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Index

Absorption, 181–184, 265, 560 catalytic thermal oxidation, 563


absorption factor, 181, 183 flare, 561
chemical absorption, 183, 184, 566 gas turbine, 564
height equivalent of a theoretical plate (HETP), 159, 172, 182, 186 minimization at source, 561
Kremser Equation, 181, 182, 184–186, 189 recovery, 556, 557, 559–561
liquid flowrate, 62, 64, 126, 159–161, 169, 172, 174, 181–183, 185, absorption, 560
208, 569 adsorption, 560
pressure, 183, 569 condensation, 557
stage efficiency, 181, 182 membrane, 559
stripping (see Stripping) thermal oxidation, 561
temperature, 183 dispersion, 574–575
Added value, 2, 14 adiabatic lapse rate, 574
Adsorption, 117, 189–193, 265, 560, 587, 592 atmospheric conditions, 574, 575
adsorbent, 265, 587 environmental lapse rate, 574
activated alumina, 190 stack height, 575
activated carbon, 190–192, 560, 587, 590–592 greenhouse effect, 552
molecular sieve zeolites, 190 oxides of nitrogen emissions, 569–573
silica gel, 190 ozone, 551
breakthrough, 191, 192, 560 ozone layer destruction, 551
chemical adsorption, 189, 190 PM10 , 551
Freundlich Isotherm, 190, 192 PM2.5 , 551
front, 191 smog, 551
physical adsorption, 189, 190 sources, 552–553
regeneration, 190–193 sulfur emissions, 565–569
Approach to process design volatile organic compounds (VOCs), 554–565
building an irreducible structure, 11 Azeotrope (see Vapor–liquid equilibrium)
creating and optimizing a superstructure, 11–12 Azeotropic distillation
Atmospheric pollution distillation boundary, 242, 251, 252, 254, 257
acid rain, 551 distillation line, 238–242, 245, 254, 255, 257
carbon dioxide, 551 distillation line map, 238, 239, 242
carbon monoxide, 551 distillation regions, 242, 254
control of combustion emissions, 573–574 entrainer, 235, 246–251
carbon dioxide, 573 entrainer selection, 253–255
minimization at source, 573 extractive distillation, 248, 250, 254
oxides of nitrogen, 569–573 heterogeneous, 251–253
oxides of sulfur, 551 lever rule, 237, 246, 251
particulates, 553–554 minimum reflux, 242–243
control of oxides of nitrogen emissions, 569–573 multicomponent, 255–256
catalytic reduction, 572 operation leaf, 245
minimization at source, 570, 571 pervaporation, 235, 255
non-catalytic reduction, 572 pinch point curve, 243, 245, 247, 249, 255
control of solid particle emissions, 553–554 pressure change, 235, 236, 257
bag filters, 554 representation (see triangular diagram)
cyclones, 554 residue curve, 240–243, 245, 247, 249, 250, 254, 255, 257
electrostatic precipitators, 554 residue curve map, 240–242, 254, 255
gravity settlers, 553 section profiles, 244–246, 249, 250, 257
inertial separators, 553 total reflux, 238–242
scrubbers, 554 trade-offs, 255
control of sulfur emissions, 565–569 triangular diagram, 236–258
fuel desulfurization, 565, 566, 576
hydrogen sulfide removal, 566, 567 Batch process, 9–10, 14, 292–315
absorption, 567 advantages, 10
Claus Process, 566, 567 campaign, 305, 306, 312, 314, 315
iron chelate oxidation, 567 crystallization (see Crystallization)
minimization at source, 565 cycle time, 293–296, 303–305, 310, 311
oxides of sulfur removal, 566, 568, 569 distillation (see Distillation)
limestone absorption, 568, 578 equipment cleaning, 306–307
reduction, 566–567 equipment utilization, 303–306, 310, 311, 315
Wellman Lord Process, 568, 578 filtration (see Filtration)
control of VOCs, 554–565 flowshop (multiproduct) production, 305, 313
biological treatment, 564 Gantt chart, 303–304
hold-up, 301, 305
intermediate storage, 305, 307, 311–313
Chemical Process Design and Integration R. Smith jobshop (multi-purpose) production, 305
 2005 John Wiley & Sons, Ltd ISBNs: 0-471-48680-9 (HB); 0-471-48681-7 (PB) makespan, 305, 306, 314
680 Index

