Designofan

EthanolDehydrationSystem

JamieHiltz ZackTaylor MarkBaier

DepartmentofChemicalEngineering
UniversityofSaskatchewan
20072008

Abstract

HaloConsultinghasbeenworkingonthedesigntopurifyethanolwithMarch
ConsultingAssociatesInc.Thesystemwasneededtodehydratealiquidfeedof95%
v/vethanol5%v/vwatertoaminimumof99.5%v/vproduct.AfterHaloConsulting
examinedavarietyofdifferentmasstransferapplicationstocarryoutthistask,itwas
decidedthattheuseofpressureswingadsorptionwouldbebest.

Thefinaldesignconsistsoftwoparallelcolumnsoneofwhichisadsorbingwhilethe
otheriseitherdesorbingorinstandby.Theliquidfeedisheatedandvaporizedbefore
itissenttotheadsorbingcolumnwhereitisdehydratedbyapackedbedofType3A
molecularsieve.Theregenerationtimeandadsorptiontimeswerefoundtobe6.33
and23.9minutesrespectively.Forthefirst6.33minutesofadsorption,40%ofthedry
ethanolproductissenttohelpregeneratethedesorbingcolumnwhiletheother60%is
condensedtothefinalproduct.Fortheremaining17.61minutesintheadsorption
cycle,theregeneratingpurgestreamisnolongerneededand100%oftheproduct
streamiscondensedtothefinalproduct.Thephysicalpropertiesofthecolumnsand
theadditionalequipmentweredeterminedusingmassbalances.

ii

Thecostsoftheequipmentandtheannualoperatingcostsforthisdesignwerefound.
Aneconomicanalysiswascompleted,comparingthecostofenergytobreakthe
azeotropewiththisdesigntothatofazeotropicdistillationanditwasdeterminedthat
thisdesignismoreeconomicallyfeasible.

AsafetyanalysiswasperformedthatconsistedofaHAZOPanalysisandaDOWFireand
ExplosionIndexanalysisononeofthecolumns.Themosthazardouspossible
deviationsweredeterminedtobehightemperatureandleaks.Recommended
preventativeactionshavebeenincludedinthisreport.

iii

Acknowledgments
ThemembersofHaloConsultingwouldliketoacknowledgethefollowingpeoplefortheir
directionandguidancethroughoutthedurationofthisdesignproject:

Dr.GordonA.Hill,ChemicalEngineering422Advisor,DepartmentofChemical
Engineering,UniversityofSaskatchewan
Dr.HuiWang,ChemicalEngineering422Advisor,DepartmentofChemicalEngineering,
UniversityofSaskatchewan
Dr.RichardEvitts,FacultyAdvisor,DepartmentofChemicalEngineering,Universityof
Saskatchewan
DongmeiFangSeniorProcessEngineer,MarchConsultingAssociatesInc.
TaraZrymiakSeniorProcessEngineer,MarchConsultingAssociatesInc.

iv

TableofContents

1.0 INTRODUCTION 1
1.1 Background 1
1.2 PurposeandProposedDesign 1

2.0 LITERATURESURVEY 2
2.1 Introduction 2
2.2 Distillation 3
2.2.1 AzeotropicDistillation 3
2.2.2 PressureSwingDistillation 4
2.3 ThermalSwingAdsorption 5

3.0 DETAILEDQUALITATIVEPROCESSDESCRIPTION 6
3.1 Introduction 6
3.2 FeedPreparation 7
3.3 Dehydration 8
3.3.1 Pressurization 10
3.3.2 Adsorption 10
3.3.3 Blowdown 13
3.3.4 Regeneration 14
3.4 CoolingandCondensing 17

4.0 SIMULATIONANDBALANCES 18
4.1 Introduction 18
4.2 FeedPreparation 19
4.3 Dehydration 21
4.4 VacuumPump 24
4.5 Condensation 25
4.6 Overall 26
v

5.0 EQUIPMENTDESCRIPTIONANDSIZES 29
5.1 Introduction 29
5.2 HeatExchangers 30
5.2.1 HeatExchanger#1 30
5.2.2 HeatExchanger#2 31
5.2.3 HeatExchanger#3 31
5.3 VacuumPump 32
5.4 AdsorptionTowers 33
5.5 MolecularSieve 39
5.6 ValvesandPiping 41

6.0 ECONOMICS 43
6.1 Introduction 43
6.2 EquipmentCosts 44
6.3 MolecularSieveCosts 46
6.4 AlternativeEconomicComparison 46

7.0 SAFETYANALYSIS 48
7.1 Introduction 48
7.2 ChemicalProperties 49
7.2.1 Ethanol 49
7.2.2 AluminoSillicate 50
7.3 HazardandOperabilityanalysis 50
7.3.1 HAZOPStrategy 50
7.3.2 HAZOPConclusions 51
7.4 DOWFireandExplosionIndexAnalysis 54
7.5 ProcessSafetyManagement 54

8.0 Conclusions 56
7.0 Recommendations 58

References 62
AppendixA:ProcessFlowDiagrams 59
vi

AppendixB:MassBalances 66

AppendixC:AdsorptionData 70

AppendixD:SizingCalculations 75
ColumnSizing 76
BreakthroughCurveCalculations 77
EquipmentSizing 81
SummaryTables 87

AppendixE:EconomicsCalculations 90

AppendixF:PipingandInstrumentationDiagram 94

AppendixG:MaterialSafetyDataSheets 96

AppendixH:HAZOP 111

vii

ListofTables

Table4.1:Molebalancedataforadsorptioncolumnwithuseofpurgestream 22
Table4.2:Molebalancedataforadsorptioncolumnwithoutuseofpurgestream23
Table4.3:Molebalancedataforregenerationstep 23
Table4.4:Molebalancedataforoverallsystem 27
Table5.1:Physicaladsorptionpropertiesofadsorptioncolumn 36
Table5.2:TypicalpropertiesofZEOCHEM.Z303 38
Table5.3:Ethanoldehydrationequipment 42
Table6.1:Summaryofequipmenteconomics 45
Table6.2:Summaryofalternativecomparison 47
TableB.1:Massbalanceforadsorbingcolumn(Bed1) 67
TableB.2:Massbalancefordesorbingcolumn(Bed2) 68
TableB.3:Massleavingsystem 69
TableB.4:Overallsystemmassbalance 69
TableC.1:Tableofgivenandcalculateddatafordeterminingthebreakthroughcurve74
TableD.1:UTubeheatexchangercalculateddataforpreheatingfeed 87
TablesD.2:Bayonetheatexchangercalculateddataforfeedvaporization 87
TableD.2a:Calculateddataforsensibleheating 87
TableD.2b:Calculateddataforphasechange 87
TableD.2c:Calculateddataforsuperheating 88

viii

TablesD.3:Bayonetheatexchangercalculateddataforproductcondensation 88
TableD.3a:CalculatedDataforphasechange 88
TableD.3b:CalculatedDataforsensiblecooling 88
TableD.4:CalculatedDataforliquidringvacuumpump 89

ix

ListofFigures

Figure3.1:Processflowdiagramofentiresystem 9
Figure3.2:Switchingsequenceforadsorptioncolumns 9
Figure3.3:Pressureswingadsorptioncyclepressurizationandadsorptionofbed11
Figure3.4:Breakthroughcurve 13
Figure3.5a:Valvesequenceforblowdownstep 14
Figure3.5b:Valvesequenceforregenerationstep 14
Figure3.6:Cyclestepsforpressureswingadsorption 16
Figure4.1a:SummaryofdataforUTubeheatexchangertopreheatfeed 20
Figure4.1b:SummaryofdataforBayonetheatexchangertovaporizefeed 20
Figure4.2:Summaryofdataforadsorptioncolumn 21
Figure4.3:HYSYSscreenshotofvacuumpump 25
Figure4.4:SummaryofdataforBayonetheatexchangertocondenseproduct 26
Figure4.5:HYSYSscreenshotofoverallmassbalance 27
Figure5.1a:Theoreticalcurve 35
Figure5.1b:Actualcurve 35
Figure5.2:Breathroughcurveswithvariedbedheights 37
Figure5.3:Visualofoneadsorptioncolumn 40
Figure5.4:Visualofaluminosilicate 38
FigureA.1:ProcessflowdiagrammimickingthedehydrationsysteminHYSYS
whenBed2(BAL2)isinregeneration 63

FigureA.2:ProcessflowdiagrammimickingthedehydrationsysteminHYSYS
whenBed2(BAL2)isdoneregenerating 64

FigureA.3:Processflowdiagramoftheethanoldehydrationsystem 65

FigureC.1:Isothermaldataforwateradsorptiononatype3Amolecularsieve 71

FigureC.2:Watervapourisothermat120forType3Amolecularsieve 72

FigureC.3:Graphforthedeterminationofequilibriumconstant
usingLanguirsform 73

FigureF.1:Processandinstrumentationdiagram 95

FigureH.1:SummaryofHAZOPanalysis 112

xi

RomanNomenclature

Symbol Name Units

A
Phusc
Phasechangearea m
2

A
scnsbIc
Sensibleheatarea m
2

A
Supchcutng
Superheatingarea m
2

A
1otuI
Totalarearequiredforheatexchanger m
2

A Crosssectionalareaofthecolumn m
2

A
c
Annualcost $
o Utilitycostcoefficient nounits
b Utilitycostcoefficient nounits
C
p
A
Heatcapacityofethanol
k]
kgK

C
p
B
Heatcapacityofwater
k]
kgK

C
p
mix
Heatcapacityofmixedstream
k]
kgK

C
s]
Costoffuelusedtogenerateutility
$
u]

c
]
Concentrationentering
kg H
2
0
m
3

adsorptioncolumn

xii

c
o
Concentrationleaving
kg H
2
0
m
3

adsorptioncolumn
Columndiameter m

AB
Diffusivityofethanolinto
cm
2
s

water

c]]
EffectiveDiffusivity
cm
2
s

K
Knudsendiffusivity
cm
2
s

p
Particlediameter m

S
Surfacediffusivity
cm
2
s


P
d Porediameter cm
F Pumpdownfactor nounits
F
1
Correctionfactor nounits
G Gassuperficialmassvelocity
kg
m
2
s

E
uds
HeatofAdsorption
kcuI
kgH
2
0

K Adsorptionequilibriumconstant nounits
K Constant nounits
k
c
Masstransfercoefficient
cm
s


xiii

I Columnlength m
I
b
Bedlength m
IES Lengthofequilibriumzone m
IuB Lengthofunusedbed m
H
A
Molecularweightofethanol
mol
g

H
B
Molecularweightofwater
mol
g

H
AB
MolecularWeightoftheethanol
mol
g

andwatermixture
H

AverageMolecularWeight
mol
g

Hw
mx
Molecularweightofthemixedstream
kg
kgmoI

m constant nounits
m Massflowrate
kg
h

m
]
Massflowrateentering
kg
h

adsorptioncolumn
m
o
Massflowrateleaving
kg
h

adsorptioncolumn

xiv

m
s]
Auxiliaryplantcapacity
kg
s

m
sw
Massflowrateentering
kg
s

vacuumpump
N
Rc
Reynoldsnumber nounits
N
Sc
Schmidtnumber nounits
N
Sh
Sherwoodnumber nounits
P
]
Pressureentering otm
adsorptioncolumn
P
n
Pressureenteringvacuumpump kPo
P
o
Pressureleaving otm
adsorptioncolumn
P
out
Pressureleavingvacuumpump kPo
P
P
Pressureofthepurgestream otm
PCI Plantcostindex nounits
Heatduty
k]
h

