Fundamentos de Los Balances de Materia

16/11/2015
Fundamentosdelosbalancesdemateria
Pgina1
CAPITULO2
2.1.INTRODUCCIN
Losbalancesdemateriasonlabasedeldiseodelproceso.Unbalancedematerialeshechocargodela
procesocompletodeterminarlascantidadesdemateriasprimasnecesariasyproductos
producido.Lossaldosmsunidadesdeprocesoindividualesestablecenloscaudalesprocesoy
composiciones.
Unabuenacomprensindelosclculosdebalancedematerialesesesencialeneldiseodeprocesos.
Enestecaptulolosfundamentosdelamateriaestncubiertos,utilizandoejemplossencillospara
ilustrarcadatema.Senecesitaprcticaparadesarrollarexperienciaenelmanejodeloquepuedeamenudo
convertidoenclculosmuyinvolucrados.Msejemplosyunadiscusinmsdetalladadela
sujetosepuedeencontrarenlosnumerososlibrosespecializadosescritosenelmaterialyenerga
clculosdebalance.Variostextosadecuadosseenumeranbajoelttulode"Ms
Lectura"alfinaldeestecaptulo.
Laaplicacindelosbalancesdemateriaalosproblemasmscomplejossediscuteen"Flow
lminas",Captulo4.
Losbalancesdemateriatambinsonherramientastilesparaelestudiodelfuncionamientodelaplantaysinproblemas
disparo.Puedenserutilizadosparacomprobarelrendimientocontraeldiseoparaextenderelmenudo
limitadosdatosdisponiblesdelainstrumentacindeplantasparacomprobarcalibracionesdeinstrumentos
ylocalizarfuentesdeprdidadematerial.
2.2.Laequivalenciaentremasayenerga
Einsteindemostrquelamasaylaenergasonequivalentes.Laenergapuedeserconvertidaenmasa,
ylamasaenenerga.EllosestnrelacionadosporlaecuacindeEinstein:
EDmc 2
2.1
dondelaenergaED,J,
masamD,enkg,
8 Sra.
cDlavelocidaddelaluzenelvaco,310
Laprdidademasaasociadaconlaproduccindeenergaessignificativasloennuclear
reacciones.Energaylamateriaseconsideransiemprequeseconservanporseparadoenqumica
reacciones.
2.3.CONSERVACINDELAMASA
Laecuacindeconservacingeneralparacualquiersistemadeprocesosepuedeescribircomo:
MaterialfueraDmaterialenCGeneracinConsumoAcumulacin
34
Pgina2
FUNDAMENTOSDESALDOSDEMATERIALES
35
Paraunprocesodeestadoestableeltrminoacumulacinsercero.Exceptoenlosprocesosnucleares,
masanisegeneraniseconsumeperosiunareaccinqumicatienelugarunparticular,
especiesqumicassepuedenformaroconsumidosenelproceso.Sinohayningnproductoqumico
reaccinelequilibriodeestadoestacionariosereducea
https://translate.googleusercontent.com/translate_f
1/74
16/11/2015
MaterialfueraDMaterialEntrar
Unaecuacindebalancesepuedeescribirparacadaespecieporseparadoidentificablespresentes,elementos,
compuestosoradicalesyparaeltotaldelmaterial.
Ejemplo2.1
2000kgdeunasuspensinal5porcientodehidrxidodecalcioenelaguaesestarpreparadodiluyendo
unasuspensinde20porciento.Calcularlascantidadesrequeridas.Losporcentajessonenpeso.
Solucin
Quelascantidadesdesconocidasdelasuspensinde20%yelaguaseanXeY,respectivamente.
BalancedemateriaenelCa(OH)
2
En
Fuera
20
5
X
D2000D
100
100
Equilibrioenelagua
X10020 CYD2000 1005
100
100
ApartirdelaecuacinaXD500kg.
SustituyendoenbecuacindaYD1500kg
Compruebebalancedematerialesenlacantidadtotal:
XCYD2000
500C1500D2000,correcta
2.4.Unidadesutilizadasparaexpresarcomposiciones
Alespecificarunacomposicinenformadeporcentaje,esimportanteestablecerclaramentelabase:
peso,ovolumenmolar.
Lasabreviaturasw/wyv/vseutilizanparadesignarlabasedelpesoylabasedevolumen.
Ejemplo2.2
cidoclorhdricodegradotcnicotieneunaresistenciade28porcientow/w,expresarestocomouna
fraccinmol.
Pgina3
36
INGENIERAQUMICA
Solucin
Basedeclculo100kgde28porcientow/wdecido.
Masamolecular:agua18,HCl36,5
MisaHClD100D0.28D28kg
AguaMisaD100D0.72D72kg
28
kmolHClD
D0.77
36.5
72
kmolaguaD
D4.00
18
Molestotales
D4.77
0.77
fraccinmolHClD
D0.16
4.77
4.00
aguafraccinmolD
D0.84
4.77
Comprobartotales
1.00
Dentrodelaprecisinnecesariaparalosclculostcnicos,fraccionesdevolumensepuedentomar
comoequivalenteaMOLfraccionesparagases,hastamoderarlaspresiones(digamos25bar).
Cantidadestrazaamenudoseexpresancomopartespormilln(ppm).Labase,elpesoo
volumen,debeserdeclarado.
2/74
16/11/2015
ppmD cantidaddecomponente
10 6
cantidadtotal
Nota.1ppmD10 4 porciento.
Pequeascantidadesavecessecitanenppb,partespormilmillones.Hayquetenercuidadoaqu,
9),NoelReinoUnidomilesdemillones(10
12).
comoelmilmillonesesporlogeneralunestadounidensemilmillones(10
2.5.ESTEQUIOMETRA
Estequiometra(delgriegostoikeion
elemento)eslaaplicacinprcticadela
laleydelasproporcionesmltiples.Laecuacinestequiomtricaparaunosestadosdereaccinqumica
sinambigedadeselnmerodemolculasdelosreactivosyproductosqueintervienende
lacualsepuedencalcularlascantidades.Laecuacindebeequilibrar.
Consimplesreaccionesporlogeneralesposibleequilibrarlaecuacinestequiomtricapor
inspeccin,oporclculosdepruebayerror.Siseexperimentadificultadenelequilibrio
ecuacionescomplejas,elproblemasiempresepuedenresolverporescritounequilibrioparacada
elementopresente.ElprocedimientoseilustraenelEjemplo2.3.
Ejemplo2.3
Escribeyequilibrarlaecuacingeneralparalafabricacindeclorurodeviniloapartirde
deetileno,cloroyoxgeno.
Pgina4
37
Solucin
Mtodo:escribirlaecuacinutilizandoletrasparaelnmerodesconocidodemolculasde
cadareactivoyproducto.Hacerunbalanceencadaelemento.Resolverelconjuntoresultantede
ecuaciones.
AC2MARIDO
4CBCl
2CCO
2DDC
2MARIDO
3ClCEH
2O
Equilibriosobrecarbn
2AD2D,ADD
enelhidrgeno
4AD3DC2E
sustituyendoDDAdaED
elcloro
eneloxgeno
LA
2
LA
2BDD,porlotanto,BD
2
2CDE,
CD
mi LA
re
2
4
poniendoAD1,laecuacinseconvierte
1
do2MARIDO
4 do 1
2MARIDO
3ClC 12MARIDO
2O
2Cl2 do 4O2 corrientecontinua
multiplicandoatravsporelmayordenominadorparaeliminarlasfracciones
4C2MARIDO
4 C2Cl2 CO 2 D4C2MARIDO
3ClC2H2O
2.6.ELECCINDELAFRONTERADELSISTEMA
Laleydeconservacinsemantieneparaelprocesocompletoycualquiersubdivisindelproceso.
Ellmitedelsistemadefinelapartedelprocesoqueseconsidera.Losflujoshacia
yfueradelsistemasonlosquecruzanlafronteraysedebeequilibrarconelmaterial
generadaoconsumidadentrodelafrontera.
Cualquierprocesopuededividirsedemaneraarbitrariaparafacilitarelbalancedemateriales
clculos.Laeleccinjuiciosadeloslmitesdelsistemaamenudopuedesimplificarenormemente
loqueseraclculosdifcilesytortuosas.
Nohayreglasdurasyrpidassepuedendarenlaseleccindeloslmitesadecuadosparatodoslostipos
delosproblemasdebalancedemateriales.Seleccindelosmejoressubdivisinparacualquierprocesoparticular
esunacuestindecriterio,ydependedelacomprensindelaestructuradelproblema,que
slopuedeseradquiridaporlaprctica.Lassiguientesreglasgeneralesservirndegua:
1.Conprocesoscomplejos,primerotomelafronteraalrededordelprocesocompletoysi
esposiblecalcularlosflujosdeentradaysalida.Lasmateriasprimasenproductosysubproductos
fuera.
2.Seleccioneloslmitessubdividirelprocesoenetapassimplesyhacerunbalance
3/74
16/11/2015
sobrecadaetapaporseparado.
3.Seleccionarellmiteredondacualquieretapaafindereducirelnmerodecorrientesdesconocidas
alosmenosposibles.
Pgina5
38
INGENIERAQUMICA
4.Comoprimerpaso,incluyenalgunacorrientesderecicladodentrodeloslmitesdelsistema(ver
Seccin2.14).
Ejemplo2.4
Seleccindeloslmitesdelsistemaylaorganizacindelasolucin.
Eldiagramamuestralosprincipalespasosenunprocesoparaproducirunpolmero.Desdeel
siguientesdatos,calcularlacorrientefluyeparaunatasadeproduccinde10.000kg/h.
Reactor,rendimientodepolmero100porciento
polimerizacinensuspensin
20porcientodemonmero/agua
conversin
90porciento
catalizadorde1kg/1.000kgmonmero
agentedeparadacorta 0,5kg/1000kgmonmerosinreaccionar
Filtrar,lavaraproxagua.1kg/1kgdepolmero
Columnaderecuperacin,rendimientodel98porciento(porcentajerecuperado)
Secadora,alimentar5porcientodeagua,lasespecificaciones0.5porcientoH
2O
Prdidaspolmeroenfiltroysecadorde1porciento
Breveparada
Monmero
agua
catalizador
Polmero
Filtrar
Secadora
Reactor
Recuperacin
columna
Reciclar
monmero
Efluente
Solucin
Sloloscaudalesnecesariosparailustrarlaeleccindeloslmitesdelsistemayelmtodode
clculosedanenlaSolucin.
Bases:1hora
TomelaprimerafronteradelsistemadelaManeraHabboysecadora.
Entrada
Filtrar
y
secadora
Agua
+Monmero
Producto
10.000kgdepolmero
0,5%deagua
Prdidas
Pgina6
39
Conel1porcientodeprdida,polmeroentrarsubsistema
re
10000
D10.101kg
0.99
Tomeelsiguientelmitealrededordelsistemadereactorlasalimentacionesalreactorpuedenserentonces
4/74
16/11/2015
calculado.
Breveparada
Agua
Monmero
Reciclar
10.101kg
polmero
Reactor
Gato.
En90porcientodeconversin,alimentacindemonmero
re
10101
D11.223kg
0.9
MonmerosinreaccionarD1122310101D1122kg
Cortoparada,en0,5kg/1000kgmonmerosinreaccionar
D11220.5D10 3 D0,6kg
Catalizador,a1kg/kgdemonmero1,000
D11223d110
3 D11kg
DejedealimentacindeaguaalreactorseaF
1,Acontinuacin,para20porcientodemonmero
0.2D
11223
F 1 C11223
F 1 re 11,22310.2 D44,892kg
0.2
Ahoraconsideresubsistemadefiltrodepelonuevo.
Aguaenpolmeroparasecadora,al5porciento(despreciandolaprdidadepolmero)
D101010,05D505kg
Equilibriosobresubsistemadereactorfiltrosecadordaflujosalacolumnaderecuperacin.
agua,44,892C10,10154,448D505kg
demonmero,monmerosinreaccionar,D1122kg
Pgina7
40
INGENIERAQUMICA
Consideremosahoraelsistemaderecuperacin
Monmero
Agua
54,488kg Columna
monmero
1122kg
Efluente
Con98porcientoderecuperacin,reciclajedereactor
D0.981122D1100kg
Composicindelefluente23kgdemonmero,54,488kgdeagua.
Considerereactoralimentacindemonmero
Fresco
alimentacin
Reactor
alimentacin
Reciclar
1100kg
Equilibriocamisetaredondadamonmerofrescorequerido
D11223D110010.123kg
2.7.ELECCINDELABASEDECLCULO
5/74
16/11/2015
2.7.ELECCINDELABASEDECLCULO
Lacorrectaeleccindelabasedeunclculoamenudodeterminarsielclculo
mentoresultasersimpleocompleja.Aligualqueconlaeleccindeloslmitesdelsistema,sin
omnmodoreglasoprocedimientossepuededarparalaseleccindelabaseadecuadaparacualquier
problema.Laseleccindependedeljuicioganadoporlaexperiencia.Algunasreglasdegua
queleayudarenlaeleccinson:
1.Tiempo:elegirlabasedetiempoenelquelosresultadossepresentarnporejemplo
kg/h,toneladas/ao.
2.Paralosprocesosporlotesutilizaunlote.
3.Seleccionecomobaselamasadelflujodelacorrienteparalaquesedamsinformacin.
4.Amenudoesmsfciltrabajarenmoles,enlugardepeso,inclusocuandonohayreaccines
involucrado.
5.Paralosgases,silascomposicionessedanenvolumen,utiliceunabasedevolumen,recordando
quelasfraccionesdevolumensonequivalentesaMOLfraccioneshastamoderarlaspresiones.
2.8.NMERODECOMPONENTESINDEPENDIENTES
Unaecuacindebalancesepuedeescribirparacadacomponenteindependiente.Notodosloscompo
nentesenunbalancedematerialessernindependientes.
Pgina8
41
Sistemasfsicos,ningunareaccin
Sinohayreaccinqumicaelnmerodecomponentesindependientesesigualala
nmerodeespeciesqumicasdistintaspresentes.
Considerelaproduccindeuncidodenitracinmediantelamezclade70porcientontricoy98porciento
cidosulfurico.Elnmerodeespeciesqumicasdistintases3agua,cidosulfrico,ntrico
cido.
MARIDO
2ASIQUE
4/MARIDO
2O
HNO
3/MARIDO
2O
Mezclador
MARIDO
2O
Nitracin
HNO
3
cido
MARIDO
2ASIQUE
4
Lossistemasqumicos,lareaccin
Sielprocesoimplicalareaccinqumicaelnmerodecomponentesindependientes
nosernecesariamenteigualalnmerodeespeciesqumicas,yaquealgunospuedenestarrelacionadospor
laecuacinqumica.Enestasituacinelnmerodecomponentesindependientespuedeser
calculadoporlasiguienterelacin:
NmerodecomponentesindependientesNUMERODdeespeciesqumicas
Nmerodeindependiente
ecuacionesqumicas
2.2
Ejemplo2.5
Sielcidodenitracinsecomponeusandooleumenlugardelcidosulfricoporciento98,hay
serdecuatroespeciesqumicasdistintas:cidosulfrico,trixidodeazufre,cidontrico,agua.
Eltrixidodeazufrereaccionaconelaguaproduciendocidosulfrico,demaneraqueslohay
trescomponentesindependientes
Oleum
MARIDO
2ASIQUE
4/MARIDO
2O/SO
3
HNO
/MARIDO
O
3 2
MARIDO
2O
Nitracin
HNO
3
cido
MARIDO
2ASIQUE
4
EcuacindereaccinSO
3 CH 2O!MARIDO
2ASIQUE
4
Ndeespeciesqumicas
No.dereacciones
4
1
No.deecuacionesindependientes
2.9.LIMITACIONESENflujosycomposicin
Esobvio,perovalelapenaenfatizar,quelasumadelacomponenteindividualfluye
encualquiercorrientenopuedeexcederelflujototaldecorriente.Adems,quelasumadelindividuo
fraccionesmolaresodepesodebeseriguala1.Porlotanto,lacomposicindeunacorrienteescompletamente
6/74
16/11/2015
definidosisedantodasmenosunadelasconcentracionesdeloscomponentes.
Pgina9
42
INGENIERAQUMICA
Losflujosdecomponentesenunacorriente(olascantidadesenunlote)estncompletamentedefinidas
porcualquieradelossiguientes:
1.Especificacindelflujo(ocantidad)decadacomponente.
2.Especificacindelflujototal(ocantidad)ylacomposicin.
3.Especificacindelflujo(ocantidad)deuncomponenteylacomposicin.
Ejemplo2.6
Lacorrientedealimentacinaunreactorcontiene:16porcientodeetileno,oxgeno9porciento,nitrgeno31
porciento,yclorurodehidrgeno.Sielflujodeetilenoes5,000kg/h,calcularelindividuo
flujosdecomponentesyelflujototaldecorriente.Todoslosporcentajessonenpeso.
Solucin
PorcentajeHClD10016C9C31D44
5000
PorcentajedeetilenoD
100D16
total
100
porlotanto,elflujototaldeD5000
D31.250kg/h
16
9
Porlotanto,elflujodeoxgenoD
31250D2813kg/h
100
31
nitrgenoD31.250
D9687kg/h
100
44
clorurodehidrgenoD31.250 D13.750kg/h
100
Reglageneral:larelacindelflujodecualquiercomponenteparaelflujodecualquierotrocomponente
eslamismaquelarelacindelascomposicionesdelosdoscomponentes.
ElflujodecualquiercomponenteenelEjemplo2.6sepodrahabercalculadodirectamentedesde
larelacindelporcentajealadeetileno,yelflujodeetileno.
44
FlujodeclorurodehidrgenoD 5000D13.750kg/h
16
2.10.MTODOGENERALALGEBRAICA
Problemasdebalancedematerialessimplesqueinvolucranslounospocosarroyosyconunpardeincgnitas
porlogeneralpuedeserresueltopormtodosdirectossimples.Larelacinentreeldesconocido
cantidadesylainformacindadaporlogeneralsepuedenverclaramente.Paramscompleja
problemas,yporproblemasconvariospasosdeprocesamiento,unaalgebraicamsformal
enfoquepuedeserutilizado.Elprocedimientoescomplicado,yamenudotediososilosclculos
tienenquehacermanualmente,perodebedarlugaraunasolucinparaigualarelmsintratable
problemas,proporcionandoinformacinsuficienteseconoce.
Pgina10
43
Smbolosalgebraicosseasignanatodoslosflujosycomposicionesdesconocidas.Equilibrar
ecuacionesseescribenalrededordecadasubsistemadeloscomponentesindependientes
(especiesqumicasoelementos).
Problemasdebalancedematerialessonejemplosparticularesdelproblemadediseoengeneral
analizanenelCaptulo1.Lasincgnitassoncomposicionesoflujos,ylarelacin
ecuacionessurgendelaleydeconservacinylaestequiometradelasreacciones.por
cualquierproblemaparatenerunasolucinnicaquedebeserposibleescribirelmismonmerode
ecuacionesindependientes,yaquehayincgnitas.
7/74
16/11/2015
ConsidereelproblemageneraldebalancedematerialesdondehayN s arroyoscada
quecontieneN
docomponentesindependientes.Acontinuacin,elnmerodevariables,N
v,esdadopor:
norte
DN
N
2.3
do s
v
SiNmiecuacionesdebalanceindependientespuedenserescritos,acontinuacin,elnmerodevariables,N
re,
quedebeespecificarseparaunasolucinnica,estdadapor:
norte
N mi
reDNs N do
Considereunproblemasimplemezclado
1
2
3
Mezclador
2.4
SeaF norte
serelflujototalenlacorrienten,yx NuevoMjico
laconcentracindelcomponenteenm
corrienten.Entonceslaecuacindelbalancegeneral,sepuedeescribir
F 1X1,mCF 2X2,mCF 3X3,mDF 4X4,m
2.5
Unaecuacindebalancetambinsepuedeescribirparaeltotaldecadacorriente:
F 1 CF 2 CF 3 DF 4
2.6
peroestopodraobtenersemediantelaadicindelasecuacionesdecomponentesindividuales,yasnose
unaecuacinindependienteadicional.Haymecuacionesindependientes,elnmerode
componentesindependientes.
Considereunaunidaddeseparacin,talcomounacolumnadedestilacin,quedivideunacorrientedeproceso
endoscorrientesdeproducto.Dejequelavelocidaddealimentacinsea10000kg/hcomposicinbenceno60por
ciento,tolueno30porciento,xileno10porciento.
Arriba
producto
Alimentacin
Sistema
lmite
Fondo
producto
Pgina11
44
INGENIERAQUMICA
Haytresarroyos,alimentacin,gastosgeneralesyelfondo,ytresnenteindependiente
nentesencadacorriente.
Nmerodevariables(tasasdeflujodecomponentes)D9
Nmerodebalancedematerialesindependiente
ecuaciones
D3
Nmerodevariablesparaespecificarpara
unasolucinnica
D93D6
Seespecificantresvariableselflujodealimentacinylacomposicinfijaelflujodecada
componenteenlaalimentacin.
NmerodevariablesaserespecificadoporeldiseadorD63D3.Cualquiertrescomponentes
flujospuedenserelegidos.
Normalmente,lacomposicinsuperioryelflujoolacomposicindefondoyflujosera
elegido.
Silafuncinprimariadelacolumnaessepararelbencenodesdeelotrocompo
nentes,seespecificaraeltoluenoyelxilenomximoenlosgastosgeneralesdecir,al
5kg/h,y3kg/h,ylaprdidadebencenoenelfondotambinespecificadosdecir,alno
mayorde5kg/h.Tresflujosseespecifican,porloquelosotrosflujospuedensercalculados.
ElbencenoenbencenogastosgeneralesDenbencenoalimentacinenfondos.
