j833

Index

– a acetyl radical 741 breakthrough curves for H2S adsorption on a absorption 108 acid aerosols 567 molecular sieve 132, 133 – activity and activity coefficients, in acid–base catalyzed reactions 11 – calculation of lads,ideal, HTZ, and LUB chloroform 111 acid catalyst 11 based on breakthrough curves 135 – basic design data, of column for absorption acidity 10 – capillary condensation of CO2 in water 116 acid-catalyzed reaction 652 –– and adsorption/desorption hysteresis 126 – Bunsen absorption coefficient 110 acid-soluble polymers 653 – competitive 128 – – fi chemical absorption of CO2 in N- acrolein 30, 476, 476, 479, 481, 483, 701 design of a xed-bed adsorption process 131 methyldiethanolamine 112, 113 acrylamide 28, 29, 487 – design of processes 130–135 – CO2 in water, and subsequent bicarbonate acrylic acid 140, 466, 467, 479, 481–483 – desorption 131 formation 110 acrylonitrile 462, 466, 467, 486–487 – dissociative 128 – design of columns 113–116 activation energy 24, 34, 201, 203, 215, 711 – equilibrium of a binary system on zeolite 128 – equilibria of chemical absorption 108 – apparent activation energy of diffusion – estimation of slope of breakthrough curve 132 – equilibria of physical absorption, processes 229, 230, 232 – height of mass transfer zone HTZ 132 comparison 109 – for chain transfer 807 – hysteresis loop during – fl – –– gas velocity and ooding of absorption correlation between activation energy and adsorption and desorption of N2 in a column 115 reaction enthalpy for a reversible cylindrical pore 127 – height equivalent of one theoretical stage reaction 212 – kinetics (influence of pore diffusion) 129, 130 (HETS) 115 – influence on reaction rate constant 203 – length of unused bed of an adsorber 134 – Henry coefficients for different gases 109 – negative 584, 587 – minimal ideal length of adsorber 133 – McCabe–Thiele diagram, for absorption active Phillips catalyst 810 – principles 120–124 process 114–116 active polymerization systems 810 – total design length of an adsorber 134 – operation conditions of sieve tray 115 activity coefficient 111, 140, 193, advanced solvents 36 – packed columns 115 194, 788 after co-precipitation 690 – principles of chemical and physical addition reactions 10 Ag-catalysts 698 absorption 108 adhesives 506 air pollutants, global emissions 510 – Raoult’s law 110 adiabatic beds 564–566 air separation processes 458 – solvent, and solute activity 111, 112 adiabatic compression 160, 161, 172 air velocity 549 – technical absorption processes 113 adiabatic expansion 40, 65, 154 Al-catalyzed reaction 755 – acetaldehyde 464, 480, 695 total work 46 AlCl3 11 – liquid phase oxidation of 739 adiabatic fixed-bed reactors 539 alcohol synthesis – oxidation 740, 741 adiabatic multiple-bed reactor 693 – by cycloalkane oxidation 475 –– acetic acid synthesis via 741 adiabatic operation 301, 317, 319, 329 – by ethylene oligomerization and Al-complex –– radical mechanism 741 – of a batch reactor 317, 318 hydrolysis 475 – production 464, 480 – choice of best reactor type for adiabatic – by fatty ester hydrogenation 475 acetic acid 28, 472, 477, 482, 739–749 operation 335 – global production 473 – anhydride 28 – of a CSTR 323, 333, 334 – from olefin and syngas 474 – commercial production technologies – of a PFR 329, 333, 334 – by olefin hydratization 475 –– direct ethylene oxidation 747 adiabatic reactors with periodic flow – by sugar fermentation 475 –– by ethane and methane oxidation 748, 749 reversal 376, 377 – from syngas 474 – consumption 740 – commercial applications 377 alcoholates 496 – dominant manufacturing process 739, 740 – temperature profiles 377 aldehydes 17 – production capacities 482, 740, 741 adipinic acid 10, 461, 464, 473, 482, 483, – distillation column 724 – synthesis 739, 740 491, 498 – hydrogenation 475, 720, 723 –– via acetaldehyde oxidation 741, 742 adipodinitrile 461, 462, 464 – industrial production 479 –– via butane or naphtha oxidation 742 adiponitrile 461, 472, 485, 487 – linear 721 –– via methanol carbonylation 743–747 adsorption 120, 458 – oxidation 481 acetone 481 – adsorption bed zones 131 – Rh-hydroformylation, selectivity for 738 acetylene 189, 198, 211, 437, 441, 461, 465, – application areas, liquid and gaseous – Rh-loss 730 470, 476, 478, 605 components 131 – selectivity to linear aldehyde 718 – – – from CaC2 470 BET isotherm 124 126 Alfol process 475 – industrial products from 471 – BET theory, originators 127 aliphatic isocyanates 487

Chemical Technology: An Integral Textbook, First Edition. Andreas Jess and Peter Wasserscheid. Ó 2013 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2013 by Wiley-VCH Verlag GmbH & Co. KGaA. 834j Index

alkanes 460, 463 – industrial routes for 486 atomic absorption spectroscopy (AAS) 31 – applications 461 amino acids 462 Aufbaureaktion 750 – chlorination 12 ammonia 20, 457 autoclave process 806, 808, 809, 813–815 – from crude oil distillation 463 – catalytic oxidation 26, 573 automotive emissions 786 – dehydrogenation 36, 462 ––concentration and temperature automotive fuels 605 – industrial processes for 463 field 577 auto-refrigeration processes 658 – oxidation of 464 ––conversion and characteristic auxiliary induction 19 – sulfoxidation 12 temperatures 582 Avogadro, Amedeo Carlo 41 n-alkanes ––technical reactor for 580 axial dispersion coefficient 648 – boiling and melting point 440 ammonia reactor – influence 648 – as feedstock 608 – inert gas, influence 532 axial temperature profiles 681 – important industrial processes for – pressure drop 531 azeotropic distillation 742, 744 conversion of 463 ammonia synthesis 525–536 – heterogeneous 107 alkenes 14, 17 – annual worldwide production, evolution – homogeneous 106 1-alkenes 527, 528 azeotroping agents 744 – fl – with chain lengths between C6 ow sheet N,N-azobisisobutyronitrile 496 – – and C18 751 historical development 525 528 – ethene polymerization 805 – Haber–Bosch process 29, 673 b – industrial applications 465, 750 – kinetics and mechanism 529–531 back-biting process 807 – Poisson distribution 751 – reaction scheme 529 bacteria 474 – polymerization to 464 – schematic energy profile 529 Barkelew diagram 320, 714 – production 749, 756 – syngas composition 538 base chemicals 460 – SASOL commercially extract 758 – technical ammonia process and synthesis BASF company – SHOP technology 756 reactors 531–536 – annual capacity of ethylene oxide 700 alkenylsulfonates 504 – thermodynamics 527–529 – carbonylation process for acetic acid alkylate quality 661 ––pressure and temperature production 743, 744 alkylation processes 26, 216, 444, 456, 463, 501, influence 528 – sales in 2007 and 2009 2, 3 503, 606, 656, 658, 661 6-aminopenicillanic acid 29 basicity 10 – of 2-butene with isobutane 654 Amoco process 484, 740 batch reactor 213–215, 298–299, – commercially applied 661, 662 Andrussow process 462 306–307 – of fatty amines 501 aniline 10, 484 Bechamp process 485 – of hexanes with ethane 653 aniline-based herbicide (S)-metolachlor 508 Beckmann rearrangement reaction 486 – HF alkylation 661 aniline hydrogenation 485 bentonite 474 – isobutane, with C3–C5 olefins 653 anionic detergents 502 benzene 11, 16, 463 – of olefins with isoparaffins 653 anionic polymerization 496 – with ammonia, direct amination of 485 – with sulfuric acid as catalyst 655, 661 annual consumption, of crude oil 21 – chlorination 458, 490 – using hydrofluoric acid as catalyst 657 annual global production, of chemicals 2 – Friedel–Crafts alkylation 502, 703 alkylbenzene sulfonates 502, 503 anthropogenic global warming 425 – important industrial products from 470 – alkyl cations 14 anthropogenic NOx emissions 511 nitration of 16 alkyl chlorides 501 anti-graying agents 501 – produced together with toluene and alkyl cyanates 488 anti-icing agents 705 xylenes 468 alkyl groups 8, 14, 469, 501, 608, 734, 750, 755, Antoine equation 50 Bergius, Friedrich 673 761, 809, 810 apparent activation energy Bergius–Pier process 431, 449, 672, 673 alkyllithiums 493 – diffusion processes 229, 230 Bernoulli, Daniel 152 alkylphenol 504 – solid catalyzed reaction 255 Bernoulli equation 154 alkylphenyl polyether glycols 504 ––influence of reaction temperature on effective Berzelius 21 alkylpolyglycosides 504, 505 rate constant 255, 256 Bessemer process 587, 589 alkylsulfonates 464, 503, 504, 736 aqueous electrorefining, of copper 801 BET-equation 124/125 alkynes 17, 441, 464 ARGE catalyst 680 biocatalysis 19, 20, 28, 29, 474 – industrially important 465 ARGE fixed bed process 675 – in chemical industry 29 allyl chloride 466, 490 aromatic compounds, industrially biodegradable detergents 750 allylic alcohol (2-propen-1-ol) 476 important 15, 465 biogas 460 aluminium-alkyl compounds 750 aromatic hydrocarbons 672 biomass aluminum 457 aromatization 606 – chemis-tree, illustration 460 – aluminum-alkyl-based Arrhenius equation 61, 203, 212, 250, 286, – to energy supply, global contribution 432 “Aufbaureaktion” 750 323, 382 – gasification 558 – based oligomerization processes 756 Arrhenius law 24, 201, 215, 583 – to liquid (BTL) processes 672 – cell for fused salt electrolysis of Arrhenius number 245, 253, 254, 285, – particle transient heating, during aluminum 802 320, 361 pyrolysis 546 – electrical energy consumption for Arrhenius plot 62, 201, 256, 403, 562 – pyrolysis 545 production 802 Arrhenius, Svante August 201 – renewable energy 421 – production by electrolysis 801–802 asphalt 443 Biot, Jean Baptiste 81 1 amination 485 Aspirin 505 Biot number 82, 546, 593 amines asymmetric carbon atom 18 biotransformation 28 – absorption 149 – priority rule for substituents 18 biphasic system 290, 291, 499, 727, 730, 733, – amine as solvent 632 asymmetric catalysis 508 735, 737 – industrially relevant amine compounds 484 asymmetric synthesis 18, 508, 654 BIPHEPHOS ligand 721 Index j835