]
Volumetricflowrateentering
m
3
h

adsorptioncolumn

xv

o
Volumetricflowrateleaving
m
3
h

adsorptioncolumn
q Adsorptioncapacity
kgH
2
0
kg

R Gasconstant
g
moIK
or
cuI
moIK

S Pumpcapacity
m
3
h

S
g
Surfaceareaofmolecularsieve
m
2
g

I Timerequiredtoreachaspecific min
vacuumlevel
I
]
Temperatureentering K
adsorptioncolumn
I
o
Temperatureleaving K
adsorptioncolumn
I
P
Temperatureofthepurgestream K
t
u
Adsorptiontime min
t
b
Breakthroughtime b
t
c
Thicknessofthecolumn mm
t
p
Regenerationtime b
t
-
Idealadsorptiontimefor b
Verticalbreakthrough

xvi

u Overallheattransfercoefficient
]
m
2
sK

u
P
UtilityPrice
$
kg o] stcum

u
o
Superficialvelocity
m
s

u
o
mux
Maximumsuperficialvelocity
m
s

I Volumeofcolumntobeevacuated t
3

I
ubs
Volumeofadsorbent m
3

I
coIumn
Volumeofthecolumn m
3

I
od
Volumeifvoidinthecolumn m
3

w
]
Molarflowrateentering
kmoI
h

adsorptioncolumn
w
o
Molarflowrateleaving
kmoI
h

adsorptioncolumn
w
s
Shaftwork Kw

xvii

GreekNomenclature

Intrinsicefficiency nounits
e
p
Particleporosity nounits
z
A
Latentheatofethanol
]
kg

z
B
Latentheatofwater
]
kg

z
mx
Latentheatofvaporization
]
kg

ofthemixedstream
p
]
Viscosityentering
kg
ms
adsorption
column
p
o
Viscosityleaving
kg
ms

adsorptioncolumn
v
C
AtomicdiffusionvolumeofCarbon nounits
v
H
AtomicdiffusionvolumeofHydrogen nounits
v
0
AtomicdiffusionvolumeofOxygen nounits
v

Averagemolecularvelocity
cm
s

(v)
A
Diffusionvolumeofethanol nounits
(v)
B
Diffusionvolumeofwater nounits
Porosity nounits

xviii

p
b
Bulkdensity
kg
m
3

p
]
Densityoffluidentering
kg
m
3

adsorptioncolumn
p
o
Densityoffluidleaving
kg
m
3

adsorptioncolumn
p
p
Particledensity
kg
m
3

Other

I
LM
Logmeantemperature K
1

Chapter1.0:Introduction

1.1 Background
Forthepasteightmonths,HaloConsultinghasbeenworkingonadesignprojectfor
MarchConsultingAssociatesInc.MarchConsultingwasincorporatedin1999andtheir
mainofficebuildingislocatedinSaskatoon,Saskatchewan.Theyofferprojectand
designservicesformanydifferentdisciplinesofengineering,andalwaysstronglystress
energyconservation.

1.2 PurposeandProposedDesign
Thepurposeofthisprojectwastodesignadehydrationsystemthatwouldpurifyafeed
of95%v/vethanol5%v/vwatertoaminimumof99.5%v/vethanolproduct.Itwas
proposedbyMarchConsultingthattwocolumnsbedesignedandsizedtousepressure
swingadsorptionwithaType3Amolecularsieve.

Chapter2.0:LiteratureSurvey:AlternativeProcesses

2.1 Introduction
Upon performing the initial research, a vast assortment of directions for this design
were discovered andconsidered. This collection of alternative processes was carefully
analysed in order to depict the design which was most favourable in regards to the
qualityoftheproduct,economicconsiderations,andenergyconsumption.Thefirstand
foremostnecessaryresolutionwastodecidewhichmasstransferapplicationwastobe
used to dehydrate the ethanol. The three modes of mass transfer investigated were
distillation,thermalswingadsorption,andpressureswingadsorption.

2.2 Distillation
Distillationisaverycommonmethodofliquidliquidseparationthatworksbythe
applicationandremovalofheattoexploitdifferencesinrelativevolatility(Africa
1996).Applyingheattoamixtureallowsitscomponentswithlowerboilingpointsto
vaporizeintoagasphasethattravelstothetopofthecolumn,separatingitfromthe
componentswithhigherboilingpointsbecausetheyretainaliquidphaseandtravelto
thebottomofthecolumn.Becausethismethodofseparationisbasedonboiling
points,itisdifficulttoseparateazeotropicfeeds.Anazeotropicfeedisaliquidmixture
thatmaintainsaconstantboilingpointandthatproducesavapourofthesame
compositionasthemixture(Africa1996).Inotherwords,becausetheinletfeedinthis
designhasa95%v/v5%v/vwater,itisclassifiedasanazeotropicfeedandcouldnot
beeasilyseparatedbytheuseofsimpledistillation.

2.2.1 AzeotropicDistillation
Azeotropic distillation can be successfully used to break the azeotropic feed but
requires certain additives to do so. It can be classified into two types; homogeneous
azeotropicdistillationandheterogeneousazeotropicdistillation.

Homogeneous azeotropic distillation requires the use of an entrainer which is a,

separating agent that forms an azeotrope with one of the components of the binary
feed (Africa 1996). The new azeotrope is easier to separate than the first one and is
4

sent to a second column that is operating at an appropriate pressure to break it. This
resultsintheformationofmanyazeotropesintheattempttobreaktheinitialone.This
makesthedesignandsimulationverydifficultasthebehavioursoftheseazeotropesare
veryunpredictable.Theentrainersthatarerequiredarealsoveryexpensive.

Heterogeneousazeotropicdistillationhastheabilitytoseparateazeotropicfeedswhile
using less entrainment than homogeneous azeotropic distillation with a selfentraining
system,butthedesignandsimulationisstillverydifficultanditresultsinlargerecycle
rates.

2.2.2 PressureSwingDistillation
Pressure swing distillation is a specialized type of distillation that has the ability to
separate azeotropic feeds without the aid of additives. This process has a series of
distillationcolumnsthatoperateatdifferentpressuresinordertobreaktheazeotrope.
Thefirstcolumnoperatesatonepressuretoseparateasmallamount ofethanolfrom
themixture.Thedistillatefromthiscolumnisthensenttoanotherdistillationcolumn
that operates at a different pressure, breaking the azeotrope, and separating a little
moreethanol.Thebottomsofthecolumnissentbacktothefeedasarecyclestream.
Thisrepeatswithanumberoftowersuntilthedesiredvolumepercentageofethanolis
achieved. Although successful, this method is not feasible for the purification of
5

ethanol to 99.5% v/v as it requires high energy consumption. It also requires many
largecolumnswhichwouldresultinhighcapitolcosts.Pressureswingdistillationcan
be used to break an ethanolwater mixture that forms an azeotope. The process
consistsofthreeormorecolumnsoperatingatdifferentpressures(Africa1996).

2.3 ThermalSwingAdsorption
Thermalswingadsorption,alsoknownastemperatureswingadsorption,isaneffective
way to remove impurities from gas streams. The problem with thermal swing
adsorption is that in order to achieve a temperature range that sufficiently affects the
separation desired, a long swing time is required. From this arises the need for larger
equipment and large amounts of energy consumption, resulting in high operation and
maintenance costs. These costs can be reduced by enhancing the system with a
microchannel architecture (Africa 1996), improving mass transfer and therefore
allowingsmallersizedequipmentandshortercycles.Thecostofenhancingthesystem,
however,stillleavesthisprocessasnoteconomicallyfeasible.

Itwasdecidedthatthebestmethodofmasstransferforthisproblemwastouse
pressureswingadsorption.
6

Chapter3.0:DetailedQualitativeProcessDescription

3.1 Introduction
Thefeedintothedehydrationsystemisatwocomponentliquidmixtureofwaterand
ethanol.Thismixtureiscominginataliquidvolumepercentof95%ethanoland5%
water,whichisregardedasanazeotropicmixture.Toobtainaliquidproductof
minimum99.5%v/vethanolthefeedmustgothroughthreemainsteps:(1)pre
heatingandvaporizingofliquidfeed,(2)dehydrationofwetethanolgasbypressure
swingadsorption,and(3)coolingandcondensingofdryethanolgastoaliquid.A
processflowdiagram(PFD)fortheproposeddehydrationsystemcanbeseeninFigure
3.1.

3.2 FeedPreparation
Beforetheazeotropicliquidfeedmixturecanbesentthroughthecolumns,certain
preparationstepsneedtobecarriedout.Theadsorptionisbeingperformedbyatype
3Aaluminosilicatethatcanbedamagedbythepresenceofliquid.Therefore,thefeed
streamtothefirstcolumnneedstobevaporizedandbroughttoatemperatureand
pressurethatwilleradicateanypossibilityofcondensationwithinthecolumns.

The95%v/vethanolfeedisfirstpreheatedusingaUtubeheatexchanger.Theliquid
feedpassesthroughtheshellsideoftheheatexchangerwhereitisheatedwithhot
productgasthatispassingthroughthetubesideoftheheatexchanger.No
vaporizationofthefeedwilloccurinthisfirstheatexchanger,itsonlypurposeisto
raisethetemperatureoftheliquidtoprepareitforvaporization.Thehotliquidmixture
isthenpassedthroughabayonetheatexchangerwhereitiscompletelyvaporized.This
iscompletedbypassingthehotliquidthroughtheshellsidewhereitisvaporizedby
superheatedsteamthatispassingthroughthetubeside.Theresultinggaswillbeata
temperatureandpressurewherethechanceofcondensationwithinthecolumnis
eliminated.Thisisparticularlyimportantbecausetheformationofliquidwithinthe
columncoulddamagethemolecularsieveandreduceitsadsorptioncapacity.

3.3 Dehydration
Oncethefeedhasbeenprepared,itcanbesenttotheadsorptioncolumntobe
dehydrated.Thehotwetethanolgasispassedthroughoneoftwoverticaladsorption
columnsthatarealignedparalleltoeachother.ThiscanbeseeninFigure3.3.These
twocolumnsutilizePressureSwingAdsorption(PSA)todehydratetheethanol.InPSA,
eachcolumn,operatesalternatelyintwohalfcyclesofequalduration(Henley2006).
Inthisdesign,awholecycleinvolves:
1)Pressurizationofthecolumnwiththefeed;
2)Adsorptionatelevatedpressure;
3)Depressurizationbyvacuumpump;
4)Desorptionbypurgestreamatloweroperatingpressure;
5)Standby
ThiscycleisaslightlymodifiedformoftheSkarstromcyclewherethecycleentails,(1)
pressurizationfollowedbyadsorption,and(2)depressurization(blowdown)followed
byapurge(Henley2006).ThesimplesetupofcolumnsandvalvesinFigure3.1shows
theflowpatterninthissubsystemofthedesignthroughoutacompletecycle.Atthe
beginningofcycle,thesaturatedbedwillundergoaregenerationprocesstodesorbthe
waterfromthebedwhiletheotherusesadsorptiontodehydratetheethanoland
becomessaturated.TheadsorbinganddesorbingcolumnsarerepresentedbyBed1
andBed2,respectivelyinFigure3.3.ThefollowingwilldescribethecycleforBed1.
9

Figure3.1Processflowdiagramofentiresystem.

Figure3.2Switchingsequenceforadsorptioncolumns

10

3.3.1 Pressurization
Initially,Bed1willexistatapressureof101.3kPa.Whenthecyclestarts,valves1and
7openrapidly,allowingflowofwetethanolgastogothroughBed1.Thewetethanol
gasflowsintothetopofBed1atanelevatedtemperatureandpressure.Thisraisesthe
pressureofthecolumntomatchthatofthefeedstream.Thepressurizationsteptakes
about10secondswhichisrelativelyshortincomparisontotheadsorptionand
regenerationsteps.Duringthisperiod,adsorptionofwaterontothemolecularsieveis
initiated,butthemajorityofadsorptionwilltakeplaceinthenextstep.
3.3.2 Adsorption
OnceBed1hasbeenpressurized,apressuretransmitteronthecolumnsignalsa
controlswitchthatallowstheadsorptionsteptobegin.Thisstepstartswiththe
openingofvalves5and6,whichallowstheregenerationgastoflowintoBed2.With
valves1,4,7,5,and6open,acontinuousflowofgaswillbeallowedthroughbothof
thebeds.ThiscanbeseenbelowinFigure3.3.Wetethanolgas,enteringatthesame
operatingconditionsasinthefirststep,willbecontinuouslydehydratedinBed1,
resultinginadryethanolgasproductflowingoutthebottom.
11

Figure3.3:Pressureswingadsorptioncyclepressurizationandadsorptionofbed1

Thisdryethanolisthensplitintotwostreamsof40and60%.The40%issenttoBed2
whereitisusedasaregenerationgas.Theremaining60%istobesentforfurther
processing.Splittingthedryethanolstreamiscontrolledbyvalves6and7,whichwill
bepartiallyopentoallow/restricttheamountofproductintoBed2.
Theconcentrationofwaterintheoutletproductwillinitiallybezerobecauseessentially
allofthewaterinthewetethanolisremoved.Theassumptionthatcomplete
separationofwaterfromethanolwouldoccurwasbasedontheoreticaldataandmade
forcalculationpurposes.Inreality,completeseparationwouldnotoccur.Astime
passes,theamountofmolecularsievesaturatedwithwaterincreases,reducingthe
capacityofthebed.Eventually,smallamountsofwaterwillbeenseenintheproduct.
Thetimeatwhichwaterisfirstobservedintheproductisreferredtoasthe
breakthroughtime.Ifthecolumnisallowedtooperatepastthebreakthroughtime,
12

increasingconcentrationsofwaterwillbeobservedintheproductuntilapointwhere
theconcentrationofwaterintheproductisequaltothatofthefeed.Atthistimethe
molecularsievewouldbeconsideredtotallysaturatedandwouldhavenocapabilityto
adsorbwater.Inthisdesign,thecolumnisallowedtooperatepastthebreakthrough
timeuntiltheproducthasaconcentrationof99.5%v/vethanol.Thetimeatwhicha
99.5%v/vethanolisreachedwascalculatedusingtheoreticalbreakthroughcurve.
UsingthebreakthroughcurveinFigure3.4,atimeof23.9minuteswasfoundto
correspondtoapurityof99.5%v/vethanolandthereforemarkedtheendofthe
adsorptionstepforBed1.Adetailedderivationofthesystemsbreakthroughcurveand
determinationofcycletimeswillbecoveredinchapter5.