0.6100005D5995kg/h
Toluenoenfondosdtoluenoentoluenoalimentacinenlosgastosgenerales
0.3100005D2.995kg/h
XilenoenfondosxilenoDenxilenoalimentacinenlosgastosgenerales
8/74
16/11/2015
0.1100003D997kg/h
2.11.TIECOMPONENTES
EnlaSeccin2.9sedemostrqueelflujodecualquiercomponenteestabaenlamismaproporcinala
flujodecualquierotrocomponente,comolarelacindelasconcentracionesdelosdoscomponentes.
Siuncomponentepasasincambiosatravsdeunaunidaddeprocesoquepuedeserutilizadoparaatarlaentrada
ylasalidacomposiciones.
Estatcnicaesparticularmentetilenelmanejodelosclculosdecombustindondelas
nitrgenoenelairedecombustinpasaatravssinreaccionaryseutilizacomoelcomponentedelazo.
EstoseilustraenelEjemplo2.8.
Esteprincipiotambinsepuedeutilizarparamedirelflujodeunacorrientedeprocesomediantelaintroduccinde
unflujomedidodealgnmaterialfcilmenteanalizada(compatible).
Ejemplo2.7
Eldixidodecarbonoseaadeaunavelocidadde10kg/hdeunacorrientedeaireyelairesemuestreaauna
suficientedistanciaaguasabajoparaasegurarlamezclacompleta.Sielanlisismuestra0,45por
cientov/vCO
2,Calcularlatasadeflujodeaire.
Pgina12
45
Solucin
Normalcontenidodedixidodecarbonodelaireesde0,03porciento
aire
CO0,03porciento
2
CO210kg/h
aire
CO0,45porciento
2
Base:kmol/h,comoporcentajessonenvolumen.
10
kmol/hdeCO
2 introducidoD44 D0.2273
SeaXelflujodeaire.
SaldoalaCO 2,Elcomponentedelazo
CO2 enD0.00030.2273XC
CO2 salidaD0,0045X
X0.00450.0003D0.2273
XD0,2273/0,0042D54kmol/h
D5429D1.560kg/h
Ejemplo2.8
Enunapruebaenunhornodecombustincongasnatural(composicin95porcientodemetano,un5por
porcientodenitrgeno)seobtuvoelsiguienteanlisisdegasesdecombustin:dixidodecarbono,9,1porciento,
monxidodecarbono0,2porciento,4,6porcientodeoxgeno,nitrgeno86,1porciento,todoslosporcentajes
porvolumen.
Calcularelporcentajedeexcesodeflujodeaire(porcentajeporencimaestequiomtrica).
Solucin
Reaccin:CH4 C2O2 !CO 2 C2H2O
Nota:elanlisisdegasesdecombustinseinformsobrelabaseseca,elaguaformadahabiendosido
condensadaacabo.
Elnitrgenoeselcomponentedelazo.
Base:100mol,gasdecombustinsecocomoseconoceelanlisisdelosgasesdecombustin,losmolesdecada
elementoenelgasdecombustin(fluir)sepuedecalcularfcilmenteyrelacionadoconelflujoenel
sistema.
Dejequelacantidaddecombustible(gasnatural)porcada100molesdegasdecombustinsecaseaX.
Equilibriosobrecarbono,molesenmolesdecombustibleDenlosgasesdecombustin
0,95XD9.1C0.2,porlotanto,XD9,79mol
Equilibrioenelnitrgeno(composicindelaireO
2 21porciento,N
2 79porciento).
SeaYelflujodeairepor100molesdegasdecombustinseco.
norte
2 enelaireCN
2 enelcombustibleDN
2 enlosgasesdecombustin
0.79YC0.059.79D86.1,porlotanto,YD108,4mol
9/74
16/11/2015
Pgina13
46
INGENIERAQUMICA
Estequiomtricaaireapartirdelaecuacindereaccin1moldemetanorequiereoxgeno2mol,
as,relacinaireD9.790.952
100
D88,6mol
21
airsuministraairestequiomtrica
PorcentajedeexcesodeaireD
100
aireestequiomtrico
108,488,6
re
D22porciento
88.6
2.12.Excesodereactivo
Enlasreaccionesdeloscomponentesindustrialesraravezsonalimentadosalreactorenestequiomtricaexacta
dimensiones.Unreactivopuedesersuministradoenexcesoparapromoverlareaccindeseadaa
maximizarelusodeunreactivocarooparaasegurarlareaccincompletadeunreactivo,
comoenlacombustin.
Elreactivoenexcesoporcentajesedefineporlasiguienteecuacin:
cantidadestequiomtricasuministrado
CientoexcesoDPer
100
cantidadestequiomtrica
2.7
Esnecesarioindicarclaramentealosqueelexcesodereactivoserefiere.Estoamenudosedenomina
reactivolimitante.
Ejemplo2.9
Paraasegurarlacombustincompleta,20porcientodeexcesodeairesesuministraaunIncinerador
gasnatural.Lacomposicindelgas(envolumen)eselmetano95porciento,etano5porciento.
Calculalosmolesdeairerequeridopormoldecombustible.
Solucin
Base:100moldegas,yaqueelanlisiseselporcentajedevolumen.
Reacciones:CH
4 C2O2 !CO 2 C2H2O
1
do2MARIDO
6 C3 2O2 !2CO 2 C3H2O
1
MolesestequiomtricosS
2 requeridoD952C5D32 D207.5
120
Con20porcientodeexcesopor,molesdeO
2 requeridoD207,5100 D249
100
AireMols(21porcientodeO
2)D249D 21 D1185.7
1185.7
AirepormoldecombustibleD
D11,86mol
100
Pgina14
47
2.13.CONVERSINYRENDIMIENTO
Esimportantedistinguirentrelaconversinyelrendimiento(vaseelVolumen3,Captulo1).
Laconversinesqueverconreactivos(reactivos)darconlosproductos.
Conversin
Laconversinesunamedidadelafraccindelreactivoquereacciona.
Paraoptimizareldiseodelreactoryparaminimizarlaformacindesubproductos,laconversindeuna
reactivoparticularesamenudomenosde100porciento.Siseutilizamsdeunreactivo,la
10/74
16/11/2015
reactivosobreelquesebasalaconversindebeserespecificado.
Laconversinsedefineporlasiguienteexpresin:
cantidaddereactivoconsumido
cantidadsuministrada
(cantidaddecorrientedealimentacin)(cantidaddecorrientedeproducto)
re
2.8
(cantidaddecorrientedealimentacin)
ConversinD
Estadefinicindalaconversintotaldelreactivoparticular,atodoslosproductos.
Aveceslascifrasdadasparalaconversinserefierenaunproductoespecfico,porlogeneraleldeseado
producto.Enestecasoelproductodebeserespecificado,ascomoelreactivo.Estees
realmenteunaformadeexpresarelrendimiento.
Ejemplo2.10
Enlafabricacindeclorurodevinilo(VC)porlapirlisisdedicloroetano(DCE),la
conversinreactorselimitaa55porcientoparareducirlaformacindecarbono,queensuciala
tubosdelreactor.
CalcularlacantidaddeDCEnecesariaparaproducir5.000kg/hVC.
Solucin
Base:5000kg/hVC(lacantidadnecesaria).
Reaccin:C2MARIDO
4Cl2 !do 2MARIDO
3HClCl+
pesosmolDCE99,VC62.5
5000
kmol/hVCproducidoD
D80
62.5
Delaecuacinestequiomtrica,1kmolDCEproduce1kmolVC.SeaXalimentacinDCE
kmol/h:
80
CientodeconversinD55DPer
100
X
80
XD
D145,5kmol/h
0.55
Pgina15
48
INGENIERAQUMICA
Enesteejemplo,lapequeaprdidadeDCEdeproductosdecarbonoyotrossehadescuidado.
TodoelDCEreaccionsehasupuestoqueserconvertidoaVC.
rendimiento
Elrendimientoesunamedidadelrendimientodeunreactorodelaplanta.Variasdefinicionesdiferentes
derendimientosonutilizados,yesimportanteestablecerclaramentelabasedelascifrasderendimiento.Esta
amenudonoserealizacuandolascifrasderendimientosoncitadosenlaliteratura,yeljuiciotiene
queseutilizarparadecidirloquesepretenda.
Paraunreactorelrendimiento(esdecir,elrendimientorelativo,Volumen3,Captulo1)sedefinepor:
molesdeproductoprodujeronfactorestequiomtrico
RendimientoD
2.9
molesdereactivoconvertidos
FactorestequiomtricoDestequiomtricasmolesdereactivosrequeridospormol
deproductoproducido
Conreactoresindustriales,esnecesariodistinguirentre"rendimientoReaccin"(qumico
derendimiento),queincluyeslolasprdidasqumicasalosproductossecundariosyReactorlageneral"
rendimiento",queincluirlasprdidasfsicas.
Silaconversinesdecasiel100porcientopuedenovalerlapenalaseparacinyelreciclaje
elmaterialquenohareaccionadoelrendimientoglobalreactorincluiraentonceslaprdidadequenohareaccionado
material.Sielmaterialquenohareaccionadoseseparayserecicla,elrendimientoglobaltomada
elpasodelreactorylaseparacinincluiralasprdidasfsicasdelaseparacin
paso.
Rendimientodelaplantaesunamedidadelrendimientoglobaldelaplantaeincluyetodoslosproductosqumicos
ylasprdidasfsicas.
Elrendimientodelaplanta(queseaplicaalaplantacompletaocualquieretapa)
re
molesdeproductoproducidofactorestequiomtrico
reactivomolesalimentaalprocesode
2.10
Cuandoseutilizamsdeunreactivo,oseproduceproducto,esesencialqueelproducto
11/74
16/11/2015
yelreactivoalaquelacifraderendimientoserefiereseafirmaclaramente.
Ejemplo2.11
Enlaproduccindeetanolporlahidrlisisdeetileno,terdietlicoseproducecomouna
subproducto.Unacomposicintpicacorrientedealimentacines:55porcientodeetileno,el5porcientodeinertes,
40porcientodeaguaycorrientedeproducto:52.26etilenoporciento,5,49porcientodeetanol,0,16
porterciento,36,81porcientodeagua,5,28porcientodelosinertes.Calcularelrendimientodeetanol
yterbasadoenetileno.
Solucin
Reacciones: do2MARIDO
4 CH 2O!do 2MARIDO
5OH
2C2MARIDO
5OH!C 2MARIDO
52OCH 2O
a
b
Base:100molesalimentan(clculomsfcilqueutilizarlacorrientedeproducto)
Pgina16
do2MARIDO
455%
Inertes5%
49
do2MARIDO
452,26%
do2MARIDO
5OH5.49%
(DO
2MARIDO
5)2O0,16%
MARIDO
2O36,81%
Inertes5,28%
Reactor
MARIDO
2O40%
Nota:elflujodeinertesserconstante,yaquenoreaccionan,ypuedeserusadopara
calcularlosotrosflujosdelascomposiciones.
Corrientedealimentacin
etileno
inertes
agua
55mol
5mol
40mol
Corrientedeproducto
52.26
5D49,49mol
5.28
5.49
etanolD
5D5,20mol
5.28
0.16
terD
5D0,15mol
5.28
CantidaddeetilenoreaccionD55.049.49D5,51mol
5.21
ElrendimientodeetanolabasedeetilenoD 100D94,4porciento
5.51
etilenoD
Como1moldeetanolesproducidopormoldeetilenoeselfactorestequiomtrico1.
0.152
RendimientodeterabasedeetilenoD
100D5,44porciento
5.51
Elfactorestequiomtricoes2,como2molesdeetilenoproducir1moldeter.
Nota:laconversindeetileno,atodoslosproductos,vienedadapor:
ConversinD
molesmolesalimentadosfuera
5549.49
re
100
molesalimentado
55
D10porciento
Elrendimientobasadoenelaguatambinpodracalcularseperonopresentaningnintersrealcomoelagua
esrelativamentebaratoencomparacinconetileno.Elaguaesclaramentealimentaalreactoren
considerableexceso.
Ejemplo2.12
Enlacloracindeetilenoparaproducirdicloroetano(DCE),laconversinde
etilenosereportacomo99,0porciento.Siseproducen94moldeDCEpor100molde
etilenoalimentado,calcularelrendimientoglobalyelreactor(reaccin)rendimientobasadoenetileno.
Eletilenosinreaccionarnoserecupera.
12/74
16/11/2015
Pgina17
50
INGENIERAQUMICA
Solucin
Factorestequiomtrico1.
Reaccin:C2MARIDO
4 CCl2 !do 2MARIDO
4Cl2
molesDCEprodujo1
Rendimientoglobal(incluidaslasprdidasfsicas)D
100
molesdeetilenoalimentado
re
94
100D94porciento
100
molesDCEprodujo
Rendimientoqumico(rendimientodelareaccin)D
100
molesdeetilenoconvertido
94
re
100D94,5porciento
99
Eldirectorsubproductodeesteprocesoestricloroetano.
2.14.PROCESOSDERECICLAR
Procesosenlosquesedevuelveunacorrientedeflujo(reciclado)aunaetapaanteriorenlatramitacin
secuenciaseutilizanconfrecuencia.Silaconversindeunreactivovaliosoenunprocesodereaccin
essensiblementeinferioral100porciento,elmaterialquenohareaccionadosesueleseparary
reciclado.Elretornodereflujoalapartesuperiordeunacolumnadedestilacinesunejemplodeuna
procedimientoderecicladoenelquenohayreaccin.
Enlosclculosdebalancedemasadelapresenciadecorrientesderecirculacinhacelosclculos
msdifcil.
Sinreciclaje,losbalancesdemateriaenunaseriedeetapasdeprocesamientosepuedenllevar
secuencialmente,teniendocadaunidadasuvezlosflujoscalculadosapartirdeunaunidadsevuelven
lasalimentacionesalasiguiente.Siunacorrientederecicloestpresente,entoncesenelpuntodondeelreciclo
sedevuelveelflujonosesabryaquedependerdelosflujosdeaguasabajoanno
calculado.Sinconocerelflujodereciclaje,lasecuenciadeclculosnopuedeser
continuadohastaelpuntoenqueelflujodereciclajesepuededeterminar.
Sonposiblesdosenfoquesparalasolucindelosproblemasdereciclaje:
1.Elcorteytratardemtodo.Loscaudalesdereciclajepuedenserestimadosyelclculo
cionescontinuaronhastaelpuntodondesecalculaelreciclaje.Losflujosestimados
acontinuacin,secomparanconloscalculadayunamejorestimacinrealizada.Elprocedimiento
secontinahastaqueladiferenciaentreelestimadoylosflujoscalculadoses
dentrodelmitesaceptables.
2.Laformal,algebraica,mtodo.Lapresenciadereciclajeimplicaquealgunasdelas
ecuacionesdebalancedemasatendrnqueserresueltossimultneamente.Lasecuacionesson
establecerconlosflujosdereciclajecomoincgnitasyresolvermediantemtodosestndarpara
lasolucindeecuacionessimultneas.
Conproblemassimples,conslounoodoslazosderecirculacin,elclculopuedeseramenudo
simplificadoporlacuidadosaseleccindelabasedeclculoyloslmitesdelsistema.
EstoseilustraenlosEjemplos2.4y2.13.
Pgina18
51
Lasolucindelosproblemasdebalancedematerialesmscomplejaqueinvolucravariosdereciclaje
lazossediscuteenelCaptulo4.
Ejemplo2.13
Eldiagramadebloquesmuestralosprincipalespasosenelprocesoequilibradoparalaproduccinde
clorurodeviniloapartirdeetileno.Cadabloquerepresentaunreactoryvariosotrosprocesos
unidades.Lasprincipalesreaccionesson:
BloqueA,lacloracin
do2MARIDO
4 CCl2 !do 2MARIDO
4Cl2,rendimientodeetileno98porciento
13/74
16/11/2015
BloqueB,oxyhydrochlorination
1
do2MARIDO
4 C2HClC 2O2 !do 2MARIDO
4Cl2 CH 2O,losrendimientos:enetilenodel95porciento,
enHCl90porciento
BloqueC,pirlisis
do2MARIDO
4Cl2 !do 2MARIDO
3ClCHCl,seobtiene:elDCE99porciento,enHCl99,5porciento
ElHCldelaetapadepirlisissereciclaalaetapaoxyhydrochlorination.Elflujo
deetilenoalosreactoresdecloracinyoxyhydrochlorinationseajustademaneraquela
produccindeHClestenequilibrioconelrequisito.Laconversinenlapirlisis
reactorselimitaa55porciento,yeldicloroetanosinreaccionar(DCE)separayse
reciclado.
Cl2
LA
Cloracin
ReciclarDCE
do
Lapirlisis
Etileno
Oxgeno
VC
segundo
Oxyhydro
cloracin
ReciclarHCL
Utilizandolascifrasderendimientodado,ydejardeladocualquierotraprdida,calcularelflujode
deetilenoacadareactoryelflujodeDCEalreactordepirlisis,paraunaproduccin
tasade12.500kg/hdeclorurodevinilo(VC).
Solucin
Lospesosmolecularesdeclorurodevinilo:62.5,99.0DCE,HCl36,5.
12500
VCporhoraD
D200kmol/h
62.5
Dibujaunafronteradelsistemaalrededordecadabloque,queencierraelreciclajedentrodelDCE
lmitedelaetapaC.
Pgina19
52
INGENIERAQUMICA
DejequeelflujodeetilenoabloquearunserXyparabloquearBseaY,yelreciclajeHClserZ.
EntonceslosmolestotalesdeDCEproducenD0.98XC0.95Y,teniendoencuentalosrendimientos,y
losmolesdeHClproducidosenelbloqueC
D0.98XC0.95Y0.995DZ
TengaencuentalosflujoshaciayproductodebloqueB
do
2MARIDO
4
Bloquear
O2
segundo
DCE
(Z)HCL
ElrendimientodeDCEbasadoenHClesdel90porciento,porloquelosmolesdeDCEprodujo
0.90Z
2
Nota:elfactorestequiomtricoes2(2molpormolHClDCE).
ElrendimientodeDCEabasedeetilenoesdel95porciento,porloque
0.9Z
D0.95Y
2
0.952Y
ZD
0.9
SustituyendoZenlaecuacin(a)da
re
0.9
YD0.98XC0.95Y0.99520.95
YD0.837X
TotalVCproducidoD0.99totaldeDCE,porlo
0.990.98XC0.95YD200kmol/h
14/74
16/11/2015
SustituyendoparaYdelaecuacin(b)daXD113,8kmol/h
y
YD0.837113.8D95.3kmol/h
HCldereciclajedelaecuacin(a)
ZD0.98113.8C0.9595.30.995D201,1kmol/h
200
Nota:rendimientoglobaldeetilenoD
100D96porciento
113.8C95.3
2.15.PURGA
Porlogeneralesnecesariopurgarunaporcindeunacorrientederecicloparaevitarquelaacumulacinde
materialnodeseado.Porejemplo,siunaalimentacindelreactorcontienecomponentesinertesquenoson
Pgina20
53
separadodelacorrientederecicladoenlasunidadesdeseparacindeestosmaterialesinertesseacumularaen
lacorrientedereciclajehastaquelacorrientefinalmenteconsistienteramentedeinertes.Unaparte
delacorrientetendraqueserpurgadaparamantenerelnivelinertedentrodelmitesaceptables.LA
normalmenteseutilizapurgacontinua.Encondicionesdeestadoestable:
PrdidadeinerteenlapurgaDvelocidaddealimentacindeinertesenelsistemade
Laconcentracindecualquiercomponenteenlacorrientedepurgaserelmismoqueelde
lacorrientederecicloenelpuntodondesetomafueradelapurga.Asquelavelocidaddepurgarequerida
puedeserdeterminadoporlasiguienterelacin:
[RSScorrientedeflujodetasa]D[concentracininerteflujoRSS]D
[Purgacorrientedeflujodetasa]D[especificado(deseada)reciclarconcentracininerte]
Ejemplo2.14
Enlaproduccindeamoniacoapartirdehidrgenoynitrgenodelaconversin,yaseasobrelabasede
materiaprima,selimitaal15porciento.Elamonacoproducidosecondensadesdeel
reactor(convertidor)corrientedeproductoyelmaterialquenohareaccionadoreciclado.Silaalimentacincontiene
0.2argnciento(desdeelprocesodeseparacindenitrgeno)por,calcularlatasadepurgarequerido
parasostenerelargnenlacorrientederecirculacinpordebajode5,0porciento.Losporcentajessonenvolumen.
Solucin
Base:100molesdealimentacin(tasadepurgaseexpresacomomolespor100molesdealimentacin,yaqueel
nosedalatasadeproduccin).
Diagramadeproceso
Purga5%deargn
Reciclar
Alimentacin
0,2%
argn
Reactor
Lquido
NUEVAHAMPSHIRE
Condensador3
Volumenporcentajessetomancomoequivalenteamolesporciento.
ArgonsistemaentrandoconalimentacinD100D0.2/100D0,2mol.
Dejequelatasadepurgapor100molesdealimentacinseaF.
Argonsistemaen5/100D0.05FpurgaDFdejando.
Enelestadoestacionario,argndejandoDargnqueentra
0.05FD0.2
0.2
FD
D4
0.05
Purganecesaria:4molespor100molesdealimentacin.
2.16.DERIVACIN
Unacorrientedeflujopuedeserdivididayunapartedesviada(bypass)alrededordealgunasunidades.
Esteprocedimientoamenudoseutilizaparacontrolarlacomposicindelacorrienteolatemperatura.
15/74
16/11/2015
Pgina21
54
INGENIERAQUMICA
Clculosdebalancedematerialesenprocesosconflujosdederivacinsonsimilaresalos
laparticipacindereciclaje,exceptoquelacorrientesealimentahaciaadelanteenlugardehaciaatrs.Estoporlogeneral
hacequelosclculosmsfcilqueconreciclaje.