Batch process (continued) process operations, 635, 642–643


optimization, 311–312 reducing waste from operations, 642
overlapping production, 303, 305, 307, 310 sources of waste, 642
profile, 10, 294–296 process waste, 635, 642, 643, 646
reaction and separation, 292–315 reactors, 636–637
reactor (see Reactor) catalyst waste, 637
recipe, 291 conversion limited, 567, 636, 637
semicontinuous steps, 9, 291 feed impurities, 637
sequential production, 304, 305, 307 sources of waste, 636
storage (see Storage) upgrading waste byproducts, 637
zero-wait transfer, 305, 314 waste byproducts, 636
Biochemical oxygen demand (BOD), 584–587, 589–592, 619, 620 separation and recycle systems, 637–642
additional reaction and separation, 642
additional separation and recycling, 641
Calorific value elimination of extraneous materials, 640
gross (higher), 26, 350, 471 feed purification, 639
net (lower), 26, 350, 471 recycling waste streams, 638
Capital cost, 17–25, 393–395, 449–450 sources of waste, 639
annualized, 24–25, 35 utility waste, 643–644
battery limits investment, 17–20 cogeneration, 643
cost indexes, 17, 19, 22, 24 cooling systems, 644
equipment cost, 17, 21–24, 31, 32 energy efficiency, 643
materials, 17, 19, 21, 25 fuel switch, 644
pressure, 17, 19, 24 local and global emissions, 643
size, 17 sources of waste, 643
temperature, 17 steam systems, 644
installation factor, 21–23, 31 Cogeneration (see Heat exchanger network target, see Steam system)
new design, 17–23 Compression, 267–268, 271–276, 536, 655–660
off-site investment, 20 isentropic, 527, 528, 655–658, 660
retrofit, 23–24 polytropic, 274, 275, 657, 658, 660
total, 21 staged, 275, 659, 660
utility investment, 20 Compressor, 271–276, 309–310, 381, 526–546
working capital, 20–21, 23, 29, 32, 287 axial, 273, 274, 536
Catalyst, 25, 114–117 dynamic, 271
biochemical, 116 ejector, 271
immobilized, 117, 118 liquid ring, 272
clean technology, 637 reciprocating, 272, 273, 289, 290, 655, 656, 658, 660
degradation, 123 rotary piston, 272
effectiveness factor, 115 screw, 272, 273
heterogeneous, 114–116 sliding vane, 272, 273
bulk, 114 surging, 272, 273
supported, 114 Condensation, 49, 211, 223, 226, 264, 317, 337–340, 354, 355, 557,
homogeneous, 114 561
hot spots, 123, 129, 130, 637 mechanism, 338
pellet, 115–117, 121, 122, 129, 133 multicomponent, 340
activity distribution, 115 Nusselt Equation, 338, 339
Dirac-delta, 115, 116 Condenser, 176, 337–341, 526
shape, 115 desuperheating, 339
size, 115 horizontal, 337–339, 354, 355
profiles, 121 subcooling, 339, 340, 356, 528
Catalytic cracker, 130, 131, 552 vertical, 337, 339, 354
Centrifugal separation Contingency, 4, 10, 14
centrifuge, 148, 153 Control, 13–14, 121–123
cyclone, 147, 148 disturbances, 13
hydrocyclone, 148 manipulated variables, 13
Chemical oxygen demand (COD), 584–587, 590, 619 measured variables, 13
Chemical product primary measurements, 13
differentiated, 1 secondary measurements, 13
life cycle, 2 Cooling systems, 513
patent, 1–3 Cooling tower
undifferentiated, 1 blowdown, 513–515
Chemicals, 1–3, 25 chemical treatment, 514–516, 522
bulk, 1 cycles of concentration, 515, 516, 526, 546, 547
commodity, 1–3, 14 draft, 514
effect, 1 drift, 513
fine, 1–3, 10 make-up, 513, 515, 516, 525, 526
functional, 1 packing, 513–515, 518, 526
specialty, 1–3, 10, 14 Cooling water system, 513–546
Clean process technology cooling water composite curve, 518, 519, 521, 522, 524, 525
economic trade-offs, 644–645 cooling water supply line, 518, 522, 524, 525
life cycle analysis, 645–646 design of cooling water networks, 518–524
impact analysis, 646 retrofit, 524–526
improvement analysis, 646 air-cooled heat exchange, 526
inventory, 646 cooling network configuration, 525
Index 681