Birkeland–Eyde process 571 1,4-butynediol formation 476 – for HDPE and LDPE 809 bisphenol A 481, 498 butyraldehyde 472, 481 – homogeneous versus heterogeneous bisulfite 17 butyraldehyde production 481 catalysis 27 bite angle 721 – immobilization 28, 716, 730, 733, 736 Blasius, Paul Richard Heinrich 155 c – market 20 ’ – – Blasius s law 153 calcination of Al(OH)3 802 major applications 27 29 blast furnace coke production 589–595 calcium chloride 696 – Nobel prices in research 21 – brick wall and coal charge, thermal capillary condensation 126/127 – recovery 26 resistances 594 capillary method (diffusion) 63 – for refinery applications 20 – coal coking, transient process 591 e-caprolactam 11, 461, 464, 486 – and support materials 29 blast furnaces 588, 595–603 carbanions 7 – specific surface areas of 227 – configuration and air preheating 595 carbenium ions 496 catalytic ammonia oxidation, heat transfer – gasification of blast furnace coke 599 carboanions 7, 8, 12 role 576 – reactions and reaction zones 597 carbocations 7, 8, 11, 12, 14, 15, 653, 655, catalytic cracking 32, 620–623 – residence time distribution in 603 656, 662 catalytic cycles 20, 22, 718 – temperature and CO/CO2 content 600 carbohydrates 28, 451, 453–455, 472, 504 cationic detergents 501 bleaching activators 501 – starch 454 catalytic gasoline reforming blow molding 805 – sugar 455 – high octane gasoline by 633–652 BMA process 461 – wood and cellulose 453–454 – plants 634 Bodenstein, Max 209 carbonaceous materials, reactivity 547, 548 – process 637, 638 Bodenstein number 209, 603 carbon/coke – reactions and thermodynamics Bodenstein principle 209 – gasification 546–549 633–636 Boltzmann, Ludwig 41, 57 – oxidation 546, 548, 549 – reforming catalyst 636, 637 bomb calorimeter 187, 188 carbon dioxide 42, 136, 137, 183, 421, 458, 550, – reforming catalyst, deactivation and Borsig transfer-line exchanger 611 665, 686, 696, 697, 748 regeneration 638, 639 Bosch, Carl 527 – chemical absorption 112 –– coke burn-off within single catalyst Boudouard reaction 542, 596, 597, 600, 604 – design data of a column for absorption 116 particle 639–645 – equilibrium of 197 – diffusivity 63 –– regeneration in technical fixed bed Boyle, Robert 41 – formation by water gas shift reaction 537, reactor 645–651 Bridgman equation 61 665 catalytic o-xylene oxidation bromination 16 – real gas factor and phase behaviour 43, 44 – data on chemical media and – 2-bromopropane 17 supercritical carbon dioxide (scCO2) 734 conditions of catalytic o-xylene Brønsted acid 11, 496 carbonization 446, 447 oxidation 710 Brunauer, Stephen 127 carbon load 637, 639, 640, 642, 644–646, 648, – simplified reaction scheme 708 bubble column 742 649, 650, 652 cationic polymerization 14, 15, 17, bubble column reactor 474 carbon nanotubes 400–402 496 builders 501 – Arrhenius plot of oxidation Cativa process 739, 743, 747 butadiene 8, 466, 477 ––based on isothermal and TG/DTG- – for acetic acid 743 butanal 466 measurements 403 caustic soda 696 1,4-butandiol 437, 465, 476–479, 482 ––best fit of measurement and C-C-coupling reactions 20 butane 461, 462 simulation 402 C4-dimerization 720 – acetic acid synthesis via 742 ––comparison of kinetic data 403 Celanese-LPO-process 742 – boiling and melting point 440 – energy-dispersive X-ray image 401 cellulose 491 – dehydrogenation 462 – equation for TG analysis 401 centrifuges – Gibbs enthalpy of system n-butane/ – evaluation of kinetic parameters based – centrifugational number 171 i-butane 199 on DTG data 402 – hydro- or aerocyclones 167 – major applications 461 – measured and simulated TG and DTG – sedimentation in 171 – oxidation 462, 463, 481, 742 curves 402 ceramic monolith 776 butanoic acid 742 carbon number 15, 469, 475, 613, 629, 634, – design 776 butanols 475, 727 665–666 Cetus process 704 – enantiomers 18 carbonyl group 17 C18 fatty acids 451 – global production 473 carbonylation 739, 743, 744 C–H bond breaking 606 – isomers 475 – alcohol 482 chain-growth – recycle 505 – BASF 743, 744 – mechanism 807, 808 – tert-butanol 475, 703 – methanol 480, 481, 739, 742, 746 – polymerization reactions 494, 495 1-butanol 472 cascade autorefrigeration process, alkylation unit, chain length distribution 755 2-butanol 17, 475 flow sheet 660 chain propagation 12 tert-butanol 465, 475 cascade auto-refrigeration refinery alkylation chain termination 495, 496, 606 2-butene 462, 463, 466, 653 process 660 chain transfer process 807 – alkylation 654 catalysts 19–37, 738 char combustion 546–549 n-butenes, important industrial products 468 – classification of pores of solid catalysts 228 char gasification tert-butyl alcohol 702 – deactivation 32–35, 638, 651, 692 – intrinsic and effective rate constants tert-butylamine 484 ––deposition of residues 33, 34 546–549 tert-butyl cation 14, 653 ––loss via gas phase 34 chemical conversion butylene hydroformylation 727 ––poisoning 33 – terms used to quantify result 179, 180 butyllithium 496 ––rate of deactivation 34, 35 chemical equilibrium 20, 108, 122, 184, 1,4-butynediol 476 ––sintering 34 188, 189 836j Index

chemical industry 2 1-chloro-2,2,2-trifluoroethane 490 constrained catalyst geometries 811 – annual global production of chemicals 2 chromacycloheptane 757 continuous ideal non-isothermal reactors – biggest “chemical nations” 3 chromium-catalyzed ethylene – optimum operation line for adiabatic – largest chemical companies by sales 3 oligomerization 749 operation 332, 334, 335 – pharmaceutical companies 3 chromophores 506 continuous stirring tank reactor (CSTR) 297, – products of German chemical industry 4 CIP system 18 305, 307, 309, 311, 313, 315, 316, 323, 326, 336, – raw materials of 408 Citronellal 28 356, 543, 726, 746, 808 – sales of the oil & gas industry 4 citronellol 506 convection (heat transfer) 80 – world production of important chemicals 4 Clapeyron, Benoit Paul Emile 50 convective heat transfer coefficient 576 chemical process structure 176 Clapeyron equation 51 conversion, definition 179, 180 chemicals production 18 Clausius–Clapeyron equation 49, 50 cooled multi-tubular reactors 708 chemical reaction engineering 1 Clausius inequality 183 coordination number 759 – aspects 176 Clausius, Rudolf Julius Emanuel 49 copolymerization 468 – basic definitions 176 Claus process 30, 625 copper catalysts 457, 689, 692 chemical reactors 296 coal copper–zinc–aluminum systems 690 – ideal and real reactors 296–298 – from acetylene 470 co-precipitation 29 – real reactors according to phases 299 – chemis-tree, illustration 460 corrosion inhibitors 501 –– fluid–fluid reactions 303, 304 – combustion 448 Cossee–Arlman mechanism 754 –– gas–solid reactions 301–303 ––chemical reactions 448 cost optimum reflux ratio 540 –– heterogeneously catalyzed gas–liquid ––and electricity production 448 covalent anchoring 731 reactions 304, 305 – fired power plant 571 covalent bonds 7, 9, 11 –– heterogeneously catalyzed single-phase – gasification 449, 542, 558 Cowper, Edward Alfred 595 reactions 300, 301 – in iron and steel production 448–449 Cowper stoves 595, 596 ––non-catalytic single-phase systems 299, 300 – liquefaction 449–450 crack gas 612 –– three-phase reactors 304 – processes and products 445–450 cracking 12, 20, 35, 441, 655 – real reactors based on mode of operation 298 – properties 445–447 – alkane 609 –– batch reactor systems 299 – pyrolysis 447–448 – catalysts 20 –– continuous mode of operation 299 – regional distribution of worldwide – furnace 606, 607, 610 –– discontinuous and semicontinuous mode production 446 – steam 463, 465, 604, 605, 720 of operation 298, 299 cobalt/iridium-catalyzed processes 745 – thermal 443, 444, 553, 616, 618, 620 – types and their characteristics (overview) 296 C–O bond 8 critical micelle concentration (CMC) 501 chemicals manufacturing/fuels Co catalysts 722, 723 cross-flow filtration reactor 732 – investment costs 518–520 cocurrent-flow tube-cooled ammonia crude oil 438, 459, 464, 517 – operating costs 522–524 reactor 534 – distillation fractions, yields of 441 – price of 517–518 coke – fractions, composition 440 – production costs of 517 – combustion and gasification 546–549, – in OPEC countries/non-OPEC countries 439 – variable costs 521, 522 604 – paraffins/aromatics/naphthenes, typical –– catalyst costs 521 – consumption in blast furnace 601 contents 441 –– energy costs 521 coked reforming catalyst – price in 1865–2009 439 –– feedstock 521 – regeneration 638–651 – production, reserves, and price of 437–440 chemical thermodynamics 182 coke-oven gas 434 – properties of 440–442 chemisorption 231 coking process 30, 590–594 – refinery, flow-sheet of 445 chiller 658 coking time 590–594, 603 – regional distribution of worldwide Chinese reed Colebrook, Cyril Frank 155 production 438 – biomass coke from 548 Colebrook’s law 154 – sulfur content of 442 – characterization 544 colorants 506 – typical nitrogen compounds 442 – rate of pyrolysis 545 combined cycle power plant 544 – typical sulfur compounds 441 – semi-technical gasifier of 552 combined gross enrollment ratio (CGER) 415 crushers 164 – technical gasifier 553 combustion of ammonia 567, 779 – types 163 chiral alcohols 28 – engines 437 cryogenetic air separation process. see Linde chiral compound 18 – of hot blast furnace coke, in contact with process chiral induction 19 air 276 cryogenic distillation, product separation 458, chiral products 18 – promoter 621 612 chiral synthons 28 CoMo-catalysts 627 crystallization 140 chlor-alkali electrolysis 791–797 composition of a reaction mixture, terms used – ideal binary eutectic phase system 140, 141 chlorination 16, 458 to characterize 179 –– system p- and m-xylene chlorine 457 compressed natural gas (CNG) 436 – ideal binary phase system (both solids soluble in chlorine applications 792 compressors 159 one another) 141–143 chlorobenzene 458, 469, 470, 489, 490 – conveyance of gases by 160 –– system anthracene and phenanthrene 142 chloroform 110, 111, 461, 488, 489 condensation 606 CSTR. see cooling stirred tank reactors chlorohydrin process 696, 700, 701, 702, 703, conduction (heat transfer) 80 Cu-catalyzed reaction 476 705, 706 confidence limits XIX, XXXI cumene hydroperoxide 496 – ethylene 695, 696 conjugative effects 8 Cu/Zn-methanol catalyst 692 – propylene 701 – stabilization of phenolate ion 9 cyanohydrin reaction 17 chlorohydrin reactor 701 conjugative stabilization 16 cyclization 606 chloromethane 461, 488, 489 constant volume bomb cycloaddition 606 chloroprene 465 calorimeter 188 cycloalkanes 608 Index j837 cyclododecanol 475, 476 dibenzoyl peroxide 496 – alkylate molecules 655 cyclohexane 10, 106, 107, 461, 464, 469, 483, dicarbonic acids 495, 498 – of carbenium ions 496 486, 763 dichlorobenzenes 489, 490 distearyl (dimethyl)ammonium chloride 502 – oxidation of 475 dichloroethane 11, 490 distillation 97, 98, 467, 474, 755 – solvent 814 1,2-dichloroethane 464 – azeotropic 106 cyclohexanol 12, 464, 475 dichloromethane 461, 488, 489 –– heterogeneous 107 cyclohexanone 464, 476 dielectric permittivity 13 –– homogeneous 106 cyclohexanone oxime 11, 486 Diels–Alder type reactions 17, 613 – design of column 101–104 – production route to e-caprolactam 487 dienes 606 – extractive 107 cyclone 171 diesel 430, 436, 463 – number of theoretical stages 104, 105 cyclopentadienyl groups 811 – fuel 443 – pressure swing 107, 108 cylindrical mills 163 – oil, statutory sulfur content, historical – principles 98–100 development 624 – reactive 108 d diethylene glycol 476 – reflux ratio 104, 105 Dalton, John 99 diethyl ether 474, 477 –– theorectical stages 104–106 Dalton’s law 179 diethyl sulfate 501 – stages of industrially important distillation Damascus steel 587 diffusion coefficient 56, 58, 64, 129, 248, 261, processes 106 Damascus swords 587 395, 577, 582, 598, 768, 769 distillation column (DC) 753 Damkoehler number 215, 582, 603, 676, 710 diffusion of liquids 230 Dobereiner€ 21 Darcy’s law 146 diffusivity 40, 52 1-dodecene 717 – deactivation mechanism 32 of CO2 in N2 63 double absorption sulfuric acid process 566 decaffeination 139 – Knudsen 89, 641 drinking water 144, 147, 148 – with supercritical CO2 139 – longitudinal 343, 378 – global drinking water coverage 515 defoamers 705 – molecular 249, 255 dual-pressure HNO3 plant 585 dehalogenation 10 diisobutene 465 dyes 506 dehydration 10 diisocyanates 498 dehydrochlorination 11, 701 dimerization 466, 468 e dehydrocyclization 634, 651 Dimersol-process 468 Eadie–Hofstee plot 289 dehydrogenation 10, 20, 30, 371, 462, 478, dimethylamine 484 Earth’s ecosystems 425 481, 606, 636, 651, 748, 765 4,6-dimethyldibenzothiophene (4,6- ecological footprint 427, 428 – alkane 462 DMDBT) 628 economy of scale 694 – catalysts 20 dimethyl ether 477 E-factor 516 – oxidative 478, 481, 748 dimethylformamide (DMF) 467 effective diffusion coefficient 89, 129, 294, 640, dehydrohalogenation 10 dimethyl sulfate 501 669, 767, 768 dehydrosulfurization 30, 35 dimethyl sulfoxide 469 effective dispersion coefficients 356, 646, 648 deisobutanizer 657, 658 dinitrogen oxide 483 effectiveness factor 250, 640, 642, 646, 766 delayed coking 617, 623 dioctyl phthalates plasticizers 493, 717 – for pore diffusion for macro- and – data and conditions 617 diolefins 441 micropores 266 – stages 618 diols 472, 495 – for reversible first-order reaction 251, 252 dendrimers 732 1,4-dioxane 478 effective rate constants 240, 255, 286, 398, 548, dendritic ligand 733 diphenyl carbonate 597, 599, 669, 670, 784 depolymerization of cellulose 36 dipole moment 8 effective reaction rate 247 depolymerization of lignin 36 direct ethylene oxidation process 740, 747 effluent refrigeration 658, 659 desulfurization 624–632 direct reduced iron (DRI) 589 – alkylation unit, flow sheet 660 desulfurization catalysts 20 direct reduction 303, 596, 600, 604 Einstein, Albert 248 detergents 500 dispersion 30 elastomers 455, 491, 497 – anionic 502–503 dispersion model 343, 603 electrochemical cell 801 – cationic 501–502 – axial dispersion and residence time electrochemical reactants 789, 790 – enzymes 501 distribution 343, 344 electrochemical reactions 786, 787, 801, 802 – molecules – axial dispersion model, for turbulent flow in electrode reactions 789, 791 –– applications 501 round tubes 352 electrolysis 786, 801 –– schematic representation 500 ––dispersion of mass, and heat in fixed bed – potential–current curves 793, 794 – neutral 504 reactors 352–354 – voltage 796 – non-ionic 504–505 ––radial variations, in bed structure 354 electrolytic copper refining 800 – structure and properties 500–501 – calculation of conversion by 348 electromagnetic spectrum 79 DFT calculations 758 – dispersion and conversion, in empty electrometallurgy 800–802 1,4-diacetoxy-2-butene 477 pipes 349 electron density 8, 9, 15 diamines 495, 498 ––axial dispersion model for laminar flow in electronic nature of bonds and atoms, factors diaphragm process 791, 792, 793 round tubes 349–351 influencing 7–8 – advantages 796 ––determination of diffusion coefficients of – conjugative effects 8 – schematic 794 fluids 352 – inductive effects 8 diastereomers 18, 19, 763–765, 767, 770 – and flow of two liquids in a pipeline 346 – mesomeric effects 8 dibenzothiophene 441, 626, 628–629 – large deviation from plug flow 346–348 – steric effect 8 – hydrodesulfurization 625 – residence time distribution 349 p-electron systems 8, 15, 17, 506 dibenzothiophene (DBT) derivatives ––prediction of conversion based on 349 electrophiles 9 – HDS 626 – small deviation from plug flow 344–346 electrophilic reagents 9 – stability diagram 626 disproportionation 469, 655 electrophilic substitution reaction 15 838j Index

