化学反应工程原理(第4版)(英文影印版)

preface . xix
1 mole balances 1
1.1 the rate of reaction, –ra 4
1.2 the general mole balance equation 8
1.3 batch reactors 10
1.4 continuous-flow reactors 12
1.4.1 continuous-stirred tank reactor 12
1.4.2 tubular reactor 14
1.4.3 packed-bed reactor 17
1.5 industrial reactors 21
summary 25
cd-rom material 26
questions and problems 29
supplementary reading 35
2 conversion and reactor sizing 37
2.1 definition of conversion 38
2.2 batch reactor design equations 38
2.3 design equations for flow reactors 40
2.3.1 cstr (also known as a backmix reactor
or vat) 43
.2.3.2 tubular flow reactor (pfr) 44
2.3.3 packed-bed reacto 45
2.4 applications of the design equations for continuous-flow reactors 45
2.5 reactors in series 54
2.5.1 cstrs in series 55
2.5.2 pfrs in series 58
2.5.3 combinations of cstrs and pfrs in series 60
2.5.4 comparing the cstr and pfr reactor volumes and
reactor sequencing 64
2.6 some further definitions 66
2.6.1 space time 66
2.6.2 space velocity 68
summary 69
cd-rom materials 71
questions and problems 72
supplementary reading 77
3 rate laws and stoichiometry 79
part 1 rate laws 80
3.1 basic definitions 80
3.1.1 relative rates of reaction 81
3.2 the reaction order and the rate law 82
3.2.1 power law models and elementary rate laws 82
3.2.2 nonelementary rate laws 86
3.2.3 reversible reactions 88
3.3 the reaction rate constant 91
3.4 present status of our approach to reactor sizing and design 98
part 2 stoichiometry 99
3.5 batch systems 100
3.5.1 equations for batch concentrations 102
3.5.2 constant-volume batch reaction systems 103
3.6 flow systems 106
3.6.1 equations for concentrations in flow
systems 107
3.6.2 liquid-phase concentrations 108
3.6.3 change in the total number of moles with reaction in the gas phase 108
summary 124
cd-rom material 126
questions and problems 131
supplementary reading 141
4 isothermal reactor design 143
part 1 mole balances in terms of conversion 144
4.1 design structure for isothermal reactors 144
4.2 scale-up of liquid-phase batch reactor data to the design
of a cstr 148
4.2.1 batch operation 148
4.3 design of continuous stirred tank reactors (cstrs) 156
4.3.1 a single cstr 157
4.3.2 cstrs in serie 158
4.3.3 cstrs in parallel 160
4.3.4 a second-order reaction in a cstr 162
4.4 tubular reactors 168
4.5 pressure drop in reactors 175
4.5.1 pressure drop and the rate law 175
4.5.2 flow through a packed bed 177
4.5.3 pressure drop in pipes 182
4.5.4 analytical solution for reaction with
pressure drop 185
4.5.5 spherical packed-bed reactors 196
4.6 synthesizing the design of a chemical plant 196
part 2 mole balances written in terms of concentration and molar flow rate 198
4.7 mole balances on cstrs, pfrs, pbrs, and batch reactors 200
4.7.1 liquid phase 200
4.7.2 gas phase 200
4.8 microreactors 201
4.9 membrane reactors 207
4.10 unsteady-state operation of stirred reactors 215
4.10.1 startup of a cstr 216
4.10.2 semibatch reactors 217
4.10.3 writing the semibatch reactor equations in terms of concentrations 219
4.10.4 writing the semibatch reactor equations in terms of conversion 223
4.11 the practical side 226
summary 227
ode solver algorithm 230
cd-rom material 231
questions and problems 234
some thoughts on critiquing what you read 249
journal critique problems 249
supplementary reading 252
5 collection and analysis of rate data 253
5.1 the algorithm for data analysis 254
5.2 batch reactor data 256
5.2.1 differential method of analysis 257
5.2.2 integral method 267
5.2.3 nonlinear regression 271
5.3 method of initial rates 277
5.4 method of half-lives 280