2.17.CLCULOSINESTABLEESTATALES
Todoslosejemplosdebalancedematerialesanterioreshansidosaldosdeestadoestacionario.Laacumulacin
plazocinsetomcomocero,ylacorrientedecaudalesycomposicionesnovari
contiempo.Sinosecumplenestascondiciones,losclculossonmscomplejos.Estable
clculosestatalessuelensersuficientesparalosclculosdelflujodelafichatcnicaproceso
(Captulo4).Elcomportamientoenestadonoestacionariodeunprocesoesimportantecuandoseconsiderala
procesodearranqueyparada,ylarespuestaaprocesarsorpresas.
Procesosporlotessontambinejemplosdefuncionamientoenestadoestacionarioaunqueeltotaldematerial
requisitossepuedencalcularmediantelaadopcindeunlotecomobaseparaelclculo.
Elprocedimientoparalasolucindelossaldosdeestadoestacionarioesestablecerlossaldosms
unpequeoincrementodetiempo,loquedarunaseriedeecuacionesdiferencialesquedescriben
elproceso.Paraproblemassimplesestasecuacionessepuedenresolveranalticamente.Params
seutilizaranproblemascomplejosmtodosinformticos.
Elenfoquegeneralparalasolucindelosproblemasdeestadoestacionarioseilustraen
Ejemplo2.15.Destilacinporlotesesunejemplomsdeunbalancedemateriaenestadonoestacionario
(vaseelVolumen2,Captulo11).
Elcomportamientodelosprocesosbajocondicionesdeestadonoestacionarioyesuncomplejo
temaespecializadoymsalldelalcancedeestelibro.Puedeserimportanteeneldiseodeprocesos
lahoradeevaluarelcomportamientodeunprocesodesdeelpuntodevistadelaseguridadycontrol.
Elusodebalancesdemateriaenelmodeladodeprocesosdeestadoinestablecomplejoses
discutidoenloslibrosdeMyersySeider(1976)yHenleyyRosen(1969).
Ejemplo2.15
Untanquederetencinseinstalaenunprocesodetratamientodeefluentesacuosaparasuavizarlasfluctuaciones
enlaconcentracinenlacorrienteefluente.Laalimentacindeefluentealtanquenormalmentenocontieneningn
msde100ppmdeacetona.Laconcentracinmximapermisibledeacetonaenel
3y
descargadeefluentessehafijadoen200ppm.Lacapacidaddeltanquedecompensacindetrabajoesde500m
puedeserconsideradoparaserperfectamentemezclado.Elcaudaldelosefluentesesde45.000kg/h.Silaacetona
concentracinenlaalimentacinderepenteselevantaa1.000ppm,debidoaunderrameenlaplantadeproceso,
ysemantieneeneseniveldurantemediahora,loharellmitede200ppmenladescargadeefluentes
superarse?
Solucin
3
Capacidad500m
45.000kg/h
1001000ppm
100(?)Ppm
Pgina22
55
Bases:incrementode ttiempo.
Parailustrarlasolucingeneralaestetipodeproblema,elsaldosecreen
trminosdesmbolosparatodaslascantidadesylosvaloresacontinuacinrealesparaesteejemplosustituido.
Vamos,MaterialdelaDMtanque,
CaudalDF,
ConcentracininicialeneltanqueDC
0,
ConcentracineneltiempotdespusdelaconcentracindelaalimentacinseincrementaDC,
ConcentracinenlaalimentacindelefluenteDC
1,
Cambioenlaconcentracindemsdeincrementodetiempo tD C,
ConcentracinpromedioeneltanqueduranteelincrementodetiempoDC
.
AV
Entonces,comonohaygeneracinenelsistema,elbalancedematerialesgeneral(Seccin2.3)
16/74
16/11/2015
seconvierteen:
InputOutputDdeAcumulacin
Balancedemateriaenacetona.
Nota:seconsideracomoeltanquequeestarperfectamentemezcladolaconcentracindesalidaser
lamismaquelaconcentracineneltanque.
AcetonaenacetonaacaboDacetonaacumulaeneltanque
FC 1 tFC
AVtDMCC CMC
C
doAV
DM t
FC1
Tomandoellmite,como t!0
C
corrientecontinua
re
,DOAV
corrientecontinua
t
dt
corrientecontinua
FC1 CDM dt
Integracin
do corrientecontinua
METRO
F
0
do
0 [C1 C]
METRO
do1 do
tD
ln
F
do1 do0
Sustituyendolosvaloresparaelejemplo,ysealquelaconcentracinmximadesalida
seproduciralfinaldelperododemediahoradelaaltaconcentracindeentrada.
t
dtD
tD0,5h
do1 D1000ppm
do0 D100ppm(valornormal)
MD500m 3 D500.000kg
FD45.000kg/h
Pgina23
56
INGENIERAQUMICA
]
500000
1000C
ln
45000
1000100
[
]
1000C
ln
900
[
0,5D
0.045D
mi0,045900D1000C
CD140ppm
Asquelaconcentracinmximaadmisiblenosesuperar.
2.18.PROCEDIMIENTOGENERALPARAMATERIALDEBALANCE
PROBLEMAS
Lamejormaneradeabordarunproblemadependerdelainformacinofrecidalainformacin
serequieredelabalanzaylaslimitacionesquesurgendelanaturalezadelproblema.
NotodosAbrazar,mejormtododesolucinsepuededarparacubrirtodoslosposiblesproblemas.
Elsiguienteprocedimientopasoapasosedacomounaayudaparalasolucineficazdelosmateriales
problemasdeequilibrio.Elmismoenfoquegeneralsepuedeempleartilmenteparaorganizarla
solucindelbalancedeenerga,yotrosproblemasdediseo.
Procedimiento
Paso1.Dibujaundiagramadebloquesdelproceso.
Muestrecadapasosignificativocomounbloque,unidosporlneasyflechasparamostrarla
conexionesdeflujoyladireccindelflujo.
Paso2.Hagaunalistadetodoslosdatosdisponibles.
Mostrareneldiagramadebloquesdelosflujosconocidos(ocantidades)ycorrientenente
siciones.
Paso3.Listatodalainformacinnecesariadelabalanza.
Paso4.Decidirloslmitesdelsistema(verseccin2.6).
Paso5.Escribetodaslasreaccionesqumicasinvolucradasenlosprincipalesproductosysubproductos
productos.
17/74
16/11/2015
Paso6.Anotecualquierotralimitacin,
talescomo:composicionesdelacorrienteespecificados,
azeotropos,
equilibriodefases,
atarsustancias(vaselaSeccin2.11).
Elusoderelacionesdeequilibriodefaseyotraslimitacionesenladeterminacindecorriente
composicionesyflujossediscuteconmsdetalleenelcaptulo4.
Paso7.Notaningncomposicionesdelacorrienteylosflujosquepuedenseraproximadas.
Paso8.Compruebeelnmerodelaconservacin(yotros)ecuacionesquesepuedenescribir,y
Compararconelnmerodeincgnitas.Decidirquvariableshandeserdediseo
lasvariablesvaselaSeccin2.10.
Estepasoseusasloparaproblemascomplejos.
Pgina24
57
Paso9.DecidirlabasedeclculovaselaSeccin2.7.
Elordenenquesetomanlasmedidassepuedevariarparaadaptarsealproblema.
2.19.Referencias(LECTURAADICIONAL)
Textosbsicos
do
,NP(ed.)Manualdeclculosdeingenieraqumica(McGrawHill,1984).
HOPEY
FMAYOR
,RMyR OUSSEAU
,RWElementaryPrinciplesofChemicalProcesses,6thedn(Pearson,1995).
MARIDO
,DMBasicPrinciplesandCalculationsinChemicalEngineering(PrenticeHall,1982).
IMMELBLAU
RUDD
,DF,P Ores ,GJandSIIROLA
,JJProcessSynthesis(PrenticeHall,1973).
WHITWELL
,JCandTONER
,RKConservationofMassandEnergy(McGrawHill,1969).
WILLIAMS
,ETandJACKSON
,RCStoichiometryforChemicalEngineers(McGrawHill,1958).
Advancedtexts
MARIDO
,EJandROSEN
,EM(1969)MaterialandEnergyBalanceComputations(Wiley).
ENLEY
METRO
,ALandS EIDER
,WD(1976)IntroductiontoChemicalEngineeringandComputerCalculations
YERS
(PrenticeHall).
2.20.NOMENCLATURA
Dimensiones
inMLT
do Concentrationaftertimet,Example2.15
doAV Averageconcentration,Example2.15
do0 Initialconcentration,Example2.15
do1 Concentrationinfeedtotank,Example2.15
C Incrementalchangeinconcentration,Example2.15
F
Flowrate
FnorteTotalflowinstreamn
F1 Waterfeedtoreactor,Example2.4
METRO
Quantityinholdtank,Example2.15
norte
do Numberofindependentcomponents
norte
re Numberofvariablestobespecified
norte
mi Numberofindependentbalanceequations
norte
s Numberofstreams
norte
v Numberofvariables
t
Time,Example2.15
t Incrementalchangeintime,Example2.15
X
Unknownflow,Examples2.8,2.10,2.13
Xn,m Concentrationofcomponentminstreamn
Y
Unknownflow,Examples2.8,2.13
Z
Unknownflow,Example2.13
1
MONTE
1
MONTE
1
MONTE
METRO
T
T
1
MONTE
1
MONTE
1
MONTE
2.21.PROBLEMAS
2.1.Thecompositionofagasderivedbythegasificationofcoalis,volumepercentage:
carbondioxide4,carbonmonoxide16,hydrogen50,methane15,ethane3,
benzene2,balancenitrogen.Ifthegasisburntinafurnacewith20percent
excessair,calculate:
(a)theamountofairrequiredper100kmolofgas,
(b)Theamountoffluegasproducedper100kmolofgas,
18/74
16/11/2015
Pgina25
58
INGENIERAQUMICA
(c)thecompositionofthefluegases,onadrybasis.
Assumecompletecombustion.
2.2.Ammoniaisremovedfromastreamofairbyabsorptioninwaterinapacked
columna.Theairenteringthecolumnisat760mmHgpressureand20 C.El
aircontains5.0percentv/vammonia.Onlyammoniaisabsorbedinthecolumn.
Iftheflowrateoftheammoniaairmixturetothecolumnis200m 3/syla
streamleavingthecolumncontains0.05percentv/vammonia,calculate:
(a)Theflowrateofgasleavingthecolumn.
(b)Themassofammoniaabsorbed.
(c)Theflowrateofwatertothecolumn,iftheexitwatercontains1%w/w
amonaco.
2.3.Theoffgasesfromagasolinestabiliserarefedtoareformingplanttoproduce
hydrogen.
Thecompositionoftheoffgas,molarpercent,is:CH
4 77.5,C2MARIDO
6 9.5,C3MARIDO
8 8.5,
do4MARIDO
4.5.
10
Thegasesenteringthereformerareatapressureof2baraand35Candthefeed
rateis2000m3/h.
Thereactionsinthereformerare:
1.C2MARIDO
C1H2
2nC2CnH2O!nCOC2
norte
2.COCH 2O!CO 2 CH 2
ThemolarconversionofC 2MARIDO
2nC2inreaction(1)is96percentandofCOin
reaction(2)92percent.
Calculate:
(a)theaveragemolecularmassoftheoffgas,
(b)themassofgasfedtothereformer,kg/h,
(c)themassofhydrogenproduced,kg/h.
2.4.Allylalcoholcanbeproducedbythehydrolysisofallylchloride.Juntoscon
themainproduct,allylalcohol,diallyetherisproducedasabyproduct.los
conversionofallylchlorideistypically97percentandtheyieldtoalcohol90
percent,bothonamolarbasis.Assumingthattherearenoothersignificantside
reactions,calculatemassesofalcoholandetherproduced,per1000kgofallyl
chloridefedtothereactor.
2.5.Anilineisproducedbythehydrogenationofnitrobenzene.Asmallamountof
cyclohexylamineisproducedasabyproduct.Thereactionsare:
1.C6MARIDO
5NO2 C3H2 !do 6MARIDO
5NUEVAHAMPSHIRE
2 C2H2O
2.C6MARIDO
5NO2 C6H2 !do 6MARIDO
11NUEVAHAMPSHIRE
2 C2H2O
Nitrobenzeneisfedtothereactorasavapour,withthreetimesthestoichiometric
quantityofhydrogen.Theconversionofthenitrobenzene,toallproducts,is96
percent,andtheyieldtoaniline95percent.
Theunreactedhydrogenisseparatedfromthereactorproductsandrecycledto
thereactor.Apurgeistakenfromtherecyclestreamtomaintaintheinertsinthe
Pgina26
59
recyclestreambelow5percent.Thefreshhydrogenfeedis99.5percentpure,
theremainderbeinginerts.Allpercentagesaremolar.
Forafeedrateof100kmol/hofnitrobenzene,calculate:
(a)thefreshhydrogenfeed,
(b)thepurgeraterequired,
(c)thecompositionofthereactoroutletstream.
2.6.Inthemanufactureofanilinebythehydrogenationofnitrobenzene,theoff
gasesfromthereactorarecooledandtheproductsandunreactednitrobenzene
condensed.Thehydrogenandinerts,containingonlytracesofthecondensed
materials,arerecycled.
Usingthetypicalcompositionofthereactoroffgasgivenbelow,estimatethe
streamcompositionsleavingthecondenser.
Composition,kmol/h:aniline950,cyclohexylamine10,water1920,hydrogen
5640,nitrobenzene40,inerts300.
19/74
16/11/2015
2.7.Inthemanufactureofaniline,thecondensedreactorproductsareseparatedina
decanter.Thedecanterseparatesthefeedintoanorganicphaseandanaqueous
fase.Mostoftheanilineinthefeediscontainedintheorganicphaseandmostof
thewaterintheaqueousphase.Usingthedatagivenbelow,calculatethestream
composiciones.
Datos:
Typicalfeedcomposition,includingimpuritiesandbyproducts,weightpercent:
water23.8,aniline72.2,nitrobenzene3.2,cyclohexylamine0.8.
Densityofaqueouslayer0.995,densityoforganiclayer1.006.Porlotanto,la
organiclayerwillbeatthebottom.
Solubilityofanilineinwater3.2percentw/w,andwaterinaniline5.15percent
w/w.
Partitioncoefficientofnitrobenzenebetweentheaqueousandorganicphases:
doorgnico
/C aguaD300
Solubilityofcyclohexylamineinthewaterphase0.12percentw/wandinthe
organicphase1.0percentw/w.
2.8.Inthemanufactureofanilinefromnitrobenzenethereactorproductsarecondensed
andseparatedintoanaqueousandorganicphasesinadecanter.Theorganic
phaseisfedtoastripingcolumntorecovertheaniline.Anilineandwaterform
anazeotrope,composition0.96molfractionaniline.Forthefeedcomposition
givenbelow,makeamassbalanceroundthecolumnanddeterminethestream
compositionsandflowrates.Takeasthebasisforthebalance100kg/hfeedand
a99.9percentagerecoveryoftheanilineintheoverheadproduct.Assumethat
thenitrobenzeneleaveswiththewaterstreamfromthebaseofthecolumn.
Feedcomposition,weightpercentage:water2.4,aniline73.0,nitrobenzene3.2,
cyclohexylaminetrace.
Note:Problems2.5to2.8canbetakentogetherasanexerciseinthecalculationofapreliminarymaterial
balanceforthemanufactureofanilinebytheprocessdescribedindetailinAppendixF,ProblemF.8.
Pgina27
CHAPTER3
FundamentalsofEnergyBalances
(andEnergyUtilisation)
3.1.INTRODUCCIN
Aswithmass,energycanbeconsideredtobeseparatelyconservedinallbutnuclear
procesos.
Theconservationofenergy,however,differsfromthatofmassinthatenergycanbe
generated(orconsumed)inachemicalprocess.Materialcanchangeform,newmolecular
speciescanbeformedbychemicalreaction,butthetotalmassflowintoaprocessunit
mustbeequaltotheflowoutatthesteadystate.Thesameisnottrueofenergy.los
totalenthalpyoftheoutletstreamswillnotequalthatoftheinletstreamsifenergyis
generatedorconsumedintheprocessessuchasthatduetoheatofreaction.
Energycanexistinseveralforms:heat,mechanicalenergy,electricalenergy,anditis
thetotalenergythatisconserved.
Inprocessdesign,energybalancesaremadetodeterminetheenergyrequirementsof
theprocess:theheating,coolingandpowerrequired.Inplantoperation,anenergybalance
(energyaudit)ontheplantwillshowthepatternofenergyusage,andsuggestareasfor
conservationandsavings.
Inthischapterthefundamentalsofenergybalancesarereviewedbriefly,andexamples
giventoillustratetheuseofenergybalancesinprocessdesign.Themethodsusedfor
energyrecoveryandconservationarealsodiscussed.
Moredetailedaccountsoftheprinciplesandapplicationsofenergybalancesaregiven
inthetextscoveringmaterialandenergybalancecalculationswhicharecitedattheend
ofChapter2.
20/74
16/11/2015
3.2.CONSERVACIONDEENERGIA
Asformaterial(Section2.3),ageneralequationcanbewrittenfortheconservationof
energy:
EnergyoutDEnergyinCgenerationconsumptionaccumulation
Thisisastatementofthefirstlawofthermodynamics.
Anenergybalancecanbewrittenforanyprocessstep.
Chemicalreactionwillevolveenergy(exothermic)orconsumeenergy(endothermic).
Forsteadystateprocessestheaccumulationofbothmassandenergywillbezero.
60
Pgina28
FUNDAMENTALSOFENERGYBALANCES
61
Energycanexistinmanyformsandthis,tosomeextent,makesanenergybalance
morecomplexthanamaterialbalance.
3.3.FORMSOFENERGY(PERUNITMASSOFMATERIAL)
3.3.1.Potentialenergy
Energyduetoposition:
PotentialenergyDgz
3.1
wherezDheightabovesomearbitrarydatum,m,
gDgravitationalacceleration(9.81m/s2).
3.3.2.Kineticenergy
Energyduetomotion:
KineticenergyD
u2
2
3.2
whereuDvelocity,m/s.
3.3.3.Internalenergy
Theenergyassociatedwithmolecularmotion.ThetemperatureTofamaterialisa
measureofitsinternalenergyU:
UDfT
3.3
3.3.4.Trabajo
Workisdonewhenaforceactsthroughadistance:
1
WD
Fdx
0
whereFDforce,N,
xandlDdistance,m.
3.4
Workdoneonasystembyitssurroundingsisconventionallytakenasnegativetrabajo
donebythesystemonthesurroundingsaspositive.
Wheretheworkarisesfromachangeinpressureorvolume:
2
WD
Pdv
3.5
1
wherePDpressure,Pa(N/m 2),
v Dvolumeperunitmass,m3/kg.
Tointegratethisfunctiontherelationshipbetweenpressureandvolumemustbeknown.
Inprocessdesignanestimateoftheworkdoneincompressingorexpandingagasis
Pgina29
21/74
16/11/2015
62
INGENIERAQUMICA
oftenrequired.Aroughestimatecanbemadebyassumingeitherreversibleadiabatic
(isentropic)orisothermalexpansion,dependingonthenatureoftheprocess.
Forisothermalexpansion(expansionatconstanttemperature):
Pv Dconstant
Forreversibleadiabaticexpansion(noheatexchangewiththesurroundings):
Pv Dconstant
whereDratioofthespecificheats,C p/C v.
ThecompressionandexpansionofgasesiscoveredmorefullyinSection3.13.
3.3.5.Calor
Energyistransferredeitherasheatorwork.Asystemdoesnotcontainheat,butthe
transferofheatorworktoasystemchangesitsinternalenergy.
Heattakeninbyasystemfromitssurroundingsisconventionallytakenaspositive
andthatgivenoutasnegative.
3.3.6.Electricalenergy
Electrical,andthemechanicalformsofenergy,areincludedintheworkterminanenergy
balance.Electricalenergywillonlybesignificantinenergybalancesonelectrochemical
procesos.
3.4.THEENERGYBALANCE
ConsiderasteadystateprocessrepresentedbyFigure3.1.Theconservationequationcan
bewrittentoincludethevariousformsofenergy.
W
Q
Salida 2
1 Inlet
z2
z1
Figura3.1.Generalsteadystateprocess
Forunitmassofmaterial:
2
U1 CP 1v1 Cu2
3.6
1/2Cz 1gCQDU 2 CP 2v2 Cu2/2Cz 2gCW
Thesuffixes1and2representtheinletandoutletpointsrespectively.Qistheheat
transferredacrossthesystemboundarypositiveforheatenteringthesystem,negative
Pgina30
63
forheatleavingthesystem.Wistheworkdonebythesystempositiveforworkgoing
fromthesystemtothesurroundings,andnegativeforworkenteringthesystemfromthe
alrededores.
Equation3.6isageneralequationforsteadystatesystemswithflow.
Inchemicalprocesses,thekineticandpotentialenergytermsareusuallysmallcompared
withtheheatandworkterms,andcannormallybeneglected.
Itisconvenient,anduseful,totakethetermsUandP v juntosdefiningtheterm
enthalpy,usualsymbolH,as:
HDUCP v
Enthalpyisafunctionoftemperatureandpressure.Valuesforthemorecommon
substanceshavebeendeterminedexperimentallyandaregiveninthevarioushandbooks
(seeChapter8).
EnthalpycanbecalculatedfromspecificandlatentheatdataseeSection3.5.
Ifthekineticandpotentialenergytermsareneglectedequation3.6simplifiesto:
MARIDO
2 MARIDO
1 DQW
3.7
22/74
16/11/2015
Thissimplifiedequationisusuallysufficientforestimatingtheheatingandcoolingrequire
mentsofthevariousunitoperationsinvolvedinchemicalprocesses.
Astheflowdependenttermshavebeendropped,thesimplifiedequationisapplicable
tobothstatic(nonflow)systemsandflowsystems.Itcanbeusedtoestimatetheenergy
requirementforbatchprocesses.