TheregenerationofBed2takeslesstimethantheadsorptionofBed1,andtherefore
theregenerationgasisnotneededfortheentire23.9minutes.Asetofcontrolshas
beenimplementedtomeasuretheconcentrationofwaterinthestreamleavingBed2.
OncetheconcentrationofwaterinthisstreamisthesameastheinletfeedtoBed2,
thecontrolssignalthesplitterstodiscontinuethepurgestream.Atthistime,thefeed
ratetotheentiresystemisalsodecreased.Thiswascalculatedtooccurat
approximately6.33minutes.Thefeedrateisdecreasedtoallowforaconstantproduct
flow.Themajorityofthedesigncalculationswereperformedusingvaluesobtained
13

fromsimulationwiththepurgestreamwasstillinuse.Thiswasdonesothatasteady
stateassumptioncouldbemade.

Figure3.4:Breakthroughcurve

3.3.3 Blowdown
ThenextstepinthePSAcycleistheblowingdownofBed1.Itisnecessarybecausethe
columnmustbedepressurizedinorderfortheregenerationsteptooccur.Thisstep
beginswiththerapidopeningofvalves2,3,and8andtheclosingofvalves1,4,5,6,
and7.ThisisshowninFigure3.5a.Oncethevalveshaveswitched,theliquidring
vacuumpumpwillautomaticallystart.Thepurposeofthispumpistobringthecolumn
toapressurethatisbelowatmosphericasapreparationstepfortheregeneration
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0 10 20 30 40 50 60
c/cf
Time,min
14

process.Thisstepiscomparabletothatofpressurizationbecausethedurationofthis
stepisrelativelyshortandmarksthebeginningoftheregenerationstep.Thevacuum
pumpwillruncontinuouslyfortheentiredurationoftheregenerationstep.

3.3.4 Regeneration
RegenerationisthelaststepinthePSAcycleandisdonetoremovetheadsorbedwater
fromthemolecularsievebedsothatitmaybereusedinthenextcycle.Pressure
sensorsandcontrolshavebeenaddedtobothcolumnstoaidinswitchingthebeds
fromadsorptiontodesorption.OncethepressuresensoronBed1measuresthatalow
enoughpressurehasbeenachieved,valves5and6open,beginningtheregeneration
stepdisplayedinFigure3.5b.Theopeningofthesevalvesallowsdryethanolgasto
enterthebottomofBed1.Valve5willbepartiallyclosed,throttlingtheregeneration
gastothesamepressureasthecolumn.Thelowoperatingpressuregivenbythe
runningvacuumpumpallowsthewatertobeeasilyremovedfromthemolecularsieve
bythedryethanolgasenteringthebottom.
15

Figure3.5aValvesequenceforblowdownstep Figure3.5bValvesequenceforregenerationstep

Theamountofpurgegasandpressurewithinthebeddeterminetheamountoftime
neededforregeneration.Alargeamountofpurgegasandalowercolumnpressure
resultsinashorterregenerationtime.Theregenerationstepforthismolecularsieveis
about6.33minutes.Thisisacceptableasitismuchlessthanthetimeneededfor
adsorption,eliminatinganypossibledowntime.Thistimeisoftendeterminedusing
experimentaldata,butthisestimationwastheresultofacorrelationinvolvingthe
pressuresandflowratesofthefeedandpurgestreams.Aconcentrationsensoratthe
topofthecolumnwillshutoffthevacuumpumpandclosevalves5and6whenno
morewaterisobservedintheproduct,asdescribedabove.
Thecompleteremovalofwaterfromthemolecularsieveisverydifficultandis
considereduneconomicalbecauseequipmentandoperatingcostswouldbeveryhigh.
Thecalculationsforthisdesignwereperformedassumingthatcompleteremovalof
16

waterwasachievedbecausefindingtheexactamountwaterthatcanberemovedat
theseconditionswouldrequireexperimentaldatathatwasnotavailable.

Withtheregenerationtimebeinglessthentheadsorptiontimetherewillbeaperiod
whereoneofthetowersisnotinoperationandisstandingby.Thisismoredesirable
thenhavingaregenerationtimegreaterthentheadsorptiontime,whichwouldresult
inasemicontinuousflowofproduct.Toremovetheproblemofstandby,additional
adsorptioncolumnscouldbeintroducedintothesystem.Acompletesequenceofcycle
stepsinPSAisshowninFigure3.6
Figure3.6Cyclestepsforpressureswingadsorption(Ruthven1994)

17

3.4 CoolingandCondensing
Theremaining60%ofthedryethanolgasthatisnotusedfortheregenerationstepis
sentthroughtwoheatexchangerswhereitiscooledtothefinalliquidproduct.Thehot
drygasisfirstpassedthroughaUtubeheatexchangerwhereitiscooledbytheliquid
feed.Thisisthesameheatexchangerthatwasusedforpreheatingtheliquidfeed.

Thecooledgasisfinallypassedthroughabayonetheatexchangerwhereitis
condensedusingcoolingwater.Thecooledgaswillcondenseasitpassesthroughthe
tubes,resultinginafinalliquidproductof99.5%v/vethanol.

18

Chapter4.0:MassandEnergyBalances:Simulations

4.1 Introduction
ThesimulationpackageHYSYSwasusedforsimulatingthevaporizingandcondensing
processeswithinthedesign.Theadsorptionanddesorptionprocessescouldnotbe
modelledinHYSYSasitisnotfitforadsorptionprocesses.Theyweretherefore
modelledbyhandusingExcel.AtotalsystemmassbalancewasdonewithHYSYSbutan
energybalanceforthesystemcouldnotbecompletedbecausetheenergytransferred
intheadsorptionprocesscouldnotbesimulated.

19

4.2 FeedPreparation
The95%v/vliquidethanolentersthesystemataninitialmolarrateof41.86
kgmoI
h

untiltheregenerationofthedesorbingbediscomplete.Oncetheregenerationis
complete,thefeedrateisdecreasedto25.11
kgmoI
h
sincenomoredrygasisneeded
forpurgingandaconstantliquidproductflowrateof1250
L
h
isdesired.

Forbothoftheflowrates,thetemperatureandpressureofthefeedenteringtheU
tubeheatexchangeis35and129kPa.Thisfeedisheatedtoatemperatureand
pressureof85Cand132kPabythehot,dryethanolgasleavingtheadsorptioncolumn
at120Cand175kPa.Thehotgas,flowingataconstantrateof21.84
kgmoI
h
,allowsthe
liquidfeedtobeheatedbutdoesnotvaporizeit.Thehotliquidfeedisthencompletely
vaporizedto120Cand250kPausingsuperheatedsteaminabayonetheatexchanger.
Thesuperheatedsteamflowratewilladjustaccordinglywiththeinletflowratesothat
thistemperatureandpressureisreachedandheldconstantbeforeenteringthe
adsorptioncolumn.Flowrates,pressures,temperatures,anddutiesforthestreamand
heatexchangers,forthefirst6.33minutes,werefoundusingtheHYSYSsimulationand
aresummarizedinFigure4.1.
20

Figure4.1aSummaryofdataforUTubeheatexchangertopreheatfeed

Figure4.1bSummaryofdataforBayonetheatexchangertovaporizefeed

21

4.3 Dehydration
Thewetethanolgasisthenpassedintothefirstheatexchangerwhereadsorptionwill
takeplaceat120Cand250kPa.Amolebalancewasfirstcompletedaround
adsorptioncolumnforthe6.33minuteperiodwhere40%ofitsproductisbeingused
toregeneratethedesorbingcolumn.Anadsorptionrateof5.47kgmole/hresultedin
0.577kgmoleofwaterbeingadsorbedduringthistime.Theadsorptionofwateris
slightlyexothermicasthemolecularsievereactswithwatertoproduceheat.
Approximately2424kJofheatisgivenoffduringthisperiod.Sincethecycletimesof
PSAaresoshortthecolumnsareassumedtobeisothermal.Theflowrates,
temperatures,pressuresandcomponentmolefractionsfortheadsorptioncolumn,Bed
1,canbeseeninFigure4.2andTable4.1.

AdsorptionColumn

Figure4.2Summaryofdataforadsorptioncolumn
T=120C
P=250kPa
T=120C
P=175kPa
22

Table4.1Molebalancedataforadsorptioncolumnwithuseofpurgestream
Streams MoleFraction
Flowrate
(kgmole/h)
Water Ethanol Feed Water Ethanol
IN 0.14 0.86 41.86 6.04 35.81
OUT 0.02 0.98 36.39 0.58 35.81
ACCUMULATED 1 0 5.47 5.47 0.00

Theoutletpressureof175kPawasdeterminedusingErgunsequationforpressure
dropinarandomlypackedcolumn.Thepressuredropwasfoundtobearound75kPa
anddoesnotcausedamagetothemolecularsieve.

Asecondmassbalancewascompletedaroundtheadsorptioncolumnforthe17.61
minutesthatthepurgestreamisnolongerneededandtheentireproductfromthe
adsorptioncolumnissenttobecondensedtothefinalliquidproduct.Forthisperiod
thereisawateradsorptionrateof3.27
kgmoI
h
,whichresultsin0.96kgmoleofwater
beingadsorbedand4041kJofheatbeingproduced.Valuesforthecomponentmole
fractionsandflowratesareshowninTable4.2.

23

Table4.2Molebalancedataforadsorptioncolumnwithoutuseofpurgestream
Streams MoleFraction
Flowrate
(kgmole/h)
Water Ethanol Feed Water Ethanol
IN 0.14 0.86 25.11 3.63 21.48
OUT 0.02 0.98 21.84 0.35 21.48
ACCUMULATED 1 0 3.27 3.28 0.00

Forthetotaladsorptiontime,23.9minutes,atotalof1.54kgmoleofwaterisadsorbed
ontothemolecularsieve.Thisamountofwaterwillessentiallybetheamountthat
needstoberemovedfromthedesorbingcolumn.Thewaterwillbedesorbedatarate
of14.81
kgmoI
h
andwillactasthegenerationterminthemassbalanceequationforthat
column.Table4.3showsthecomponentmolefractionsandflowratesforremoving
the1.54kgmoleofwaterduringtheregenerationstep(6.33minutes).

Table4.3Molebalancedataforregenerationstep
Streams MoleFraction
Flowrate
(kgmole/h)
Water Ethanol Feed Water Ethanol
IN 0.02 0.98 14.56 0.23 14.33
GENERATED 1.00 0.00 14.58 14.58 0.00
OUT 0.51 0.49 29.14 14.81 14.33

Theoutletproductoftheregeneratingcolumnisconsideredabyproductofthe
processandissentoutofthisdesigntobefurtherprocesses.