5.5 differential reactors 281
5.6 experimental planning 289
5.7 evaluation of laboratory reactors 289
5.7.1 criteria 289
5.7.2 types of reactors 290
5.7.3 summary of reactor ratings 290
summary 291
cd-rom material 293
questions and problems 294
journal critique problems 302
supplementary reading 303
6 multiple reactions 305
6.1 definitions 305
6.1.1 types of reactions 305
6.2 parallel reactions 310
6.2.1 maximizing the desired product for one reactant 311
6.2.2 reactor selection and operating conditions 317
6.3 maximizing the desired product in series reactions 320
6.4 algorithm for solution of complex reactions 327
6.4.1 mole balances 327
6.4.2 net rates of reaction 329
6.4.3 stoichiometry: concentrations 334
6.5 multiple reactions in a pfr/pbr 335
6.6 multiple reactions in a cstr 343
6.7 membrane reactors to improve selectivity
in multiple reactions 347
6.8 complex reactions of ammonia oxidation 351
6.9 sorting it all out 356
6.10 the fun part 356
summary 357
cd-rom material 359
questions and problems 361
journal critique problems 372
supplementary reading 375
7 reaction mechanisms, pathways, bioreactions, and bioreactors 377
7.1 active intermediates and nonelementary rate laws 377
7.1.1 pseudo-steady-state hypothesis (pssh) 379
7.1.2 searching for a mechanism 383
7.1.3 chain reactions 386
7.1.4 reaction pathways 391
7.2 enzymatic reaction fundamentals 394
7.2.1 enzyme–substrate complex 395
7.2.2 mechanisms 397
7.2.3 michaelis-menten equation 399
7.2.4 batch reactor calculations for enzyme reactions 404
7.3 inhibition of enzyme reactions 409
7.3.1 competitive inhibition 410
7.3.2 uncompetitive inhibition 412
7.3.3 noncompetitive inhibition (mixed inhibition) 414
7.3.4 substrate inhibition 416
7.3.5 multiple enzyme and substrate systems 417
7.4 bioreactors 418
7.4.1 cell growth 422
7.4.2 rate laws 423
7.4.3 stoichiometry 426
7.4.4 mass balances 431
7.4.5 chemostats 434
7.4.6 design equations 435
7.4.7 wash-out 436
7.4.8 oxygen-limited growth 438
7.4.9 scale-up 439
7.5 physiologically based pharmacokinetic (pbpk) models 439
summary 447
cd-rom material 449
questions and problems 454
journal critique problems 468
supplementary reading 469
8 steady-state nonisothermal reactor design 471
8.1 rationale 472
8.2 the energy balance 473
8.2.1 first law of thermodynamics 473
8.2.2 evaluating the work term 474
8.2.3 overview of energy balances 476
8.2.4 dissecting the steady-state molar flow rates to obtain the heat of reaction 479
8.2.5 dissecting the enthalpies 481
8.2.6 relating _hrx(t ), _h_rx (tr ), and _cp 483
8.3 adiabatic operation 486
8.3.1 adiabatic energy balance 486
8.3.2 adiabatic tubular reactor 487
8.4 steady-state tubular reactor with heat exchange 495
8.4.1 deriving the energy balance for a pfr 495
8.4.2 balance on the coolant heat transfer fluid 499
8.5 equilibrium conversion 511
8.5.1 adiabatic temperature and equilibrium conversion 512
8.5.2 optimum feed temperature 520
8.6 cstr with heat effects 522
8.6.1 heat added to the reactor, 522
8.7 multiple steady states 533
8.7.1 heat-removed term, r(t) 534
8.7.2 heat of generation, g(t) 534
8.7.3 ignition-extinction curve 536
8.7.4 runaway reactions in a cstr 540
8.8 nonisothermal multiple chemical reactions 543
8.8.1 energy balance for multiple reactions in plug-flow reactors 544
8.8.2 energy balance for multiple reactions in cstr 548
8.9 radial and axial variations in a tubular reactor 551
8.10 the practical side 561
summary 563
cd-rom material 566
questions and problems 568
journal critique problems 589
supplementary reading 589
9 unsteady-state nonisothermal reactor design 591