hot blowdown extraction, 526 flow parameter, 172–174


other options, 526 Gilliland Correlation, 170, 179
targeting minimum cooling water flowrate, 516–518 height equivalent of a theoretical plate (HETP), 159, 172, 182,
Cost, 17–31 186
capital (see Capital cost) key components, 164–168
fixed, 21, 28, 29, 33 limitations, 176–177
operating (see Operating cost) packing, 158, 159
raw materials (see Operating cost) random (dumped), 158
variable, 25, 28, 29, 33 structured, 158
Critical point, 59–61, 178, 533 partition column, 222, 223, 230, 628
Crystallization, 203–206, 323, 587 Petlyuk column, 222
batch, 296, 301 pinch, 164, 166, 167, 169
agitation, 296, 301, 302 plate (tray), 158, 159, 171, 172
cooling, 301, 302 flooding, 171, 173
optimization, 311–312 high capacity, 158
cooling crystallization, 205 sieve, 158, 171
crystal growth, 204 weeping, 158
crystal habit, 204 prefractionator, 218, 219, 222–225, 228, 230
eutectic point, 203 pressure, 172, 175, 176
evaporation, 205 reboiler, 158
hydrate, 203 partial, 162
labile region, 204, 205 thermosyphon, 162, 163
melt crystallization, 205 reflux ratio, 160, 175
metastable region, 204–206 minimum, 163–171, 175, 176
nucleation, 204 optimization, 175, 176
primary, 204 side-rectifier, 220–224, 226, 228
secondary, 204 sidestream, 159
pH switch, 205 side-stripper, 220–224, 228
reaction crystallization, 205 stage efficiency, 171
salting, 205 Underwood Equations, 166–170, 179, 213, 214, 217
seeding, 204 Distillation heat integration
solute, 184, 203 appropriate placement, 445–446
solution crystallization, 205 capital cost considerations, 449–450
solvate, 203 characteristics, 450–454
solvent, 184–186, 203 double effecting, 447, 448
solvent selection, 184, 297 economic trade-offs, 449, 450, 453
supersolubility, 204, 206 evolution of simple columns, 447–449
vacuum crystallization, 205 grand composite curve, 446–447
heat pumping, 449
intermediate condenser, 448
Design problem intermediate reboiler, 448, 449
bottleneck, 10 reflux ratio optimization, 175, 176
debottleneck, 10 Distillation sequence
formulation, 3–4 azeotropic (see Azeotropic distillation)
new plant (grassroot), 10 constraints, 211
retrofit (revamp), 10–11 direct sequence, 211, 218, 220, 221
Distillation distributed (sloppy) distillation, 218
azeotropic (see Azeotropic distillation) dividing wall column (see Distillation)
batch, 297, 298, 300, 301, 303, 313, 314 heat integration, 211–230
McCabe–Thiele, 298, 299 superstructure optimization, 228–230
optimization, 300 heuristics, 212–213, 216, 231
Rayleigh Equation, 298, 299 indirect sequence, 211, 219–221, 225, 226, 228, 231
binary, 160–163 key components, 211, 212, 218, 231
McCabe–Thiele, 162, 163 nonkey components, 212, 216
q-line, 162, 163 optimization of a superstructure, 228–230
rectifying section, 160–162 partition column (see Distillation)
stripping section, 161, 162 Petlyuk column (see Distillation)
capacity parameter, 173 prefractionator (see Distillation)
condenser, 157, 165, 170, 175, 176, 179 retrofit, 224–225
partial, 157, 175, 176, 179 side-rectifier, 220–224, 226, 228
total, 157, 165, 170, 175, 176 side-stripper, 220–224, 228
constant molar overflow, 160, 161, 163, 169, 173 simple column, 211
crude oil, 225–228 superstructure optimization, 228–230
atmospheric, 226, 227 task, 228–231
overflash, 226 thermal coupling, 220–224
pumparound, 226 vapor rate, 213
pumpback, 226 Dryer heat integration
vacuum, 227 characteristics, 459–460
dividing wall column (see partition column) evolution, 460–461
downcomer, 158, 172, 174 Dryers, 153–154, 459–461
extractive distillation (see Azeotropic distillation) drum, 153
feed condition, 176 efficiency, 154
Fenske Equation, 165–168, 170, 178 fluidized bed, 153
flooding, 172–174 rotary, 153
682 Index