24

4.4 VacuumPump
ThevacuumpumpwasmodelledasacompressorusingHYSYS.Thisvacuumpumpisof
aliquidringtypeanditspurposeistomaintainapressureof50kPainthedesorbing
bed.Thispumptakesthewetdesorbedgasandsendsitawaytobefurtherprocessed.
Thegasenteringthevacuumpumpisflowingatarateof29.14
kgmoI
h
,whichisequalto
theoutletflowrate.Theexitingpressureofthegaswillbeat101.3kPa.HYSYS
calculatedthepumptohaveapowerratingof26.10kWwithanefficiencyof75%.This
powerratingisveryclosetopowerratingof21.73kWthatwascompletedbyhand
calculationsforthespecificpump.Thepumpiscontinuouslyrunningduringthe
regenerationperiodandisshutoffonlywhenthebedisfullydesorbed,after6.33
minutes.AHYSYSscreenshotofthevacuumpumpcanbeseeninFigure4.3alongwith
thecorrespondingvaluesforthestreamsandthevacuumpump.Thepurgegas
enteringthedesorbingbedisfirstthrottleddowntoapressureof50kPabythe
butterflyvalveV11inFigure3.1.
25

Figure4.3HYSYSscreenshotofvacuumpump

4.5 Condensation
Thedryethanolgas,thatissenttobecondensed,flowsintotheUtubeheatexchanger
ataconstantflowrateof21.84
kgmoI
h
.Theproductgasinstream5,isatatemperature
andpressureof120Cand175kPa,andiscooledto91Cand165kPabytheliquidfeed
stream1.Atthispointsomecondensationofthedryethanolgashasalreadystartedto
occur.Figure4.1isarepresentationoftheUtubeheatexchanger.Theremainderof
thegasiscompletelycondensedto30Cand130kPabycoolingwaterinabayonetheat
exchanger.Thefinal99.5%v/vethanolproductisflowingoutofthesystemat21.85
kgmoI
h
or12Su
L
h
whichwasspecifiedbyMarchConsulting.Figure4.4isarepresentation
ofthebayonetheatexchanger.
26

Figure4.4SummaryofdataforBayonetheatexchangertocondenseproduct

4.6 Overall
Aftermassbalancesaroundthetwocolumnswerecompleted,anoverallmassbalance
forthesystemforahalfcyclewasdone.Theoverallmassbalanceforthesystemwas
slightlymorecomplicatedduetothefactthatacertainamountofwaterisbeing
accumulatedintheadsorptionbedandbeingdesorbedintheregeneratingbed.There
isalsoadynamicstepchangethatoccursininletflowratewhenoneofthebedsisdone
regenerating.Thisalsocomplicatesthemassbalance.

ItcanbeseeninTable4.4thataftertheadsorptionforonebediscompleted,the
amountenteringthesystemisequaltotheamountleavingofthesystem.
27

Table4.4Molebalancedataforoverallsystem
Stream
Substance
(kgmole)
Water Ethanol Total
IN(feed) 1.70 10.08 11.79
OUT(Product) 0.138 8.58 8.71
OUT(ByProduct) 1.56 1.51 3.08
= 0.00 0.00 0.00

Itshouldbenotedthatthemassbalancewascompletedwhilemaintainingthefinal
liquidproductat99.5%v/vethanol.Inreality,thiscompositionwillvarybetween100
and99%v/vethanol.Figure4.5showshowHYSYSwasusedtosimulateanoverall
massbalanceforthetimeperiod6.33minutes.
Figure4.5HYSYSscreenshotofoverallmassbalance

Thedashedbluelinerepresentstheamountofwaterthatisaccumulatedinthe
molecularsieveoverahalfcycleandneedstoberemovedintheregenerationstep.
28

The5.47
kgmoI
h
istherateofwaterthatisadsorbedinthefirst6.33minutes,andthe
9.11
kgmoI
h
istherateatwhichthewaterwasadsorbedinthetimeperiodof17.61
minutes.Completestreamandunitoperationinfoforbothmassandenergybalances
canbefoundintheDESIGN.HSCfileforHYSYSsimulationintheattachedCD.

29

Chapter5.0:EquipmentDescriptionandSizes

5.1 Introduction
Oncethemassbalanceswerecompleted,eachpieceofequipmentintheprocesscould
thenbesized.TheequipmentsizeswerecalculatedusingtheShortCutEquipment
DesignMethoddevelopedbyUlrichandVasudevanintheirtextbook,Chemical
EngineeringProcessDesignandEconomics:APracticalGuide.Thefinaldesign,as
mentionedearlier,consistedofthreeheatexchangers,onevacuumpump,andtwo
identicaltowers.Sinceethanoldoesnothaveanycorrosivepropertiesandthe
pressuresandtemperatureswithinthesystemarenottoextreme,alloftheequipment
forthisdesignwillbeconstructedoutofcarbonsteel.Thoughtwasinvestedintousing
somestainlesssteelwithinthesystem,however,thiswouldbeanunnecessaryexpense
andintroducingasecondtypeofmetalbringsacceleratedbimetalliccorrosionintothe
system.AsummaryoftheequipmentsizescanbeseeninTable5.3attheendofthis
chapter.

30

5.2 HeatExchangers
5.2.1 HeatExchanger#1
Inthisdesigntherewerethreeheatexchangersused,allofwhichareofshellandtube
type.Thefirstheatexchangerisusedtopreheatthefeedstreamandcoolthefinal
productstream.UsingTable4.12fromUlrichstextbook,itwasdeterminedthataU
Tubeheatexchangerhadthecompatibilityandserviceratingsthatwereappropriatefor
thistaskandwasthereforechosen.

TheUtubeheatexchangerusestheproductstreamfromtheadsorptioncolumnasthe
heatingsourcetopreheattheliquidfeedatcooltheproductsimultaneously.Thefinal
areaofthisheatexchangerwasfoundtobe2.21m
2
.GuidelinesgivenbyUlrichwere
usedtodeterminewhichstreamwouldflowthroughtheshellsideandwhichwould
flowthroughthetubeside.Becauseitisflowingatahigherpressure,itwas
determinedthatthehotproductstreamshouldflowthroughthetubeside.Thecool
feedstreamwouldthereforeflowthroughtheshellside.

31

5.2.2HeatExchanger#2
Thesecondheatexchangertakesthepreheatedfeedfromheatexchanger#1and
vaporizesitusingsuperheatedsteamasaheatingsource.Becauseofthevaporization
andsuperheatinginvolved,aUtubeheatexchangercouldnotbeused.Ofthefive
typesofheatexchangersgiveninTable4.12(Ulrich2004),itwasfoundthatabayonet
heatexchangeristheonlyoneabletohandlethesuperheatingaspectsofthese
conditions.Thefinalareaofthisheatexchangerwasfoundtobe15.22m
2
andthe
steamwouldflowthroughthetubeside,whilethefeedwouldflowthroughtheshell
side.

5.2.3HeatExchanger#3
Thethirdheatexchangerisusedtocoolandcondensethesemicooledproductstream
comingoutofheatexchanger#1.Becausethereiscondensationinvolved,itwas
determinedthatanotherbayonetheatexchangerwouldservebestforthistask.The
finalareaofthisheatexchangerwasfoundtobe10.02m
2
andthesemicooledproduct
wouldflowthroughthetubeside,whilethecoolingwaterwouldflowthroughtheshell
side.

32

5.3 VacuumPump
ThevacuumpumpchosenforoursystemwasaLiquidRingVacuumPumpas,Liquid
ringvacuumpumpsarecommonlyusedtohandlewetgasmixtures(Aliasso2003).
Inthesetypesofmixtures,itispossibleandcommonforthelubricantwithinthepump
tobewashedaway,causingprematurefailure(Aliasso2003).Ratherthanusinga
lubricant,liquidringvacuumpumpseliminateanymetalonmetalcontacttoreducethe
chanceoffailure.Thisalsoreducesthewearandtearonthepump,extendingits
lifespan.Animpellerinsidethepumprotatesandthrowsthewaterbycentrifugal
force,creatingaliquidringwiththecasingandthusgeneratescompression.Asthegas
enters,itisentrappedbytheimpellerbladesandtheliquidring.Astheimpeller
rotates,itcreatesacompressiononthegasandforcesitthoughthepumpoutlet.To
eliminatethepossibilityofcontaminationfromtheliquidtothegasphase,thepump
willusewatertocreatetheliquidring.

Theequationusedtodeterminethepumpsizewas
T
F V
S

= (5.1)(Graco2008).
whereSisthevacuumpumpsizeincubicfeetperminute,Visthevolumeofthe
columntobeevacuatedincubicfeet,Fisthepumpdownfactor,andTisthetime
33

requiredtoreachaspecificvacuumlevelinminutes.Usingthisequation,alongwith
thevalues,V=15.9ft
3
,F=2,andT=0.17min,andsomeunitconversions,itwas
determinedthatthepumphadamaximumpumpingcapacityof325
m
3
h
andashaft
powerof18kW.Thispumpwasusedtobringthepressureofthecolumndownto
approximately50kPa.Thefinaloutputpressureonthepumpisatatmospheric
pressure(101.3kPa).

5.4 AdsorptionColumns
Thesizingoftheadsorptioncolumnwasconsideredthemostimportantaspectofthe
design.Inmostinstancesthedesignofanadsorptioncolumnisbasedonexperimental
data,butforthisdesignthiswasnotavailable.Thesizingoftheadsorptionbedwas
completedusingequationsandguidelinesgivenbyHenleyandZEOCHEM,the
manufacturerofthemolecularsievebeingusedindesignedadsorptioncolumn.

Thefirststepindesigninganadsorptioncolumnistocalculatethediameterofthe
molecularsievebed.Thediameterofthebedshouldbeassmallaspossiblewithout
damagingthemolecularsieve,Adiametersmallenoughtomaintainaturbulentgas
flowisnecessary,otherwisethemasstransfercharacteristicsareverypoorbecauseof
theincreasedfilmresistancetomassandenergytransfer(ZEOCHEM20072008).The
34

maximumgasvelocitybeforeerosionorcrushingof1/8beadsisapproximatedbythe
followingequationgivenbyZEOCHEM:
I [Jown low,
]t
mIn
= 61.S_p
gus
(
Ibs
]t
3
) (5.2)(ZEOCHEM20072008).
Foradownwardmaximumvelocityof0.697
m
s
,abeddiameterfortheadsorption
columnwascalculatedtobe0.55m.

Oncethebeddiameterwascalculated,theamountofmolecularsieveneededforwater
adsorptioncouldbedetermined.Sincenoexperimentaldatawasavailable,aconstant
pattern scale up of an adsorption column could not be readily completed. Therefore,
estimations of bed heights were made for an ideal fixedbed adsorption column and
laterusedtomodelarealfixedbedadsorber.Aninitialbedheightwasdeterminedby
calculating the length of the equilibrium zone (LES), which was completed by doing a
water mass balance around the system. The amount of water adsorbed in each cycle
wasfoundbymultiplyingtheadsorptionratebythedurationoftheadsorptionstep.A
typicalcycletimeforPSArangesfrom530minutes,soforthepurposeofthisdesign
the adsorption time was taken as twothirds of maximum value, 20 minutes. In one
cycle,1.82kgmolofwaterisadsorbed.Basedonthisvalue,theamountofmolecular
sievewaspredictedusingtheequilibriumloadingcapacityforthemolecularsievefound
in Table 5.2. ZEOCHEM recommends using half of this value, 10%
kgH
2
0
kg
adsorbent,
35

because polar compounds in the gas will reduce the equilibrium capacity (ZEOCHEM
20072008).AresultingLESof2misrequiredforthebed.

This length is not acceptable because there are many assumptions associated with it,
especially that, local equilibrium between the fluid and the adsorbent is achieved
instantaneously,resultinginashocklikewave,calledastoichiometricfront,thatmoves
as a sharp concentration front through the bed (Henley 2006). This type of wave is
showninFigure5.1a.Inarealfixedbedadsorberthiswillnotoccurandtherewouldbe
amasstransferzone(MTZ)andalengthofunusedbed(LUB)withaconcentrationfront
likethatinFigure5.1b.This 2mlengthisaninitialguessinmodellingabreakthrough
curvethatwillbeusedindeterminingatruebedlength.

Figure5.1aTheoreticalcurve Figure5.1bActualcurve(Henley2006).