Formanyprocessestheworktermwillbezero,ornegligiblysmall,andequation3.7
reducestothesimpleheatbalanceequation:
QDH 2
MARIDO
1
3.8
Whereheatisgeneratedinthesystemforexample,inachemicalreactor:
QDQ p CQ s
3.9
Qs Dheatgeneratedinthesystem.Ifheatisevolved(exothermicprocesses)Q
s estomado
aspositive,andifheatisabsorbed(endothermicprocesses)itistakenasnegative.
Qp Dprocessheataddedtothesystemtomaintainrequiredsystemtemperature.
Hence:
Qp DH 2 MARIDO
3.10
1 Qs
MARIDO
1 Denthalpyoftheinletstream,
MARIDO
2 Denthalpyoftheoutletstream.
Ejemplo3.1
Balancewithnochemicalreaction.Estimatethesteamandthecoolingwaterrequiredfor
thedistillationcolumnshowninthefigure.
Steamisavailableat25psig(274kN/m2 abs),drysaturated.
Theriseincoolingwatertemperatureislimitedto30DO.
Columnoperatesat1bar.
Pgina31
64
INGENIERAQUMICA
Piensos(F)
1000kg/h
10%Acetone
90%Water
35C
Destilado(D)
99%Acetone
1%Water
25C
Allcompositions
byweight
refluxratio10
Bottoms(W)
<100ppmacetone
100C
Solucin
Materialbalance
Itisnecessarytomakeamaterialbalancetodeterminethetopandbottomsproduct
caudales.
Balanceonacetone,acetonelossinbottomsneglected.
10000.1DD0.99
Distillate,DD101kg/h
Bottoms,WD1000101D899kg/h
Energybalance
Thekineticandpotentialenergyoftheprocessstreamswillbesmallandcanbeneglected.
Takethefirstsystemboundarytoincludethereboilerandcondenser.
MARIDO
F
Sistema
MARIDO
re
Qdo
Q
23/74
16/11/2015
segundo
MARIDO
W
Inputs:reboilerheatinputQsegundo
CfeedsensibleheatH F.
Outputs:condensercoolingQdoCtopandbottomproductsensibleheatsH reCH W.
Theheatlossesfromthesystemwillbesmallifthecolumnandexchangersareproperly
lagged(typicallylessthan5percent)andwillbeneglected.
Basis25C,1h.
Pgina32
sesentaycinco
Heatcapacitydata,fromVolume1,averagevalues.
Acetone:25 Cto35do 2.2kJ/kgK
Agua:
25Cto100do 4.2kJ/kgK
Heatcapacitiescanbetakenasadditive.
Feed,10percentacetoneD0.12.2C0.94.2D4.00kJ/kgK
Tops,99percentacetone,takenasacetone,2.2kJ/kgK
Bottoms,aswater,4.2kJ/kgK.
Qdomustbedeterminedbytakingabalanceroundthecondenser.
Qdo
MARIDO
V
V
MARIDO
L
L
D=101kg/h
MARIDO
re
V=Vapourflow
L=Refluxflow
H=Enthalpy
Refluxratio(seeChapter11)
L
D10
re
LD10101D1010kg/h
RD
VDLCDD1111kg/h
Fromvapourliquidequilibriumdata:
boilingpointof99percentacetone/waterD56.5do
Atsteadystate:
inputDoutput
MARIDO
V DH reCH L CQ do,
QdoDH V MARIDO
re MARIDO
L
Hence
Assumecompletecondensation.
EnthalpyofvapourHV DlatentCsensibleheat.
Pgina33
66
INGENIERAQUMICA
24/74
16/11/2015
Therearetwowaysofcalculatingthespecificenthalpyofthevapouratitsboiling
punto.
(1)LatentheatofvaporisationatthebasetemperatureCsensibleheattoheatthe
vapourtotheboilingpoint.
(2)LatentheatofvaporisationattheboilingpointCsensibleheattoraiseliquidto
theboilingpoint.
Valuesofthelatentheatofacetoneandwaterasfunctionsoftemperaturearegivenin
Volume1,sothesecondmethodwillbeused.
Latentheatacetoneat56.5C(330K)D620kJ/kg
Waterat56.5C(330K)D2500kJ/kg
Takinglatentheatsasadditive:
MARIDO
VD1111[0.012500C0.99620C56.5252.2]
D786,699kJ/h
Theenthalpyofthetopproductandrefluxarezero,astheyarebothatthebase
latemperatura.Bothareliquid,andtherefluxwillbeatthesametemperatureastheproduct.
Hence
QdoDH V D786,699kJ/h218.5kW
isdeterminedfromabalanceovercompletesystem
Qsegundo
Entrada
Produccin
Qsegundo
CH F DQ doCH reCH W
MARIDO
F D10004.003525D40,000kJ/h
MARIDO
W D8994.210025D283,185kJ/h
(boilingpointofbottomproducttakenas100DO).
hence
Qsegundo
DQ doCH WCH re MARIDO
F
D786,699C283,185C040,000
D1,029,884kJ/h286.1kW
Qsegundo
issuppliedbycondensingsteam.
Latentheatofsteam(Volume1)D2174kJ/kgat274kN/m2
1,029,884
SteamrequiredD
D473.7kg/h
2174
Qdoisremovedbycoolingwaterwithatemperatureriseof30do
QdoDwaterflow304.2
786,699
WaterflowD
D6244kg/h
4.230
Pgina34
67
3.5.CALCULATIONOFSPECIFICENTHALPY
Tabulatedvaluesofenthalpyareavailableonlyforthemorecommonmaterials.enel
absenceofpublisheddatathefollowingexpressionscanbeusedtoestimatethespecific
enthalpy(enthalpyperunitmass).
Forpurematerials,withnophasechange:
T
MARIDO
re
dop dT
3.11
T
Tre
whereHT DspecificenthalpyattemperatureT,
dop Dspecificheatcapacityofthematerial,constantpressure,
TreDthedatumtemperature.
Ifaphasetransitiontakesplacebetweenthespecifiedanddatumtemperatures,the
latentheatofthephasetransitionisaddedtothesensibleheatchangecalculatedby
equation3.11.Thesensibleheatcalculationisthensplitintotwoparts:
Tp
T
dTC
MARIDO
dop
dop dT
3.12
T re
1
Tre
Tp 2
25/74
16/11/2015
whereTp Dphasetransitiontemperature,
dop Dspecificheatcapacityfirstphase,belowTp,
1
dop Dspecificheatcapacitysecondphase,aboveTp.
2
Thespecificheatatconstantpressurewillvarywithtemperatureandtouseequations
3.11and3.12,valuesofC p mustbeavailableasafunctionoftemperature.Forsolids
andgasesC p isusuallyexpressedasanempiricalpowerseriesequation:
dop DaCbTCcT 2 CdT 3
3.13a
o
dop DaCbTCcT 2.1
3.13b
Absolute(K)orrelative(C)temperaturescalesmaybespecifiedwhentherelationship
isintheformgiveninequation3.13a.Forequation3.13babsolutetemperaturesmust
serusado.
Ejemplo3.2
Estimatethespecificenthalpyofethylalcoholat1barand200
temperatureas0DO.
C,takingthedatum
dop liquid0C24.65cal/moldo
100C37.96cal/moldo
dop gastC14.66C3.75810 2t2.09110
Boilingpointofethylalcoholat1barD78.4DO.
LatentheatofvaporisationD9.22kcal/mol.
5t 2 C4.74010 9t 3 cal/mol
Pgina35
68
INGENIERAQUMICA
Solucin
Note:asthedatatakenfromtheliteraturearegivenincal/molthecalculationiscarried
outintheseunitsandtheresultconvertedtoSIunits.
AsnodataaregivenontheexactvariationoftheC p oftheliquidwithtemperature,
useanequationoftheformC p DaCbt,calculatingaandbfromthedatagivenesta
willbeaccurateenoughovertherangeoftemperatureneeded.
37.9624.65
aDvalueofC p a0 C,bD
D0.133
100
78.4
200
3 do
MARIDO
dore
24.65C0.133tdtC9.2210
14.66C3.75810 2t
200
0
78.4
2.09110 5t 2 C4.74010 9t 3dt
78.4
200
re [ 24.65tC0.133t2/2]C9.2210 3 do [ 14.66tC3.75810 2t 2/22.091
0
78.4
10 5t 3/3C4.74010 9t 4/4]
D13.9510 3 cal/mol
D13.9510 3 4.18D58.3110 3 J/mol
SpecificenthalpyD58.31kJ/mol.
Molecularweightofethylalcohol,C2MARIDO
5OHD46
SpecificenthalpyD58.31103/46D1268kJ/kg
3.6.MEANHEATCAPACITIES
Theuseofmeanheatcapacitiesoftenfacilitatesthecalculationofsensibleheatchanges
meanheatcapacityoverthetemperatureranget
1 nene
2 isdefinedbythefollowingequation:
t2
t2
dop re
dop dt
dt
3.14
metrot
t1
1
Meanspecificheatvaluesaretabulatedinvarioushandbooks.Ifthevaluesarefor
unitmass,calculatedfromsomestandardreferencetemperature,t r ,thenthechangein
enthalpybetweentemperaturest1 Yt 2 esdadopor:
HDC pm,tt2 t rC pm,tt1 t r
3.15
2
1
dondeT isthereferencetemperaturefromwhichthevaluesofC secalcularon.
26/74
16/11/2015
IfC pr isexpressedasapolynomialoftheform:C p DaCbtCct

pmetro
2 Cdt3,entoncesel
integratedformofequation3.14willbe:
segundo
do
3
att r C2 t2 t 2
r C3 t
dopmetro
re
tt r
re
t r3C t4
4
t 4r
3.16
wheretisthetemperatureatwhichC pmetro
esrequerido.
Pgina36
Ifthereferencetemperatureistakenat0C,equation3.16reducesto:
2 dt 3
bt Connecticut
dopmetro
DaC
do do
2
3
4
69
3.17
andtheenthalpychangefromt1 nene
2 seconvierteen
HDC pm,tt 2
2
dopm,tt 1
1
3.18
TheuseofmeanheatcapacitiesisillustratedinExample3.3.
Ejemplo3.3
Thegasleavingacombustionchamberhasthefollowingcomposition:CO
2 7.8,CO0.6,
O2 3.4,H2O15.6,N2 72.6,allvolumepercentage.Calculatetheheatremovedifthegas
iscooledfrom800to200DO.
Solucin
Meanheatcapacitiesforthecombustiongasesarereadilyavailableinhandbooksand
textsonheatandmaterialbalances.ThefollowingvaluesaretakenfromKAKobe,
ThermochemistryofPetrochemicals,reprintNo.44,Pet.rbitro.1958convertidasaunidadesSI,
J/molC,referencetemperature0DO.
do
200
800
norte
2
29.24
30.77
O2
29.95
32.52
CO2
40.15
47.94
CO
29.52
31.10
MARIDO
2O
34.12
37.38
Heatextractedfromthegasincoolingfrom800to200C,foreachcomponent:
DM do
800C
Cpm,800
200
pm,200
whereMdoDmolsofthatcomponent.
Basis100molgas(asanalysisisbyvolume),substitutiongives:
CO2
7.847.9480040.15200D236.5110 3
CO
0.631.1080029.52200D 11.39103
O2
3.432.5280029.95200D 68.09103
MARIDO
O
15.637.3880034.12200D360.0510 3
2
norte
72.630.7780029.24200D1362.5610 3
2
D2038.60kJ/100mol
D20.39kJ/mol
Pgina37
70
INGENIERAQUMICA
3.7.THEEFFECTOFPRESSUREONHEATCAPACITY
27/74
16/11/2015
Thedataonheatcapacitiesgiveninthehandbooks,andinAppendixA,are,usuallyfor
theidealgasstate.Equation3.13ashouldbewrittenas:
2
3
do
p DaCbTCcT CdT
3.19
wherethesuperscript referstotheidealgasstate.
Theidealgasvaluescanbeusedfortherealgasesatlowpressures.Athighpressures
theeffectofpressureonthespecificheatmaybeappreciable.
Edmister(1948)publishedageneralisedplotshowingtheisothermalpressurecorrection
forrealgasesasafunctionofthereducedpressureandtemperature.Hischart,converted
2000
1000
800
600
400
200
100
80
60
)
1K 40
1
20
(Jmol
p
do
10
p 8
do
6
4 Tr=0.60
0.70
0.80
0.90
2
0.95
1.0
1.05
1.1
1.2
1.0
1.3
1.4
0.8
15
16
0.6
1.8
2.0
0.4
2.5
3.0
3.25
0.2
3.5
4.0
0.1
0.08
0.06
0.04
0.01 0.02 0.040.060.1
0.2 0.40.60.81.0
2 4
Pr
Tr =Reducedtemperature
Pr =Reducedpressure
1.0
1.05
1.10
1.20
1.30
16
1.8
2.0
2.2
2.5
3.0
4.0
6 810
Figure3.2.Excessheatcapacitychart(reproducedfromSterbaceketal.(1979),withpermission)
Pgina38
71
toSIunits,isshownasFigure3.2.Edmister'schartwasbasedonhydrocarbons,butcan
beusedforothermaterialstogiveanindicationofthelikelyerroriftheidealgasspecific
heatvaluesareusedwithoutcorrections.
ThemethodisillustratedinExample3.4.
Ejemplo3.4
Theidealstateheatcapacityofethyleneisgivenbytheequation:
2
5T2 C17.610 9T3 J/molK
do
p D3.95C15.610 T8.310
Estimatethevalueat10barand300K.
Solucin
Ethylene:criticalpressure 50.5bar
criticaltemperature283K
2 3008.310
do
D3.95C15.610
p
5 300 2 C17.610 9 300 3
D43.76J/molK
P r re
10
D0.20
50.5
28/74
16/11/2015
300
D1.06
283
FromFigure3.2:
Tr re
dop
Asique
do
p '5J/molK
dop D43.76C5D49J/molK
TheerrorinCp iftheidealgasvaluewereuseduncorrectedwouldbeapproximately10
porciento.
3.8.ENTHALPYOFMIXTURES
Forgases,theheatsofmixingareusuallynegligibleandtheheatcapacitiesandenthalpies
canbetakenasadditivewithoutintroducinganysignificanterrorintodesigncalculations
aswasdoneinExample3.3.
dopmixtureDx
dop Cxdo
do
3.20
ladoplaCxsegundo
segundopdoC.
dondexla,Xsegundo
,Xdo
,etc.,arethemolfractionsofthecomponentsa,b,c.
Formixturesofliquidsandforsolutions,theheatofmixing(heatofsolution)maybe
significant,andsomustbeincludedwhencalculatingtheenthalpyofthemixture.
Forbinarymixtures,thespecificenthalpyofthemixtureattemperaturetisgivenby:
MARIDO
DxlaMARIDO
MARIDO
3.21
mixture,t
a,tCxsegundo
b,tC H m,t
whereHa,t yH b,t arethespecificenthalpiesofthecomponentsaandband H m,t
istheheatofmixingwhen1molofsolutionisformed,attemperaturet.
Pgina39
72
INGENIERAQUMICA
Heatsofmixingandheatsofsolutionaredeterminedexperimentallyandareavailable
inthehandbooksforthemorecommonlyusedsolutions.
Ifnovaluesareavailable,judgementmustbeusedtodecideiftheheatofmixingfor
thesystemislikelytobesignificant.
Fororganicsolutionstheheatofmixingisusuallysmallcomparedwiththeotherheat
quantities,andcanusuallybeneglectedwhencarryingoutaheatbalancetodetermine
theprocessheatingorcoolingrequirements.
Theheatsofsolutionoforganicandinorganiccompoundsinwatercanbelarge,
particularlyforthestrongmineralacidsandalkalies.
3.8.1.Integralheatsofsolution
Heatsofsolutionaredependentonconcentration.Theintegralheatofsolutionatany
givenconcentrationisthecumulativeheatreleased,orabsorbed,inpreparingthesolution
frompuresolventandsolute.Theintegralheatofsolutionatinfinitedilutioniscalled
thestandardintegralheatofsolution.
Tablesoftheintegralheatofsolutionoverarangeofconcentration,andplotsofthe
integralheatofsolutionasafunctionofconcentration,aregiveninthehandbooksfor
manyofthematerialsforwhichtheheatofsolutionislikelytobesignificantinprocess
designcalculations.
Theintegralheatofsolutioncanbeusedtocalculatetheheatingorcoolingrequired
inthepreparationofsolutions,asillustratedinExample3.5.
Example3.5
AsolutionofNaOHinwaterispreparedbydilutingaconcentratedsolutioninanagitated,
jacketed,vessel.Thestrengthoftheconcentratedsolutionis50percentw/wand2500kg
of5percentw/wsolutionisrequiredperbatch.Calculatetheheatremovedbythecooling
waterifthesolutionistobedischargedatatemperatureof25C.Thetemperatureofthe
solutionsfedtothevesselcanbetakentobe25DO.
Solucin
IntegralheatofsolutionofNaOHH 2O,at25do
molsH2O/molNaOH
H
solnkJ/molNaOH
2
22.9
4
34.4
5
37.7
10
42.5
29/74
16/11/2015
infinito
Conversionofweightpercenttomol/mol:
42.9
50percentw/wD50/1850/40D2.22molH 2O/molNaOH
5percentw/wD95/185/40D42.2molH 2O/molNaOH
Pgina40
73
Fromaplotoftheintegralheatsofsolutionversusconcentration,
H
soln2.22mol/molD27.0kJ/molNaOH
42.2mol/molD42.9kJ/molNaOH
HeatliberatedinthedilutionpermolNaOH
D42.927.0D15.9kJ
HeatreleasedperbatchDmolNaOHperbatch15.9
re
250010 3 0.05
15.9D49.710 3 kJ
40
Heattransferredtocoolingwater,neglectingheatlosses,
49.7MJperbatch
InExample3.5thetemperatureofthefeedsandfinalsolutionhavebeentakenasthe
C,tosimplifythecalculation.
sameasthestandardtemperaturefortheheatofsolution,25
Heatsofsolutionareanalogoustoheatsofreaction,andexamplesofheatbalanceson
processeswherethetemperaturesaredifferentfromthestandardtemperaturearegiven
inthediscussionofheatsofreaction,Section3.10.
3.9.ENTHALPYCONCENTRATIONDIAGRAMS
Thevariationofenthalpyforbinarymixturesisconvenientlyrepresentedonadiagram.
AnexampleisshowninFigure3.3.Thediagramshowstheenthalpyofmixturesof
ammoniaandwaterversusconcentrationwithpressureandtemperatureasparameters.
Itcoversthephasechangesfromsolidtoliquidtovapour,andtheenthalpyvaluesgiven
includethelatentheatsforthephasetransitions.
Theenthalpyisperkgofthemixture(ammoniaCwater)
Referencestates:enthalpyammoniaat77 CDzero
enthalpywaterat0CDzero
Enthalpyconcentrationdiagramsgreatlyfacilitatethecalculationofenergybalances
involvingconcentrationandphasechangesthisisillustratedinExample3.6.
Example3.6
Calculatethemaximumtemperaturewhenliquidammoniaat40Cisdissolvedinwater
at20Ctoforma10percentsolution.
Solucin
Themaximumtemperaturewilloccuriftherearenoheatlosses(adiabaticprocess).Como
noheatormaterialisremoved,theproblemcanbesolvedgraphicallyintheenthalpy
concentrationdiagram(Figure3.3).Themixingoperationisrepresentedonthediagram
Pgina41
74
INGENIERAQUMICA
700
700
650
650
2800
30/74
16/11/2015
Dewlines(1961)kN/m
600
(588)
(981)
(196)
(392)
(39.2)
(98.1)
(9.81)
(1.96)
550
500
600
2400
550
500
450
450
400
400
350
350
300
300
250
250
2000
1600
1200
200C
200
Enthalpy,kcal/kg
200 180
800
160
Enthalpy,kJ/kg
150
150 140
120
(1961)xN/m
20kg./sq.cm.
40 100
(1373)2
Boilinglines
100 100
400
20
(981)
80
14.0
(588)
do
10.0
80
60
(392)
6.0 0
50
50 40
(196)
4.0 20
60
(98.1)
40
20
2.0
40 Lquido
(49.0)
1.0 60
Agua, 0C
(19.6)
20
0.5 80
0
0deg.DO.
(9.81)
0.2
NUEVAHAMPSHIRE
0C
3lquido
0.1
77C
(1.96)
20
50
50
0.02
40
Freezingline
Ice,
60
NUEVAHAMPSHIRE
3slido
0deg.DO.
77C
400
80
100
100
150
200
0
Slido
Freezingline
Slido
150
800
200
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ammoniaconcentration,weightfraction
Figura3.3.Enthalpyconcentrationdiagramforaqueousammonia.Referencestates:enthalpiesofliquidwater
a0 Candliquidammoniaat77Carezero.(Bosniakovic,TechnischeThermodynamik,T.Steinkopff,
Leipzig,1935)
byjoiningthepointArepresentingpureammoniaat40CwiththepointBrepresenting
purewaterat20C.Thevalueoftheenthalpyofthemixtureliesonaverticallineatthe
requiredconcentration,0.1.Thetemperatureofthemixtureisgivenbytheintersection
ofthisverticallinewiththelineAB.Thismethodisanapplicationoftheleverrulefor
phasediagrams.Foramoredetailedexplanationofthemethodandfurtherexamplessee
Pgina42
75
Himmelbau(1995)oranyofthegeneraltextsonmaterialandenergybalanceslistedatthe
endofChapter2.ThePonchonSavaritgraphicalmethodusedinthedesignofdistillation
columns,describedinVolume2,Chapter11,isafurtherexampleoftheapplicationof
theleverrule,andtheuseofenthalpyconcentrationdiagrams.
80
60
40
segundo
0C 20
Agua
a
Solucin
20C
a40C
40
20
0
20
LA
NUEVAHAMPSHIRE
3
a
40C
0.1%NH
3
3.10.HEATSOFREACTION
31/74
16/11/2015
Ifaprocessinvolveschemicalreaction,heatwillnormallyhavetobeaddedorremoved.