Dryers (continued) Gas turbine


spray, 153 aero-derivative, 478
tunnel, 153 heat rate, 480
heat recovery steam generator (HRSG), 479–481, 498, 499
Economic criteria industrial, 478
discounted cash flow rate of return, 30 integration, 378, 379
economic potential, 29 regenerator, 477
net present value, 30 single shaft, 477
payback time, 29 split-shaft, 477
return on investment, 29 staged combustion, 479
total annual cost, 29 steam injection, 479
Economic potential (see Economic criteria) treatment of exhaust gases, 479
End-of-pipe treatment, 635 twin-spool, 477
Enthalpy Willans’ Line, 473–476, 479
calculation from equations of state, 73 Grand composite curve, 372–374, 376–378, 380, 382, 383, 385,
departure, 73 442–443, 446–447, 461, 487, 488, 539, 540, 650
ideal gas, 73 Graph theory, 387
Entropy Greenhouse effect (see Atmospheric pollution)
calculation from equations of state, 74
departure, 74 Heat engine integration, 376, 377, 381–383, 410
Equations of state appropriate placement, 382, 383
compressibility factor, 57, 58, 64 gas turbines, 477–482
cubic equations, 57, 58, 64 steam turbines, 471–477
ideal gas, 57 Heat exchanger
mixing rules, 58 air-cooled, 332, 526
Peng–Robinson, 57–59, 73, 107, 170, 214, 215, 273, 535, 553 extended surfaces, 332–333
Evaporation fouling, 318, 319, 323, 329
backward feed, 207 gasketed plate, 346, 347
degrees of freedom, 207 plate-fin, 347
forward feed, 206 shell-and-tube, 319–332
heat transfer area, 207, 459 FT correction factor, 325, 326, 328, 329, 336, 339
mixed feed, 207 XP factor, 326, 328, 329
number of stages, 208 allocation of fluids, 329–332
parallel feed, 207 baffle cut, 321
pressure, 207, 208 fluid velocity, 322, 323, 329, 331, 332
Evaporator heat integration heat transfer enhancement, 332, 334, 335, 337, 346
appropriate placement, 459 minimum FT correction factor, 328
characteristics, 459 overall heat transfer coefficient, 317–319, 323–325, 329, 331,
evolution, 459 332, 334, 336, 341, 344, 345, 354
Explosion retrofit, 333–337
chemical energy, 626 shell diameter, 322, 342
confined, 626 shell-side film coefficient, 318, 662–666
deflagration, 626 shell-side fouling coefficient, 318
detonation, 626 shell-side pressure drop, 321, 322, 662–666
efficiency, 627 single pass, 317
physical energy, 626 temperature approach, 326
vapor cloud, 626, 627 temperature cross, 324, 326, 329
Extractive distillation (see Azeotropic distillation) tube configuration, 320
tube wall coefficient, 318
Filtration tube-side film coefficient, 318, 661–662
aids, 151 tube-side fouling coefficient, 318
bag, 150 tube-side pressure drop, 329, 661–662
batch, 302 two pass, 317
cake, 150, 151 spiral, 347
deep-bed, 151 welded plate, 347
depth, 150 Heat exchanger network, 317–356
high temperature, 150 CP inequalities, 399
membrane, 151 CP table, 399
plate-and-frame, 150, 195 data extraction, 430–437
Fire, 625–626 grid diagram, 363, 399, 400, 408
Fired heater (Furnace) loop, 387
acid dew point, 353 near pinch, 409, 410
draft, 332, 349, 353 optimization, 413–416
efficiency, 349, 353, 354 path, 387, 414, 415
heat balance, 350, 352 pinch, 361–364, 399–404
heat of combustion, 349, 350, 356 multiple, 408–411
stack loss, 353 pinch design method, 399–404
theoretical flame temperature, 349, 351–354 remaining problem analysis, 411–413
Flammability limits (see Safety) retrofit, 419–424
Flash point (see Safety) area addition, 424–425
Flowsheet, 5, 6, 11, 14 network pinch, 420, 421, 423, 425
Fugacity, 60, 97, 98, 107 new match, 421
Fugitive emissions, 556, 627, 642, 643 repipe, 421
Index 683