electrorefining 800 – ethylene oligomerization schematic 753 –– reaction chemistry of SCR 781 electrostatic precipitator (ESP) 780 ethylene 461, 462, 480 –– SCR reactor, reaction kinetics and elephant function 234, 235 – acetaldehyde, production of 480 design 781–785 elimination reactions 10 – direct oxidation 705 (see also ethylene experimental reaction orders, differ from emissions, by mobile sources 510 oxidation) stoichiometric coefficients 212, 213 emissivity 79 – ligands, oxidative coupling 759 external effectiveness factor 244 Emmett, Paul Hugh 127 – oligomerization 759, 761 (see also ethylene – Arrhenius number 245 emulsion 499, 500, 656, 659 oligomerization) – for exothermic heterogeneously catalyzed gas – formation 728 – partial oxidation 696 reaction 244–246 – liquid 727 – pipeline system 806 – Prater number 245 – polymerization 499 – polymerization 805 – Sherwood number 244 enantiomers 18, 19 ––schematic representation 808 external heat transfer 283, 284 – 2-butanol 17 – production 462 – coefficient 329, 678 – nomenclature 19 – silver-catalyzed direct oxidation 697 external mass transfer – (R)- and (S)-enantiomers 18, 19 – steam-cracking process 465 – coefficient 641 enantioselective hydrogenation 25 ethylene chlorohydrin 695 – estimation of required length of fixed bed enantiotopic halves 18 ethylenediamine 484, 485 reactor for gas phase reaction controlled by energy barrier 23, 24 ethylene dichloride, via ethylene oxy- external mass transfer 239 energy consumption 411, 422–425, 521, 522 chlorination 407 – external effectiveness factor hex 237 enthalpy 45, 184–188 ethylene hydratization 474 –– for Langmuir–Hinshelwood kinetics 237, entrained-flow gasifier 552. see also ethylene oligomerization 751, 756, 758 238 Koppers-Totzek process – aluminum-alkyl-based –– for negative reaction order 237, 238 – zones for modeling 551 “Aufbaureaktion” 750–753 – influence of external mass, and heat transfer on entrained flow reactor 550 – linear 1-alkene production 749–762 effective rate 239, 240 entropy 48–51, 183, 186 – nickel-catalyzed oligomerization, shell higher – interaction with chemical reaction 235–237 environmental aspects 509 olefins process (SHOP) 753–756 – through boundary layer 282, 283 – air pollution 510–512 – 1-olefins, industrial relevance 749 extractive distillation 469, 474 – green chemistry 515–516 – selective, metallacycle mechanism 757–762 extra- and intraparticle mass and heat transfer – water consumption and pollution 512–515 ––catalytic cycles, elementary steps limitations, criteria for 286 environmental catalysts 20 758–759 extrusion 761 enzyme 19 ethylene oxidation epichlorohydrin 701 – on Pt wire 242 f epimerization 763–771, 773 – Wacker–Hoechst process 480 falling film evaporator 726 epoxidation 701–703, 706, 750 ethylene oxide 464, 472, 476, 478, 695, 705 Faraday constant 787, 796 1,2-epoxypropane 700 – application 478 Faraday’s law 786, 787 equilibrium by minimization of G of reaction – commercial production 695–700 Faraday, Michael 786 system, calculation 198 ––chlorohydrin process 695, 696 fats and oils equilibrium composition 572 ––ethylene, direct oxidation 696–699 – composition and production 451 – –– – of SO2 oxidation 190 ethylene oxide, products made 699, 700 industrial routes to convert 452 equilibrium of gas reaction, influence of – consumption 699, 700 fatty acid esters, hydrolysis 451 pressure 189 – industrial epoxides 478 fatty acid methyl esters 11, 452 equilibrium of NH3 synthesis, influence of real – producer 700 fatty alcohol ether sulfates 504 gas behavior on 191 – production 696 fatty alcohol polyether glycols 504 ethane 461, 462 ethylene oxide plant fatty alcohols 452, 473, 475, 504, 505 – dehydrogenation 189, 606 – degree of utilization 523, 524 – non-ionic surfactants based on 455 – oxidation processes 747 – fixed and variable costs 523 fatty alcohol sulfates 504 ethanol 474 – flow sheet 699 fatty amines 484, 485 – age-old aerobic fermentation 739 ethylene trimerization 757 fatty carboxylates 502 – alcoholic beverages 472 eutectic phase system 140 fatty nitrile 485 – chemical production routes 474 exhaust gas cleaning 20 FCC. see fluid catalytic cracking (FCC) – isolation proceeds, via distillative exhaust gases treatment FCC-process. see fluid catalytic cracking processes 474 – automotive emission control 773–778 Fe-Cr catalyst 539 – as solvent 690 ––car engine emissions reduction, catalytic Fe-modified bismuth-phosphorous molybdate ethene 11 converters 775–778 contact 486 – decomposition 805 ––engine emissions reduction and emission fermentation processes 28, 474, 739 – oligomerization 28, 288 standards 773–775 fertilizers 20, 558 – process for solution polymerization of 814 – catalytic treatment, ceramic monolith 777 – applications 459 – single-site catalysts for ethene – composition of exhaust gas without Fick, Adolf Eugen 54 polymerization 811 treatment 773, 774 Fick’s law 54, 218, 579, 768 ethene/propene/diene copolymerizations – from mobile and stationary sources 773–786 Fick’s law, second 85 (EPDM) 499 – NOx, selective catalytic reduction (SCR) film diffusion 229 ethene–vinyl acetate copolymers 499 from 778–785 filtration ether, industrially importance 477 ––catalysts and reactors 779, 786 – cake filtration 168 ethylbenzene 11, 703 ––flue gas treatment from power plants 778, – pressure 168 – ethylbenzene hydroperoxide 702 779 of a suspension of CaCO3 168 ethyl chloride 481 ––nitrogen oxides formation during fuel fine chemicals 28, 505, 763–772 Ethyl Corporation process 753 combustion in power plants 778 – adhesives 506 Index j839