Theamountofheatgivenoutinachemicalreactiondependsontheconditionsunder
whichthereactioniscarriedout.Thestandardheatofreactionistheheatreleasedwhen
thereactioniscarriedoutunderstandardconditions:purecomponents,pressure1atm
(1.01325bar),temperatureusually,butnotnecessarily,25DO.
Valuesforthestandardheatsofreactionsaregivenintheliterature,ormaybecalculated
bythemethodsgiveninSections3.11and3.12.
Whenquotingheatsofreactionthebasisshouldbeclearlystated.Eitherbygivingthe
chemicalequation,forexample:
NOC 1O2 !NO 2
H
r D56.68kJ
2
(Theequationimpliesthatthequantityofreactantsandproductsaremols)
Or,bystatingtowhichquantitythequotedvalueapplies:
H
r D56.68kJpermolNO 2
Thereactionisexothermicandtheenthalpychange H
r isthereforenegative.Elcalor
denotesavalueatstandardconditions
ofreaction H
ispositive.Thesuperscript
r
andthesubscriptrimpliesthatachemicalreactionisinvolved.
Thestateofthereactantsandproducts(gas,liquidorsolid)shouldalsobegiven,if
thereactionconditionsaresuchthattheymayexistinmorethanonestateporejemplo:
MARIDO
O (g)!MARIDO
2(g)C 1
2O(g), H
r D241.6kJ
2 2
1
MARIDO
2(g)C 2O2(g)!MARIDO
2O(l), H r D285.6kJ
Thedifferencebetweenthetwoheatsofreactionisthelatentheatofthewaterformed.
Pgina43
76
INGENIERAQUMICA
Inprocessdesigncalculationsitisusuallymoreconvenienttoexpresstheheatof
reactionintermsofthemolsofproductproduced,fortheconditionsunderwhichthe
reactioniscarriedout,kJ/molproduct.
Standardheatsofreactioncanbeconvertedtootherreactiontemperaturesbymakinga
heatbalanceoverahypotheticalprocess,inwhichthereactantsarebroughttothestandard
temperature,thereactioncarriedout,andtheproductsthenbroughttotherequiredreaction
temperatureasillustratedinFigure3.4.
H r,t D H
r C H pinchar. H react.
Reactants
tC
Reactionat
temperaturat
?H
r,t
3.22
Productos
tC
react
.
?Hpinchar.
Reactants
25C
Reactionat
25C
H
r
Productos
25C
Figura3.4. H
r attemperaturet
dnde
H r,t Dheatofreactionattemperaturet,
H react.Denthalpychangetobringreactantstostandardtemperature,
H pinchar.
Denthalpychangetobringproductstoreactiontemperature,t.
Forpracticalreactors,wherethereactantsandproductsmaywellbeattemperatures
differentfromthereactiontemperature,itisbesttocarryouttheheatbalanceover
theactualreactorusingthestandardtemperature(25 C)asthedatumtemperatureel
standardheatofreactioncanthenbeusedwithoutcorrection.
Itmustbeemphasisedthatitisunnecessarytocorrectaheatofreactiontothereaction
temperatureforuseinareactorheatbalancecalculation.Todosoistocarryouttwoheat
balances,whereaswithasuitablechoiceofdatumonlyoneneedbemade.Forapractical
reactor,theheatadded(orremoved)Qp tomaintainthedesignreactortemperaturewill
begivenby(fromequation3.10):
Qp DH productosMARIDO
reactivosQr
3.23
whereH productos
isthetotalenthalpyoftheproductstreams,includingunreacted
materialsandbyproducts,evaluatedfromadatumtemperatureof25DO
32/74
16/11/2015
MARIDO
reactivos
isthetotalenthalpyofthefeedstreams,includingexcessreagentand
DO
inerts,evaluatedfromadatumof25
Pgina44
77
Qr isthetotalheatgeneratedbythereactionstakingplace,evaluatedfromthe
C(298K).
standardheatsofreactionat25
Qr re
H
(molofproductformed)
3.24
r
where H
r isthestandardheatofreactionpermoloftheparticularproduct.
Note:Anegativesignisnecessaryinequation3.24asQ r ispositivewhenheatis
evolvedbythereaction,whereasthestandardenthalpychangewillbenegativefor
reaccionesexotrmicas.Q
p willbenegativewhencoolingisrequired(seeSection3.4).
3.10.1.Effectofpressureonheatsofreaction
Equation3.22canbewritteninamoregeneralform:
)
(
) ]
[(
P H pinchar.
H react.
H r,P,TD H
do
dP
r
P
P
1
T
T
[(
)
(
)
]
T
Hpinchar.
H react.
do
dT
T
T
298
P
P
3.25
Iftheeffectofpressureislikelytobesignificant,thechangeinenthalpyoftheproducts
andreactants,fromthestandardconditions,canbeevaluatedtoincludeboththeeffects
oftemperatureandpressure(forexample,byusingtabulatedvaluesofenthalpy)andthe
correctionmadeinasimilarwaytothatfortemperatureonly.
Example3.7
Illustratesthemanualcalculationofareactorheatbalance.
Vinylchloride(VC)ismanufacturedbythepyrolysisof1,2,dichloroethane(DCE).los
reactionisendothermic.Theflowratestoproduce5000kg/hat55percentconversion
areshowninthediagram(seeExample2.13).
Thereactorisapipereactorheatedwithfuelgas,grosscalorificvalue33.5MJ/m 3.
Estimatethequantityoffuelgasrequired.
Reactor
2bar
DCE145.5kmol/h500C
liquid20C
VC80kmol/h
DCE65.5
HCL80
Q
Solucin
Reaction:C2MARIDO
H
4Cl2(g)!do 2MARIDO
3Cl(g)CHCl(g)
r D70,224kJ/kmol.
Thesmallquantityofimpurities,lessthan1percent,thatwouldbepresentinthefeed
havebeenneglectedforthepurposesofthisexample.Also,theyieldofVChasbeen
takenas100percent.Itwouldbeintheregionof99percentat55percentconversion.
Pgina45
78
INGENIERAQUMICA
Heatcapacitydata,forvapourphase
VC
2
3
do
p DaCbTCcT CdT kJ/kmolK
2
la
b10
c10 5
d10 9
5.94
20.16
15.34
47.65
33/74
16/11/2015
HCl
30.28
0,761
1.325
4.305
DCE
20.45
23.07
14.36
33.83
forliquidphase:DCEat20C,Cp D116kJ/kmolK,
takenasconstantovertemperaturerisefrom20to25DO.
LatentheatofvaporisationofDCEat25CD34.3MJ/kmol.
At2barpressurethechangeinC p withpressurewillbesmallandwillbeneglected.
Takebasetemperatureas25C(298K),thestandardstatefor H .
r
EnthalpyoffeedD145.5116293298D84,390kJ/hD84.4MJ/h
773
EnthalpyofproductstreamD
dopdT
nyo
298
Componente
VC
HCl
DCE
norte
dop
yo
773
298
norte
yo
(mol/h)
norte
la
yo
norte
b10 2
yo
norte
c10 5
yo
norte
d10 9
yo
80
80
65.5
475.2
2422.4
1339.5
1612.8
60.88
1511.0
1227.2
106.0
940.6
3812.0
344.4
2215.9
4237.1
3063.0
2061.8
5683.5
norte
dop dT
yo
773
2
4237.1C3063.010 T2061.810
298
D7307.3MJ/h
re
5T2 C5683.510 9T3

dT
HeatconsumedinsystembytheendothermicreactionD H
r molsproduced
D70,22480D5,617,920kJ/hD5617.9MJ/h
Heattovaporisefeed(gasphasereaction)
D34.3145.5D4990.7MJ/h
Heatbalance:
OutputDInputCconsumedCQ
QDH productoMARIDO
Cconsumed
alimentacin
D7307.384.4C5617.9C4990.7D18,002.3MJ/h
Pgina46
79
Takingtheoverallefficiencyofthefurnaceas70%thegasraterequired
Heatinput
re
calorificvalueefficiency
18,002.3
re
D768m3/marido
33.50.7
3.11.STANDARDHEATSOFFORMATION
ofacompoundisdefinedastheenthalpychange
Thestandardenthalpyofformation H
F
whenonemolofthecompoundisformedfromitsconstituentelementsinthestandard
estado.Theenthalpyofformationoftheelementsistakenaszero.Thestandardheatof
anyreactioncanbecalculatedfromtheheatsofformation H
F oftheproductsand
reactantsiftheseareavailableorcanbeestimated.
Conversely,theheatsofformationofacompoundcanbecalculatedfromtheheatsof
reactionforuseincalculatingthestandardheatofreactionforotherreactions.
Therelationshipbetweenstandardheatsofreactionandformationisgivenby
equation3.26andillustratedbyExamples3.8and3.9
H
H
H
3.26
r re
F,products
F,reactants
AcomprehensivelistofenthalpiesofformationisgiveninAppendixD.
Aswithheatsofreaction,thestateofthematerialsmustbespecifiedwhenquoting
heatsofformation.
34/74
16/11/2015
Example3.8
Calculatethestandardheatofthefollowingreaction,giventheenthalpiesofformation:
4NH3(g)C5O2(g)!4NO(g)C6H 2O(g)
StandardenthalpiesofformationkJ/mol
NUEVAHAMPSHIRE
3(gramo) 46.2
NO(g)
C90.3
MARIDO
241.6
2O(g)
Solucin
Note:theenthalpyofformationofO2 iszero.
H
H
r re
F,products
H
F,reactants
D490.3C6241.6446.2
D903.6kJ/mol
Heatofreaction H
r D904kJ/mol
Pgina47
80
INGENIERAQUMICA
3.12.HEATSOFCOMBUSTION
Theheatofcombustionofacompound H
doisthestandardheatofreactionforcomplete
combustionofthecompoundwithoxygen.Heatsofcombustionarerelativelyeasyto
determineexperimentally.Theheatsofotherreactionscanbeeasilycalculatedfromthe
heatsofcombustionofthereactantsandproducts.
Thegeneralexpressionforthecalculationofheatsofreactionfromheatsof
combustionis
,reactants
H
re
H
H
,products
3.27
r
do
do
Note:theproductandreactanttermsaretheoppositewayroundtothatintheexpression
forthecalculationfromheatsofformation(equation3.26).
Forcompoundscontainingnitrogen,thenitrogenwillnotbeoxidisedtoanysignificant
extentincombustionandistakentobeunchangedindeterminingtheheatofcombustion.
Caution.Heatsofcombustionarelargecomparedwithheatsofreaction.Donotround
offthenumbersbeforesubtractionroundoffthedifference.
Twomethodsofcalculatingheatsofreactionfromheatsofcombustionareillustrated
inExample3.9.
Example3.9
Calculatethestandardheatofreactionforthefollowingreaction:thehydrogenationof
benzenetocyclohexane.
(1)C6MARIDO
6(g)C3H2(g)!do 6MARIDO
12(gramo)
(2)C6MARIDO
O (g)!6CO 2(g)C3H2O(l)
H
6(g)C7 1
doD3287.4kJ
2 2
D3949.2kJ
(3)C6MARIDO
(g)C9O
!6CO
(g)C6H
O(l)
H
12
2
2
2
do
(4)C(s)CO 2(g)!CO 2(gramo)
H
doD393.12kJ
D285.58kJ
(5)H2(g)C 1O2(g)!MARIDO
O(l)
H
2
do
2
Note:unlikeheatsofformation,thestandardstateofwaterforheatsofcombustionis
C,1atm.
lquido.Standardpressureandtemperaturearethesame25
Solucin
Mtodo1
Usingthemoregeneralequation3.26
H
re
H
r
F,products
H
F reactivos
theenthalpyofformationofC 6MARIDO
6 andC6MARIDO
12 canbecalculated,andfromthesevalues
theheatofreaction(1).
Fromreaction(2)
COC3 HHO H CMARIDO
H C6MARIDO
2
do 6D6 Hdo
do 2
F 6 6
MARIDO
3287.4D6393.12C3285.58 H
C
F 6 6
35/74
16/11/2015
H
6D3287.43215.52D71.88kJ/mol
FC6MARIDO
Pgina48
81
Fromreaction(3)
H
C6MARIDO
12D3949.2D6393.12C6285.58 H FC6MARIDO
12
do
H
MARIDO
FC6 12D3949.24072.28D123.06kJ/mol
H
12 H FC6MARIDO
6
r D H FC6MARIDO
H
r D123.0671.88D195kJ/mol
Note:enthalpyofformationofH2 iszero.
Mtodo2
Usingequation3.27
CMARIDO
H H CMARIDO
H
6 6C3 Hdo
2
r D Hdo
do 6 12
D3287.4C3285.883949.2D196kJ/mol
Heatofreaction H
r D196kJ/mol
3.13.COMPRESSIONANDEXPANSIONOFGASES
Theworkterminanenergybalanceisunlikelytobesignificantunlessagasisexpanded
orcompressedaspartoftheprocess.Tocomputethepressureworkterm:
2
WD
Pd v
equation3.5
1
arelationshipbetweenpressureandvolumeduringtheexpansionisneeded.
Ifthecompressionorexpansionisisothermal(atconstanttemperature)thenforunit
massofanidealgas:
Pv Dconstant
andtheworkdone,
P
RT1 P2
ln
WDP 1v1ln 2 re
P1
METRO
P1
3.28
3.29
dondeP1 Dinitialpressure,
P 2 Dfinalpressure,
v1 Dinitialvolume.
Inindustrialcompressorsorexpandersthecompressionorexpansionpathwillbe
polytropic,approximatedbytheexpression:
Pvnorte
Dconstant
3.30
Pgina49
82
INGENIERAQUMICA
Theworkproduced(orrequired)isgivenbythegeneralexpression(seeVolume1,
Chapter8):
[(
]
[(
]
)
)
norte P 2 n1/n
RT1 norte P 2 n1/n
WDP 1v1
1 DZ
1
3.31
n1
P1
METRO
n1
P1
whereZDcompressibilityfactor(1foranidealgas),
36/74
16/11/2015
RDuniversalgasconstant,8.314JK 1 mol 1,
T1 Dinlettemperature,K,
MDmolecularmass(weight)ofgas,
WDworkdone,J/kg.
Thevalueofnwilldependonthedesignandoperationofthemachine.
Theenergyrequiredtocompressagas,ortheenergyobtainedfromexpansion,canbe
estimatedbycalculatingtheidealworkandapplyingasuitableefficiencyvalue.Forrecip
rocatingcompressorstheisentropicworkisnormallyused(nD)(seeFigure3.7)y
forcentrifugaloraxialmachinesthepolytropicwork(seeFigure3.6andSection3.13.2).
3.13.1.Mollierdiagrams
IfaMollierdiagram(enthalpypressuretemperatureentropy)isavailablefortheworking
fluidtheisentropicworkcanbeeasilycalculated.
WDH 1
MARIDO
2
3.32
whereH 1 isthespecificenthalpyatthepressureandtemperaturecorrespondingto
point1,theinitialgasconditions,
MARIDO
2 isthespecificenthalpycorrespondingtopoint2,thefinalgascondition.
Point2isfoundfrompoint1bytracingapath(line)ofconstantentropyonthediagram.
ThemethodisillustratedinExample3.10.
Example3.10
Methaneiscompressedfrom1barand290Kto10bar.Iftheisentropicefficiencyis0.85,
calculatetheenergyrequiredtocompress10,000kg/h.Estimatetheexitgastemperature.
Solucin
FromtheMollierdiagram,showndiagrammaticallyinFigure3.5
MARIDO
1 D4500cal/mol,
MARIDO
2 D6200cal/mol(isentropicpath),
IsentropicworkD62004500
D1700cal/mol
Pgina50
480K
H=6500
2
460K
MARIDO
2=6200
83
p=10
p=1
Actualpath
Enthalpy
Isentropic
camino
290K
MARIDO
1=4500
Entropy
Figura3.5.Mollierdiagram,methane
90
Axialflow
80
,%
p
Centrfugo
37/74
16/11/2015
70
Efficiency,E
60
1.0
100
10
3/s
Volumetricflowrate(suctionconditions),m
Figura3.6.Approximatepolytropicefficienciescentrifugalandaxialflowcompressors
Foranisentropicefficiencyof0.85:
ActualworkdoneongasD
1700
D2000cal/mol
0.85
So,actualfinalenthalpy
0 DH 1 C2000D6500cal/mol
MARIDO
2
Page51
84
INGENIERAQUMICA
100
90
Alcance
80
Isentropicefficiency
70
60
1
15
2.0
2.5
3.0
3.5
ndicedecompresin
4.0
Figura3.7.Typicalefficienciesforreciprocatingcompressors
FromMollierdiagram,ifalltheextraworkistakenasirreversibleworkdoneonthegas,
theexitgastemperatureD480K
MolecularweightmethaneD16
EnergyrequiredD(molsperhour)(specificenthalpychange)
10000
re
200010 3
16
D1.2510 9 cal/h
D1.2510 9 4.187
D5.2310 9 J/h
5.2310 9
PowerD
D1.45MW
3600
3.13.2.Polytropiccompressionandexpansion
IfnoMollierdiagramisavailable,itismoredifficulttoestimatetheidealworkin
compressionorexpansionprocesses.Schultz(1962)givesamethodforthecalculationof
thepolytropicwork,basedontwogeneralisedcompressibilityfunctions,XandYcual
supplementthefamiliarcompressibilityfactorZ.
(
)
T V
XD
1
3.33
V T P
(
)
P V
YARDA
3.34
V P T
HischartsforXandYasfunctionsofreducedtemperatureandpressurearereproduced
asFigures3.9and3.10.Thefunctionsareusedtodeterminethepolytropicexponentn
38/74
16/11/2015
Pgina52
85
foruseinequation3.31andapolytropictemperatureexponentmforuseinthefollowing
ecuacin:
(
)
P metro
T2 DT 1 2
3.35
P
(
) 1
ZR 1
dnde
mD
CX forcompression,
3.36
dop mip
ZR
mD
3.37
dop Ep CXforexpansion
mip isthepolytropicefficiency,definedby:
polytropicwork
forcompressionEp re
actualworkrequired
actualworkobtained
forexpansionEp re
polytropicwork
AnestimateofEp canbeobtainedfromFigure3.6.
1
nD
3.38
Ym1CX
Atconditionswellremovedfromthecriticalconditionsequations3.36,3.37and3.38
reduceto:
mD 1
3.36a
mip
mD
1Ep
3.37a
1
nD
3.38a
1m
Theseexpressionscanbeusedtocalculatethepolytropicworkandoutlettemperature
bysubstitutioninequations3.31and3.35.Theycanalsobeusedtomakeafirstestimate
amenudo
2 inordertoestimatethemeanreducedtemperatureforusewithFigures3.9and3.10.
TheuseofSchultz'smethodisillustratedinExamples3.11and3.16.
Example3.11
Estimatethepowerrequiredtocompress5000kmol/hofHClat5bar,15C,to15bar.
Solucin
ForHCl,P doD82bar,T doD324.6K
2TC12.510 6T2
do
p D30.300.7210
EstimateT2 fromequations3.35and3.36a.
Fordiatomicgases'1.4.