36

Abreakthroughcurveisarelationshipbetweentheratiooftheproductandfeedwater
concentrations,(c/c
F
)versustime.Usingthiscurvethetimethatcorrespondstoac/c
F

of0.068(maxratiogiving99.5%v/vethanol)canbefound.Atheoreticalbreakthrough
curveforthesystemwasapproximatedbyKlinkenbergsequation:
c
c
F
=
1
2
_1 +eif ( - +
1
8:
+
1
8{
)_ (5.3)
Where,
=
kKz
u
[
1-c
b
c
b
= imcnsionlcss Jistoncc coorJinotc (5.4)
And,
= k [t -
z
u
= imcnsionlcss timc coorJinotc corrcctcJ or Jisploccmcnt (5.5)

Theadsorptionequilibriumconstant,K,wasdeterminedbyfittingequilibrium
absorptiondatagivenbyZEOCHEMtoalinearadsorptionisothermoftheformq=Kc.
Theoverallmasstransfercoefficient,k,wasthendeterminedbymethodsdevelopedin
HenleyandSeaders,SeparationProcessPrinciples,whichinvolvestherelationship:
1
kK
=
R
p
3k
c
+
R
p
2
15
c
(5.6)(Henley2006).
The values of K and k for the adsorption bed were found to be 245 and 0.309 s
1

respectively.Thevaluesusedinthedevelopmentofthetheoreticalbreakthroughcurve
can be found in Table C.1. The height was then scaled up until a breakthrough time
37

around 20 minutes was achieved. The resulting height of 3.5 m was chosen, giving an
adsorptiontimeofaround24minutes.Theresultingbreakthroughcurvesareshownin
Figure5.2

Figure5.2Breakthroughcurveswithvariedbedheights

Oncethefinaldimensionsofthebeddetermined,thepressuredropwasverifiedusing
Eurgans equation. A pressure drop of 75 kPa was found across the bed which is an
acceptablepressuredrop.

The column is to be constructed from carbon steel as corrosion effects are not a
problem in this process. Using correlations from Ulrichs, the wall thickness for a
vertical cylindrical column was found to be 4 mm. All physical adsorption column
0
0.2
0.4
0.6
0.8
1
1.2
0 10 20 30 40 50
c
/
c
F
Time(min)
2meterbed
3meterbed
3.5meterbed
38

properties can be found in Table 5.1. A visual of an adsorption column can be seen in
Figure5.3.

Figure5.3Visualofoneadsorptioncolumn

Table5.1Physicaladsorptionpropertiesofadsorptioncolumn
unit value
Material CarbonSteel
Columninnerdiameter m 0.55
Columnwallthickness mm 4
Columnheight m 4.5
Bedheight m 3.5

39

5.5 MolecularSieve
Theadsorbentusedwithinthetwoidenticaltowersisatype3Amolecularsievezeolite.
Thisisthemostcommonlyusedadsorbentintheapplicationofdehydratingethanol.
Thismolecularsieve,isthepotassiumformoftheAtypestructure;andhasan
effectiveporeopeningof3Angstrom(0.32nm)(ZEOCHEM20072008).InTypeA
structuredzeolite,thetetrahedralaregroupedtoformatruncatedoctahedronwitha
silicaaluminatetrahedronateachpoint(ZEOCHEM20072008).Avisualofthiscanbe
seeninFigure5.4.Thestructureisrepresentedbythechemicalformula:
0.45K
2
O0.55Na
2
OAl
2
O
3
2SiO
2
XH
2
O (ZEOCHEM20072008).
Forthedesigncalculations,valuesgivenbyZEOCHEMfortheirZEOCHEMZ303
wereused.ThesevaluescanbeseeninTable5.2.ZEOCHEMislargemanufacturerof
commerciallyusedadsorbentsand,suppliesaround80%oftheworldmarketfor
ethanoldehydration(ZEOCHEM20072008).TheirZEOCHEMZ303isspecifically
designedfordryingethanolusingpressureswingadsorption.

Thismolecularsievezeoliteispolarhydrophilicinnatureandthereforestrongly
adsorbswater.Inthecaseofthisdesignadsorptionofwaterontothisadsorbentwill
purelyphysical.Inphysicaladsorption,theintermolecularattractiveforcesbetween
moleculesofasolidandthegasaregreaterthanthosebetweenmoleculesofthegas
40

itself(Henley2006).TheseforcesarecommonlyreferredtoasvanderWaals
interactions.

Figure5.4Visualofaluminosillicate
Thephysicaladsorptionofjustwaterisdirectlyrelatedtotheeffectiveporesizeofthe
molecularsieve.Thisadsorbentwillabsorbanymoleculewithadiameterlessthen0.32
nmandexcludethosethatarelarger.Awatermoleculehasadiameterof2.8Angstrom
andiseffectivelyadsorbedontothemolecular,whereasethanolhasadiameterof4.4
Angstromandisthereforeexcluded.
Table5.2TypicalpropertiesofZEOCHEMZ303

unit value
Tappedbulkdensity,ENISO78711 kg/m3 750
Beadsizenominal mm 2.55
CrushStrength N 70
Equilibriumwateradsorptioncapacity,
@20C/50%rh/24h % 20
Residualwatercontent,550Casshipped % 1.5
Heatofadsorption kJ/kgwater 4200
Specificheat(approx) kJ/kgC 1.07
(ZEOCHEM20072008).
41

5.5 ValvesandPiping
Thevalveschosenforourdesignwerepneumaticbutterflyvalves.Therationalefor
choosingbutterflyvalveswasthattheyareoneofthemostsuccessfulhigh
performancevalves(Dickenson1999).Dickensonalsomentionsthatthesevalvesare
idealforsmallerunits,whichreducescost,weightandspacerequirements,andthat
theyhavefewparts,creatingeasymaintenance,installation,andoperation.Theywere
alsofoundtohaveahighratingforbothliquidandgasservices,on/offswitching,
throttling,flowcontrol,andquickopening.Thepurposeofhavingthempneumatically
operatedissothatacontrolboardoperatorcaneasilymonitorandmanipulatethe
positionthatthevalveisin.Thepipingbeingusedinthisdesignisonceagaincarbon
steelwithainnerdiameterofapproximately6inchandathicknessof
1
2
inch.Thiswas
determinedusingPerrysHandbook.

42

Table5.3Ethanoldehydrationequipment
Equipment Type EquipmentName Size
HeatExchangers
UTube E112 1.96m2
Bayonet(Heating) E122 15.2m2
Bayonet(Cooling) E132 10.0m2
VacuumPump LiquidRing G113 21.7kW
AdsorptionTower Tower1or2
D110
D120
Diameter:0.55m
Height:4.5m
*SamplecalculationscanbeseeninAppendixD

43

Chapter6.0:Economics

6.1 Introduction
Oncesized,thepricesofeachpieceofequipmentwerethenestimatedusingthe
programEconExpert(EconExpert2008),whichhasabuiltinequipmenteconomics
calculator.Thecalculatorusespricesandcorrelationsfromthementionedtextbookby
UlrichandVasudevan.Thesepriceswerethenscaledupusingtheappropriatecost
index.
Foraneconomicanalysis,acomparisonbetweenourdesignandanalternativewas
completed.Therationalebehindthistypeofanalysiswasthatwewerenotabletodoa
discountedcashflowrateofreturnonthedesignproposedsinceitisasubsystemofa
largerprocess.Therefore,aneconomicfeasibilitystudycouldnotbedonesinceallthe
partsofthelargerprocessareinterrelatedandrequiredtodeterminetheeconomic
viability.Asaresult,acomparisonwascompletedonthecostofenergyrequiredto
44

breaktheazeotropeofethanolat95%v/vinadistillationcolumnversususingPSA.

6.2 EquipmentCosts
Asmentionedearlier,thecostsfortheequipmentwerecalculatedusingmethods
presentedbyUlrichandVasudevanintheprogramEconExpert.Toscaleupthese
prices,aChemicalEngineeringPlantCostIndexof528.2,retrievedfromtheChemical
EngineeringJournals,wasused.Thescaledupcostsofeachindividualpieceof
equipmentissummarizedinTable6.1.Thetotalgrassroostscapitalwascalculatedto
beapproximately$370,000.Thiscostbreaksdownintoatotalmodulecostandan
auxiliaryfacilitiescost.Withinthetotalmodulecost,itincludessubsectionsincluding
baremodulecostsaswellascontingencyandfeecosts.Thebaremodulecoststake
intoaccountfreight,taxes,insurance,constructionoverhead,andengineering
expenses.Theauxiliaryfacilitycostsincludesitedevelopment,auxiliarybuildings,and
offsitefacilities.Abreakdownofthesesectionsandtherespectivecostsarelistedin
Table6.1.Thecalculationofthecontingencyandfeecostsisbasedonapercentageof
thetotalbaremodulecostwhereastheauxiliarycostsarebasedonapercentageofthe
totalmodulecost.Therespectivepercentagesarelistedinbracketsbehindthe
applicabledescriptions.

45

TABLE6.1Summaryofequipmenteconomics
Equipment Type BareModuleCost
HeatExchangers
UTube $11,000
Bayonet(Heating) $33,000
Bayonet(Cooling) $27,800
VacuumPump LiquidRing $49,500
AdsorptionTower
Tower1 $59,500
Tower2 $59,500
TotalBareModuleCost $240,000
Contingency(15%)andFee(3%) $43,300
TotalModuleCost $284,000
AuxiliaryFacilities(30%) $85,100
GrassRootsCapital $369,000

46

6.3 Molecularsievecosts
Themolecularsieveneedstobereplacedapproximatelyevery4000cycles,whichworks
outtobeaboutapproximatelyevery3monthsresultinginthreebedchangesperyear.
Thecostofthesieveisapproximately$9perkilogram.Witheachcolumnhaving600kg
init,acostperreplacementisequalto$10,800withatotalcostof$32,400peryear.

6.4 AlternativeEconomicComparison
Todeterminethecostofenergyrequiredinazeotropicdistillation,thesteamflowrate
withinthesystemneededtobedetermined.Apaperonsalineextractivedistillation
wasfirstusedtofindtheenergyrequirementtobeapproximately5MJforbreakingthe
azeotrope.Comparingthisvaluewiththeenergyrequirementfortheproposeddesign,
itwasfoundtohavearatioof3to1.Inotherwords,azeotropicdistillationusedthree
timesasmuchenergytobreaktheazeotrope.Knowingthisratio,andthatthisdesign
requiresasteamflowrateofapproximately4.2
kg
s
,thesteamflowraterequiredin
azeotropicdistillationwasfoundtobeapproximately12.6
kg
s
.Finalcostswerethen
calculatedusingcorrelationsoutofUlrichstextbookagainanddeterminedtobe
approximately$2.2MMforPSAand$6.6MMforazeotropicdistillation.Asummaryof
thevaluesneededinthecalculationofthefinalcostscanbeseeninTable6.2.

47

Table6.2Summaryofalternativecomparison

PressureSwing
Adsorption AzeotropicDistillation
Aux.BoilerSteamCapacity, s,(kg/s) 40 40
Pressure,P,(kPa) 250 250
PriceofFuel,CS,f,($/GJ) 4.75 4.75
PlantCostIndex 528.2 528.2
UtilityPrice($/kg) 0.0173 0.0173
OperatingTimePerYear(s) 3.02E+07 3.02E+07
SteamFlowRate(kg/s) 4.2 12.6
AnnualEnergyCost $2,200,000 $6,610,000
*SamplecalculationscanbeseeninAppendixE

48

Chapter7.0:SafetyAnalysis

7.1 Introduction
Anotherimportantaspectofanydesignprojectistheevaluationofitssafety.Forthis
project,itwasspecifiedthatasafetyanalysis,includingahazardandoperability
(HAZOP)analysisandaDOWFireandExplosionIndexanalysisbeperformedonone
pieceofequipment.Thesafetyanalysiswasperformedononeofthecolumnsasithas
themostpotentialforproblematicoccurrences.Thechemicalpropertiesofthesystem
werealsoanalyzedbyobtainingvariousmaterialandsafetydatasheets(MSDS).In
orderforthisdesigntobedeemedacceptable,everypossibledeviationthatcould
occurneededtobeinvestigatedandtheproperpreventativemeasurestaken.Thiswas
completedintheHAZOPanalysis.Aprocesssafetymanagementplanhasalsobeen
completedineffortstomakesafetyanimportantconsiderationtoemployeesfromthe
beginningoftheprocessandtocontinuetostresssafetythroughoutitslifespan.Safety
isaveryimportantpartofanydesignandshouldnotbetakenlightly.
49

7.2 ChemicalProperties
7.2.1 Ethanol
MSDSsheetswerefoundforsolutionsof95%v/vethanol,5%v/vwaterandfor100%
ethanolasthesearetheminimumandmaximumconcentrationsofethanolfoundin
oursystem.FromtheseMSDSsheetsitwasfoundthatthevaluesforboth
concentrationsareequivalent.Thethresholdlimitvalueofpureethanolwasfoundto
be1000ppm.Althoughethanolisanonreactivesubstance,itisveryexplosiveand
flammablewiththelowerandupperflammablelimitsforbothsolutionsbeing3.3%
and19%respectively.Italsohasaverylowflashpointof17.78Cor64F.Onthe
basisofafourhourexposuretime,theacuteoraltoxicity(LD50)ofethanolwasfound
tobe3450
kg
mg
andtheacutetoxicityofthevapour(LC50)ofethanolwasfoundtobe
39000
3
m
mg
.AllofthesevaluescanbefoundinAppendixG.Thisclassifiesethanoltobe
slightlyhazardousinthecaseofingestionorinhalation.Itisalsoanirritantinthecase
ofskincontact.