– fragrance and flavor chemicals 506 fluid–fluid reactions 292 gasification – menthol and menthol production 763–764 – industrial reactions 216 – chemical reactions 448 – menthol isomers epimerization – kinetics of 216, 217 – computations 551 –– mass transfer influence 766–771 fluidization velocity 157 – reactors 302 –– thermodynamics and kinetics 764–766 fluidized bed Fischer–Tropsch (FT) gas–liquid interface – pesticides 506–508 reactor 663 – mass transfer 217, 218 – pharmaceutical 508, 509 fluidized-bed gasifier. see Winkler process gas–liquid reactions – vitamins, food, and animal feed additives fluid–solid extraction 136 – equations according to two-film 508 – design 139 theory 225 – vs. petrochemicals, characteristic – effective extraction rate, factors – influence of Ha on enhancement factor differences 505 influencing 136 E 224 fine particles, fluidization regimes – ideal solvent, requirements 136, 137 – kinetics, on solid catalysts 291 with 622 – influence of particle size on rate of external – reactor types 293, 304 finite element method 578 mass transfer 138, 139 gasoline 430, 442, 443 first law of thermodynamics 45 – principles 136 – limit values of sulfur in 624 first-order rate constants 618 – solubility of caffeine in CO2 138 – production of 437 first-order reaction 204 fluoropolymer 493 gasoline spark ignition engines 775 Fischer, Franz 664 fluorous phases 733 gas-phase PE-process 814 Fischer–Tropsch synthesis 29, 437, 449, food additives 508 gas recycle hydroformylation processes 725 662, 664–685, 665, 666, 670, 673, 679, 708, food grade phosphoric acid 458 gas recycle process 724, 738 717, 797 food industry 139 gas–solid reactions 157, 172, 175, 181, 195, 196, – chemical media and reaction conditions 677 food ingredients 28 203, 547, 641, 642 – commercial plants 671 formaldehyde 106, 254, 285, 476, 478, 479, 496, – equilibrium of 195–197 – GTL plant, main parts 675 694, 742 – kinetics 268 – history, current status, and perspectives formic acid – reactors for 301, 302 670–674 – methanol, carbonylation 481 – spectrum of factors influencing rate – intrinsic and effective reaction rate – production capacities 482 of 269 668–670 N-formylmorpholine 467 –– influence of external and internal mass – kinetic scheme 665 fossil fuels transfer 269 – mechanisms scheme 665 – CHO content 433 gas-to-liquid (GTL) FTS technology 670 – multi-tubular fixed bed Fischer–Tropsch – consumption 446 Gay-Lussac, Joseph Louis 4 reactor modeling 677–684 – crude oil 408 Gibbs enthalpy, of gas phase system 199 – processes and reactors 674–677 – reserves, and resources 408, 419, 420 Gibbs free enthalpy 789 – product distribution 667 – conventional and non-conventional fossil Gibbs functions 184, 185, 559, 570, 571 – product streams 758 fuels 418–420 Gibbs, Josiah Willard 184 – reactions and mechanisms 664–668 fouling 723 Gini coefficient 413 – reactors used 675 Fourier, Jean Baptiste Joseph 53 global anthropogenic sulfur emissions 510 fission power 421 Fourier number 82, 593 Global Footprint Network 426, 427 fixed bed gasifier. see Lurgi reactor Fourier’s law, first 52, 66 global warming 424, 425, 483, 781 fixed-bed reactor 300, 301 Fourier’s law, second 81 glucose 453, 454, 505, 704 fixed bed reactors, modeling 355 fragrances, role 501, 506 – non-ionic surfactants based 455 – criteria used to exclude a significant influence Frasch process 458 glutaminic acid 508 of dispersion 357 friction factor 153, 154 glycerol 451, 452, 473, 477, 701, 792 –– axial dispersion of heat 360, 361 Friedel–Crafts acylation reactions 14 glycidol 28 –– axial dispersion of mass 357, 358 Friedel–Crafts alkylation 469, 703 glycol ethers 705 –– radial dispersion of heat 361, 362 Fritz Haber 526 greenhouse gas producers 35, 425 –– radial dispersion of mass 358–360 FT GTL plant, main parts 675 Grignard reagents 8 –– radial variations in bed structure 363 FT multi-tubular reactor 664 gross domestic product (GDP) 410 – dispersion processes 356, 357 FT reactors, design 674 gross national product (GNP) 410 – fundamental balance equations 355–357 FTS. see Fischer-Tropsch synthesis – per capita (pc) vs. primary energy consumption fixed-matrix regenerator system 595 fuels (pc) 412 flame velocity 435 – average price and world demand 518 GTL plant 674 flavor chemicals 506 – consumption 599 guano, fertilizer and gunpowder ingredient flow-sheet 658 – equipment costs 518 525 flue gas 778 – production costs of 517 Gulf process 752 – treatment 786 – purification 775 gutta-percha (trans-1,4-polyisoprene) 456 flue gas desulfurization (FGD) 778 – solid, typical composition 447 gypsum, applications 459 – unit 780 fugacity coefficients 687, 695, 787 fluid catalyst 620 fugacity, influence of pressure on 191, 687 h fluid catalytic cracking (FCC) 463, 620, 621, 623. functionalizations 20, 36 Haarmann & Reimer process 764, 772 see also cracking fungicides 506, 507, 508 Haber–Bosch process 29, 525, – block diagram 622 fusion power 421 568, 673 – chemical media and reaction conditions, data Haber, Fritz 526, 527 on 621 g Hagen, Gotthilf Heinrich Ludwig 155 – heat balance 622 galvanic cell 788, 791 Hagen-Poiseulle’s law 153 – regenerator, minimum fluidization and gas compressor 611 Halcon process 703 discharging velocity 623 gas hourly space velocity (GHSV) 565 haloalkane 13 840j Index

Haldor Topsoe process for methanol – role in chemical technology 26 Hougen–Watson type equation 561, 668 production 693 – typical conditions, and catalyst lifetimes 32 human development index (HDI) 413, 414 half-cell reaction 790 heterogeneously catalyzed hydrodesulfurization – happiness and life satisfaction Hall–Heroult process 802 (HDS) 626, 627, 631, 633 of nations 416 halogenated compounds 490 heterogeneously catalyzed reaction – purchasing power parity (PPP) 415 – applications 489 – kinetics of 226 – subjective well-being index (SWB) 416, happiness and life satisfaction of nations 416 – reactors used for 300 417, 418 hard coal, liquefaction 450 – spectrum of factors influencing 227 – vs. energy consumption per capita 413 hardening agent 587 – steps of gas catalyzed reaction 229 – vs. gross national product (GNP) 415 Hastelloy C 484, 744 heterogeneously catalyzed surface reactions Huttig€ temperature 692 Hatta number 226 – Eley–Rideal mechanism 233 hydrated lime 696 HDPE fluid bed process 815 – Langmuir–Hinshelwood–Hougen–Watson hydratization 17 HDS process, configuration 632 rate equations 233, 234 b-hydride elimination 754 heat 235 – Langmuir–Hinshelwood mechanism 232, hydroamination 485 – dispersion coefficient 647 233 hydrochloric acid 457, 458 – loss estimation – monomolecular mechanism 232 hydrochlorination 458 –– hot wire by radiation and convection 80 – rate equations for 231, 232 hydrocyanation 28, 29 –– human body 80 heteropoly acid 748 hydrodealkylation 469 heat capacities 45, 434, 805 hexamethylenediamine 461, 464, 484, hydrodesulfurization 291, 625 heat conduction 52 485, 487 – and reaction engineering aspects – Fourier’s first law 66 hexamethylene diisocyanate 461, 464 629–633 – in spherical shell 67 1-hexene – reaction network 627 – through wall of tube with externally cooled – extrusion 761 – thermodynamics and kinetics 625–629 surface 66 – heterogeneously catalyzed gas phase hydrodynamic entrance region 84 heat exchangers 93, 94–97 hydrogenation 394 hydroelectricity 421 – counter-flow and parallel-flow heat exchangers, – hydroformylation 720 hydrofluoric acid 653 comparison 96 – selectivities 757 hydrofluoric acid alkylation process 656, 657 – logarithmic mean temperature difference in a cis/trans-3-hexene formation 720 hydroformylation 25, 28, 464, 472, 474, 475, heat exchanger 95–97 HF-catalyzed reaction 661 480, 716–738 heat of polymerization 805 high-density polyethene 803, 816 – advanced catalyst immobilization technologies heat transfer high density polyethylen 499, 521, 522 for 730–738 – analogy to mass transfer 579 high-dust system (in SCR) 780 –– catalyst separation by size exclusion – boiling 78, 79 high fructose corn syrup 29 membranes 732, 733 – coefficient 546, 575, 679, 710 higher olefins 25, 720, 727–729 –– homogeneous catalysts immobilization on – fluid and external surface of tube (cylinder) 73 – liquid–liquid multiphasic solid surfaces by 731–732 – fluid and internal surface of empty tube 71, 72 hydroformylation 728 –– liquid–liquid biphasic reaction systems – fluid and particles of packed bed 77 – Shell higher olefins process (SHOP) using 733–736 – fluid and single particle 75, 76 753–757 –– supported liquid hydroformylation – local, for flow of fluid across cylinder 73, 74 – solubility limitation 729 catalysis 736–738 – plane walls and cylindrical shells surrounded high-pressure Hastelloy reactor 744 – allyl alcohol 476 by fluids 77, 78 high-pressure LDPE processes 816 – catalytic cycle 719 – by radiation 79, 80 high-pressure methanol synthesis 527 – current catalyst heat transfer by convection high-pressure steam 611 –– and process technologies 722–730 – contribution of free convection to overall heat high-throughput experimentation 36 – 1-dodecene 718 transfer 76 Hinterland ratio 226 – ethylene 475 – estimations of heat transfer coefficients (a)67 Hirschfelder equation 58 – homogeneous nature 718 –– Nusselt number 68, 69 Hock process, for phenol production 481 – industrial relevance 717, 718 – from a stagnant or a flowing fluid to a solid 67 Hoechst process 812 – of internal olefins to linear aldehydes 721 heat transport, in chemical engineering 66 H2O electrolysis 797 – plant 716, 730, 733 heavy oils 139, 304, 434, 444, 449, 543, 612 – efficiency 799 – propene 475, 716, 717, 718 – cracking – energy demand 799 – propylene 481, 717 –– fluid catalytic cracking (FCC) 620–623 homogeneous catalysis 19, 287, 731, – supported liquid catalyst for 737 –– thermal cracking (delayed coking) 616–620 736 hydrogen 457, 536–558 – gasification 553, 554 – advantages 731 – hydrogen by gasification of biomass height of transfer zone (HTZ) 134/135 – applications 716 544–552 hemicellulose 453 homogeneous catalysts 20, 26, 722, 723 – production Henry coefficient 64, 109, 110, 116, 146, 293, – advantages 27, 28 –– and application 437 669 – catalyst deactivation 34, 35 –– options to produce 536–541 Henry’s law 109, 217, 627 ––rate 35 – syngas and 536 Henry, William 109 – chemical industry, examples 28 hydrogenations 16, 17, 20, 21, 29, 30, 35, 205, herbicides 506, 508 – filtration 732 291, 292, 394–396, 475 heterogeneous catalysis. see heterogeneously – properties 26 – aldehyde 720, 723 catalyzed process – transition metal complex 28 – catalysts 20 heterogeneous catalysts 19, 20, 23, 27, 29, 269, homogeneous reactions – fatty ester 475 485, 758 – kinetics of 21, 200 – nitrobenzene 485 – production, and characterization 29–32 – vs. heterogeneous catalysis 27 – olefin 720 – properties 27 homogeneous two-phase catalysis 290 – rate of octene 397, 398 Index j841

– selective 613 – application areas 35 – linear 1-alkene production, ethylene hydrogen bonding 736 ––chemical synthesis 36 oligomerization processes 749–762 hydrogen cyanide 461, 462 ––environmental catalysis 35 – nitric acid 568–587 hydrogen–nitrogen–ammonia ––production of polymers and materials 36 – polyethene (PE) production 803–816 equilibrium 527 ––refinery and energy applications 35–36 – refinery alkylation 652–662 hydrogen peroxide to propylene oxide (HPPO) – importance for development of efficient – steam cracking, basic chemicals by 604–616 process 704 processes 36 – sulfuric acid 558–567 hydrogen sulfide 612 industrial coal liquefaction processes 450 – syngas and hydrogen 536–558 hydrogen transfer 720 industrial electrolysis 786–802 – o-xylene to phthalic acid anhydride, catalytic hydroperoxidation reaction 701, 703 – chlorine and sodium hydroxide 791–802 oxidation 706–716 hydroperoxides 702 ––applications 791, 792 industrial soda ash 458 hydrophilicity 500 ––chlor-alkali electrolysis processes 792, 793 initiation 606 hydrophobicity 500 ––diaphragm process 793–795 initiator 495 hydrothermal synthesis 29 ––electrolysis of water 797–800 injection molding 805 hydrotreating ––membrane process 796 inorganic fibers, applications 459 – clean liquid fuels by 624–633 ––mercury cell process 795 inorganic products – history, current status, and perspective 624, – electrochemical kinetics, and – ammonia and nitric acid 457 625 thermodynamics 786–791 – applications 457 – hydrodesulfurization (see ––electrical work and thermoneutral enthalpy – in chemical technology 457 hydrodesulfurization) voltage 789–791 – chlorine and sodium hydroxide 458 hydrotreating reactions 624, 626 ––electrochemical potentials 787, 788 – phosphoric acid and phosphate salts 458 – equilibrium data 626 ––Faraday’s law and current efficiency 786, – soda ash (sodium carbonate) 458–459 hydrotreating reactor 637 787 – structure 457 hydroxide 13 ––galvanic and electrolysis cells, Nernst’s – sulfur and sulfur dioxide 458 hyper-branched polymers 732 law 788, 789 insecticides 506 hypochlorous acid 791 ––overpotentials 791 insertion–elimination mechanism 759, 760, ––standard electrode potentials 789 761 i – electrometallurgy 800–802 insertion polymerization reactions 496 ICI low-pressure process 693 ––electrolytic refining in aqueous solution 800, inspection, of equilibrium 189 ideal gas behavior 801 interfacial and internal mass transport effects, – compressibility factor 42, 44 ––fused salt electrolysis 801, 802 simultaneous occurrence 254 – magnitude of deviation 42 industrial organic chemistry 459, 460 – irreversible first-order reaction 254, 255 –– effect of temperature 43 – alkanes and syngas 460–464 – overall effectiveness factor 255 –– influence of pressure 42 – alkenes, alkynes, and aromatic interfacial transport of mass 235 ideal gas constant 40 hydrocarbons 464–471 intermediates 460 ideal gas law 40, 41 – organic compounds containing oxygen, internal heat transfer 284–286 – originators 41 nitrogen, halogens 472 – influence on effective reaction rate 285 ideal isothermal reactors 305, 306 ––acids 481–484 internal mass transfer 284 – comparison of ideal reactors 314 ––alcohols 472–477 internal olefins to n-aldehydes, selective – continuously operated ––aldehydes 478–481 hydroformylation 721 –– cascade of tank reactors 311 ––amines and nitrogen-containing intraparticle T-gradients, for gas and liquid phase –– ideal tank reactor 307, 308 intermediates 484–486 reactions 253 –– ideal tubular reactor 308, 309 ––epoxides 478 intrinsic pseudo-first-order rate constant 782 –– tubular reactor with laminar flow ––ether syntheses 477–478 intrinsic rate of chemical reaction 229 309–311 ––halogenated organic intermediates 488–491 investment costs 518–524, 703 – conversion for a given Da number 313 ––ketones 481 ionic liquid–organic biphasic catalysis 736 – equations for conversion of reactant in ideal ––lactams, nitriles, and isocyanates 486–488 ionic liquids (ILs) 64, 290, 630, 662, 733–737 reactors 314 – polymers 491 – application 736 – influence of changing volume on ––polyesters, polyamides, and – cations and anions 735 performance 315 polyurethanes 497–500 ion pair 13 –– mixed flow reactor 315 ––polyolefins and polydienes 492–493 iridium catalysts 747 –– plug flow reactor 315 ––vinyl-polymers and polyacrylates 493–497 iron 457 – influence of reactor type on product yields and industrial processes isenthalpic expansion 47 selectivity 316 – acetic acid 739–749 isobutane 463, 467, 468, 653–657, 660, 703, 813 – tubular recycle reactor 311–313 – ammonia synthesis 525–536 isobutane-to-olefin ratio (I/O) 656 – well-mixed (discontinuous) isothermal batch – catalytic reforming, high octane gasoline isobutanol 475, 478 reactor 306, 307 by 633–652 isobutene 465, 466 I-effect 8 – coke and steel 587–604 isocyanates 486, 487 ignition–extinction behavior 240, 268 – ethylene and propylene oxide 695–706 iso-hexane 11 ignition of Pt-wire during oxidation of – exhaust gases treatment from 773–786 isomerizations 20, 35, 469, 606, 721 ethylene 242, 243 – fine chemicals production 763 isooctene 468 ignition temperature 435 – fuels and chemicals from syngas, methanol and isophthalic acid 465 impregnation 30 Fischer–Tropsch synthesis 662–695 isopropanol 7, 475 indenoxide 28 – heavy oils cracking, liquid fuels by 616–624 isotacticity 492 indirect oxidation of propylene 702 – hydroformylation (oxosynthesis) 716–738 isothermal compression 160 inductive effects 8 – hydrotreating, clean liquid fuels by 624–636 isothermal plug flow reactor 618 industrial catalysts 20 – industrial electrolysis 786–802 isotope-labeled carbon dioxide 690 842j Index

