546–548 Damkohler¨ number 81–82, 547 – catalyst stability, assessing 554–555 de Donder concept 32 – data collection 543–546 deactivation, catalyst 58–64 – effective experimental strategies 541–543 – due to irreversible reactions 65–64 – – two-variables system 542 – due to multinuclear complexes formation – encouraging effectiveness 536–540 61–62 – ensuring efficiency 540–555 – due to non-reactive complexes formation – ideal flow pattern, establishing 548–549 61 – isothermal conditions, ensuring 549–551 dehydrogenases 176–178 – quality guidelines 540 – alcohols synthesis 176–177 – selectivity 544 – amino acids synthesis 177–178 – space–time yield 545 – formate dehydrogenase (FDH) 178 – transport, diagnosing and minimizing the – polyethylene glycol (PEG) 178 effects of 552–554 – Prelog-rule 177 – – ‘DrySyn’ Beta vs commercial Beta dehydrogenation 126–132 performance 553 – cyclohexane dehydrogenation 131 – – diagnostic tests for interphase (external) – mechanism of 126 transport 552 – olefin hydrogenation kinetics 126–127 – – diagnostic tests for intraparticle (internal) density functional theory (DFT) 209, 367, transport 553 395–397 – yield 545 deposition precipitation 427–428 cobalt 312 desulfurization 291 – cobalt catalyst formation 321–322 development of catalytic materials 445–459 – cobalt promoter 394–395 – catalytic OCM reaction, reaction mechanism co-catalysts 59 and kinetics of 448–449 co-catalyzed carbonylation 241 – combinatorial approaches in 453–459 cofactor regeneration 178 – fundamental aspects 446–448 632 Index development of catalytic materials (contd.) electrophilic catalysis 154–157 – high-throughput technologies in enantioselective ring-closing metathesis 405 456–459 enzyme catalysis 8–9, 155 – kinetic analysis 450–451 ethane hydrogenolysis mechanism 127–132 – micro-kinetics and solid-state properties as ethylene/propylene rubber (EPR) 264 knowledge source 448–453 Evonik-Uhde process 361–362 – – electronic conductivity 452 exocyclic methylation reaction 45 – – ion conductivity 452 extended X-ray absorption fine spectroscopy – – redox properties 452 (EXAFS) 400, 499 – – structural defects 451–452 external and internal transfer resistances, – – supported catalysts 453 combination 96–101 – – surface acidity and basicity 452 – external and internal temperature gradient – surface oxygen species in methane 100–101 conversion 449–450 – in isothermal pellets 96–98 development of catalytic processes 11–13 – mass transfer implication on temperature – history 11–13 dependence 98–99 – future 11–13 external mass and heat transfer 78–85 dibenzothiophene 392 dihydroxyacetone phosphate (DHAP) f 191–192 falling-film contactors 617 – DHAP-dependent aldolases 192 ‘fingerprinting’ 267 dilution rate 580 Fischer–Tropsch (FT) synthesis 40, direct alkane activation 139–141 301–323, 569 direct desulfurization (DDS) 392 – catalysts, general 311–313
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