resequence, 421, 423 coefficient of performance, 382, 383


stream split, 421 integration, 381–383, 449
stream splitting, 405–408 vapor compression, 381
superstructure optimization, 416–419 Hierarchy of design, 5–9, 649–651
blocks, 418 Hybrid reaction and separation, 284–286
threshold problem, 404–405 membrane distillation, 265
tick-off heuristic, 401 reactive distillation, 286
utility path, 414–416, 419, 421, 425 Hydrocracker, 130
utility pinch, 408–410
Heat exchanger network target Industrial symbiosis, 639
Tmin , 357, 358, 361, 363, 364, 395, 397 Inherent safety (see Safety)
Tmin contribution, 370, 376 Intensification of hazardous materials (see Safety)
area target, 388–392 Ion exchange, 467, 581, 587
variable heat transfer coefficients, 389, 393, 394
areas of integrity, 371, 372
Life-cycle analysis (see Clean process technology)
capital cost targets, 393–395
Liqiud–liquid equilibrium
capital-energy trade-off, 390, 395
activity coefficient models, 71
cogeneration (combined heat and power), 376–381
NRTL Equation, 71, 72, 75
cold streams, 357, 388–390
UNIFAC Equation, 71
components, 387–395
UNIQUAC Equation, 62, 71
composite curves, 357–361
distribution coefficient, 70
balanced, 388, 390
heteroazeotrope, 70, 72
enthalpy intervals, 388–390, 392
tie line, 70
shifted, 365, 366, 368
Liquid–liquid extraction
constraints, 370–372
choice of solvent, 184, 205
cross-pinch heat flow, 362, 363, 412, 414, 419, 432, 437, 443
distribution coefficient, 184–186
energy target, 357–385
extraction factor, 184, 185
enthalpy intervals, 388–390, 392
height equivalent of a theoretical plate (HETP), 182, 186
furnaces, 348–354, 374–376
Kremser Equation, 181, 182, 184–186, 189
acid dew point, 353, 375, 376
raffinate, 184, 185, 187
efficiency, 349, 353, 354, 374, 375
separation factor, 184, 185, 193, 196
stack loss, 353, 374, 375
solvent, 184, 185, 187, 198, 203
theoretical flame temperature, 349, 351–354, 374–376
gas turbine integration, 378, 379
grand composite curve, 372–374, 376–378, 380, 382, 383, 385 Membranes, 193–203, 255, 256, 265, 286, 287, 559, 560
grid diagram, 363, 399, 400, 408 asymmetric, 194, 196, 198
heat cascade, 368, 369, 378, 427 dense, 193, 194, 199
heat engine appropriate placement, 382, 383 dialysis, 198
heat pump appropriate placement, 382, 383 electrodialysis, 198, 199
heat pump integration, 381–383 fast gases, 195, 265
hot streams, 357, 389 flow pattern, 194, 201, 202
loops, 387 gas permeation, 195, 200
number of 1–2 shells for a single unit, 326, 329, 392 micro-filtration, 198
number of heat exchange units, 387–388 microporous, 193, 194, 198
number of shells target, 392–393 nano-filtration, 198
pinch, 361–364 permeability, 193–196
problem table algorithm, 365–369 permeance, 193, 194, 199
problem table cascade, 368, 372, 373, 376, 380, 384, 396 permeate, 193–199, 201, 209
process changes, 429 permselective layer, 194, 195, 209
plus/minus principle, 429, 433 pervaporation, 199
refrigeration appropriate placement, 535, 539 retentate, 193, 194, 199, 201, 203
refrigeration integration (see Refrigeration) reverse osmosis, 196–198, 201
segments of stream, 358 concentration polarization, 197
shells are target for 1–2 shells, 392, 674 osmotic pressure, 196–198, 201, 202
shifted composite curves, 365, 366 Van’t Hoff Equation, 197, 201
steam turbine integration, 377, 379 selectivity, 184, 193, 194, 201
supply temperature, 357, 373, 427, 518, 519, 522, 633 slow gases, 195, 265
target temperature, 357, 359, 366, 367 substrate, 194
temperature interval, 365–367, 373 ultra-filtration, 198
temperature shift, 522 concentration polarization, 198
threshold problems, 364–365 Monochlorodecane, 262–264
total cost targets, 395
utility path, 414, 415 Onion diagram, 7, 14, 635, 649, 651
utility selection, 372–373 Operating cases, 13, 492, 502
Heat integration, 5, 439–443, 445–455, 459–461 Operating cost
distillation columns (see Distillation heat integration) catalyst and chemicals, 25
dryers (see Dryer heat integration) cooling water, 27, 28, 32
evaporators (see Evaporator heat integration) labor, 28
heat engines (see Heat engine) maintenance, 28
heat pumps (see Heat pump) raw materials, 25
reactors (see Reactor heat integration) refrigeration, 27, 211, 214, 287, 538, 559
refrigeration (see Refrigeration) royalties, 28
Heat pump steam, 25–27, 502–506
appropriate placement, 382, 383 utility, 25
684 Index