j lactams 486 logarithmic mean temperature 94, 95 jet fuel 444 lambda value 776 “loop reactor process” 489, 813 Jost pot 768, 769 laminar flow 783 – schematic view 813 Joule, James Prescott 46 Langmuir–Hinshelwood–Hougen–Watson Loschschmidt, Johann Joseph 41 Joule–Thomson coefficient 45, 47 (LHHW) model 234 Lotka–Volterra model – calculation 47 Langmuir–Hinshelwood mechanism 697, 767 – for cyclic oscillations 327, 328 – liquids 48 Langmuir, Irving 122 low-density polyethene 803, 804 – sign 48 Langmuir’s adsorption isotherm 231 – autoclave process 806 Joule–Thomson effect 45, 435, 458, 540 L-asparaginic acid 508 – formation, free-radical process 806 Joule–Thomson throttling process 46, 47 LD converter 589 – tubular reactor process LDPE autoclave process 808 –– schematic view 807 k LDPE tubular process 808 low density polyethylene 498 Karman’s law 154 leaving group 14 lower heating values (LHV) 520, 532, 798, 799 Karman, Theodore von 155 Le Chatelier, Henry Louis 189 – ethylene oxide (EO) plant 520 Katzschmann process 483 Le Chatelier’s principle 189, 609 low-pressure methanol carbonylation 744 Keim, Wilhelm 753 length of unused bed (LUB) 134 low-pressure oxo process (LPO) 724 Kellogg process 693 Lewis acids 11, 496 lubricants 443, 493, 705, 750, 753, 762, 792 Kelvin, Lord 46 Liebig 21 Lurgi process for methanol production 694 kerosene 443 life expectancy index (LEI) 415 Lurgi reactor for coal gasification 543 ketone 14 ligand association 759 lynx-hare cycle 326, 327 kieselguhr 474 – reaction 754, 759 kinetic data 379 ligand back bone 721 m – case studies 392 ligand bite angle 721 macropores 31 –– heterogeneously catalyzed hydrogenation of ligand dissociation 759 macroradical 495 hexene 394, 395 ligand effect 27 magnetic suspension balance 63 –– heterogeneously catalyzed multiphase ligand–metal complexation equilibria 731 maleic acid 483 reaction 395–400 light crack-fuel, composition 614 maleic acid anhydride 30, 461, 464, 468, 469, ––non-isothermal oxidation of carbon nanotubes light heating oil 443 470, 482, 483 and fibers 400 light hydrocarbons maleic anhydride 476 –– thermal conversion of naphthalene – autothermic reforming 557 Mariotte, Edme 41 392–394 lignin 453, 454, 456 Markovnikov’s rule 17 – evaluation of 382–385 lignite, liquefaction 450 mass transfer – laboratory-scale reactors for kinetic limestone, applications 459 – analogy to heat transfer 579 measurements 385–388 limit cycle (oscillation) 326, 327 – by diffusion 53–57 – measurement and evaluation 379, 380 Linde process for air separation 540, 541 – with fast/instantaneous reaction near/at gas/ – principal methods for determining 379, 380 linear alkylbenzene sulfonates (LABS) 503, 750 liquid interface 220–225 –– laboratory reactors 380–382 linear low-density polyethene 750, 803 – with (slow) homogeneous gas/liquid reaction in –– macrokinetics 380 Lineweaver-Burk plot 289 bulk phase 219, 220 –– microkinetics 380 liquefied natural gas (LNG) 419, 436 mass transfer coefficient 86, 294, 574, 578, 597 –– pros and cons of integral and differential liquefied petroleum gas (LPG) 2, 443 – influence of temperature 575 method 382 liquid acid catalysts 656 mass transfer resistance kinetic energy 56, 60, 62, 152, 155, 201 liquid catalysis 736 – heterogeneously catalyzed gas–liquid kinetic racemic resolution 19 liquid filled porous catalyst 669, 685 reaction 293 kinetic resolution 29 liquid fuels 670, 672 – heterogeneously catalyzed gas or liquid kinetics 22 – production capacity 673 reaction 229 – of biochemical reactions 177 liquid hourly space velocity (LHSV) 637 mass transport 84 – birth and death of a rumor 209, 210 liquid–liquid biphasic catalytic reaction 27, 29, – diffusion in porous solids 89, 90 kinetic theory of gases 57 485, 730, 733, 735, 737, 738, , 753 – forced flow in empty tubes 84, 85 Kirchhoff’s law 79 liquid–liquid equilibrium – hydrodynamic entrance region 84, 85 Knudsen diffusivity 90–93, 249, 641 – calculation based on Gibb’s enthalpy 195 – interrelation of diffusion and convection 87, Koppers-Totzek process 543 – and link to gas-phase reaction 194 88 Kuhlmann process 723 liquid–liquid extraction 116 – Knudsen diffusion, and related – design 118, 119 phenomena 90–92 l – number of theoretical separation stages of – limitation 697 laboratory-scale continuous fixed bed extraction 120 – steady-state and transient diffusive mass reactor 765 – principles 116–118 transfer 85, 86 laboratory-scale reactors for kinetic liquid–liquid phase separator 727, 734 Maxwell–Boltzmann distribution 60 measurements 380, 385, 404 liquid–liquid reactions McCabe-Thiele approach 101–105 – batchwise operated stirred tank reactor 387 – equilibrium of 193, 194 mechanical unit operations – classification of laboratory reactors 386 – industrial reactions 216 – compressors and pumps 159 – fixed bed reactor with taps 387 liquid phase esterification, equilibrium of 195 –– conveyance of gases by compressors 160, – gradientless reactor 380 liquid recycle process 725, 738 161 –– with internal recycle 388 – advantage 725 –– conveyance of liquids by pumps 159 – integral reactors 381 – schematic view 725 –– estimation of energy requirement for the –– differential evaluation of data 381, 382 liquid–vapor equilibrium 541 conveyance of fluids 161 – laboratory-scale semi-batch reactor 764 living polymerization 496 – contacting and mixing of fluids 161, 162 – laboratory-scale trickle bed reactor 631 L-methionine 462 – conveyance of fluids 152 Index j843

–– pressure loss in empty tubes 152–156 – carbonylation 742, 743 – with indirect cooling 533 ––pressure loss in fixed, fluidized, and entrained – carbonylation, catalytic cycle and – with quench cooling 533 beds 156–159 mechanism 745 multifunctional reactors 36 – crushing and screening of solids – Co-catalyzed carbonylation 745 multiphase catalytic processes 28 –– particle size analysis 164, 165 – industrial production 686 multiple-bed reactor 693 –– particle size reduction 163, 164 – Ir-catalyzed carbonylation 745 multiple catalyst bed reactors 693 –– sieve analysis and particle size distribution, – oxidation 478 multiple catalyst beds 561 granular material 165 – production multi-purpose plant (MPP) 505 –– sieve analysis of sand 166 ––copper–zinc–alumina catalyst 690 multi-scale modeling 36 – cyclone for separation of solid particles from ––high-pressure plant 689 multistage cascade reactor 660 gases or liquids 171 – Rh-catalyzed carbonylation, catalytic cycle multi-tubular reactors 695, 698, – plate-type electrostatic precipitator 172 for 745 708, 716 – screening and classification of particles 166, – synthesis 24, 664, 671, 685–695 – cooling temperature, influence 682 171 ––catalysts for 689–692 – FT reactor 680, 681 –– sedimentation in centrifuges 171 ––equilibrium 688, 689 – modeling and simulation 677 –– sedimentation in electrical fields 171, 172 ––flow sheet 693 – runaway diagram 683 – separation of solids from fluids 168 ––kinetic mechanism 691 –– filtration 168 ––processes and synthesis reactors n –– sedimentation 168–172 692–695 nanofiltration 732 – solid–solid separation (sorting of different ––reaction steps 691 naphtha 443, 463, 613–615, 739, 740, solids) 167 ––thermodynamics 686–689 742, 749 – tubular electrostatic precipitator 172 methanol-to-olefin (MTO) 694 – cracking 463 mega methanol 694 methylaluminoxane (MAO) 492, 496, naphtha oxidation 742 melting enthalpy 51 757, 811 naphthalenes 140, 359, 379, 392–394, 441, melting point of selected liquids 51 methylaluminoxane co-catalyst 758 707, 716 melting temperature 50 methylamine 484 naphthenes 189, 441, 634, 636, 638, 651 membrane process 792, 796 methyl tert-butyl ether (MTBE) 465, 478, natural dyes 455 membrane reactors 305, 370, 371, 372, 732, 733 694, 703 natural gas 464 – hydroformylation catalysis 733 methyl carbocation 14 – autothermic reforming 557 membrane separation 458 methyl chloride 481 – based plant for ammonia 532 – principles 144–146 N-methyldiethanolamine 113 – composition 434 menthol diastereomers 770 methylene diphenyl diisocyanate (MDI) 498 – conditioning 435–437 – epimerization, reaction scheme 764 methyl ethyl ketone 481, 742 – conversion 435 – equilibrium concentrations 765 methyl iodide 744 – overview of processes based on natural – structure 763 N-methylpyrrolidone (NMP) 728 gas 435 menthol isomers, diffusion coefficients 768 N-methylpyrrolidone/water – properties of 433–435 menthol stereoisomers 769 mixtures 469 – reforming 555–557 Menton, Maud Leonora 288 methyl tert-butyl ether (MTBE) 478 – used for heating and electricity 436 mercury cell process for chlor-alkali metolachlor 28 natural gas production 434. see also methane electrolysis 791, 795 (S)-metolachlor stereoisomer 508 – safety parameters 434 mercury porosimetry 32 Michaelis, Leonor 288 – worldwide production, regional distribution mesomeric effects 8 Michaelis–Menten equation 288–290 of 434 mesopores 31 Michaelis–Menten kinetics 29 natural oils 11 metabolism 21 microorganisms 28 natural rubber (cis-1,4-polyisoprene) metal atoms 8 micropores 31 455, 491 metal carbonyls 34 microreactor technology 36 – molecular structure of 456 metal hydrides 17 middle temperature pyrolysis 604, 605 n-butanol 475 metallacycle mechanism 757–762 mixing 162 n-butenes 465 metallocene catalysts 20, 811 – dynamic/static mixers 162 Nernst equation 787, 788, 790, 793, 797 metal–organic vapor deposition 30 – fluids 161 Nernst’s partition coefficient 117 metal oxide 776 modified Thiele modulus 251 Nernst, Walther Hermann 117 metal plating 726 molar heat capacity 45, 317 neutral NaCl solution, scheme of metathesis 755 molecular interaction forces 42 electrolysis 791 methacrylic esters 462 molecular speeds in gas, distribution 60 Newton, Isaac 54 methane 8, 460–461 molybdenum naphthenate 703 Newton number 162 – chemical products from 461, 489 monoethylene glycol 699 Newton’s law 53 – chlorination 7, 458 monomers 12, 491 NH3 combustion 32 – coal mining 446 monophasic reaction system 729 n-hexane 11 – equilibrium content during steam monopropylene glycol 701 NH3 synthesis 32 reforming 555 Monsanto low-pressure process, for acetic – from natural gas 457 – equilibrium of methane pyrolysis 197 acid 744–747 nickel alkyl 754 – formation in Fischer-Tropsch synthesis 665 Monsanto process 743, 744, 747, 749 nickel catalyst 288, 394, 395, 398, 468, 481, – hydrogen cyanide production 461 – flow scheme 746 555, 753, 762 – natural gas 433, 434 montmorillonite 474 – ethylene oligomerization mechanism 753 – syngas production 462 motor octane numbers 652 nickel hydride 754 methanol 8, 63, 100, 104, 108, 377, 449, 472, moving-bed process 639 nitration 464 477, 483, 662, 685, 689, 692, 695, 743, 749 multibed ammonia reactor 533 nitration reaction 16 844j Index