9.1 the unsteady-state energy balance 591
9.2 energy balance on batch reactors 594
9.2.1 adiabatic operation of a batch reactor 594
9.2.2 batch reactor with interrupted isothermal operation 599
9.2.3 reactor safety: the use of the arsst to find hrx, e and to size pressure relief valves .. 605
9.3 semibatch reactors with a heat exchanger 614
9.4 unsteady operation of a cstr 619
9.4.1 startup 619
9.4.2 falling off the steady state 623
9.5 nonisothermal multiple reactions 625
9.6 unsteady operation of plug-flow reactors 628
summary 629
cd-rom material 630
questions and problems 633
supplementary reading 644
10 catalysis and catalytic reactors 645
10.1 catalysts 645
10.1.1 definitions 646
10.1.2 catalyst properties 648
10.1.3 classification of catalysts 652
10.2 steps in a catalytic reaction 655
10.2.1 step 1 overview: diffusion from the bulk to the external transport 658
10.2.2 step 2 overview: internal diffusion 660
10.2.3 adsorption isotherms 661
10.2.4 surface reaction 666
10.2.5 desorption 668
10.2.6 the rate-limiting step 669
10.3 synthesizing a rate law, mechanism, and rate-limiting step 671
10.3.1 is the adsorption of cumene rate-limiting? 674
10.3.2 is the surface reaction rate-limiting? 677
10.3.3 is the desorption of benzene rate-limiting? 678
10.3.4 summary of the cumene decomposition 680
10.3.5 reforming catalysts 681
10.3.6 rate laws derived from the pseudo-steady-state hypothesis 684
10.3.7 temperature dependence of the rate law 687
10.4 heterogeneous data analysis for reactor design 688
10.4.1 deducing a rate law from the experimental data 689
10.4.2 finding a mechanism consistent with experimental observations 691
10.4.3 evaluation of the rate law parameters 692
10.4.4 reactor design 694
10.5 reaction engineering in microelectronic fabrication 698
10.5.1 overview 698
10.5.2 etching 700
10.5.3 chemical vapor deposition 701
10.6 model discrimination 704
10.7 catalyst deactivation 707
10.7.1 types of catalyst deactivation 709
10.7.2 temperature–time trajectories 721
10.7.3 moving-bed reactors 722
10.7.4 straight-through transport reactors (sttr) 728
summary 733
ode solver algorithm 736
cd-rom material 736
questions and problems 738
journal critique problems 753
supplementary reading 755
11 external diffusion effects on heterogeneous reactions 757
11.1 diffusion fundamentals 758
11.1.1 definitions 758
11.1.2 molar flux 759
11.1.3 fick’s first law 760
11.2 binary diffusion 761
11.2.1 evaluating the molar flux 761
11.2.2 boundary conditions 765
11.2.3 modeling diffusion without reaction 766
11.2.4 temperature and pressure dependence of dab 770
11.2.5 modeling diffusion with chemical reaction 771
11.3 external resistance to mass transfer 771
11.3.1 the mass transfer coefficient 771
11.3.2 mass transfer coefficient 773
11.3.3 correlations for the mass transfer coefficient 774
11.3.4 mass transfer to a single particle 776
11.3.5 mass transfer–limited reactions in packed beds 780
11.3.6 robert the worrier 783
11.4 what if...? (parameter sensitivity) 788
11.5 the shrinking core model 792
11.5.1 catalyst regeneration 793
11.5.2 pharmacokinetics—dissolution of monodispersed solid particles 798
summary 800
cd-rom material 801
questions and problems 802
supplementary reading 810
12 diffusion and reaction 813
12.1 diffusion and reaction in spherical catalyst pellets 814
12.1.1 effective diffusivity 814
12.1.2 derivation of the differential equation describing
diffusion and reaction 816
12.1.3 writing the equation in dimensionless form 819
12.1.4 solution to the differential equation for a first-order reaction 822
12.2 internal effectiveness factor 827