Optimization, 35–54 propagation step, 80


batch processes, 311–312 termination step, 80
binary variables, 48, 454 Process waste
branch and bound, 52 process operations, 635
capital-energy trade-off, 390 reactors, 635
concavity, 37, 47 separation and recycle systems, 635
constrained, 42–43 Process yield, 280–281
continuous variables, 52, 295, 312 Project cash flow, 29–30
contour diagram, 42, 284 Pump, 267–276
convexity, 37, 47 centrifugal, 271
degrees of freedom, 35, 220, 221, 223, 226, 407, 414, 416, 494, 498 positive displacement, 271
design equations, 42, 294 Pumping
design variables, 42 pressure drop, 267–269, 271, 273, 275
deterministic, 39 pipe fittings, 268, 269
direct search, 39 straight pipes, 268, 270
indirect search, 39
disjunctive constraints, 49
dynamic, 47 Quench, 122, 139, 441
equality (inequality) constraints, 35, 42, 46, 54
equation solving, 52–53
Reaction
genetic algorithm, 41, 42, 54
autocatalytic, 86, 93
integer variables, 312
benzene production, 11, 81, 113, 265, 266, 289
linear, 43–45
benzyl acetate production, 87, 313
linear program, 43–45
biochemical (fermentation), 77, 80, 93, 114
degenerate, 45
concentration, 114
shadow price, 45
enzyme, 81, 93
simplex, 45
inhibitors, 93
mixed integer linear program (MILP), 49–52, 230, 417, 418, 423,
oxygen level, 114
425
pH, 114
relaxed solution, 50
temperature, 114
mixed integer nonlinear program (MINLP), 50, 52, 228
butyl hydrogen sulfate production, 132
multivariable, 37–42
dichloroethane production, 109, 639–641
Newton’s method, 38, 40
elementary, 83
nonlinear, 45–46
ethanolamines production, 80, 131
nonlinear program (NLP), 46, 51, 52, 423, 425
ethyl acetate production, 88, 90, 109, 313
objective function, 35–37
mixed parallel and series, 79, 80, 92, 113
parameter, 5, 7
monochlorobutanoic acid production, 137, 138, 262, 295
profile, 46–48
parallel reactions, 112
quadratic program (QP), 46
path, 77–78
recovery from waste streams, 35
polymerization (see Polymerization)
region elimination, 37, 38
primary reaction, 79, 91, 95
sequential simplex, 39
rate, 82–83, 104–106, 108, 114, 115
simulated annealing, 40, 41, 43, 46, 52, 54
reversible, 109, 636
single variable, 37–38
secondary reaction, 79, 81, 94
steepest descent (ascent), 40
series reactions, 112
stochastic, 40
single reactions, 79, 90, 94, 95, 104–106, 108
structural, 48–52
vinyl chloride production, 77, 78, 639, 640
structural and parameter, 11
Reaction catalyst (see Catalyst)
successive (sequential) quadratic program (SQP), 46, 48
Reaction equilibrium
unimodal, 36
ammonia production, 118, 571
univariate search, 39
endothermic, 104
Optimum
equilibrium constant, 98–100
global, 12, 39
ethyl acetate production, 109
local, 12, 37, 39–44, 46, 47, 51–54
exothermic, 105
saddle point, 37
Gibbs free energy, 97
Overall strategy
heterogeneous reactions, 99
final design, 651
homogeneous reactions, 98–99
hierarchy, 649–651
gas phase, 98
objectives, 649
liquid phase, 99
Overdesign (see Contingency)
hydrogen production, 110, 111
inert concentration, 111
Partial pressure, 57–74 Le Châtelier’s principle, 100, 104, 106, 108, 111
Dalton’s Law, 57 pressure, 107–108
Patent, 1–3, 291, 313 decrease in the number of moles, 108
Petlyuk column (see Distillation) increase in the number of moles, 108
Phthalic anhydride, 435 multiple reactions, 108
Piping and instrumentation, 14 single reactions, 108
Polymerization product removal, 111, 113
active center, 80 Reaction rate, 82–83, 104, 106, 115
active life, 80, 93 concentration, 109–114
free radical, 80, 93 temperature, 100–107
initiation step, 80 activation energy, 104, 119
polycondensation, 80 frequency factor, 104
Index 685