nitric acid 457, 568–586 – well-mixed (discontinuously operated) non- organometallic catalyst 735 – ammonia, catalytic oxidation kinetics isothermal batch reactor 317 – complexes, immobilization 734 572–583 non-solar renewables 429 – system 809 –– in industrial reactor, on series of Pt normalize standard electrode potentials 802 organometallic complexes 735, 736 gauzes 579–583 northern hemisphere (NH), temperature organophosphorous 730 –– on single Pt wire for cross-flow of gas deviation 426 osmosis 147 – 573 579 NOx adsorber catalyst 778 Ostwald process 29 – NO oxidation 583, 583, 584 NOx emissions 511 Ostwald, Wilhelm 21, 22 – plant 567, 587 NOx storage catalysts, principle 778 overall turnover number 20 – processes 584–586 NTP (normal temperature and pressure) 185 overheating of coke particle, during combustion –– block diagram 569 nuclear power 420–421 with air 286 –– reaction scheme 569 nucleophiles 9 oxidations 20, 292 – production nucleophilic additions 17, 18 – acetic acid synthesis –– stability diagram 570 – prochiral carbonyl compound 18 –– by ethane and methane oxidation 748 –– thermodynamics 570 nucleophilic reagents 9 –– via acetaldehyde oxidation 740, 741 – production, reactions and nucleophilic substitution reactions 15 –– via butane or naphtha oxidation 742 thermodynamics 568–572 Nusselt number 68, 575, 578, 579 – alcohol 481 nitric oxide (NO) 568 – for cross flow over a long cylinder 76, 77 – aldehyde 481 – equilibrium content in air 572 – and heat transfer through fluid between two – alkene 479 nitriles 486, 487 parallel plates 68 – catalytic oxidation of ammonia on 573–580 nitrobenzene 10, 15, 469, 485 – local and average Nu number for laminar flow – catalytic oxidation of o-xylene to phthalic acid nitrobenzene hydrogenation 16 in a circular tube 72, 73 anhydride 706 nitrogen by air separation 540, 541 – variation, along circumference of a cylinder – combustion chamber for oxidation of nitrogeneous fertilizers 568 for 74 sulfur 560 – production 569 Nusselt, Wilhelm 66 – cycloalkane 475 nitrogen fertilizers 525 – direct oxidation of ethylene 696 nitrogen oxides 779 o – equilibrium composition of SO2 N-methylpyrrolidone (NMP) 467 octane number (ON) 14, 440, 443, 634, 651, 656, oxidation 190 N,N-azobisisobutyronitrile 496 674, 685 – ethylene 480 non-ideal flow, and residence time 1-octene – ignition of a Pt-wire during oxidation of distribution 336, 337 – hydroformylation 733, 734 ethylene 242 – pulse experiment 338 – hydrogenation 395, 398 – indirect oxidation of propylene 702 – step experiment 339, 340 – liberation 759, 762 – intrinsic rate constants for oxidation (and nonionic alkylphenol ethoxylates 700 – liberation from 759 gasification) of coke 546 non-ionic surfactants – selectivity 758 – of NH3 to to N2 and NO and of NO to – based on fatty alcohols and glucose 455 trans-4-octene, isomerization/hydroformylation NO2 571 non-isothermal ideal reactors 316 of 721 – non-isothermal oxidation of carbon – adiabatic operation of a batch reactor 317, 318 Octol process 468 nanotubes 400 – fi – choice of best reactor type, for adiabatic ole ns 441 NO oxidation to NO2 583 operation 335 – hydroformylation 721, 722 – number 759 – continuous ideal non-isothermal reactors – hydrogenation 720 – partial oxidation (of methane, heavy oil) 461, –– optimum operation line for adiabatic – isomerization 720, 721 552 operation 332, 334, 335 – sources 654 – reactions 11–12 – continuous ideal non-isothermal reactors, 1-olefins 472 oxidative addition 746, 760 optimum operating lines 332 – Schulz–Flory type distribution 753 oxidative coupling 759, 760 – continuously operated non-isothermal ideal – solubility 728 oxidative dehydrogenation 481 tank reactor 322, 323 a-olefin sulfonates (AOS) 750 oxide-supported catalyst 809 – continuously operated non-isothermal ideal oligomerization 655, 805 oxidizing agent 559 tubular reactor 328, 329 – aluminum-based 757 oxosynthesis 716. see also hydroformylation –– adiabatic operation of PFR 329, 330 – catalytic cycle of ethene 288 oxychlorination 458 – cooled batch reactor, with exothermic – 1-decene 750 oxygen 457 reaction 318–322 – ethylene oligomerization for linear 1-alkene oxygenates 443 – cooling stirred tank reactors (see cooling stirred production 749 oxygen content 549 tank reactors) – Ni-catalyzed 753–755 o-xylene 484 – and criteria for prevention of thermal – reactor 755 runaway 316, 317 oligomers 504, 504, 609, 752 p – critical condition for thermal runaway, for a – Schulz–Flory distribution 752 paraffins 131, 433, 440, 443–445, 651, 655 zero-order reaction 322 one-dimensional fixed bed reactor model 680 paraformaldehyde 479 – decomposition of H2O2 in adiabatic batch one dimensional pseudo-homogeneous reactor parallel reactions 206 reactor 318 model 645 – cycle 653 – evolution of reactor temperature, in cooled optical brighteners 501 particle size batch reactor 319 optimum operation line (of reactor) 332–336 – analysis 164, 165 – optimum operation line for non-adiabatic organic acids, production capacities. 482 – distribution curve 166 operation of PFR 335 organic S-species, reactivity 628 –– Rosin–Rammler–Sperling–Bennett (RRSB) – optimum path to minimize volume of organic sulfur compounds 537 function 165 PFR 335, 336 organic transformations 7 – distribution of a granular material 165 – wall-cooled ideal tubular reactor 330, 331 organocatalyst 19 – influence on pressure drop of fixed bed 157 Index j845

– reduction 163, 164 – natural dyes 455–456 polymerization 7, 17, 498, 655, 699 – reduction ratios – natural resins 456 – cationic 15, 17, 496 ––and maximum sizes (charge) of crushers and – natural rubber 455 – emulsion 499, 500 millers 163 plasticizer alcohol 717 – exothermicity 815 particle temperature 240 plastics 21 – grade 612 – maximum temperature difference between platinum-rhodium gauzes 572 – grade ethene, specification 806 center and outer surface 252 – alloy ammonia oxidation gauze 573 – in solution 498 – maximum temperature difference between platinum-rhodium wire 578 – in-substance 498 particle and surrounding fluid 240 plug flow behavior 602, 782 – mechanism 492 Peclet number 350–353 plug flow reactor 215, 262, 264, 297, 305, – precipitation 499 perfect gas equilibria 183 308–310, 312, 315, 353, 355, 360, 381, 388, 628, – reaction mixture vs. monomer conversion, perfluorohexane 733 646, 710, 767, 784 viscosity 500 peroxidation reactor of propylene oxide – adiabatic 646 – reactor 812 process 703, 704 – continuous 767 – slurry-phase 499 peroxide 702 – ideal 297, 308, 311, 314, 353, 357, 360, 388, – suspension 499 pesticides 506 603, 628 polymers 12, 491 petrochemical base chemicals, global Poiseulle, Jean Louis Marie 155 polymer process technologies 492 production 450 poisoning 32 polymethacrylate 12 petrochemicals vs. fine chemicals Poisson-type distribution 751 poly(methyl methacrylate) (PMMA) production 505 polarization 14 493, 496 petrochemistry 605 – of bonds 8 polyolefins, applications 492 petroleum industry 437 polyacrylates 493, 496, 506 polyols 472 petroleum residues 623 – applications 494 polypropylene (PP) 492 Petukhov’s law 154 polyacrylonitrile 496 polysiloxanes 732 PFR. see plug flow reactor polyaddition 494, 495 polystyrene (PS) 12, 493, 496 pharmaceutical 508 polyamide 6 495, 498 – acrylonitrile (SAN) 493 phenol 8, 472 polyamide 6.6 495 – butadiene–acrylonitrile (ABS) phenol production 477 polyamides 486, 495, 498 copolymers 493 – Hock process 481 – applications 497 – butadiene rubber (SBR) 493 a-phenylethanol 703 – formation, from diamines and dicarbonic polysulfide 495 Phillips catalyst 809, 810, 813 acids 495 polytetrafluoroethylene (PTFE) 493 Phillips Particle Form Process 813 polyarylate 495 polyurea 494 phosgene 487, 498 polybutadienes 465, 492, 493, 496 polyurethanes 494, 498 phosphates 457 polycarbonate 495, 498 – applications 497 phosphite ligands 730 polycondensation 494 poly(vinyl acetate) 496, 740 phosphoric acids 457 polydienes 492, 493, 496, 506 poly(vinyl chloride) (PVC) 493, 496, 717 phosphoryl chloride (POCl3) 542 – applications 493 – hard 493 phosphotungstic acid 748 polyesters 495 – soft 493 photosynthesis 21 – applications 497 pony-tails 734 phthalic acid 484 – fibers 740 pore diffusion 530, 685, 782 – anhydride 472, 521 – formation, from diols and dicarbonic – and intraparticle heat transport 252, 253 – esters 493 acids 495 – limitations 264, 265 – production capacities. 482, 484 polyethene (PE) production 803–816 pore diffusion resistance 229, 247 phthalic anhydride 707, 708, 712, 717 – classification and industrial use 803–805 pore effectiveness factor 530, 531 – cooling temperature influence 713 – HDPE and LLDPE, catalysts for – temperature and particle size – production 706 production 809–812 influence 530 physical transformations, of pure ––Phillips catalyst systems 810–811 pores, of catalyst 228 substances 48 ––single-site metallocene catalyst systems 811, – overall pore length 228 – change of entropy 48 812 – pore diameter 228 – Clausius inequality 48 ––Ziegler catalyst systems 809, 810 – pore dimensions 228 – influence of pressure on phase transition – HDPE and LLDPE, production porosity 158 process 51 processes 812–815 – of membrane 145 –– Clapeyron equation 51 – LDPE production, reaction meachanism porous catalyst – melting enthalpy 51 ––and process equipment 806–809 – particles 249 – melting point of selected liquids 51 – production economics, and modern – with slab geometry in case of consecutive first- – phase boundaries 50, 51 developments 815, 816 order reactions –– critical values 50, 51 – production processes, characteristics –– pore diffusional limitations 264, 265 – –– supercritical state 50, 51 purity 805 potassium nitrate (KNO3) 525 – work done by system 48 ––reaction exothermicity and thermal potential energy surface, for reaction 202 physisorption 31, 231 stability 805 practical cell voltage 798 Pier, Matthias 673 polyether polyols 705 Prandtl, Ludwig 71 pig iron production, in blast furnace polyethylene (PE) 20, 491, 492, 521, 751 Prandtl number 71 595–603 poly(ethylene terephthalate) (PET) 495, 497, Prandtl’s law 153 – coke consumption 599–601 740 Prater number 254, 285 – residence time distribution 601–603 polyisobutene 465 precipitation 29 Planck, Max 41 polyisoprenes (IR) 493, 496 pre-desulfurized diesel oil 629 plants, extracts/excreta 455–457, 508 polymer 460 pre-exponential factor 201 846j Index