12.3 falsified kinetics 833
12.4 overall effectiveness factor 835
12.5 estimation of diffusion- and reaction-limited regimes 838
12.5.1 weisz–prater criterion for internal diffusion 839
12.5.2 mears' criterion for external diffusion 841
12.6 mass transfer and reaction in a packed bed 842
12.7 determination of limiting situations from reaction data 848
12.8 multiphase reactors 849
12.8.1 slurry reactors 850
12.8.2 trickle bed reactors 850
12.9 fluidized bed reactors 851
12.10 chemical vapor deposition (cvd) 851
summary 851
cd-rom material 852
questions and problems 855
journal article problems 863
journal critique problems 863
supplementary reading 865
13 distributions of residence times for chemical reactors 867
13.1 general characteristics 868
part 1 characteristics and diagnostics 868
13.1.1 residence-time distribution (rtd) function 870
13.2 measurement of the rtd 871
13.2.1 pulse input experiment 871
13.2.2 step tracer experiment 876
13.3 characteristics of the rtd 878
13.3.1 integral relationships 878
13.3.2 mean residence time 879
13.3.3 other moments of the rtd 881
13.3.4 normalized rtd function, e(_) 884
13.3.5 internal-age distribution, i(_) 885
13.4 rtd in ideal reactors 885
13.4.1 rtds in batch and plug-flow reactors 885
13.4.2 single-cstr rtd 887
13.4.3 laminar flow reactor (lfr) 888
13.5 diagnostics and troubleshooting 891
13.5.1 general comments 891
13.5.2 simple diagnostics and troubleshooting using the rtd for ideal reactors 892
13.5.3 pfr/cstr series rtd 897
part 2 predicting conversion and exit concentration 902
13.6 reactor modeling using the rtd 902
13.7 zero-parameter models 904
13.7.1 segregation model 904
13.7.2 maximum mixedness model 915
13.7.3 comparing segregation and maximum mixedness predictions 922
13.8 using software packages 923
13.8.1 heat effects 927
13.9 rtd and multiple reactions 927
13.9.1 segregation model 927
13.9.2 maximum mixedness 928
summary 933
cd-rom material 934
questions and problems 936
supplementary reading 944
14 models for nonideal reactors 945
14.1 some guidelines 946
14.1.1 one-parameter models 947
14.1.2 two-parameter models 948
14.2 tanks-in-series (t-i-s) model 948
14.3 dispersion model 955
14.4 flow, reaction, and dispersion 957
14.4.1 balance equations 957
14.4.2 boundary conditions 958
14.4.3 finding da and the peclet number 962
14.4.4 dispersion in a tubular reactor with laminar flow 962
14.4.5 correlations for da 964
14.4.6 experimental determination of da 966
14.4.7 sloppy tracer inputs 970
14.5 tanks-in-series model versus dispersion model 974
14.6 numerical solutions to flows with dispersion and reaction 975
14.7 two-parameter models—modeling real reactors with combinations of ideal reactors 979
14.7.1 real cstr modeled using bypassing and dead space 979
14.7.2 real cstr modeled as two cstrs with interchange 985
14.8 use of software packages to determine the model parameters 988
14.9 other models of nonideal reactors using cstrs and pfrs 990
14.10 applications to pharmacokinetic modeling 991
summary 993
cd-rom material 994
questions and problems 996
supplementary reading 1005
appendix a numerical techniques 1009
appendix b ideal gas constant and conversion factors 1017
appendix c thermodynamic relationships involving the equilibrium constant 1021
appendix d measurement of slopes on semilog paper 1027
appendix e software packages 1029
appendix f nomenclature 1033
appendix g rate law data 1037
appendix h open-ended problems 1039
appendix i how to use the cd-rom 1043
appendix j use of computational chemistry software packages 1049
index 1051
about the cd-rom ... 1088