Reactor, 628 horizontal thermosyphon, 342, 343, 354


batch, 291–297 kettle, 342, 345, 354
agitation, 296 natural circulation, 342, 344
contacting, 291 pool boiling, 343, 345, 354
operating conditions, 294 recirculation ratio, 342
optimization, 311–312 vertical thermosyphon, 342, 343, 346, 354
solvent selection, 297 Recycle
temporal superstructure, 292–294 byproduct formation, 259
cold shot and hot shot, 121, 439 byproduct recycle for improved selectivity, 260
fixed-bed catalytic, 129 damaging contaminants, 260
fixed-bed noncatalytic, 130 diluents and solvents, 261
fluidized bed catalytic, 130 feed impurities, 260
fluidized bed noncatalytic, 131 function, 259
gas–liquid, 124–127 heat carrier, 261
kilns, 131 optimization, 281–285
liquid–liquid, 124–127 reactor conversion, 281–283
mixer-settler, 127 recycle inert concentration, 283, 284
stirred tank, 128 purges, 264
superstructure optimization, 133–139 simulation, 276–280
isothermal, 134 direct substitution, 277, 278
nonisothermal adiabatic, 136 equation oriented, 276
nonisothermal, 136 partitioning, 279
trickle bed, 125 tearing, 279
tubular, 127 Wegstein Method, 278
Reactor choice, 77–94, 97–117, 121–139 vapor recycle, 264, 265, 282, 308
parallel reactions, 112 vapor versus liquid, 267, 282
polymerization reactions, 80 Refrigeration, 513–546
series reactions, 106, 112, 113 absorption, 544–546
single reactions, 90, 94 appropriate placement, 535, 539
Reactor concentration cascade, 530, 535, 547
biochemical, 114 choice of refrigerant, 532–535
mixed parallel and series reactions, 113 coefficient of performance, 528, 529, 533, 534
parallel reactions, 112 compression, 532–535
series reactions, 112 costs, 27, 28, 55, 211, 214, 287, 355, 538, 559
single irreversible reactions, 109 economizer, 529, 538, 547
single reversible reactions, 109 heat integration, 539–542
feed ratio, 109 indirect, 546
inert concentration, 111 mixed refrigerant, 542–544
product removal during reaction, 111 multiple level, 536
Reactor heat integration pre-saturator, 529, 530
adiabatic operation, 439 process expander, 530–532
appropriate placement, 441–442 simple cycle, 535
characteristics, 439–441 subcooling, 528, 538
cold shot or hot shot, 439 targeting refrigeration power, 535–538
evolution for improved heat integration, 443 Retrofit (Revamp), 10–11
grand composite curve, 442–443 distillation sequence (see Distillation sequence)
heat carrier, 439 heat exchanger (see Heat exchanger)
indirect heat transfer, 439 heat exchanger network (see Heat exchanger network)
quench, 441 Royalties, 28
Reactor models
biochemical, 77, 80, 93
Michaeli’s Constant, 93 Safety
Monod Equation, 93 attenuation of hazardous materials, 630–631
ideal batch, 83, 84 autoignition temperature, 625
mixed-flow (continuous well-stirred, CSTR), 83, 84 distillation, 628
plug-flow, 83, 85 explosion, 626–627
Reactor performance factor (see Contingency)
conversion, 82, 84, 85, 88, 90, 91, 94 fire, 625–626
selectivity, 82, 91, 92, 94–96 flammability limits, 625
yield, 82, 92, 95 flash point, 625
Reactor phase, 108–109 high pressure, 630
Reactor temperature, 100–107 heat transfer, 628
catalyst profile, 121 high temperature, 630
cold shot, 121 inherent, 625–632
endothermic reactions, 104 intensification of hazardous materials, 628–630
exothermic reactions, 105 limiting oxygen concentration of dust, 625
heat carrier, 439 low pressure, 630
hot shot, 121, 129 low temperature, 630
indirect heat transfer, 439 minimum ignition temperature of dust, 625
multiple reactions, 106 minimum oxygen concentration, 625
quench, 122 overall inventory, 629
Reboiler quantitative measures, 631
critical heat flux, 343, 345 reactors, 628, 632
forced circulation, 344 relief systems, 629, 632
686 Index

Safety (continued) desuperheater, 483, 486


runaway reactions, 628, 629 flash steam recovery, 484, 486
Seveso incident, 629 gas turbine (see Gas turbine)
storage, 629 let-down station, 483–485, 492, 497, 499
toxic release, 627 optimization, 498–502
Safety factor (see Contingency) pressure optimization, 478, 501
Scrubbing steam and power balance, 484–487
packed tower, 152 steam trap, 483
spray tower, 152 steam turbine (see Steam turbine)
venturi, 152 turbogenerator, 465, 504
Sedimentation (see settling and sedimentation) Steam turbine
Semicontinuous processes, 9, 291, 293, 303 back-pressure, 478
Separation of heterogeneous mixtures, 154 condensing, 500
centrifugal separation, 147–149 impulse, 471
centrifuge, 148 induction, 472
cyclone, 147, 148 integration, 508
hydrocyclone, 148 isentropic efficiency, 473, 502
drying (see Drying) mechanical efficiency, 473, 475
electrostatic precipitation, 149–150 reaction, 471
filtration (see Filtration) Willans’ Line, 473–476, 479
flotation, 152–153, 586 Stoichiometric factor, 81, 263, 280
inertial separation, 147–149 Storage
scrubbing (see Scrubbing) active/inactive stock, 287
settling and sedimentation, 143–147 batch, 312–313
aggregates, 145 feed storage, 286–288
clarifier, 145 flexible membrane roof, 555
classifier, 146 floating roof, 555
decanter, 144, 145, 147, 154 intermediate storage, 286–288, 305
drag coefficient, 144 product storage, 286–288
flocculating agent, 145 ullage, 287
flocs, 145 vapor treatment of vent, 559, 563, 577
Stoke’s Law, 144, 146, 147 Stripping, 181–184
terminal settling velocity, 144, 145, 154 Kremser Equation, 181, 182, 184–186, 189
thickener, 145, 151 stripping factor, 182, 183
Separation of homogeneous fluid mixtures, 157–178, 181–209 Sulfuric acid production, 111, 112, 119, 552, 565, 568
absorption (see Absorption) Superstructure, 11, 133–139, 228–230, 416–419, 454–455, 604–606,
adsorption (see Adsorption) 616–617
crystallization (see Crystallization) Synthesis, 5, 307–311, 650
distillation (see Distillation)
evaporation (see Evaporation) Theoretical oxygen demand, 584
liquid–liquid extraction (see Liquid–liquid extraction) Thermal coupling (see Distillation)
Seveso incident, 629 Thermal oxidizer
Simulation, 5, 276–280 catalytic, 563
Site fluidized bed, 561, 578
cogeneration efficiency, 465, 496–498 hearth, 645
composite curves, 487–490 rotary kiln, 645
heat recovery, 465, 469 Total organic carbon (TOC), 584
driver choice, 506–507 Total oxygen demand (TOD), 584
pinch, 490–492, 495 Toxic exposure
power-to-heat ratio, 496 acute, 627
Steam boilers chronic, 627
acid dew point, 469, 470, 509 lethal concentration, 627, 631
air preheater, 469 lethal dose, 627
blowdown, 468–470, 484, 507 threshold limit values, 627
draft, 469 Toxic release, 627
economizer, 469 Triple point, 59
efficiency, 470, 471
feedwater treatment (see Steam system)
fire-tube (shell), 468, 471 Utility, 5, 7, 372–373, 432, 643–644, 650
water-tube, 468, 469 Utility waste, 635, 643
Steam cost
fixed steam loads, 503 Vapor–liquid equilibrium
marginal cost, 504, 506 activity coefficient, 71
variable steam loads, 503, 506, 604 activity coefficient models, 60, 61
Steam system NRTL Equation, 62, 63, 75
boiler feedwater treatment, 466–468 UNIFAC Equation, 62
chemical treatment, 468 UNIQUAC Equation, 62, 63
deaeration, 468, 485, 503 Wilson Equation, 62, 68
deionization, 467, 468 azeotrope, 66
membrane, 467 maximum boiling, 66
softening, 466, 467, 507 minimum boiling, 66
cogeneration, 465–507 bubble point, 65, 70
cogeneration target, 490–493 bubble pressure, 65
configuration, 482–484 dew point, 65
Index 687