Note:couldbeestimatedfromtherelationshipD
3.910 9T3 kJ/kmolK

dop
dop
re
dov dop R
Pgina53
86
INGENIERAQUMICA
Attheinletconditions,theflowrateinm3/s
5000
288 1
re
22.4
re D6.56
3600
273 5
FromFigure3.6Ep D0.73
1.41
Fromequations3.36aand3.35
mD
D0.39
1.40.73
(
)
15 0.39
T D288
D442K
39/74
16/11/2015
5
442C228
T
re
D1.03
rmean2324.6
5C15
P
re
D0.12
rmean282
EnT
do
p D29.14kJ/kmolK
mean
CorrectionforpressurefromFigure3.2,2kJ/kmolK
dop D29.14C2'31kJ/kmolK
FromFigures3.8,3.9and3.10atmeanconditions:
XD0.18,YD1.04,ZD0.97
ZatinletconditionsD0.98
Fromequations3.36and3.38
(
)
0.978.314
1
mD
C0.18 D0.40
31
0.73
1
nD
D1.76
1.040.41C0.18
Fromequation3.31
( (
)
)
1.76
15 1.761/1.76
WpolytropicD0.982888.314
1
1.761
5
D3299kJ/kmol
polytropicwork
mip
3299
re
D4520kJ/kmol
0.73
4520
PowerD
5000D6275kW
3600
Say,6.3MW
(
)
15 0.4
T2 D288
D447K
5
ActualworkrequiredD
Pgina54
1.1
1.2
1.4
16
2.0
3
4
68
10
15
3
Reducedtemperature,T
r =1.0
2
15 2.0
1.8
16
1.4
1.3
1.2
1.15
1.1
1.0
0.8
0.70
0.6
0.75
0.80
0.4
0.85
0.90
0.95
ALS
1.0
0.5
0.9 0.6
1.05
1.03
1.0 1.01
Compressibilityfactor,Z
0.3
FUNDAMENT
1.1
O
F
mi
NERGY
1.0
BALANCES
1.2
0.7
0.8
0.8
0.9
0.2
0.7
0
r
0.1
0.2
0.3
0.4
Lowpressurerange,P
r
0.10
0.1
0.2
0.3
0.4
0.6 0.81.0
6 78910
2025
30
Reducedpressure,P
r
40/74
16/11/2015
Figura3.8.Compressibilityfactorsofgasesandvapours
87
Pgina55
88
2.8
12
11
10
() 1
X=TV
V TP
P
Pr= P
do
Tr= T
Tdo
0.95
2.4
2.0
X
0.90
16
1.2
=0.85
Tr
8
0.8
=1.00
r
1.00
1.05
5
1.10
Compressibilityfunction,X
4
0.1
0.2
1.30
1.50
0.2
0.4
0.6
0.8
0.3
0.4
15
QUMICO
mi
NGENIERA
1.05
1.10
1.20
1.15
1.20
1
0
0.80
1.15
1.05
1.10
1.15
1.20
1.30
1.50
2.00
165.00
0.4 0.60
0.70
1.00
1.30
1.50
2.00
1.0 1.2 1.4 16 1.8 2.0

Reducedpressure,P
r
5.00
2.2
2.4
2.6
2.8
3.0
Figura3.9.GeneralisedcompressibilityfunctionX
Pgina56
1.7
0.95
P V
Y=
V Pr
16
Pr = P
Pdo
4 Tr = TP
do
15
1.1
1.00
1.05
1.10
0.80
0.70
0.60
0.1
0.2
0.3 0.4
Pr
1.00
1.05
=0.85
Tr
1.2
2
Compressibilityfunction,Y
0.90
1.4
Y
1.3
0.5
1.10
1.15
1.20
1.30
1.50
2.00
5.00
0.6
FUNDAMENT
ALS
O
F
mi
NERGY
BALANCES
41/74
16/11/2015
=1.00
ReducidoTr
latemperatura,
1.15
1.20
1.30
1.50
2.00
5.00
0.2
0.4
0.6
0.8
1.0
1.2
1.4
16
1.8
1.20
1.05
1.00
0
1.30
1.15
1.10
2.0
2.2
2.4
2.6
2.8
3.0
Reducedpressure,P
r
89
Figura3.10.GeneralisedcompressibilityfunctionY
Pgina57
94
INGENIERAQUMICA
TPODER
3.2.ENERGY1,asimpleenergybalanceprogram
10REMSHORTENERGYPROGRAM,REWRITTENINGWBASIC,MARCH92
20PRINT"HEATBALANCEPROGRAM,BASISkmol/h,TEMPK,DATUM298K"
30PRINT"INPUTTHENUMBEROFCOMPONENTS,MAXIMUM10"
40INPUTN1
50PRINT"INPUTHEATCAPACITYDATAFOREQUATIONA+BT+CT^2+DT^3"
60FORI=1TON1
70PRINT
80PRINT"FORCOMPONENT"YO"INPUTA,B,C,D,INCLUDINGANYZEROVALUES"
90INPUTA(I),B(I),C(I),D(I)
100NEXTI
110H4=H5=H6=Q1=0
120PRINT"INPUTTHENUMBEROFFEEDSTREAMS"
130INPUTS1
140FORI=1TOS1
150PRINT"FORFEEDSTREAM"YO"INPUTSTREAMTEMPANDNUMBEROFCOMPONENTS"
160INPUTT1,N2
170GOSUB580
180PRINT"STREAMSENSIBLEHEAT="H4"kJ/h"
190REMTOTALSENSIBLEHEATFEEDSTREAMS
200H5=H5+H4
210NEXTI
220PRINT"INPUTNUMBEROFPRODUCTSTREAMS"
230INPUTS1
240FORI=1TOS1
250PRINT"FORPRODUCTSTREAM"YO"INPUTSTREAMTEMPANDNUMBEROFCOMPONENTS"
260INPUTT1,N2
270GOSUB580
280PRINT"STREAMSENSIBLEHEAT="H4"kJ/h"
290REMTOTALSENSIBLEHEATPRODUCTSTREAMS
300H6=H6+H4
310NEXTI
320PRINT"INPUTTHENUMBEROFREACTIONSANDPHASECHANGES"
330INPUTN4
340IFN4=0THEN450
350PRINT"FOREACHREACTIONORPHASECHANGEINPUTTHEHEATOFREACTION"
360PRINT"ORTHELATENTHEAT,kJ/kmolANDQUANTITYINVOLVEDkmol/h"
370PRINT"REMEMBER:HEATENVOLVED:POSITIVEHEATABSORBED:NEGATIVE"
380FORI=1TON4
390PRINT
400PRINT"NEXTREACTION/PHASECHANGE:INPUTVALUES"
410INPUTR,F2
420H7=F2*R
430Q1=Q1+H7
440NEXTI
450REMHEATBALANCE
460Q=H6H5Q1
470IFQ<0THEN500
480PRINT"HEATINGREQUIRED="Q"kJ/h"
490GOTO510
500PRINT"COOLINGREQUIRED="Q"kJ/h"
510PRINT"REPEATCALCULATIONWANTED?TYPEYFORYES,NFORNO"
520INPUTP$
530IFP$="N"THEN560
540PRINT"REPEATCALCULATION"
550GOTO110
560PRINT"CALCULATIONSFINISHED"
570STOP
580REMSUBROUTINETOCALCULATESTREAMSENSIBLEHEATS
590PRINT
600PRINT"FOREACHCOMPONENT,INPUTTHECOMPONENTNUMBERANDFLOWRATE"
610H4=0
620FORI1=1TON2
630PRINT"NEXTCOMPONENT"
640INPUTJ,F
650REMHEATCAPACITYEQUATIONSPLITOVER2LINES
660H1=A(J)*(T1298)+B(J)*(T1^2298^2)/2
670H2=C(J)*(T1^3298^3)/3+D(J)*(T1^4298^4)/4
680H3=F*(H1+H2)
690H4=H4+H3
700NEXTI1
710RETURN
42/74
16/11/2015
Pgina58
90
INGENIERAQUMICA
3.13.3.Multistagecompressors
Singlestagecompressorscanonlybeusedforlowpressureratios.Athighpressureratios,
thetemperaturerisewillbetoohighforefficientoperation.
Tocopewiththeneedforhighpressuregeneration,thecompressionissplitintoa
numberofseparatestages,withintercoolersbetweeneachstage.Theinterstagepressures
arenormallyselectedtogiveequalworkineachstage.
Foratwostagecompressortheinterstagepressureisgivenby:
P yo
re P1 P 2
3.39
dondeP yoistheintermediatestagepressure.
Example3.12
Estimatethepowerrequiredtocompress1000m 3/hairfromambientconditionsto
700kN/m2 gauge,usingatwostagereciprocatingcompressorwithanintercooler.
Solucin
Taketheinletpressure,P1,as1atmosphereD101.33kN/m2,absolute.
Outletpressure,P2,D700C101.33D801.33kN/m 2,absolute.
Forequalworkineachstagetheintermediatepressure,Pyo
,
2
re 1.0133105 8.013310 5D2.8495105 NuevoMjico
Forair,takeratioofthespecificheats,,tobe1.4.
Forequalworkineachstagethetotalworkwillbetwicethatinthefirststage.
Taketheinlettemperaturetobe20 C,Atthattemperaturethespecificvolumeis
dadapor
29
293
v1 re
re
D1.39m 3/kg
22.4 273
WD21.013310 5 1.39
Workdone,
1.4
1.41
[(
]
)
2.8495 1.41/1.4
1
1.0133
D338,844J/kgD339kJ/kg
FromFigure3.7,foracompressionratioof2.85theefficiencyisapproximately84%.Asique
workrequired
D339/0.84D404kJ/kg
Massflowrate
Powerrequired
1000
D0.2kg/s
1.393600
D4040.2D80kW
re
Pgina59
91
Example3.13
Inthehighpressureprocessfortheproductionofpolyethylene,ethyleneiscompressedin
atwostepprocess.Intheprimarystep,thegasiscompressedinatwostagecompressorto
25to30MPa.Thisisfollowedbycompressioninahypercompressorto150to320MPa.
Estimatetheworkrequiredtocompressethyleneto25MPainatwostagecompressor.
Cand
Areciprocatingcompressorwillbeused.Thegasisataninitialtemperatureof15
iscooledto25Cafterthefirststagecompression.
Solucin
Asthecalculationswillberepetitive,useaspreadsheet.
Datos
Ten288KP en1barP fuera
250baRD8.1345J/molK
T 282.4KP 50.4barM28.05C datafromAppendixD
43/74
16/11/2015
do
do
Firststage
IntermediatepressureP2 D15.811388bar
p
eqn3.39
CompressionratioDP 2/P1 D15.814

dop forethylene
TenD288useeqn3.11a
LA
segundo
3.806
0.15359
3.806
44.23392
41.535011kJ/kmolK
Coef.
dop
sum,C p re
do
8.35E05
6.924165
re
1.755E08
0.419256
gammaD
dop/Cp RD1.2502821
FromFigure3.7,extrapolated,EpD0.86.
0.232768
eqn3.36a
mD
T2 re 547.52197
eqn3.35
MeantempDT
1 Connecticut
2/2D417.76099
dop atmeantempof419.6K
3.806
0.15359
3.80664.446364
8.35E051.755E08
14.697841.2966068
sum,Cp D54.851135kJ/kmolK
newgammaD
1.1786657
revisedmD
0.1811049
revisedT2 re
474.76117
revisedmeantempD381.38058
littlechangesoleaveTmedia
a
419.6K
Tr DT media
/Tdore
1.48583571.5
Pgina60
92
INGENIERAQUMICA
P media
DP1 P2/2D0.5
P r DP media
/PcD0.00992060.17
FromFigure3.2correctiontoCp forpressureisnegligible.
FromFigures3.8,3.9,3.10
ZD1.0
XD0
YD0
Essentiallyidealatthispressure
mD
0.1762593
eqn3.36a
nD
1.2139743
eqn3.38a
WD
303.47285kJ/kmoleqn3.31
ActualworkrequiredDpolytropicwork/efficiencyD
Decir
352.87541
353kJ/kmol
Secondstagework
Astheintermediatepressurewasselectedtogiveequalworkineachstagethesecond
stageworkcouldbetakenasequaltothefirststagework.Thiswillbechecked.
TenD298K
compressionratioD
P 3/P2 re 15.822785,iesameasfirststage
So,takegammaandefficiencyasforfirststage
mD
0.1811049
T3 re
491.24593K
Tmedia
D394.62296K
dop atmeantemp
Coef.
3.806
0.15359
dop
3.806
60.610141
sum,Cp D52.494599kJ/kmolK
8.35E05
13.00011
1.755E08
1.0785715
44/74
16/11/2015
Littlechangefromfirststage,sousesamegammaandTmedia
TrD
15
Pmedia
D20.4bar
PrD
0.4047619(0.4)
FromFigure3.2correctiontoCp forpressureisapproximately2.5J/mol.
Thisislessthan5percent,soneglect.
FromFigures3.8,3.9,3.10
ZD1.0
XD0.1approx.
YD0
So,gascanbetakenasideal
WD314.01026slightlyhigherasT enesmsalto
Pgina61
ActualworkD
93
365.12821365kJ/kmol
TotalworkrequiredfirststepD718kJ/kmol
ThespreadsheetusedforthisexamplewasMicrosoftWorks.Acopyofthesolutionusing
MicrosoftExcelcanbefoundontheButterworthHeinemannwebsite:bh.com/compa
nions/0750641428.
3.13.4.Electricaldrives
Theelectricalpowerrequiredtodriveacompressor(orpump)canbecalculatedfroma
knowledgeofthemotorefficiency:
PowerD
Wmassflowrate
mimi
3.40
whereWDworkofcompressionperunitmass(equation3.31),
mimiDelectricmotorefficiency.
Theefficiencyofthedrivemotorwilldependonthetype,speedandsize.Losvalores
giveninTable3.1canbeusedtomakearoughestimateofthepowerrequired.
Tabla3.1.Approximateefficiencies
ofelectricmotors
Size(kW)
Eficiencia(%)
5
80
15
85
75
90
200
92
750
95
97
>4000
3.14.ENERGYBALANCECALCULATIONS
Energybalancecalculationsarebestsolvedusingspreadsheetsorbywritingashort
programadecomputadora.AsuitableprogramislistedinTable3.2anditsusedescribedbelow.
TheuseofaspreadsheetisillustratedinExample3.14b.
Energy1,asimplecomputerprogram
Thisprogramcanbeusedtocalculatetheheatinputorcoolingrequiredforaprocess
unit,wherethestreamenthalpiesrelativetothedatumtemperaturecanbecalculatedfrom
thespecificheatcapacitiesofthecomponents(equation3.11).
Thedatumtemperatureintheprogramis25 C(298K),whichisstandardformost
heatofreactiondata.Specificheatsarerepresentedbyacubicequationintemperature:
dop DACBTCCT 2 CDT 3
Anyunspecifiedconstantsaretypedinaszero.
Iftheprocessinvolvesareaction,theheatgeneratedorconsumediscomputedfrom
theheatofreactionperkmolofproduct(at25C)andthekmolsofproductproduced.
45/74
16/11/2015
Pgina62
95
Ifanycomponentundergoesaphasechangeintheunit,theheatrequirediscomputed
fromthelatentheat(at25C)andthequantityinvolved.
Thecomponentspecificheatcapacitycoefficients,A,B,C,D,arestoredasamatrix.
Ifanenergybalanceistobemadeonseveralunits,thespecificheatcoefficientsforall
thecomponentscanbeenteredatthestart,andtheprogramrerunforeachunit.
Theprogramlistingcontainssufficientremarkstatementsfortheoperationofthe
programtobeeasilyfollowed.ItiswritteninGWBASICforpersonalcomputers.Ello
caneasilybeadaptedforotherformsofBASICandforuseonprogrammablecalcu
lators.TheuseoftheprogramisillustratedinExample3.14a.Ithasalsobeenusedfor
otherexamplesinthischapterandintheflowsheeting,Chapter4.
Example3.14a
UseofcomputerprogramENERGY1
Afurnaceburnsaliquidcoaltarfuelderivedfromcokeovens.Calculatetheheattrans
ferredinthefurnaceifthecombustiongasesleaveat1500K.Theburnersoperatewith
20percentexcessair.
Takethefuelsupplytemperatureas50 C(323K)andtheairtemperatureas15 do
(288K).
Thepropertiesofthefuelare:
Carbn
Hidrgeno
Oxgeno
Nitrgeno
Azufre
Ceniza
87.5percentw/w
8.0
3.5
1.0
rastro
equilibrar
Netcalorificvalue
Latentheatofvaporisation
Heatcapacity
39,540kJ/kg
350kJ/kg
1.6kJ/kgK
do
p ofgases,kJ/kmolK,
Componente
1 CO2
2 MARIDO
2O
3 O2
4 norte
2
dop DACBTCCT 2 CDT3

segundo
do
7.332E2
5.518E5
19.207E4
10.538E6
3.674E6
17.431E6
1.354E2
26.752E6
LA
19.763
32.190
28.06
31.099
re
17.125E9
3.591E9
10.634E9
11.662E9
Solucin
Materialbalance
Basis:100kg(asanalysisisbyweight).
Assumecompletecombustion:maximumheatrelease.
Pgina63
96
INGENIERAQUMICA
Reactions:CCO 2 !CO 2
1
MARIDO
2 do 2O2 !MARIDO
2O
Elemento
kg
kmol
StoichiometricO2
kmol
do
87.5
MARIDO
8.0
2
O2
3.5
norte
1.0
2
7.29
4.0
0.11
0.04
7.29
2.0
11.44
9.29
Total
kmol,products
7.29,CO2
4.0,H2O
0.11
0.04
O2 requiredwith20percentexcessD9.291.2D11.15kmol.
UnreactedO2 fromcombustionairD11.159.29D1.86kmol.
46/74
16/11/2015
79
norte
2 withcombustionairD11.15 21 D41.94kmol.
Compositionofcombustiongases:
CO2
D7.29kmol
MARIDO
D4.0
2O
O2 0.11C1.86D1.97
norte
2 0.04C41.94D41.98
Presentationofdatatotheprogram:
dop offuel(component5),takenasconstant,
AD1.6,BDCDDD0
Heatofreactionandlatentheat,takentobevaluesatdatumtemperatureof298K.
ThereisnoneedtoconverttokJ/kmol,providingquantitiesareexpressedinkg.por
thepurposesofthisexamplethedissociationofCO2 yH 2Oat1500Kisignored.
Computerprintout
Datainputsshownafterthesymbol(?)
CARRERA
HEATBALANCEPROGRAM,BASISkmol/h,TEMPK,DATUM298K
INPUTTHENUMBEROFCOMPONENTS,MAXIMUM10
?5
INPUTHEATCAPACITYDATAFOREQUATIONA+BT+CT^2+DT^3
FORCOMPONENT1INPUTA,B,C,D,INCLUDINGANYZEROVALUES
?19.763,7.332E2,5.518E5,1.7125E8
?32.19,1.9207E3,1.0538E5,3.591E9
?28.06,3.67E6,1.74E5,1.0634E8
?31.099,1.354E2,2.6752E5,1.1662E8
?1.6,00,0,0
Pgina64
97
INPUTTHENUMBEROFFEEDSTREAMS
?2
FORFEEDSTREAM1INPUTSTREAMTEMPANDNUMBEROFCOMPONENTS
?323,1
FOREACHCOMPONENT,INPUTTHECOMPONENTNUMBERANDFLOWRATE
NEXTCOMPONENT
?5,100
STREAMSENSIBLEHEAT=4000kJ/h
FORFEEDSTREAM2INPUTSTREAMTEMPANDNUMBEROFCOMPONENTS
?288,2
NEXTCOMPONENT
?3,11.15
NEXTCOMPONENT
?4,41.94
STREAMSENSIBLEHEAT=15,484.61kJ/h
INPUTNUMBEROFPRODUCTSTREAMS
?1
FORPRODUCTSTREAM1INPUTSTREAMTEMPANDNUMBEROFCOMPONENTS
?1500,4
NEXTCOMPONENT
?1,7.29
NEXTCOMPONENT
?2,4.0
NEXTCOMPONENT
?3,1.97
NEXTCOMPONENT
?4,41.98
STREAMSENSIBLEHEAT=2319620kJ/h
INPUTTHENUMBEROFREACTIONSANDPHASECHANGES
?2
FOREACHREACTIONORPHASECHANGEINPUTTHEHEATOFREACTION
ORTHELATENTHEAT,kJ/kmolANDQUANTITYINVOLVEDkmol/h
REMEMBER:HEATENVOLVED:POSITIVEHEATABSORBED:NEGATIVE
NEXTREACTION/PHASECHANGE:INPUTVALUES
?+39540,100
NEXTREACTION/PHASECHANGE:INPUTVALUES
?350,100
COOLINGREQUIRED=1587896kJ/h
REPEATCALCULATIONWANTED?TYPEYFORYES,NFORNO
?norte
CALCULATIONSFINISHED
Heattransferred(coolingrequired)D1,590,000kJ/100kg
Note:thoughtheprogramreportskJ/h,anyconsistentsetofunitscanbeused.Parael
examplethebasisusedwas100kg.
Useofspreadsheets
47/74
16/11/2015
Aspreadsheetcanbeusedforrepetitivecalculationsasasimpleralternativetowritinga
programa.TheprocedureissetoutbelowandillustratedinExample13.14b.
Fromequation13.11theenthalpyofastream,duetosensibleheat,isgivenby
HDm
T
[2
]
mDn
ATCBT2/2CCT 3/3CDT 4/4
mD1T1
13.11a
whereHDthestreamsensibleheat/enthalpy
mDflowrateofthesteamcomponentkg/sorkmol/s
nDnumberofstreamcomponents
Pgina65
98
INGENIERAQUMICA
Procedimiento
1.Setupthespecificheatcoefficientsasamatrix.
2.Useequation3.11atocalculatetheenthalpyofeachcomponent.Tabulatetheresults.
Sumthecolumnstofindthetotalstreamsensibleenthalpy.
3.Repeatforalltheinletandexitstreams.
4.Calculateandaddtheenthalpyfromanyreactionorphasechangeandaddtothe
streamenthalpies.
5.Subtractthetotalenthalpyoftheoutletstreamsfromtheinlettofindthechange
inenthalpy.
Example13.14b
RepeatthecalculationsforthesolutionofExample13.4ausingaspreadsheet.
Solucin
ThespreadsheetusedforthisexampleisMicrosoftWorks.Acopyoftheexampleusing
MicrosoftExcelcanbefoundonthecompanionwebsite:http://books.elsevier.com/
companions.
Example3.14b
Datos
Fueloil
CpkJ/kg,K
%CD
87.5
%oO2D
3.5
1.6CVkJ/kg
%H2D
%N2D
39540
lat.heatkJ/kg
350
Specificheatsgases
comp.
LA
segundo
CO2
19.763
0.0733
H2O
32.19
0.0019207
O2
28.06
3.67E06
N2
31.099
0.01354
Tinfuel,K
323Tinair,K
Basis100kg,asanalysisisbyweight.
do
re
5.52E05
1.713E08
1.054E05
3.59E09
1.743E05
1.06E08
2.675E05
1.17E08
288Tout,K
1500
MATERIALBALANCE
ReactionsCCO2DCO2
H2C1/2O2DH2O
elemento kg
kmol
do
87.5
7.29
H2
8
4.00
O2
3.5
0.11
N2
1
0.04
Totales
100
11.44
O2with20%excess,kmolD
N2withcombustionair,kmolD
stoichiometricO2,kmol
7.29
2.00
9.29
11.15
41.95
products,kmol
7.29CO2
4.00H2O
0.11
0.04
11.44
unreactedO2,kmolD 1.86
Page66
48/74
16/11/2015
99
Compositionofcombustiongases
CO2
7.29
H2O
4.00
O2
1.97
N2
41.98
ENERGYBALANCE
Takedatumtemp,Tobe
298K
En
mols
LA
segundo do
re
Aire O2
11.15
28.06 3.67E061.743E05 1.06E08
N2
41.95
31.099
0.01354 2.675E05 1.17E08
molsCpO2
312.869 4.1E050.0001944 1.19E07
N2
1304.455 0.5679390.0011221 4.89E07
SUMA
1617.324 0.5679790.0013165 6.08E07
EnergykJ Estao
A
total
451671.39
467157.83
Diff 15486.44
465789.30 23555.2510482.593 1045.259

481962.54 25219.4311612.883 1198.17
Fuelsensibleheat
combustin
massCpTin
ToD 4000
mascvD
3954000
total 3958000
TotalenergyinsensibleCcombustion:3942513.6kJ
Fuera
molsA
segundo do
re
CO2
7.29 19.763 0.0733 5.52E05 1.713E08
H2O
4.00
32.19 0.00192071.054E05 3.59E09
O2
1.97
28.06 3.67E06 1.743E05 1.06E08
N2
41.98 31.099 0.01354 2.675E05 1.17E08
molsCpCO2
144.07227 0.534357 0.000402 1.248E07
H2O
128.76 0.00768284.215E05 1.44E08
O2
55.2782 7.24E06 3.434E05 2.09E08
N2
1305.536 0.568409 0.001123 4.9E07
SUMA
1633.6465 0.026377 0.0008
4.0E7
Energa Revendedor 2.45EC06 29673.72 896937.56 506303.8total
A
486826.65 1171.175 7032.9451 788.6988
Diff
latentheatmassLvD
35000
TotaloutDsensibleClatentD 2354530.1
CoolingrequiredDHeatin
heatoutD 1587983.5kJ/100kgfuel
2811429.8
491899.72
2319530.1
3.15.UNSTEADYSTATEENERGYBALANCES
Alltheexamplesofenergybalancesconsideredpreviouslyhavebeenforsteadystate
procesoswheretherateofenergygenerationorconsumptiondidnotvarywithtimeand
theaccumulationterminthegeneralenergybalanceequationwastakenaszero.