Personalprotectiveequipmentsuchasprotectivegloves,safetygoggles,andfire
retardantclothingarerecommendedwheneverworkingwithornearethanol.
Concentratedethanolsolutionsshouldbestoredinatightlyclosedandsealed
containerinacoolwellventilatedareathatwillnotexceedatemperatureof23C.
Properventilationandaccessibleeyewashstationsanddrychemicalfireextinguishers
arealsonecessary.
50

7.2.2 AluminoSillicate
AnMSDSsheetwasalsofoundforthetype3Amolecularsieve,whichisaluminosilicate
andcanbefoundinAppendixG.Thisisaverystable,nonflammablesubstanceandis
onlyslightlyhazardousinthecaseofinhalation.Itisnontoxictohumanswith
exceptiontothecaseofchronicexposurewhichcanpossiblyresultindamagetothe
lungsduetoinhalationofdustformedbythemolecularsieve.Itcanalsobeclassified
asaslightirritanttotheskinasitcanreactwithmoisturetocreateheat.Thisisnota
seriouseffectandcanbeeasilyremovedwithsoapandwater.Thepersonalprotective
equipmentthatisrecommendedwhendirectlyhandlingaluminosilicatearesafety
goggles,safetygloves,labcoat,andadustrespirator.

7.3 HazardandOperabilityAnalysis
7.3.1 HAZOPStrategy
Ahazardandoperability(HAZOP)analysiswascompletedononeofthetowers.Inthis
analysis,allpotentialdeviationsthatcouldoccuronthetowerwereconsidered,rated,
andpossiblesafeguardswereimplementedorrecommended.Thiswasdonefollowing
themethodgiveninUlrichsChemicalEngineering:ProcessDesignandEconomics,A
PracticalGuide.Inthismethod,deviationswerefirstidentifiedandifpossible
eliminated.Ifthedeviationcouldnotbeeliminateditwasminimizedandisolated.

51

TheHazardReviewLeader2008software,createdbyABSconsulting,wasusedto
conducttheidentificationportionoftheHAZOPanalysis.Thissoftwaregivesalistof
possibledeviationsforspecificpiecesofequipment.Forthetowerinthisdesign,it
gavethefollowingpossibledeviations;hightemperature,lowtemperature,high
pressure,lowpressureandleaks(ABSConsulting2008).Thepossiblecausesand
possibleconsequenceswerethenlistedandanalyzedandeachdeviationwasthen
rated,basedontheseverityoftheconsequencesandthelikelihoodofthedeviation
occurring.Withthisratingsystem,eachdeviationwasgivenavaluefrom1to4based
ontheseverityofitsconsequences,with1beingtheleastsevere,causingasinglefirst
aidinjury,and4beingthemostsevere,causingmultiplesevereinjuries.Theywere
thengivenavaluefrom1to4basedonthelikelihoodofoccurrences,with1signifying
thatitisnotexpectedtooccurever,and4representingthatitcouldpotentiallyoccurat
leastonceayear.Multiplyingbothvaluestogethergavetheoverallratingforthe
deviation.Oncethedeviationswereidentifiedandrated,theproperprecautionary
actionsweretakentopreventandminimizetheeffectsandlikelihoodofthem
occurring.

7.3.2HAZOPConclusions
Usingthestrategydescribedabove,eachdeviationwasgivenaratingandanalyzed.
ThisissummarizedinFigureH.1.Hereitcanbeseenthatthemosthazardous
deviationsthatcouldoccurweredeterminedtobehightemperatureonthetowerand
52

aleak,withratingsof4and8,respectively.Thesetwoshouldthereforebegiven
priorityforpreventativeaction.

Hightemperatureonthecolumncouldbecausedbyeitherofthetwoproceedingheat
exchangersnotworkingproperly.Ifthisweretooccur,thepressureinsidethecolumn
wouldbeincreased,increasingthechancesofcondensationoccurinsidethecolumn
anddamagingthemolecularsieve.Damagetothemolecularsievehasnosafety
relatedconsequencesitself,however,replacingthemolecularsievecanbeapotentially
hazardousjobasitrequiresdirectexposuretotheethanolandthemolecularsieve.If
thetemperatureweretoreachtheautocombustiontemperatureofethanol(363C)an
explosioncouldoccur.Eventhoughthisisnotexpectedtoeveroccurinthelifetimeof
thesystem,theextremenatureoftheconsequencesmakesthisaveryhazardous
deviation.Inordertopreventthis,ahightemperaturealarmthatwillsoundat200C
hasbeenincludedonthecolumn.Temperaturecontrolshavealsobeenputonthe
secondoftheproceedingheatexchangers.ThesecontrolscanbeseenonFigureF.1.

Aleakcouldpossiblyoccurduetocorrosion,rundownofequipmentorwearonthe
sealsandconnectionstothetower.Ifthisweretohappen,thegaseousethanolcould
escapeintotheatmosphereandtherewerebeariskofexplosionifitweretocomeinto
contactwithanignitionsource.Inordertopreventanddetectaleak,leakdetection
monitors,suchasLELmonitors,andlowpressurealarmsandcontrolshavebeen
implemented.ThesecanbeseenonFigureF.1.Thepressurecontrolsarealsousefulto
53

controlthevacuumpumptomakecertaintheregenerationcolumnisbeing
depressurizedadequately.

AsseeninFigureF.1flowratetransmittershavebeenplacedonstreams,12,18,20and
29tocontrolsplitters5and6.Thesecontrolswereaddedtoensurethat40%ofthe
productbesenttotheregeneratingtowertoaidintheregenerationprocess.These
splittersarealsocontrolledbyasetofcontrolsthatmeasurestheconcentrationof
waterinstream25leavingtheregenerationtower.Oncetheconcentrationinthis
streamreacheszero,itisnolongernecessarytopurgethedesorptiontowerwiththe
product.Atthispointthesplittersarechangedtoensurethat100%oftheproductis
senttothefinalheatexchangerforcooling.

Thecoolingwaterbeingfedintothethirdheatexchangerisregulatedbytemperature
controlsthataresignalledbyatemperaturetransmitteronthefinalproductstream17.
Thisistomakesurethattheproductiscooledenoughtocompletelycondenseittoa
liquidform.Oneofthestipulationsofthisdesignwasthattheliquidproductstream
wastohaveaflowrateof1250
L
h
.Tosatisfythiscondition,flowtransmittershavebeen
implementedontheoutletstream14thatwillsignalvalve1toopenorclose
accordingly.

54

InFigureF.1,itcanalsobeseenthatvalveshavebeenplacedinthesystemsoasto
maketheisolationofeverypieceofequipmentpossible.Thisisnecessarytocarryout
maintenance,replacementofequipment,andforinthecaseofemergencies.

7.4 DOWFireandExplosionIndexAnalysis
AFireandExplosionIndexanalysiswascompletedononeofthetowers.This
concludedthatthisadsorptionsystemhadafireandexplosionindexof95.5which
meansthatitisamoderatehazard.Theradiusofexposurewasfoundtobe
approximately80ft.Thetotalvalueofequipmentforthissystemisabout$400,000,
however,becausethevalueoftherestofthefacilityisunknown,anextra$10,000,000
hasbeenaddedtothevalueofareaofexposuretoaccountforttherestofthefacility.
Thisgivesabaseandactualmaximumpropertydamage(MPPD)of$6,000,000and
$4,360,000respectively.TheMPDOandBusinessInterruptionLosswerefoundtobe
15daysand$230,000respectively.

7.5 ProcessSafetyManagement
Aspartofaprocesssafetymanagementplan,amonthlysafetymeetingwillbeheld
thatiscompulsoryforallemployeestoattend.Thesemeetingswillconsistofthe
discussionofanyincidentsornearmissesthatmayhaveoccurredintheprevious
month.Therewillbeamonthlysafetythemethatwillberesearchedandpresentedby
thechairofthemeeting.Eachmeetingwillalsohaveanallottedtimeslotforanyone
55

presenttobringforwardanysafetyconcernstheymayhave.Scheduledpreventative
maintenanceandscheduledshutdownswillalsobecarriedoutasseennecessary.

Thetrainingfornewemployeeswillhaveaverysafetyorientedoutlook,withjob
shadowing,operatingmanualsandvideos,andthecompletionofcertainsafety
courses.ItisrecommendedthatallemployeescompletetheWHMIS,basicfire
extinguishing,confinedspace,andfirstaidcoursesbeforestartingworkwiththis
process.

56

Chapter8.0:Conclusions

Afterconductingextensiveresearch,performingcalculations,andtestingsimulations,
HaloConsultinghasdeterminedthatpressureswingadsorptionisthebestsolutionfor
dehydratingafeedof95%v/vethanoltoafinalproductof99.5%v/vethanol.The
designwouldconsistofthreeheatexchanges,oneliquidringvacuumpump,andtwo
identicaladsorptiontowersfilledwithaType3Amolecularsieve.

Thetowerswerefoundtobemoreefficientwhentallandslender.Thus,the
dimensionsofthetowersare4.5minheightwithabeddiameterof0.55mandawall
thicknessof4mm.Theheightoftheadsorptionbedwasfoundtobe3.5m.Thetotal
cycletimeforonetowerwasapproximately48minutes,24minutesforadsorption,6
minutesforregenerationand18minutesforstandby,pressurization,andblowdown.
Duringthe6minutesofregeneration,40%ofthedryethanolgasproductissenttothe
regeneratingcolumntoaidindesorption.

57

Theareasofthethreeheatexchangersusedinthisprocesswerecalculatedtobe1.96,
15.2,and10.0m
2
.Thevacuumpumpwassizedtobe21.7kW.

Afteraneconomiccomparison,itwasestablishedthattheannualcostofenergy
requiredforazeotropicdistillationwasapproximatelythreetimesthatofpressure
swingadsorption,beingapproximately$6.6MMand$2.2MMrespectively.Thetotal
modulecostandtheoverallgrassrootscapitalforthepressureswingadsorptiondesign
werecalculatedtobeapproximately$284,000and$369,000,respectively.

Finally,aftercompletingananalysisforbothHAZOPandDowsFireandExplosionIndex
ononeofthetowers,itwasdeterminedthatthemaindeviationsofthesystemwere
leaksandhightemperaturesinthecolumnandthatthesystemwasclassifiedasa
moderatehazard.Duetotheflammableandexplosivenatureofethanol,aprocess
safetymanagementplanhasalsobeenimplemented.

58

Chapter9.0:Recommendations
Aftercompletingthisdesignprocess,thefollowingrecommendationshavebeen
suggested.

1. Gatheringofexperimentaldataattheseconditionstoobservetheactual
declineinadsorptionratesovertimeisstronglyrecommended.Thisdata
wouldbeusedtoperformascaleupoperationofthedesign.

2. Itisrecommendedthatasimulationpackagewithadsorptionprocessesto
simulatethepressureswingadsorption.Thiscouldnotbedoneforthis
designastimedidpermitlearninganewsimulationprogram.

59

References

Aliasso,Joe.HowtoSizeLiquidRingVacuumPumps.PumpsandSystemsMagazine.
2003,13.<ht t p: / / www. graham- mfg. com/ downloads/ 212. pdf>

Africa,Michael;Kendrick,Robert;Scramlin,Jeff;Catalano,Sam;Messacar,Julie;Palazzolo,
Joseph.
ChemicalEngineeringEquipment.Macromedia,Inc.1996.

Basmadjian,Diran.TheLittleAdsorptionBook:APracticalGuideforEngineers&
Scientists.CRCPress,Inc:1997.

Change,Hua;Yuan,XiGang;Tian,Hua;Zeng,AiWu.Experimentandpredictionof
breakthroughcurvesforpackedbedadsorptionofwatervapouroncornmeal.
ElsevierB.V.2006,18.

Dickenson,T.Christopher.Valves,PipingandPipelinesHandbook.3
rd
Ed.Elsevier
AdvancedTechnology.1999.

EconExpert.Ulrich,GaelD.;Vasudevan,Palligarnai.February2008.
<www.ulrichvasudesign.com>.