presaturated one-liquid flow (POLF) q –– rate limited by film diffusion and internal reactor 764, 765, 771 quenching 611 diffusion 272, 273 – epimerization in 764 quench-system 610 –– reaction and external mass transfer 273 pressure drop 536 –– shrinking non-porous unreacted core – comparison in a fixed bed and in a r 270–272 monolith 785 racemic mixture 19 –– shrinking non-porous unreacted core and – empty tube 152–154 racemic resolution processes 19 gaseous product(s) 273, 274 – entrained bed 158, 159 racemization processes 19 –– slow chemical reaction 272 – fixed (packed) bed 156, 157 radial carbon profiles 643 –– solid product layer 270–272 – fluidized bed 157, 158 radial dispersion 710 – with a porous solid 276 Presto program 646 radial effective thermal conductivity 678 –– basic equations for conversion 277 primary amines 484 radial heat dispersion 389 –– border cases and general situation 277 primary cracking 608 radial heat flux 683, 684 –– border cases and models 276 primary energy consumption radial heat transfer in packed bed reactors. –– chemical reaction, rate-determining – global 423 see also fixed bed reactors, modeling step 281 –– forecast 424 – effective radial conductivity lrad of a packed –– equations for conversion 281 – regional distribution of 409 bed 368, 369 –– general closed solution by combined – shares 408, 423 – heat transfer coefficient and Nu number 369, model 277–279 – world 429 370 –– homogeneous uniform conversion probability, of chain growth 666 – and methods to account 363 model 280 prochiral compounds 18, 19 – one-dimensional model of a wall-cooled –– rate controlled by diffusion through solid products extracted, using supercritical reactor 365–368 product layer 281 CO2 137 – two-dimensional model of a wall-cooled –– reaction and diffusion in product layer propagation 606 reactor 363–365 determine rate 281 propane 461, 462 radial temperature profiles (Fischer-Tropsch –– shrinking unreacted core model 280 1,3-propanediol 476 reactor, o-xylene oxidation) 681, 713 reaction of n-th order 204, 205 propanols 475 radiation 79 reaction quotient (QR) 185 propene 17 radiation zone 610 reaction rates 23, 24 – gas-phase hydroformylation 737 radical chain propagation 12 – different forms and units 230, 231 – rhodium-catalyzed hydroformylation 724 radical chlorination 461, 488 reactions, general classification 10 2-propen-1-ol. see allylic alcohol radical cracking taking place in a steam – acid–base catalyzed reactions 11 propionic acid 742 cracker 606 – addition reactions 10 propylene 461 radical mechanism of acetaldehyde – electrophilic addition reactions 17 – direct oxidation 701 oxidation 740, 741 – electrophilic substitution reactions at aromatic – indirect oxidation 702 radical polymerization reactions 495 compounds 15–17 – indirect propylene oxidation 704 radical reactions 11 – elimination reactions 11 – oxidation, pilot plant reactor 704 – steam cracking 605 – nucleophilic addition reactions 17, 18 – Rh-catalyzed hydroformylation processes 728 radicals 7, 490 – nucleophilic substitution reactions 13 – Wacker-Hoechst oxidation of 481 radicals I 495 –– choice of solvent: 13 propylene glycol ether 478 Raffinate 1 467, 468 –– groups surrounding carbon atom 13 propylene oxide 466, 472, 478, 706 Raffinate 2 468 –– nature of incoming group 13–14 – application 478 Raffinate 3 468 –– nature of leaving group 14 – chlorohydrin process, flow sheet 702 Raney-copper 29 – reactions via carbocations 14, 15 – commercial production 700–706 Raney-nickel 29 – reactions via free radicals 11, 12 –– chlorohydrin process 701, 702 Raoult, Francois-MarieS 99 – rearrangement/isomerization reactions 11 –– propylene, indirect oxidation 702–705 Raoult’s law 99 – substitution reactions 10 –– propylene oxide, products made rate equation 200 reactions in series 206 705, 706 – influence of temperature and reaction reactions with varying volume 213–215 – Halcon process, flow sheet 704 order 200 reaction time 180, 181 – industrial epoxides 478 rates of reactions 178 reactors. See also chemical reactors – polyethers from 705 – windows of rates, biochemical and chemical – batch 181 – world consumption 705 processes 177 – catalytic 23 PS–butadiene–acrylonitrile (ABS) raw coke oven gas, composition 590 – chemical reactor copolymer 493 reaction energy 187 –– disciplines needed for design 176 PS–butadiene rubber 493 – calorimetric measurements 187 –– scale-up dimensions 177 pseudo-first-order rate constant 668 reaction mechanism 200, 201 – influence of mixing on the reactor size 178 PtRh-gauze 583 – view of chemist and chemical engineer – influence of reactor type on productivity 178 – geometry 580 200 – tube 35 pumps, conveyance of liquids by 159 reaction of gases reactor technology, novel developments 370 purchasing power parity (PPP) 410, 415 – with a non-porous solid 270 – adiabatic reactors, with periodic flow purified enzymes 28 ––border cases and models 270 reversal 376, 377 pygas 613 ––chemical reaction determines effective – hybrid (multifunctional) reactors 370 pyrolysis gasoline 612 rate 274 –– catalytic distillation 372 pyrolysis oil 613 ––conversion different cases 275 ––coupling membranes and reaction 370, 371 pyrolysis of solid fuels (coal, biomass) 544 ––effective rate limited by external –– coupling reaction and adsorption 371, – chemical reactions 448 diffusion 274 372 – kinetic parameters for biomass 545 ––equations 275 – microreactors 373 Index j847

–– advantages 373 reserves of fossil fuels 418–420, 423 –– selectivity of reactions in series 259–262 –– drawbacks 373, 374 residence time 180, 181, 608 – influence of pore diffusion –– heat transport 375, 376 – distribution 336–343 –– on selectivity of parallel reactions 267 –– mass transport, and residence time resources of fossil fuels 418–420, 423 ––on selectivity of reactions in series 263, 264 distribution 374 reverse osmosis 147 self-alkylation 655 –– typical values of characteristic – basic principle 147 self-ignition 699 parameters 374 reversible reactions 210–212 semi-batch stirred tank reactor 764 – monolithic reactors 372, 373 – activation energies 212 semi-regenerative reforming process, flow reagent induction 19 – first-order reaction scheme 637 reagents classification 9, 10 ––effectiveness factor (pore diffusion) 251, 252 separation by membranes 144 real gas ––exothermic 258 – applications of technology 144 – adiabatically expansion 46 ––with influence of external and internal mass – basic principle of reverse osmosis 146 – properties 40 transfer 256–259 – mass transport through real gas equilibria 190, 191 – ratio of rate constants 212 –– non-porous membrane 146 rearrangement or isomerization – relation between equilibrium –– porous membrane 145, 146 reactions 10 ––and rate of forward and reverse reaction 213 – membrane separation processes, reciprocal reaction rate 564, 565 – standard reaction enthalpy and entropy 212 applications 147 recycle compressor 630 Reynolds number 70, 71 –– desalination of sea water 147 recycle gas, composition 684 Reynolds, Osborne 71 –– gas separation 147–149 recycle ratio Rh-based hydroformylation 722–724, 730, 738 – principles of membrane separation 144, – definiion 676 Rh-BIPHEPHOS 721 145 – influence 677 Rh catalyst 729 –– dense (non-porous) membranes 144 recycle reactor 676 Rh-catalyzed propene hydroformylation 728 –– porous membranes 144 recycling 27 rhodium catalyst 731 – seawater desalination process 147 Redlich–Kwong equation 44 riboflavin 508 – spiral-wound membrane element 147 reduce CO2 emissions 426 risertype reactor 658 separation processes, based on the reducing agent 780 Roelen, Otto 717 wettability 167 reductive cleavage 761 Rosin–Rammler–Sperling–Bennett (RRSB) sequestrants 501 reductive elimination 720, 760 function 165 Shell catalyst system 707, 715, 723 refineries Ruhrchemie/Rhone-Poulenc^ process 726, 727, Shell higher olefins process (SHOP) 25, 750, – flow-sheet of crude oil refinery 445 733 753– 757 – processes 443–445 – flow scheme 753 – products, properties of 442–443 s Sherwood numbers 86, 138, 239, 574, 579, 582, refinery alkylation 463, 652–662 a-SABLIN technology 757 641, 783 – alkylation feedstock and products 654, 655 saccharose (a-D-glucopyranosyl-b-D- Sherwood, Thomas Kilgore 86 – commercial alkylation processes 657–662 fructofuranoside) 455 shrinking core model 644 –– commercially applied alkylation processes Sachsse–Bartholome process 461, 470 side-fired primary reformer 556 comparison 661, 662 sanitation, global 514 Siemens-Martin (SM) process 589 –– using hydrofluoric acid as liquid saponification 503, 701 sieve analysis, of sand 166 catalyst 657, 658 SASOL tetramerization system 761 sigmoidal heat production function 587 –– using sulfuric acid as liquid catalyst SATP (standard ambient temperature and silicates 459 658–661 pressure) 185 silicones 459 – process variables 655–657 saturated fatty acids 451 silicotungstic acid 748 –– acid strength and composition 656 saturated monoalcohols, industrial SILP catalyst 737 –– effect of mixing 656, 657 production 474 SILP materials 737 –– isobutane concentration 656 Schmidt, Ernst 86 simultaneous equilibria, calculation 197 –– reaction temperature 655, 656 Schmidt number 86 single-phase system 287 – reaction and reaction mechanism 652–654 Schulz–Flory product distributions 752, 755 – homogeneous and enzyme catalysis 287 reforming catalysts (reforming of gasoline) 636, SCR reactor 781 – mechanism of homogeneous catalysis 639 – pressure drop 785 288 – characteristic data 641 scrubbers 658 – turn over number 287 – deactivation and regeneration 639 secondary amines 484 single-pressure nitric acid plant 585 – mechanisms 636 second law of thermodynamics 48 single-site catalysts 811 refractory-lined furnace for sulfur second-order reaction 205 – development 811 combustion 559, 560 sedimentation 168, 169 – Kaminsky-catalyst, formation 811 regeneration process (decoking of reforming – estimation of size of sand trap of sewage – metallocene catalysts 809 catalyst) 645 plant 170 single-stage reactor 659 regioisomers 16 – in gravitational field 169 sintering 34 regioselectivity 738 – separation of solids from fluids 168 size exclusion membranes 732 regulators 501 – single sand particles in water 170 slurry-phase polymerization 499 renewable energy 421–422, 424, 430 selective catalytic reduction (SCR) 586, 778 slurry process 812 renewable raw materials selectivity 25 Smochulowski, Marian 248 – base chemicals 450–451 – definition 179, 180 Snia-Viscosa process 486 – carbohydrates 453–455 selective hydrogenation reactions 613 SN1 reaction 13 – – extracts and excreta from plants 455 457 selectivity of reactions 259 SN2 reaction 13 – – – fl fats and vegetable oils 451 453 in uence of external mass transfer on SO2 research octane numbers (RONs) 652, 634 ––selectivity of parallel reactions 262, 263 – catalytic conversion into SO3 560–566 848j Index