Ifabatchprocessisbeingconsidered,oriftherateofenergygenerationorremoval
varieswithtime,itwillbenecessarytosetupadifferentialenergybalance,similartothe
differentialmaterialbalanceconsideredinChapter2.Forbatchprocessesthetotalenergy
requirementscanusuallybeestimatedbytakingasthetimebasisforthecalculation1
lotebutthemaximumrateofheatgenerationwillalsohavetobeestimatedtosizeany
heattransferequipmentneeded.
Pgina67
100
INGENIERAQUMICA
TheapplicationofadifferentialenergybalanceisillustratedinExample3.13.
Example3.15
Differentialenergybalance
Cinajacketed,
Inthebatchpreparationofanaqueoussolutionthewaterisfirstheatedto80
C.Ifthejacketareais300ft2
agitatedvessel1000Imp.galn(4545kg)isheatedfrom15
1F 1
(27.9m2)andtheoverallheattransfercoefficientcanbetakenas50Btuft 2 marido
(285Wm 2 K 1),estimatetheheatingtime.Steamissuppliedat25psig(2.7bar).
Solucin
Therateofheattransferfromthejackettothewaterwillbegivenbythefollowing
expression(seeVolume1,Chapter9):
dQ
a
dt DUAts t
wheredQistheincrementofheattransferredinthetimeintervaldt,and
49/74
16/11/2015
UDtheoverallheattransfercoefficient,
t s Dthesteamsaturationtemperature,
tDthewatertemperature.
Theincrementalincreaseinthewatertemperaturedtisrelatedtotheheattransferred
dQbytheenergybalanceequation:
dQDWC p dt
whereWCp istheheatcapacityofthesystem.
Equatingequations(a)and(b)
Integracin
Batchheatingtime
dt
WCp DUAts t
dt
tsegundo
WCp t2 dt
dtD
UA t ts t
0
1
WCp t s
tsegundo
re
ln
UA
ts
t2
t1
ForthisexampleWCp D4.18454510 3 JK 1
UAD28527WK 1
t 1 D15 C,t 2 D80C,t s D130do
4.18454510 3 13080
tsegundo
re
ln
28527.9
13015
D1990sD33.2min
Inthisexampletheheatcapacityofthevesselandtheheatlosseshavebeenneglected
porsimplicidad.Theywouldincreasetheheatingtimeby10to20percent.
Pgina68
101
3.16.ENERGYRECOVERY
Processstreamsathighpressureortemperature,andthosecontainingcombustible
material,containenergythatcanbeusefullyrecovered.Whetheritiseconomictorecover
theenergycontentofaparticularstreamwilldependonthevalueoftheenergythatcan
beusefullyextractedandthecostofrecovery.Thevalueoftheenergywilldependon
theprimarycostofenergyatthesite.Itmaybeworthwhilerecoveringenergyfroma
processstreamatasitewhereenergycostsarehighbutnotwheretheprimaryenergy
costsarelow.Thecostofrecoverywillbethecapitalandoperatingcostofanyadditional
equipmentrequired.Ifthesavingsexceedtheoperatingcost,includingcapitalcharges,
thentheenergyrecoverywillusuallybeworthwhile.Maintenancecostsshouldbeincluded
intheoperatingcost(seeChapter6).
Someprocesses,suchasairseparation,dependonefficientenergyrecoveryfor
economicoperation,andinallprocessestheefficientutilisationofenergyrecovery
techniqueswillreduceproductcost.
Someofthetechniquesusedforenergyrecoveryinchemicalprocessplantsare
describedbrieflyinthefollowingsections.Thereferencescitedgivefullerdetailsof
cadatcnica.Miller(1968)givesacomprehensivereviewofprocessenergysystems
includingheatexchange,andpowerrecoverfromhighpressurefluidstreams.
Kenney(1984)reviewstheapplicationofthermodynamicprinciplestoenergyrecovery
intheprocessindustries.
3.16.1.Heatexchange
Themostcommonenergyrecoverytechniqueistoutilisetheheatinahightemperature
processstreamtoheatacolderstream:savingsteamcostsandalsocoolingwater,if
thehotstreamrequirescooling.Conventionalshellandtubeexchangersarenormally
utilizado.Moretotalheattransferareawillbeneeded,overthatforsteamheatingandwater
cooling,astheoveralldrivingforceswillbesmaller.
Thecostofrecoverywillbereducedifthestreamsarelocatedconvenientlyclose.
Theamountofenergythatcanberecoveredwilldependonthetemperature,flow,
heatcapacity,andtemperaturechangepossible,ineachstream.Areasonabletemper
aturedrivingforcemustbemaintainedtokeeptheexchangerareatoapracticalsize.
Themostefficientexchangerwillbetheoneinwhichtheshellandtubeflowsare
trulycountercurrent.Multipletubepassexchangersareusuallyusedforpracticalreasons.
Withmultipletubepassestheflowwillbepartcountercurrentandpartcocurrentand
temperaturecrossescanoccur,whichwillreducetheefficiencyofheatrecovery(see
50/74
16/11/2015
Chapter12).
Thehotprocessstreamsleavingareactororadistillationcolumnarefrequentlyused
topreheatthefeedstreams.
3.16.2.Heatexchangernetworks
Inanindustrialprocesstherewillbemanyhotandcoldstreamsandtherewillbe
anoptimumarrangementofthestreamsforenergyrecoverybyheatexchange.los
problemofsynthesisinganetworkofheatexchangershasbeenstudiedbymanyworkers,
Pgina69
102
INGENIERAQUMICA
Sh1
Sh2
Sh3
Sh4 Sh5
Sh6
E1
E2
E3
E4
E6
E6
E7
Su2
Su1
E5
SC1
E8
DO)
Smarido
1 Dresidue(360
DO)
Smarido
2 Drefluxstream(260
DO)
Smarido
3 Dheavygasoil(340
DO)
Smarido
4 Dlightgasoil(260
DO)
Smarido
5 Drefluxsteam(180
DO)
Smarido
6 Drefluxstream(165
DO)
Sdo
1 Dcrudeoil(15
DO)
Su1 y Su2 Dcoolingwater(50
Figura3.11.Typicalheatexchangernetwork
particularlyinrespectofoptimisingheatrecoveryincrudepetroleumdistillation.Un
exampleofcrudepreheattrainisshowninFigure3.11.Thegeneralproblemofthe
synthesisandoptimisationofanetworkofheatexchangershasbeendefinedbyMasso
andRudd(1969).
ConsiderthatthereareMhotstreams,SHola
iD1,2,3,...,MtobecooledandNcold
streamsScjjD1,2,3,...,Ntobeheatedeachstreamhavinganinlettemperaturet F,
oranoutlettemperaturet 0,andastreamheatcapacityW yo
.TheremayalsobeS ReinoUnido
kD
1,2,3,...,Lauxiliarysteamheatedorwatercooledexchangers.
Theproblemistocreateaminimumcostnetworkofexchangers,thatwillalsomeetthe
designspecificationsontherequiredoutlettemperaturet0 ofeachstream.Ifthestrictly
mathematicalapproachistakenofsettingupallpossiblearrangementsandsearchingfor
theoptimum,theproblem,evenforasmallnumberofexchangers,wouldrequirean
inordinateamountofcomputertime.BolandandLinnhoff(1979)pointoutthatfora
processwithfourcoldandthreehotstreams,2.41018 arrangementsarepossible.Lamayora
workershavetakenamorepragmatic,heuristic,approachtotheproblem,usingrules
ofthumbtogeneratealimitednumberoffeasiblenetworks,whicharethenevaluated.
PortonandDonaldson(1974)suggestasimpleprocedurethatinvolvestherepeated
matchingofthehotteststream(highestt F)againstthecoldstreamwiththehighest
requiredoutlettemperature(highestt0).
Ageneralsurveyofcomputerandmanualmethodsforoptimisingexchangernetworks
isgivenbyNishidaetal.(1.977)vasetambinSiirola(1974).
ThedesignofheatexchangernetworksiscoveredinmoredetailisSection3.17.
3.16.3.Wasteheatboilers
Iftheprocessstreamsareatasufficientlyhightemperaturetheheatrecoveredcanbe
usedtogeneratesteam.
Pgina70
103
51/74
16/11/2015
Wasteheatboilersareoftenusedtorecoverheatfromfurnacefluegasesandtheprocess
gasstreamsfromhightemperaturereactors.Thepressure,andsuperheattemperature,of
thestreamgeneratedwilldependonthetemperatureofthehotstreamandtheapproach
temperaturepermissibleattheboilerexit(seeChapter12).Aswithanyheattransfer
equipment,thearearequiredwillincreaseasthemeantemperaturedrivingforce(log
mean T)isreduced.Thepermissibleexittemperaturemayalsobelimitedbyprocess
consideraciones.Ifthegasstreamcontainswatervapourandsolublecorrosivegases,such
asHClorSO2,theexitgasestemperaturemustbekeptabovethedewpoint.
Hinchley(1975)discussesthedesignandoperationofwasteheatboilersforchemical
planta.Bothfiretubeandwatertubeboilersareused.Atypicalarrangementofawatertube
boileronareformerfurnaceisshowninFigure3.12andafiretubeboilerinFigure3.13.
Theapplicationofawasteheatboilertorecoverenergyfromthereactorexitstreamsin
anitricacidplantisshowninFigure3.14.
Waterin
Gasoutlet
Steam/Waterout
Metalshroud
Refractory
revestimiento
Gasinlet
Figura3.12.ReformedgaswasteheatboilerarrangementofverticalUtubewatertubeboiler(Reprintedby
permissionoftheCounciloftheInstitutionofMechanicalEngineersfromtheProceedingsoftheConference
onEnergyRecoveryintheProcessIndustries,London,1975.)
Theselectionandoperationofwasteheatboilersforindustrialfurnacesisdiscussed
intheEfficientUseofEnergy,Dryden(1975).
3.16.4.Hightemperaturereactors
Ifareactionishighlyexothermic,coolingwillbeneededand,ifthereactortemper
atureishighenough,theheatremovedcanbeusedtogeneratesteam.Theloweststeam
pressurenormallyusedintheprocessindustriesis2.7bar(25psig)andsteamisnormally
Pgina71
104
INGENIERAQUMICA
Ferrulewrappedwith
insulatingfibre
Steam/Water
riserpipes
Processgas
outlet550C
Alloy800ferrule
Alloy800
productionplate
Hormign
Externalinsulation
Waterdowncomerpipes
Processgas
1200/1000C
Blowdownconnection
Refractoryconcrete Insulatingconcrete
Figura3.13.Reformedgaswasteheatboiler,principalfeaturesoftypicalnaturalcirculationfiretubeboilers
(ReprintedbypermissionoftheCounciloftheInstitutionofMechanicalEngineersfromtheProceedingsof
theConferenceonEnergyRecoveryintheProcessIndustries,London,1975.)
52/74
16/11/2015
Aire
Corriente
6 7
Amonaco
2
Tostack
Fromabsorption
Airfrom towerno.5
blanqueador
AireSecundario
....
.... 8 ....
....
1.Airentry
2.Ammoniavaporiser
3.Ammoniafilter
4.Controlvalves
5.Airscrubbingtower
13
11
10
14
15
12
Agua
Agua12HNO
3
6.Airpreheater
7.Gasmixer
8.Gasfilters
9.Converters
16 17
Tooxidation
tower
202HNO
3 Toabsorption
10.Lamontboilers
11.Steamdrum
12.GascoolerNo.1
13.Exhaustturbine
14.Compressor
15.Steamturbine
16.Heatexchanger
17.GascoolerNo.2
(De NitricAcidManufacture
,Miles(1961),withpermission)
Figura3.14.Connectionsofanitricacidplant,intermediatepressuretype
distributedataheaderpressureofaround8bar(100psig)soanyreactorwithatemper
atureabove200Cisapotentialsteamgenerator.
Threesystemsareused:
1.Figure3.15a.Anarrangementsimilartoaconventionalwatertubeboiler.Steamis
generatedincoolingpipeswithinthereactorandseparatedinasteamdrum.
Pgina72
105
2.Figure3.15b.Similartothefirstarrangementbutwiththewaterkeptathighpressure
topreventvaporisation.Thehighpressurewaterisflashedtosteamatlowerpressure
inaflashdrum.Thissystemwouldgivemoreresponsivecontrolofthereactor
latemperatura.
3.Figure3.15c.Inthissystemaheattransferfluid,suchasDowtherm(seePerryand
Green(1984)andSingh(1985)fordetailsofheattransferfluids),isusedtoavoid
theneedforhighpressuretubes.Thesteamisraisedinanexternalboiler.
Vapor
Vapor
Steamdrum
Flashdrum
Bombadealimentacin
Reactor
(la)
Reactor
(segundo)
Vapor
Caldera
Alimentacin
agua
Reactor
(do)
Figure3.15.Steamgeneration
3.16.5.Lowgradefuels
Thewasteproductsfromanyprocess(gases,liquidsandsolids)whichcontainsignificant
quantitiesofcombustiblematerialcanbeusedaslowgradefuelsforraisingsteamor
directprocessheating.Theirusewillonlybeeconomiciftheintrinsicvalueofthefuel
justifiesthecostofspecialburnersandotherequipmentneededtoburnthewaste.Siel
combustiblecontentofthewasteistoolowtosupportcombustion,thewastewillhave
tobesupplementedwithhighercalorificvalueprimaryfuels.
Reactoroffgases
Theoffgases(ventgas)fromreactors,andrecyclestreampurgesareoftenofhighenough
53/74
16/11/2015
calorificvaluetobeusedasfuels.
Thecalorificvalueofagascanbecalculatedfromtheheatsofcombustionofits
constituentsthemethodisillustratedinExample3.14.
Otherfactorswhich,togetherwiththecalorificvalue,willdeterminetheeconomic
valueofanoffgasasafuelarethequantityavailableandthecontinuityofsupply.
Wastegasesarebestusedforsteamraising,ratherthanfordirectprocessheating,asthis
decouplesthesourcefromtheuseandgivesgreaterflexibility.
Pgina73
106
INGENIERAQUMICA
Example3.16
Calculationofawastegascalorificvalue
Thetypicalventgasanalysisfromtherecyclestreaminanoxyhydrochlorinationprocess
fortheproductionofdichloroethane(DCE)(BritishpatentBP1,524,449)isgivenbelow,
percentagesonvolumebasis.
O2 7.96,CO 2 CN 2 87.6,CO1.79,C
Estimatetheventgascalorificvalue.
2MARIDO
4 1.99,C 2MARIDO
6 0.1,DCE0.54
Solucin
Componentcalorificvalues,fromPerryandChilton(1973)
CO67.6kcal/molD283kJ/mol
do2MARIDO
D1560.9
4 372.8
do2MARIDO
D1411.9
6 337.2
ThevalueforDCEcanbeestimatedfromtheheatsofformation.
Combustionreaction:
1
do2MARIDO
4Cl2(g)C2 2O2(gramo)!2CO
2(g)CH 2O(g)C2HCl(g)
H
F fromAppendixD
CO2 D393.8kJ/mol
MARIDO
2OD242.0
HClD92.4
DCED130.0
H
H
H
dore
F productos
F reactivos
D[2393.8242.0C292.4][130.0]
D1084.4kJ
Estimationofventgascv,basis100mols.
Componente
mols/100mols
CO
do2MARIDO
4
do2MARIDO
6
DCE
1.79
1.99
0.1
0.54
Calorificvalue
(kJ/mol)
re
Heatingvalue
283.0
1560.9
1411.9
1084.4
re
506.6
3106.2
141.2
585.7
Total
4339.7
4339.7
D43.4kJ/mol
100
43.4
3at1bar,0do
re
10 3 D1938kJ/m352Btu/ft
22.4
CalorificvalueofventgasD
Pgina74
107
Barelyworthrecovery,butifthegashastobeburnttoavoidpollutionitcouldbeused
54/74
16/11/2015
inanincineratorsuchasthatshowninFigure3.16,givingausefulsteamproductionto
offsetthecostofdisposal.
Formaldehydeoffgas
Oxychlorination
ventfume
VCMwastefume
Lquido
chlorinatedHC
Monochem.
fume
Nat.gas
Vapor
Feedwater
NaOH
soln.
88C
85C
MARIDO
2O
1090C
316C
min.
Humo
Wasteheat
incinerator
boiler
Primario Secundario
Combustin
scrubber scrubber
aire
HCL
soln.
Figure3.16.Typicalincineratorheatrecoveryscrubbersystemforvinylchloridemonomerprocesswaste
(CourtesyofJohnThurleyLtd.)
Liquidandsolidwastes
Combustibleliquidandsolidwastecanbedisposedofbyburning,whichisusually
preferredtodumping.Incorporatingasteamboilerintheincineratordesignwillenable
anotherwiseunproductive,butnecessaryoperation,tosaveenergy.Ifthecombustion
productsarecorrosive,corrosionresistantmaterialswillbeneeded,andthefluegases
scrubbedtoreduceairpollution.Anincineratordesignedtohandlechlorinatedand
otherliquidandsolidwastesisshowninFigure3.16.Thisincineratorincorporatesa
steamboilerandafluegasscrubber.Thedisposalofchlorinatedwastesisdiscussedby
Santoleri(1973).
DunnandTomkins(1975)discussthedesignandoperationofincineratorsforprocess
desechos.Theygiveparticularattentiontotheneedtocomplywiththecurrentcleanair
legislation,andtheproblemofcorrosionanderosionofrefractoriesandheatexchange
superficies.
3.16.6.Highpressureprocessstreams
Wherehighpressuregasorliquidprocessstreamsarethrottledtolowerpressures,energy
canberecoveredbycarryingouttheexpansioninasuitableturbine.
Gasstreams
Theeconomicoperationofprocesseswhichinvolvethecompressionandexpansion
oflargequantitiesofgases,suchasammoniasynthesis,nitricacidproductionandair
Pgina75
108
INGENIERAQUMICA
separation,dependsontheefficientrecoveryoftheenergyofcompression.Theenergy
recoveredbyexpansionisoftenusedtodrivethecompressorsdirectlycomosemuestraen
Figura3.14.Ifthegascontainscondensiblecomponentsitmaybeadvisabletoconsider
heatingthegasbyheatexchangewithahighertemperatureprocessstreambefore
expansin.Thegascanthenbeexpandedtoalowerpressurewithoutcondensationand
thepowergeneratedincreased.
AninterestingprocessincorporatinganexpansionturbineisdescribedbyBarlow(1975)
whodiscussesenergyrecoveryinanorganicacidsplant(aceticandpropionic).Enesto
processathirteenstageturboexpanderisusedtorecoverenergyfromtheoffgases.los
pressurerangeisdeliberatelychosentoreducetheoffgasestoalowtemperatureatthe
expanderoutlet(60 C),foruseforlowtemperaturecooling,savingrefrigeration.
Theenergyrecoverablefromtheexpansionofagascanbeestimatedbyassuming
polytropicexpansionseeSection3.13.2andExample3.17.
ThedesignofturboexpandersfortheprocessindustriesisdiscussedbyBlochetal.
(1982).
Example3.17
Considertheextractionofenergyfromthetailgasesfromanitricacidadsorptiontower,
suchasthatdescribedinChapter4,Example4.4.
55/74
16/11/2015
Gascomposition,kmol/h:
O2
371.5
norte
10,014.7
2
NO
21.9
NO2
Rastro
MARIDO
saturatedat250do
2O
Ifthegasesleavethetowerat6atm,25 C,andareexpandedto,say,1.5atm,calculate
theturbineexitgastemperatureswithoutpreheat,andifthegasesarepreheatedto
400Cwiththereactoroffgas.Also,estimatethepowerrecoveredfromthepreheated
gases.
Solucin
Forthepurposesofthiscalculationitwillbesufficienttoconsiderthetailgasasall
nitrogen,flow10,410kmol/h.
PdoD33.5atm,T doD126.2K
Figure3.6canbeusedtoestimatetheturbineefficiency.
10,410
1
22.4
3600
15
'43m 3/s
ExitgasvolumetricflowrateD
Pgina76
109
fromFigure3.6EP D0.75
6
D0.18
33.5
298
Tr inletD
D2.4
126.2
Pr inletD
Forthesevaluesthesimplifiedequationscanbeused,equations3.37aand3.38a.