GracoHomepage.GracoLiquidControl.January2008.
<ht t p: / / www. graco. com/ LCC/ et oolbox/ vacuum. ht ml> .

60

HazardReviewLeader2006Software.ABSConsulting.January2008April2008.
<http:/www.absconsulting.com/TC/103.html>.

Henley,ErnestJ.;Seader,J.D.SeparationProcessPrinciples.2
nd
Ed..JohnWiley&
Sons:NewYork,2006.

Kirk,Othmer.ConciseEncyclopediaofChemicalTechnology.4
th
Ed.JohnWiley&
Sons:NewYork,1999.

MarchConsultingAssociatesInc.Homepage.MarchConsultingAssociatesInc.
September2007April2008.http://www.marchconsulting.com.

Nevers.NoelDe.FluidMechanicsforChemicalEngineers.3
rd
Ed.McGrawHill:
NewYork,2005.

Perry,RobertH.;Green,DonW.PerrysChemicalEngineersHandbook.7
th
Ed.
McGrawHill:NewYork,1997.

Peters,MaxS.ElementaryChemicalEngineering.2
nd
Ed.McGrawHillBook
Company:NewYork,1984.

Pinto,R.T.P.;WolfMacial,M.R.;Lintomen,L.Salineextractivedistillationprocessfor
ethanolpurification.ElsevierB.V.2000,16.

61

Ruthven,DouglasM.;Farooq,Shamsuzzaman;Knaebel,KentS.PressureSwing
Adsorption.VCHPublishers,Inc,1994.

Suzuki,Motoyuki.AdsorptionEngineering.KodanshaLtd,1990.

Tien,Chi.AdsorptionCalculationsandModeling.ButterworthHeinemann,1994.

Ulrich,GaelD.;Vasudevan,Palligarnai.ChemicalEngineering:ProcessDesignand
Economics:APracticalGuide.2
nd
Ed.ProcessPublishing:Durham,New
Hampshire,2004.

ZEOCHEMHomepage.Zeochem.September2007April2008.
<http:/www.zeochem.com>.

62

AppendixA:
ProcessFlowDiagrams
63

FigureA.1:ProcessFlowDiagrammimickingthedehydrationsysteminHYSYSwhenbed2(BAL2)isinregeneration
64

FigureA.2:ProcessflowdiagrammimickingthedehydrationsysteminHYSYSwhenbed2isdoneregenerating
65

FigureA.3Processflowdiagramoftheethanoldehydrationsystem
66

AppendixB:
MassBalances

67

TableB.1Massbalanceforadsorbingcolumn(Bed1)

timespanforbalance 0.106 h
Streams MoleFraction
Flowrate
(kgmole/h)
Amount
(kgmole)
Water Ethanol Feed Water Ethanol Feed Water Ethanol
IN 0.14 0.86 41.86 6.04 35.81 4.42 0.64 3.78
OUT 0.02 0.98 36.39 0.58 35.81 3.84 0.06 3.78
ACCUMULATED(adsorptionrate) 1 0 5.47 5.47 0.00 0.58 0.58 0.00
timespanforbalance 0.293 h
Streams MoleFraction
Flowrate
(kgmole/h)
Amount
(kgmole)
Water Ethanol Product Water Ethanol Feed Water Ethanol
IN 0.14 0.86 25.11 3.63 21.48 7.37 1.06 6.30
OUT 0.02 0.98 21.84 0.35 21.48 6.41 0.10 6.30
ACCUMULATED(adsorptionrate) 1.00 0.00 3.27 3.28 0.00 0.96 0.96 0.00
timespanforbalance 0.399 h = 23.94 AdsorptionTime
Stream
Amount
(kgmole)
Total Water Ethanol
IN 11.79 1.70 10.08
OUT 10.25 0.16 10.08
ACCUMULATED(adsorptionrate) 1.54 1.54 0.00
68

TableB.2Massbalancefordesorbingcolumn(Bed2)
time 0.11 h
Streams MoleFraction
Flowrate
(kgmole/h)
Amount
(kgmole)
Water Ethanol Feed Water Ethanol Feed Water Ethanol
IN 0.02 0.98 14.56 0.23 14.33 1.54 0.02 1.51
GENERATED(desorptionrate) 1.00 0.00 14.58 14.58 0.00 1.54 1.54 0.00
OUT 0.51 0.49 29.14 14.81 14.33 3.08 1.56 1.51
Stream
Amount
(kgmole)
Total Water Ethanol
IN 1.5366284 0.024366 1.512262083
OUT 3.076000272 1.563738 1.512262083
GENERATED(desorptionrate) 1.54 1.54 0.00
69

TableB.3Massleavingsystem
Time
(hours)
MoleFraction
Flowrate
(kgmole/h)
Amount
(kgmole)
Water Ethanol Product Water Ethanol Product Water Ethanol
0.11 0.02 0.98 21.84 0.35 21.49 2.31 0.04 2.27
0.29 0.02 0.98 21.84 0.35 21.49 6.41 0.10 6.31
Total 8.71 0.14 8.58

TableB.4Overallsystemmassbalance
Stream
Substance
(kgmole)
Water Ethanol Total
IN(feed) 1.70 10.08 11.79
OUT(Product) 0.138 8.58 8.71
OUT(ByProduct) 1.56 1.51 3.08
= 0.00 0.00 0.00

70

AppendixC:
AdsorptionData
71

FigureC.1Isothermaldataforwateradsorptiononatype3Amolecularsieve
72

FigureC.2Watervapourisothermat120Cfortype3Amolecularsieve
0
0.2
0.4
0.6
0.8
1
1.2
1.4
0 10 20 30 40 50 60
W
a
t
e
r

l
o
a
d
i
n
g

i
n

w
t
.

o
f

m
o
l
e
c
u
l
a
r

s
i
e
v
e
VaporPressureinkPa
73

FigureC.3GraphforthedeterminationofequilibriumconstantusingLangmuir'sform

y=0.048x+0.039
R=0.998
0
0.5
1
1.5
2
2.5
3
0 10 20 30 40 50 60
r
a
t
i
o

o
f

p
a
r
t
i
a
l

p
r
e
s
s
u
r
e

a
n
d

w
a
t
e
r

l
o
a
d
i
n
g
,

p
/
q

PartialPressure,p(kPa)
74

TableC.1Tableofgivenandcalculateddatafordeterminingthebreakthroughcurve
Value Units Description
MWmix,M
ab
25.90 g/mol 337Henley
DiffusionVolumeethanol,
a
51.17 Table3.1Henley
DiffusionVolumewater,
b
13.1 Table3.1Henley
Diffusivity,D
ab
1.03E01 cm
2
/s 336Henley
1.03E05 m
2
/s
EffectiveDiffusivity,D
eff
1.08E02 cm
2
/s 1575Henley
1.08E03 m
2
/s
Averagemolecularvelocity,
i
4.45E+02 1420Henley
Knudsendiffusion,D
k
4.75E10 cm
2
/s 1419Henley
4.75E14 m
2
/s
SurfaceDiffusion,D
s
9.40E05 cm
2
/s 1576Henley
9.40E09 m
2
/s
ReynoldsNumber,N
Re
7.21E+02 Table3.3Henley
SchmidtNumber,N
Sci
2.60E01 Table3.3Henley
SherwoodNumber,N
sh
1.23E+01 1562Henley
MassTransferCoefficient,k
c
4.20E02 m/s 1560Henley
4.20E+00 cm/s
overallmasstransfercoefficient,k 3.39E01 s
1
15106Henley
K 245 SeeIsothermSheet
75

AppendixD:
SizingCalculations
76

ColumnSizing:
1. Calculationofmaxvelocitythroughcolumn

I [
]t
mIn
=
61.5
_p_
lbs
]t
3
]

=
61.5
_0.200
lbs
]t
3

mn
60 scc

m
3.28]t

= 1S7
]t
mn

mn
60 scc

m
3.28]t

= u.699
m
s

2. Calculationofthecolumndiameter:

A =

P
I
=
S47.S
m
3
b

b
S6uus
u.699
m
s
= u.217m
2

= _
4A
n

= _
40.217m
2
n

= u.S2Sm = u.SSm

3. Calculationofthelengthofequilibriumzone:

IES =
t AJsorption Rotc
q p A

77

=
20mn
h
60 min
5.47
kgmclc H
2
O
h

18.01 kg H
2
O
kgmclc H
2
O
0.1
kg H
2
O
kg Adscrbcnt

20kg
m
3
0.217m
2

= 1.92m = 2.uum

BreakthroughCurveCalculation:
subAisethanol,subBiswater

1. Calculationofthemolecularweightofthemixture:
H
AB
=
2
[
1
H
A
+[
1
H
B

=
2
_
1
46.u7gmol
] +_
1
18.u1gmol
]
= 2S.9
g
mol

2. DeterminationoftheDiffusionvolumeofethanol:
[v
A
= (2)(v
C
) +(6)(v
H
) +(1)(v
0
)
= (2)(1S.9) +(6)(2.21) +(1)(6.11)
= S1.17

3. CalculationoftheDiffusivityofethanolinwater:

AB
=
u.uu14SI
1.75
PH
AB
0.5
_(v)
A
1
3
+(v)
B
1
3
_
2

=
u.uu14S(S9S.1SK)
1.75
(2.47otm) _
2S.9g
mol
]
0.5
_(S1.17)
1
3
+(1S.1)
1
3
_
2

78

= u.u888
cm
2
s

4. Calculationoftheaveragemolecularvelocity:
v

= _
8RI
nH

]
12
= _
8(8.S14gmol K)(S9S.1SK)
n(42.u2gmol)
_
12
= 44S.1
cm
s

5. CalculationoftheKnudsenDiffusionCoefficient:

K
=
J
p
v

S
=
(S.2 1u
-12
cm)(44S.1cms)
S
= 4.7S 1u
-10
cm
2
s

6. CalculationoftheSurfaceDiffusivity:

s
= 1.6 1u
-2
cxp _-
u.4S(-E
uds
)
mRI
_

= 1.6 1u
-2
cxp _-
u.4S _-99u
kcol
kg E
2
0

18.u1g
mol
]
(2) [
1.987col
mol k
(S9S.1SK)
_

= 9.4u 1u
-5
cm
2
s

7. CalculationoftheReynoldsNumber:

N
Rc
=

p
0
p
=
(u.uuSm) _2.uS7
kg
m
2
s
]
8.S6 1u
-6
kg
m s
= 7.21 1u
2

79

8. CalculationoftheSchmidtNumber:

N
Sc
=
p
p
AB
=
8.S6 1u
-6
kg
m s
_S.21
kg
m
2
] _u.u888
cm
2
s
]
= u.S

9. CalculationoftheSherwoodNumber:

N
Sh
= 2 +u.6uN
Rc
1
2
N
Sc
1
3
= 2 +u.6u(7.21 1u
2
)
1
2(u.S)
1
3
= 1.28

10. CalculationoftheMassTransferCoefficient:

k
c
=
N
Sh

AB

p
=
(1.28) _u.u888
cm
2
s
]
u.uuSm
=
S.78cm
s

11. Determinationofbreakthroughtime:

=
kKz
u
_
1 -e
b
e
b
]
=
u.SS9s
-1
24S 2
1.28
m
s
_
1 -u.S
u.S
]
= Su2

= k [t -
z
u

= u.SS9s
-1
_129us -
2.um
1.28
m
s
_
= 2.Su

c
c
F
=
1
2
_1 +eif _ - +
1
8:
+
1
8{
]_
80

=
1
2
j1 +eif [2.Su -Su2 +
1
82.50
+
1
8302
[
= u.999

Solverforac/c
F
=0.068fora2meterbedgaveadsorptiontimeofaround13.15
minutes.Lengthscaledupto3.5meterswhichgaveadsorptionofaround23.9minutes.