–– selectivity conversion vs. dimensionless ––hydrocarbon partial pressure in cracking sulfur 457 reactor volume 565 oven 609, 610 – emissions 624 –– selectivity of reactions conversion vs. ––residence time 608, 609 sulfuric acid 457, 474, 558–567 temperature plot 564, 565 ––temperature in cracking oven 608 – processes for production 566 –– production routes 559 – product separation and purification 613 – production, reactions and – emissions – propylene 465 thermodynamics 558, 559 – fi – soap formation 503 simpli ed scheme 612 sulfur dioxide conversion into SO3 Soave–Redlich–Kwong equation 44, 687 – steam cracker process, economic 560–566 soda ash 457 aspects 615 – sulfur dioxide production 559, 560 sodium carbonate. see industrial soda ash steam cracker unit – use as catalyst for alkylation 658 sodium hexafluoroaluminate 802 – mass balance 614 supercritical carbon dioxide (scCO2) 734 sodium hydroxide 457 – simplified scheme 614 – immobilization, schematic sodium nitrate (NaNO3) 525 steam reforming process 32, 536 representation 734 sodium salt of tris(m-sulfonatophenyl) phosphine – ammonia plant, block diagram and supercritical fluids 93, 136, 137, 139, 150, (Na-TPPTS) 726 temperature profile 538 485, 735 Sohio process 462, 486 – feed for 537 – solvation properties 137 solar energy 430 steel 603 supercritical hydrocarbons 139 sol–gel processes 29 – iron ore to 603 superheated steam 610 solid catalysts – production processes 588 supported Ag particles, REM pictures 698 – individual steps of catalysis 292 steel production 587–589 supported aqueous phase (SAP) catalysts 737 – kinetics of gas–liquid reactions on – based on blast furnace route 588, 589 supported ionic liquid phase (SILP) catalyst 737 291–294 – based on scrap and direct reduced iron surface kinetics 231 – reaction and interfacial transport of mass and (DRI) 589 surface renewal theory for gas-liquid mass heat 235 – coal and coke in steel production transfer 217 – sorption on surface of 231 449, 587 surfactants 500 solidification temperature curves 140 Stefan-Boltzmann law 79 – applications 502, 503 solvation 13 Stefan flow 87 – molecules Solvay process 458 Stefan, Joseph 79 –– application field 501 – process scheme of 459 step-growth polymerization 494 –– schematic representation 500 – solid-fluid separation 168 stereochemical environment 811 – neutral, applications 504 – solid-solid separation processes 167 stereoisomers 18 – structure and properties 500–501 soot–naphtha suspension 553 steric demand 13 suspension polymerization 499 sorting of solids 167 steric effects 8 suspension process. see slurry process sour gases 435 – reactivity of two trityl radicals 9 sustained strong economic growth 423 space–time yield 23, 181, 499 stirred tank reactor 746 Sutherland constant 58 space velocity 181 stirred tank reactors Sutherland, William 58 spectrum of factors, influencing rate of – adiabatic operation 323 SWB 416–418 reaction 227, 228 – derivation of Eu- and F-function 340 Symrise process 763 speed of reactions 177 – dynamic behavior and oscillations 326 syndiotacticity 492 sprouting of PtRh catalyst for ammonia – dynamic stability 325 synfuels, limitations 672 oxidation 572 – equations 324, 326 syngas 460, 464, 536–558, 716 S-sensitive DeNOx-storage catalysts 625 – heat production function, and heat removal – by partial oxidation of heavy oils 552–555 standard Gibbs function of reaction 189 lines 324 – from solid fuels (coal, biomass) 542–552 standard of living 415 – parameters of styrene polymerization 325 –– basic principles and reactions 542 standard potentials 787, 789, 790, – static stability 325 –– by gasification 543, 544 800, 802 – typical devices for 319 –– by gasification of biomass 544–552 standard reaction enthalpy 186, 187 stoichiometric coefficient 560, 787 – by steam reforming of natural gas – calorimetric measurements 187 Stokes’ law 169, 170 555–558 standard reaction entropy 186, 187 STP (standard temperature and pressure) 185 – treatment 537 standard reference conditions 184 straight-run gasoline 651 synthesis gas. see syngas starch 454, 491 stranded gas 694 synthetic ammonia 525 1 TM – molecular segments 455 STRATCO Contactor reactor 657 synthetic fuels starch-containing substrates 472 – setup 659 – Fischer–Tropsch synthesis (FTS) 684 steam cracker/cracking 10, 464, 604, 605, stripper 612 – production 664, 672 607 styrene 464, 469, 702 synthetic hydrocarbons (SHC) 750 – basic chemicals by 604–616 – copolymers 703 synthetic lubricants 750 – benzene 468 subjective well-being index (SWB) 416, 417, synthetic rubber. see elastomers – butadiene, isobutene, and butenes 466 418 – C4-cut, technical processing 466 substitution reactions 10 t – economics 615 substrate induction 19 Takasago process 763, 772 – ethylene 464 sugar 454 tanks-in-series model 340, 602, 603 – general and mechanistic aspects 605–608 – based surfactants 454 – calculation of conversion by tanks-in-series – industrial steam cracker process sulfochlorination 12, 463, 504 model 342, 343 610–615 sulfolene 465 – derivation of number of tanks-in-series by E u – product distribution, influencing factors sulfonation 16 function 342 608–610 sulfoxidation 504 – residence time distribution of cascade of –– applied feedstock 608 – route 464 340–342 Index j849

Teller, Edward 127 transport coefficients of liquids 61–63 valence electrons (VE) 759 tensides 453, 478, 504 – Bridgman equation 61 valuable organic intermediates 717 terephthalic acid 465, 483, 740 – diffusion coefficient, calculation 62 vanadium-based catalyst 561 – production capacities. 482, 483 ––Wilke–Chang equation 62 Van der Waals constants, of selected terephthalic dimethyl ester 483 – influence of temperature on viscosity 62 gases 42 tert-butylamine, production 485 – methods to measure diffusion coefficient in van der Waals equation 42 tertiary amines 484 liquids 63 – estimation of critical data based tetrachloromethane 488 ––capillary method 63 on 44 1,1,1,2-tetrafluoroethane 490 ––magnetic suspension balance 63, 64 van der Waals interactions 736 tetrahydrofuran (THF) 478 – thermal conductivity 61 Van der Waals, Johannes Diderik 42 Texaco process for heavy oil gasification 553 transport limitations, in experimental catalytic van’t Hoff equation 188 – feedstock and raw syngas reactors van’t Hoff, Jacobus Henricus 188 composition 554 – criterion to exclude influence of dilution of vaporization 49 thermal conductivity 69, 229, 546, 580, 592, catalytic fixed bed 392 – change of entropy 49 593, 647 – gradientless ideal particle behavior – enthalpy 49, 50 thermal conductibility 81 389, 390 – Trouton’s constant 50 thermal cracking of heavy oils 616 ––interfacial heat transfer 391 – vapor pressure equation 49 thermal diffusion 56 ––interfacial mass transfer 390 vapor pressures 50, 51, 541 thermal entrance region 71 ––internal heat effects 391 – for curved systems 51, 52 thermal runaway during PE production 806 ––internal mass transfer 391 variable costs 521–524 thermodynamic data – ideal plug flow behavior 388–390 vegetable oils 452 – NH3 synthesis 192 transport properties 52 Verbund 615 – selected species 185 – and density of selected gases 53 vibration mills 163 thermogravimetry (TG) 92, 400, 404 – equations for transport of mass, heat, and vinyl acetate (VAM) 467, 740 thermoplastic polymers 491 momentum 52, 53 vinyl chloride 11, 465, 472, 490 thermoset resins 491 – in liquids and solids 53 vinyl ester 465 thickness d of thermal boundary layer 68 trays 723 vinyl ether 465 – definitions 68 trickle bed reactor 629–632, 633 vinylidenes 758 Thiele modulus 252, 254, 640, 641, 642, 669, triethylene glycol 476 vinyl-polymers 496 715 triglycerides 451 – applications 494 Thomson, William 46 trimethylamine 484 viscoelastic polymer 804 three-phase system 629, 633 trioxane 479 viscosity of gases and liquids 52, 53 three-way catalyst 776, 786 triphenylphosphine 737 vitamin B2. see riboflavin tidal power 422 – ligand 732 vitamin B3 508 time-tank process for alkylation 658, 661 trityl radicals 9 vitamin C 508 – scheme 659 Tropsch, Hans 664 vitamin E 508 titanium-silicate catalyst 703 Trouton, Frederik Thomas 50 vitamins 508 Ti-V-W catalyst 782 Trouton’s rule 50, 629 V2O5 catalyst 561 toluene 463 turnover frequency (TOF) 23 volatile platinum oxides 573 toluene diisocyanate 498 turnover number (TON) 20, 22, 23 volatility, relative 99 2,4-toluene diisocyanate 488 two-dimensional finite element method 577 toluene diisocyanate (TDI) 498 two-dimensional fixed bed reactor model 678, w total oxidation 701 685, 709 Wacker–Hoechst process 480 TPPTS 726 two-film theory 217 – ethylene oxidation 480 transalkylation reactor (TR) 469, 753 – equations 218, 219 washing machine powder 501 transfer-line heat exchangers, design two first-order reactions in series 207–209 washing powders 28, 504 objectives 611 two parallel first-order reactions 206, 207 washing towers 612 transient heat two-phase reactor 631 waste-heat boiler (WHB) 553 – coke production from coal 591 water alkaline electrolysers 798 – of plate for Bih 82–84 u water consumption, domestic 513, 514 – transfer by conduction and convection 80–82 Union Carbide Corporation (UCC) 696 water content/consumption, transition states 23, 24 Union Carbide/Davy Powergas gas recycle virtual 514 transport coefficients of gases 57 process 724 water electrolysis 797 – binary gas mixtures 58 – disadvantages 725 water footprint 513, 514 –– binary gas diffusion coefficients 59 – schematic view 724 water-gas shift reaction 24, 539, 555, 600, 669, –– calculation of binary diffusion Union Carbide’s Ethoxene process 748 682, 687 coefficients 58 Union Carbide’s induced phase separation – equilibrium constant, influence of temperature –– experimental values, correlation 59 process on 539 –– Hirschfelder equation 58 – schematic view 729 water/NMP/catalyst 729 –– special diffusion volumes derived 59 unsaturated fatty acids 451 water resources – experimental values deviation 57 UOP process 657, 658 – global 512 – gas mixture, more than three components 59 urea 457 – renewable 513 – for ideal gases 57 UV-irradiation 490 Weisz modulus 252 –– influence of T and p 57 whole cell 26 – mean free path 57 v Wilke–Chang equation 62, 669, 769 – mean velocity of molecules 57 vacuum distillation 616 wind turbines 422 – Sutherland constant 58 vacuum residue oil 618, 619 Winkler process 543 850j Index

wood ––effective rate 715 z – to cellulose 454 ––multi-tubular reactor 706 Zeldovich, Yakov Borisovich 248 – constituents of 454 – to phthalic acid anhydride zeolites 26 – production of forest products 454 ––catalytic oxidation 706–716 – adsorbents 121 ––multi-tubular reactor, design and – role in refinery, and petrochemical x simulation 708–716 processes 26 xenon 457 ––phthalic anhydride, production and use 707, Ziegler Aufbaureaktion 751, 753, 757 X-ray diffraction 31 708 Ziegler, Karl 751 X-ray photoelectron spectroscopy 32 p-xylene 465, 483, 484 Ziegler–Natta catalysts 21, 492, 493, 496, 750, XTL plant 674 809, 810, 811 xylenes 463 y Ziegler–Natta polymerization 492 o-xylene 469 yeasts 474 ZnO/Cr-oxide catalysts 689 – oxidation yield, definition 179, 180