dew pressure, 65 nitrogen and phosphorous removal, 592


equation of state models, 67, 73, 74 ultra-filtration, 592
fugacity coefficient, 60, 64, 98, 99, 107 Wastewater treatment system
liquid phase, 60, 65 composite effluent treatment line, 607
vapor phase, 60, 64, 65 data extraction, 617–620
Henry’s Law, 61, 75 environmental limits, 620
lever rule, 66, 70 treatment data, 619
Raoult’s Law, 61, 66, 69, 70 design for minimum treatment flowrate, 610–613
relative volatility, 61, 65 distributed, 582, 583, 619, 620
Vapor pressure, 59–61, 67–69, 71, 75, 535, 553, 559, 576, 577 effluent treatment line, 583, 608–610
Antoine Equation, 60, 67–69, 71, 75, 76, 535, 559, 576, 577 multiple treatment processes, 610, 612, 616
Clausius–Clapeyron Equation, 60 pinch, 608–612
regeneration recycle, 581, 613, 615, 617, 618
regeneration reuse, 581, 613–618, 620
Wastewater biological treatment superstructure optimization, 616, 617
aerobic, 588, 589 targeting minimum treatment flowrate, 607–610
activated sludge treatment, 589, 590 minimum outlet composition, 607
attached growth, 590 removal ratio, 608–610, 612, 619
suspended growth, 589, 590 Water minimization
anaerobic, 589, 590 aqueous contamination, 583–585
attached growth, 590 data extraction, 617–620
suspended growth, 590, 591 contaminants, 618
anoxic, 589 data accuracy, 618
denitrification, 589 flowrate constraints, 618
nitrification, 589, 590 limiting conditions, 618
reed bed, 591 water balance, 617
Wastewater primary treatment design for maximum reuse, 596–606
adsorption, 592 limiting concentration, 594, 595, 597, 619
chemical oxidation, 588 limiting concentration composite curve, 595, 596, 601, 604
chemical precipitation, 588 limiting water profile, 593, 620
coalescence, 585 multiple contaminants, 594, 604, 605, 616, 620
crystallization, 587 multiple water sources, 600
evaporation, 587 pinch, 596, 600–602, 604
flotation, 586 process changes for reduced water consumption, 606–607
ion exchange, 587 reuse, 581, 613–616
liquid–liquid extraction, 587 superstructure optimization, 604–606
membrane, 586 targeting maximum reuse, 594–596, 601
pH adjustment, 588 water loss, 601, 602
solid separation, 585 water main, 596–599, 601–603
sterilization, 588 water supply line, 595, 596, 600, 601
stripping, 586 Whisky distillery, 461
wet oxidation, 587
Wastewater tertiary treatment
adsorption, 587 Yield, 206
disinfection, 593 process, 280–281
filtration, 592 reactor, 82, 95, 106, 108, 112, 113, 117, 121

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