81

EquipmentSizing:
HeatExchangerFirstBayonet(heating)
1. Calculationofsensibleheatarea:
1a.Calculationofheatcapacityofmixedstream:
C
p
mix
= [C
p
B
(moss %
B
) +[C
p
A
(moss %
A
)
= [4.174
k]
kgK
(u.u619) +[2.46
k]
kgK
(u.9S81)
= 2.S7
k]
kgK

1b.Calculationofheatduty:
= m C
p
mix
I
= [17S9
kg
h
[2.S7
k]
kgK
(96.6-8S.u)
= S2S64.7
k]
h

1c.Calculationoflogmeantemperature:
I
1
= Iubc Inlct -Sbcll 0utlct
= 4S7K -S69.9K
= 87.4

I
2
= Iubc 0utlct -Sbcll Inlct
= 4S6.6K -SS8.uK
= 98.6K

82

I
LM
=
(1
2
-1
1
)
In[
T
2
T
1

=
(98.6K-87.4K)
In[
98.6K
8.4K

= 92.89K

1d.Calculationofsensibleheatarea:
A
scnsbIc
=

F
1
uI
IM

=
S2S6S
k[
b
(1) [9uu
[
s K m
2
(92.89K)

= u.174m
2

2. Calculationofthephasechangearea:

2a.Calculationofspecificheatmixture:
z
mx
= (z
B
)(moss %
B
) +(z
A
)(moss %
A
)
= _226u
k[
kg
] (u.u619) +_8SS
k[
kg
] (u.9S81)
= 941.97
k[
kg

83

2b.Calculationofheatduty:

= mz
mx

= _17S9
kg
b
] _941.97
k[
kg
]
= 16S7
H[
b

2c.Calculationoflogmeantemperature:

I
1
= Iubc Inlct -Sbcll 0utlct
= 4S7K -S9SK
= 64K

I
2
= Iubc 0utlct -Sbcll Inlct
= 4S6.6K -SS8.uK
= 98.6K

I
LM
=
(1
2
-1
1
)
In[
T
2
T
1

=
(98.6K-64K)
In[
98.6K
64K

= 8u.1K

84

2d.Calculationofphasechangearea:
A
phusc
=

FuI
IM

=
16S6924
k[
b
(1) [9uu
[
s K m
2

S6uus
b

k[
1uuu[
(8u.1K)

= 14.61m
2

3. Calculationofsuperheatingarea:
3a.Calculationofheatcapacityofmixedstream:
C
p
mix
= (C
p
B
)(moss %
B
) +(C
p
A
)(moss %
A
)
= _4.174
k[
kg K
] (u.u619) +_2.46
k[
kg K
] (u.9S81)
= 2.S7
k[
kg K

3b.Calculationofheatduty:
= mC
p
mix
I
= [17S9
kg
h
[2.S7
k]
kgK
(S9S-S69.6)
= 1uS6S2.S
k]
h

85

3c.Calculationoflogmeantemperature:
I
1
= Iubc Inlct -Sbcll 0utlct
= 4S7K -S9SK
= 64K

I
2
= Iubc 0utlct -Sbcll Inlct
= 4S6.6K -S69.6K
= 87K

I
LM
=
(1
2
-1
1
)
In[
T
2
T
1

=
(87K-64K)
In[
8K
64K

= 74.91K

3d.Calculationofsuperheatingarea:
A
supchcutng
=

FuI
IM

=
1uS6S2.S
k[
b
(1) [9uu
[
s K m
2

S6uus
b

k[
1uuu[
(74.91K)

= u.4SSm
2

86

4. Calculationoftotalheatexchangerarea:
A
1otuI
= A
scnsbIc
+A
phusc
+A
supchcutng

= u.174m
2
+14.61m
2
+u.4SSm
2

= 1S.22m
2

VacuumPump
1. Calculationofthepumpcapacity:
S =
IF
I

=
(1S.92t
3
) _
m
S.28u8t
] (2)
(1us) [
min
6us
[
b
6umin

= S24.72
m
3
b

2. Calculationoftheshaftwork:
ws =
m
sw
I
n
K_[
P
out
P
n

K-1
K
-1_
Hw
mx
(K -1)e

=
_u.2S7
kg
s
] (S9S.1SK)(1.1S9) _[
1u1.SkPo
SukPo

1.139-1
1.139
-1_
_S8.u9
kg
kgmol
] (1.1S9 -1)(u.7S)

= 21.7Skw

87

TableD.1UTubeheatexchangercalculateddataforpreheatingfeed
Value Units
Cp,mix 2.57 kJ/kmol*K
Delta T 50.00 K
Heat Duty (Q) 225709.97 kJ/h

T1 35.00 K
T2 53.21 K
T
LM
43.47 K

A= 2.21 m2

TablesD.2.Bayonetheatexchangercalculateddataforfeedvaporization
TableD.2aCalculateddataforsensibleheating
Value Units
Cp,mix 2.57 kJ/kg*K
Delta T 11.60 K
Heat Duty (Q) 52364.71 kJ/h

T1 87.40 K
T2 98.60 K
T
LM
92.89 K

A= 0.17 m
2

TableD.2bCalculateddataforphasechange
Value Units
,mix 941.97 kJ/kmol
Delta T 35.00 K
Heat Duty (Q) 1656924.35 kJ/h

T1 64.00 K
T2 98.60 K
T
LM
80.06 K

A= 14.61 m
2

88

TableD.2cCalculateddataforsuperheating
Value Units
Cp,mix 2.57 kJ/kmol*K
Delta T 23.40 K
Heat Duty (Q) 105632.27 kJ/h

T1 64.00 K
T2 87.00 K
T
LM
74.91 K

A= 0.44 m
2

TablesD.3Bayonetheatexchangercalculateddataforproductcondensation
TableD.3aCalculatedDataforphasechange
Value Units
,mix -941.97 kJ/kmol
Heat Duty (Q)
-
938390.02 kJ/h

T1 65.89 K
T2 20.00 K
T
LM
38.49 K

A= 8.69 m
2

TableD.3bCalculatedDataforsensiblecooling
Value Units
Cp,mix 2.47
Delta T -58.21 K
Heat Duty (Q)
-
143280.09 kJ/h

T1 20.00 K
T2 65.89 K
T
LM
-38.49 K

A= 1.33 m
2

89

TableD.4CalculatedDataforliquidringvacuumpump
Value Units
Size 191.116 ft
3
/min
5.412 m
3
/min
324.72 m
3
/h

Shaft Work(ws) 21.733754 kW
Fluid Power 16.300315 kW

90

AppendixE:
EconomicsCalculations

91

Cost Summary

The cost index is 528.2

Heat Exchangers : Shell and Tube : Fixed tube sheet and U-tube
Total purchased cost = $ 3461
Material factor = 1.00
Pressure factor = 1.00
The bare module cost is = $ 11006

Heat Exchangers : Shell and Tube : Bayonet
Total purchased cost = $ 10391
Material factor = 1.00
Pressure factor = 1.00
The bare module cost is = $ 33044

Heat Exchangers : Shell and Tube : Bayonet
Total purchased cost = $ 8733
Material factor = 1.00
Pressure factor = 1.00
The bare module cost is = $ 27772

Gas Movers and Compressors : Blowers and compressors (cost of drive
excluded) : Liquid ring
Total purchased cost = $ 22517
The bare module cost is = $ 49538

Process Vessels (including towers) : Vertically oriented : With adsorbents, ion-
exchange/chromatographic resins, catalysts
Total purchased cost = $ 11878
Material factor = 1.00
Material factor for tower packing = 1.73
The bare module cost of tower packing is = $ 8552
The bare module cost is = $ 59459

Process Vessels (including towers) : Vertically oriented : With adsorbents, ion-
exchange/chromatographic resins, catalysts
Total purchased cost = $ 11878
Material factor = 1.00
Material factor for tower packing = 1.73
The bare module cost of tower packing is = $ 8552
The bare module cost is = $ 59459

*This was determined from econ expert and does not include replacement beds

92

EconomicsofanAzeotropicDistillation
1. Calculationofutilitycostcoefficienta:
o = (2.S 1u
-5
)m
s
0.9

= (2.S 1u
-5
) _4u
kg
s
]
0.9

= 8.S2 1u
-7
units?

2. Calculationofutilitycostcoefficientb:
b = (S.4 1u
-3
)P
0.05

= (S.4 1u
-3
)(2.Sboro)
0.05

= S.S6 1u
-3
units.

3. Calculationofutilityprice:
u
P
= (o)(PCI) +(b)(C
s]
)
= (8.S2 1u
-7
)(S28.2) +(S.S6 1u
-3
) _4.7S
$
0[
_
= u.u17SS
$
kg o stcom

4. Calculationoftheoperatingtimeperyear:
0pcroting timc = _
SSu opcroting Joys
yr
] _
24b
Joy
] _
S6uus
b
]
93

= S.u2 1u
7
s
yr

5. Calculationoftheannualcost:

A
c
= (u
p
)(0pcroting timc)(m
s]
)
= _u.u17SS
$
kg
_(S.u2 1u
7
) _12.6
kg
s
]
= 6,61u,uuu
$
yr

94

AppendixF:
PipingandInstrumentationDiagram
95

FigureF.1(1)TemperaturecontrolstocontrolHX#2;(2)Pressurecontrolsforleakdetectionandtoensurefeedisatahighenoughpressureto
preventcondensationinsidethecolumn;(3)Pressurecontrolsforleakdetectionandtocontrolvacuumpump;(4)Concentrationtransmittersto
regulatetheuseofthepurgestream;(5)Flowratecontrolstocontrolthesplitters5and6;(6)Concentrationtransmitterstoensureproductquality;
(7)Flowratecontrolstocontroloutputrate;(8)TemperaturecontrolstoregulatetheamountofcoolingwatertoHX#3.
96

AppendixG:
MaterialSafetyDataSheets
97

98

99

100

101

102

103

104

105

106

107

108

109

110

111

AppendixG:
MaterialSafetyDataSheets
T

Halo Consult ing
Met hod: HAZOP
Team Member s: Ma
No.: 2 Tow
Dr awi ng: PI D
I t em Devi a
2.1 High
t empera


2.2 Low
t empera
2.3 High pre

2.4 Low pres
Pl
Type: Column
ark Baier, Jamie Hilt z,
wer (D-120)
at i on
t ure
HX # 1 not
HX # 2 not


t ure
HX # 1 not
HX # 2 not
essure High t emp
# 1
High t emp
# 2
High flow f
Block in pr
column

ssure Low t empe
# 1
Low t empe
# 2
ant :
n
, Zack Taylor
Causes
t working properly
t working properly
t working properly
t working properly
perat ure from HX
perat ure from HX
from supply
rocess aft er
erat ure from HX
erat ure from HX
Si t e
Consequence
I ncreased pressure in
column
High enough(500C) d
t o sieve
Aut o-combust ion of e
= 363C
Possibilit y of condens
in column
Damage t o molecula
Possibilit y of condens
in column
Reduced product

112
e:
Desi gn I nt ent : Pa
es Cat
n
damage 4
et hanol 4
sat ion
r sieve
sat ion

Uni t :
acked bed of aluminos
S L R
1 3 3 Te
# 2
Hig
(at
4 1 4
4 1 4
2 1 2 Te
# 2
Lo
co
1 2 2 Pre
(V-
Pre
co
Flo
5)
Hig
st r
2 1 2
1 1 1 Pre
(V-
Pre
co
Tower # 1
silicat e t o be used t o
Saf eguar ds
emperat ure cont rol on
2
gh t emp alarm on col
t 200C)
emperat ure cont rol on
2
w t emp alarm on t he
lumn (100C)
essure cont rol on valv
-2)
essure relief valve on
lumn
ow cont rol on split t er
gh pressure alarm on
ream ent ering column
essure cont rol on valv
-2)
essure relief valve on
lumn
Syst em
dehydrat e Et hanol
n HX
umn
Rec 2. Consid
cont rol on HX


n HX

Rec 2. Consid
cont rol on HX
ve

(S-

n


ve


m: Dehydr at i on of E
Act i on I t ems
der put t ing t emperat u
X # 1
der put t ing t emperat u
X # 1
t hanol
ure
ure

No.: 2 Tow
Dr awi ng: PI D
I t em Devi a
2.5 Loss of
cont ainm
(leak)



FigureH.1Summ
wer (D-120)
at i on
ment
Rundown o
Corrosion
Wear on se
t ower



maryofHAZOPan
Causes
of equipment
eal/ connect ions t o
nalysis
Consequence
Leakage of et hanol in
at mosphere
Lower product
Pot ent ial explosion
Decreased pressure
column; possible
condensat ion

113
es Cat
nt o

4
on
S L R
Lo
st r
Flo
5)
2 2 4 Le
(LE
1 2 4
4 2 8
1 2 2 Lo
st r
co
Saf eguar ds
w pressure alarms on
reams ent ering colum
ow cont rol on split t er
ak det ect ion monit ors
ELs et c)
w pressure alarms on
reams ent ering t he
lumn
n
mn
(S-
s


n
Act i on I t ems