ForN2 D1.4
1.41
mD
0.75D0.21
1.4
1
1
nD
re
D1.27
1m
10.21
(
)
15 0.21
withoutpreheatT2 D298
D223K
6.0
D50 C(acidicwaterwouldcondenseout)
(
)
15 0.21
withpreheatT2 D673
D503K
6.0
D230do
Fromequation3.31,workdonebygasesasaresultofpolytropicexpansion
{(
}
)
1.27
15 1.271/1.27
1
D16738.314
1.271
6.0
D6718kJ/kmol
ActualworkDpolytropicworkE p
D67180.75D5039kJ/kmol
PoweroutputDwork/kmolkmol/sD5039
10,410
3600
D14,571kJ/sD14.6MW
Liquidstreams
Asliquidsareessentiallyincompressible,lessenergyisstoredinacompressedliquidthan
56/74
16/11/2015
agas.However,itisworthconsideringpowerrecoveryfromhighpressureliquidstreams
(>15bar)astheequipmentrequiredisrelativelysimpleandinexpensive.Centrfugo
pumpsareusedasexpandersandareoftencoupleddirectlytopumps.Thedesign,
operationandcostofenergyrecoveryfromhighpressureliquidstreamsisdiscussed
byJenett(1968),Chada(1984)andBuse(1985).
Pgina77
110
INGENIERAQUMICA
3.16.7.Heatpumps
Aheatpumpisadeviceforraisinglowgradeheattoatemperatureatwhichtheheatcan
beutilised.Itpumpstheheatfromalowtemperaturesourcetothehighertemperature
sink,usingasmallamountofenergyrelativetotheheatenergyrecovered.
Heatpumpsareincreasinglyfindingapplicationsintheprocessindustries.Atpico
applicationistheuseofthelowgradeheatfromthecondenserofadistillationcolumn
toprovideheatforthereboilerseeBarnwellandMorris(1982)andMeili(1990).Calor
pumpsarealsousedwithdryers,heatbeingabstractedfromtheexhaustairandused
topreheattheincomingair.Theuseofaheatpumpwithanevaporatorisdescribedin
Volume2,Chapter14.
Detailsofthethermodynamiccyclesusedforheatpumpscanbefoundinmost
textbooksonEngineeringThermodynamics,andinReayandMacMichael(1988).En
theprocessindustriesheatpumpsoperatingonthemechanicalvapourcompressioncycle
wouldnormallybeused.Avapourcompressionheatpumpappliedtoadistillationcolumn
isshowninFigure3.17a.Theworkingfluid,usuallyacommercialrefrigerant,isfedto
thereboilerasavapourathighpressureandcondenses,givingupheattovaporisethe
processfluid.Theliquidrefrigerantfromthereboileristhenexpandedoverathrottle
valveandtheresultingwetvapourfedtothecolumncondenser.Inthecondenserthe
wetrefrigerantisdried,takingheatfromthecondensingprocessvapour.Therefrigerant
vapouristhencompressedandrecycledtothereboiler,completingtheworkingcycle.
Iftheconditionsaresuitabletheprocessfluidcanbeusedastheworkingfluidforthe
heatpump.ThisarrangementisshowninFigure3.17b.Thehotprocessliquidathigh
Condensador
Vapour Bajo
prensa
Alimentacin
Expansin
vlvula Compresor
Alto
prensa
Rehervidor
Lquido
(la)
(segundo)
Figure3.17.Distillationcolumnwithheatpump(a)Separaterefrigerantcircuit(b)Usingcolumnfluidasthe
refrigerant
Pgina78
111
pressureisexpandedoverthethrottlevalueandfedtothecondenser,toprovidecooling
tocondensethevapourfromthecolumn.Thevapourfromthecondenseriscompressed
andreturnedtothebaseofthecolumn.Inanalternativearrangement,theprocessvapour
57/74
16/11/2015
istakenfromthetopofthecolumn,compressedandfedtothereboilertoprovideheating.
Theefficiencyofaheatpumpismeasuredbythecoefficientofperformance,COP:
COPD
energydeliveredathighertemperature
energyinputcompressor
TheCOPwilldependprincipallyontheworkingtemperatures.
Theeconomicsoftheapplicationofheatpumpsintheprocessindustriesisdiscussed
byHollandandDevotta(1986).Detailsoftheapplicationofheatpumpsinawiderange
ofindustriesaregivenbyMoserandSchnitzer(1985).
3.17.PROCESSINTEGRATIONANDPINCHTECHNOLOGY
Processintegrationcanleadtoasubstantialreductionintheenergyrequirementsofa
proceso.Inrecentyearsmuchworkhasbeendoneondevelopingmethodsforinvestigating
energyintegrationandtheefficientdesignofheatexchangernetworksseeGundersen
andNaess(1988).Oneofthemostsuccessfulandgenerallyusefultechniquesisthat
developedbyBodoLinnhoffandotherworkers:pinchtechnology.Thetermderivesfrom
thefactthatinaplotofthesystemtemperaturesversustheheattransferred,apinch
usuallyoccursbetweenthehotstreamandcoldstreamcurves,seeFigure3.22.Tiene
beenshownthatthepinchrepresentsadistinctthermodynamicbreakinthesystemand
that,forminimumenergyrequirements,heatshouldnotbetransferredacrossthepinch,
LinnhoffandTownsend(1982).
Inthissectionthefundamentalprinciplesofthepinchtechnologymethodforenergy
integrationwillbeoutlinedandillustratedwithreferencetoasimpleproblem.Elmtodo
anditsapplicationsaredescribedfullyinaguidepublishedbytheInstitutionofChemical
Engineers,IChemE(1994)seealsoDouglas(1988).
3.17.1.Pinchtechnology
Thedevelopmentandapplicationofthemethodcanbeillustratedbyconsideringthe
problemofintegratingtheutilisationofenergybetween4processstreams.Twohot
streamswhichrequirecooling,andtwocoldstreamsthathavetobeheated.Elproceso
dataforthestreamsissetoutinTable3.3.Eachstreamstartsfromasourcetemperature
Ts,andistobeheatedorcooledtoatargettemperatureT t .Theheatcapacityofeach
streamisshownasCP.Forstreamswherethespecificheatcapacitycanbetakenas
constant,andthereisnophasechange,CPwillbegivenby:
CPDmCp
wheremDmassflowrate,kg/s
CpDaveragespecificheatcapacitybetweenTs Yt
t kJkg
1do 1
Pgina79
112
INGENIERAQUMICA
Table3.3.Dataforheatintegrationproblem
Corriente
Heatcapacity Ts
Tt
Heatload
do
do
do
nmero
Escribe CP,kW/
kW
1
caliente
3.0
180
60
360
2
caliente
1.0
150
30
120
3
fro
2.0
20
135
230
4
fro
4.5
80
140
270
Theheatloadshowninthetableisthetotalheatrequiredtoheat,orcool,thestream
fromthesourcetotargettemperature.
Thefourstreamsareshowndiagrammaticallybelow,Figure3.18:
Thereisclearlyscopeforenergyintegrationbetweenthesefourstreams.Tworequire
heatingandtwocoolingandthestreamtemperaturesaresuchthatheatcanbetransferred
fromthehottothecoldstreams.Thetaskistofindthebestarrangementofheatexchangers
toachievethetargettemperatures.
CP=3.0kW/C
Stream1180C60C
1.0
Stream2150C30C
2.0
Stream320C135C
4.5
Stream480C140C
58/74
16/11/2015
Figure3.18.Diagrammaticrepresentationofprocessstreams
Simpletwostreamproblem
BeforeinvestigatingtheenergyintegrationofthefourstreamsshowninTable3.3,the
useofatemperatureenthalpydiagramwillbeillustratedforasimpleprobleminvolving
onlytwostreams.Thegeneralproblemofheatingandcoolingtwostreamsfromsourceto
targettemperaturesisshowninFigure3.19.Someheatisexchangedbetweenthestreams
intheheatexchanger.Additionalheat,toraisethecoldstreamtothetargettemperature,
isprovidedbythehotutility(usuallysteam)intheheaterandadditionalcoolingtobring
thehotstreamtoitstargettemperature,bythecoldutility(usuallycoolingwater)inthe
enfriador.
Ts
Caliente
corriente
Tt
Fro
utilidad
Tt
Caliente
utilidad
Intercambiador
Ts
Fro
corriente
Figure3.19.Twostreamexchangerproblem
Pgina80
113
InFigure3.20thestreamtemperaturesareplottedontheyaxisandtheenthalpychange
ineachstreamonthexaxis.Forheattobeexchangedaminimumtemperaturedifference
mustbemaintainedbetweenthetwostreams.Thisisshownas min
T onthediagram.los
practicalminimumtemperaturedifferenceinaheatexchangerwillusuallybebetween
10and20DOseeChapter12.
?Hcaliente
?Hcaliente
Coldstream
Caliente
corriente
Latemperatura
DTmin
DT
min
?Hex
?H ?H
fro ex
?H
fro
Enthalpy
(la)
Enthalpy
(segundo)
Figure3.20.Temperatureenthalpyfor2streamexample
Theheattransferredbetweenthestreamsisshownonthediagramas H ex,andthe
heattransferredfromtheutilitiesas Hfro and H caliente
:
HDCPtemperaturechange
ItcanbeseenbycomparingFigure3.20aandbthattheamountofheatingandcooling
neededwilldependontheminimumtemperaturedifference.Decreasing T min ser
increasetheamountofheatexchangedbetweenthetwostreamsandsodecreasethe
consumptionofthehotandcoldutilities.
Fourstreamproblem
InFigure3.21athehotstreamsgiveninTable3.3areshownplottedonatemperature
enthalpydiagram.
Asthediagramshowschangesintheenthalpyofthestreams,itdoesnotmatterwhere
aparticularcurveisplottedontheenthalpyaxisaslongasthecurverunsbetween
thecorrecttemperatures.Thismeansthatwheremorethanonestreamappearsina
temperatureinterval,thestreamheatcapacitiescanbeaddedtogivethecompositecurve
showninFigure3.21b.
59/74
16/11/2015
InFigure3.22,thecompositecurveforthehotstreamsandthecompositecurvefor
coldstreamsaredrawnwithaminimumtemperaturedifference,thedisplacementbetween
thecurves,of10C.Thisimpliesthatinanyoftheexchangerstobeusedinthenetwork
thetemperaturedifferencebetweenthestreamswillnotbelessthan10DO.
Pgina81
114
INGENIERAQUMICA
200
180
160
DO
140
Stream1
120
100
Stream2
80
60
Latemperatura,
40
20
0
0 100 200 300 400 500600 0
Enthalpy,kW
(la)
Streams1
CP=3.0
Streams1+2
CP=3.0+1.0=4.0
Stream2CP=1.0kW/C
100 200 300 400 500600
Enthalpy,kW
(segundo)
Figure3.21.Hotstreamtemperaturev.enthalpy(a)Separatehotstreams(b)Compositehotstreams
Hotutility
50kW
200
180
160
d
o
140
Hotstreams
120
Coldstreams
100
Pinch
DT =10C
80
min
Latemperatura,
60
40
30kW
20
Coldutility
0
0
100 200 300 400 500 600
Enthalpy,kW
Figure3.22.Hotandcoldstreamcompositecurves
Asforthetwostreamproblem,thedisplacementofthecurvesatthetopandbottom
ofthediagramgivesthehotandcoldutilityrequirements.Thesewillbetheminimum
valuesneededtosatisfythetargettemperatures.Thisisvaluableinformation.Itgivesthe
designertargetvaluesfortheutilitiestoaimforwhendesigningtheexchangernetwork.
Anydesigncanbecomparedwiththeminimumutilityrequirementstocheckiffurther
improvementispossible.
Inmostexchangernetworkstheminimumtemperaturedifferencewilloccuratonly
onepoint.Thisistermedthepinch.Intheproblembeingconsidered,thepinchoccursat
between90Conthehotstreamcurveand80Conthecoldstreamcurve.
Pgina82
115
Significanceofthepinch
Thepinchdividesthesystemintotwodistinctthermodynamicregions.Theregionabove
thepinchcanbeconsideredaheatsink,withheatflowingintoit,fromthehotutility,
butnotoutofit.Belowthepinchtheconverseistrue.Heatflowsoutoftheregionto
thecoldutility.Noheatflowsacrossthepinch.
60/74
16/11/2015
Ifanetworkisdesignedthatrequiresheattoflowacrossthepinch,thentheconsumption
ofthehotandcoldutilitieswillbegreaterthantheminimumvaluesthatcouldbeachieved.
3.17.2.Theproblemtablemethod
TheproblemtableisthenamegivenbyLinnhoffandFlowertoanumericalmethodfor
determiningthepinchtemperaturesandtheminimumutilityrequirementsLinnhoffand
Flower(1978).Onceunderstood,itisthepreferredmethod,avoidingtheneedtodrawthe
compositecurvesandmanoeuvrethecompositecoolingcurveusing,forexample,tracing
paperorcutouts,togivethechosenminimumtemperaturedifferenceonthediagram.
Theprocedureisasfollows:
1.ConverttheactualstreamtemperaturesT actointointervaltemperaturesT int por
subtractinghalftheminimumtemperaturedifferencefromthehotstreamtemperatures,
andbyaddinghalftothecoldstreamtemperatures:
Tmin
2
Tmin
coldstreamsTintDT acto
do
2
hotstreamsTintDT acto
Theuseoftheintervaltemperatureratherthantheactualtemperaturesallowsthe
minimumtemperaturedifferencetobetakenintoaccount. min
T D10Cfortheproblem
beingconsideredseeTable3.4.
Table3.4.Intervaltemperaturesfor
Tdo
minD10
Corriente Actualtemperature Intervaltemperature
1
180
60
175
55
2
150
30
145
25
3
20
135
(25)
140
4
80
140
85
(145)
2.Noteanyduplicatedintervaltemperatures.ThesearebracketedinTable3.4.
3.Ranktheintervaltemperaturesinorderofmagnitude,showingtheduplicatedtemper
aturesonlyonceintheorderseeTable3.5.
4.Carryoutaheatbalanceforthestreamsfallingwithineachtemperatureinterval:
Forthenthinterval:
H norte
D CPdo CPmarido
nT
orte
where H norte
Dnetheatrequiredinthenthinterval
CP doDsumoftheheatcapacitiesofallthecoldstreamsintheinterval
CP marido
Dsumoftheheatcapacitiesofallthehotstreamsintheinterval
T norte
DintervaltemperaturedifferenceDT
n1 Tnorte
Pgina83
116
INGENIERAQUMICA
SeeTable3.6.
Table3.5.Rankedorderofintervaltemperatures
Intervalo
Streamsin
do
Rango
Tnorte
intervalo
175do
145
30
1
140
5
4 2C1
85
55
3C4
1C2
55
30
3 1C2
25
30
3 2
Note:Duplicatedtemperaturesareomitted.Theinterval
Tandstreamsintheintervalsareincludedastheyare
neededforTable3.6.
Table3.6.Problemtable
Intervalo
Tnorte CPdo CPmarido
H
do
do
Intervalo temperatura
kW/do
kW
175
1
145
30
3.0
90
2
140
5
0.5
2.5
3
85
55
2.5
137.5
4
55
30
2.0
60
5
25
30
1.0
30
Note:ThestreamsineachintervalaregiveninTable3.5.
Surplusor
Dficit
s
re
re
s
re
5.Cascadetheheatsurplusfromoneintervaltothenextdownthecolumnofinterval
61/74
16/11/2015
temperaturesFigure3.23a.
Cascadingtheheatfromoneintervaltothenextimpliesthatthetemperaturedifference
issuchthattheheatcanbetransferredbetweenthehotandcoldstreams.Lapresencia
Intervalo
temperatura
0kW
175do
50kW
90kW
145do
90kW
2.5kW
140do
87.5kW
137.5kW
85do
50kW
60kW
55do
10kW
30kW
25do
20kW
(la)
DO.
From(b)pinchoccursatintervaltemperatureD85
90kW
140kW
2.5kW
135.5kW
137.5kW
0.0kW
60kW
60kW
30kW
30kW
(segundo)
Figure3.23.Heatcascade
Pgina84
117
ofanegativevalueinthecolumnindicatesthatthetemperaturegradientisinthewrong
directionandthattheexchangeisnotthermodynamicallypossible.
Thisdifficultycanbeovercomeifheatisintroducedintothetopofthecascade:
6.Introducejustenoughheattothetopofthecascadetoeliminateallthenegative
valoresseeFigure3.23b.
Comparingthecompositecurve,Figure3.22,withFigure3.23bshowsthattheheat
introducedtothecascadeistheminimumhotutilityrequirementandtheheatremovedat
thebottomistheminimumcoldutilityrequired.ThepinchoccursinFigure3.23bwhere
theheatflowinthecascadeiszero.Thisisaswouldbeexpectedfromtherulethatfor
minimumutilityrequirementsnoheatflowsacrossthepinch.InFigure3.23bthepinch
temperaturesare80and90C,aswasfoundusingthecompositestreamcurves.
Itisnotnecessarytodrawupaseparatecascadediagram.ThiswasdoneinFigure3.23
toillustratetheprinciple.Thecascadedvaluescanbeaddedtotheproblemtableastwo
additionalcolumnsseeexample3.16.
Resumen
Formaximumheatrecoveryandminimumuseofutilities:
1.Donottransferheatacrossthepinch
2.Donotusehotutilitiesbelowthepinch
3.Donotusecoldutilitiesabovethepinch
3.17.3.Theheatexchangernetwork
Gridrepresentation
ItisconvenienttorepresentaheatexchangernetworkasagridseeFigure3.24.los
processstreamsaredrawnashorizontallines,withthestreamnumbersshowninsquare
cajas.Hotstreamsaredrawnatthetopofthegrid,andflowfromlefttoright.Thecold
streamsaredrawnatthebottom,andflowfromrighttoleft.Thestreamheatcapacities
CPareshowninacolumnattheendofthestreamlines.
Hotstreamnorte
no.norte
LA
LA
Intercambiador
Enfriador
Coldstream
metro
no.metro
Figure3.24.Gridrepresentation
Heatexchangersaredrawnastwocirclesconnectedbyaverticalline.Thecircles
connectthetwostreamsbetweenwhichheatisbeingexchangedthatis,thestreamsthat
62/74
16/11/2015
wouldflowthroughtheactualexchanger.Heaterandcoolersaredrawnasasinglecircle,
connectedtotheappropriateutility.
Pgina85
118
INGENIERAQUMICA
Networkdesignformaximumenergyrecovery
TheanalysiscarriedoutinFigure3.22,andFigure3.23,hasshownthattheminimum
utilityrequirementsfortheproblemsetoutinTable3.3are50kWofthehotand30kW
ofthecoldutilityandthatthepinchoccurswherethecoldstreamsareat80andthe
hot90DO.
ThegridrepresentationofthestreamsisshowninFigure3.25.Theverticaldottedlines
representthepinchandseparatethegridintotheregionsaboveandbelowthepinch.
180C
90C80C
CP
(kW/C)
60C
3.0
150C
30C
135C
20C
2.0
3
140C
80C
4.5
4
1.0
Figure3.25.Gridfor4streamproblem
Formaximumenergyrecovery(minimumutilityconsumption)thebestperformanceis
obtainedifnocoolingisusedabovethepinch.Thismeansthatthehotstreamsabove
thepinchshouldbebroughttothepinchtemperaturesolelybyexchangewiththecold
arroyos.Thenetworkdesignisthereforestartedatthepinchfindingfeasiblematches
betweenstreamstofulfilthisaim.Inmakingamatchadjacenttothepinchtheheat
capacityCPofthehotstreamshouldbeequaltoorlessthanthatofthecoldstream.Esta
istoensurethattheminimumtemperaturedifferencebetweenthecurvesismaintained.
Theslopeofalineonthetemperatureenthalpydiagramisequaltothereciprocalofthe
heatcapacity.So,abovethepinchthelineswillconvergeifCPcaliente
exceedsCPfro andas
thestreamsstartwithaseparationatthepinchequalto Tmin,theminimumtemperature
conditionwouldbeviolated.
Belowthepinchtheprocedureisthesametheaimbeingtobringthecoldstreams
tothepinchtemperaturebyexchangewiththehotstreams.Forstreamsadjacenttothe
pinchthecriterionformatchingstreamsisthattheheatcapacityofthecoldstreammust
beequaltoorgreaterthanthehotstream,toavoidbreakingtheminimumtemperature
differencecondition.
Thenetworkdesignabovethepinch
CP caliente
CP fro
1.Applyingthisconditionatthepinch,stream1canbematchedwithstream4,but
notwith3.
Pgina86
119
Matchingstreams1and4andtransferringthefullamountofheatrequiredtobring
stream1tothepinchtemperaturegives:
H exDCPTs Tpinch
H ex D3.018090D270kW
Thiswillalsosatisfytheheatloadrequiredtobringstream4toitstargettemperature:
63/74
16/11/2015
H ex D4.514080D270kW
2.Stream2canbematchedwithstream3,whilstsatisfyingtheheatcapacityrestriction.
Transferringthefullamounttobringstream3tothepinchtemperature:
H exD1.015090D60kW
3.Theheatrequiredtobringstream3toitstargettemperature,fromthepinchtemper
ature,is:
HD2.013580D110kW
Soaheaterwillhavetobeincludedtoprovidetheremainingheatload:
H caliente
D11060D50kW
Thischeckswiththevaluegivenbytheproblemtable,Figure3.23b.
TheproposednetworkdesignabovethepinchisshowninFigure3.26.
90C 80C
180C
1
150C
2
135C
140C50kW 60kW
270kWPinch
CP
kW/C
60C
3.0
30C
1.0
20C
3
80C
4
2.0
4.5
Figure3.26.Networkdesignabovepinch
Networkdesignbelowthepinch
CP caliente
CPfro
4.Stream4isatthepinchtemperature,Ts D80DO.
5.Amatchbetweenstream1and3adjacenttothepinchwillsatisfytheheatcapacity
restrictionbutnotonebetweenstreams2and3.So1ismatchedwith3transferringthe
fullamounttobringstream1toitstargettemperaturetransferring:
H exD3.09060D90kW
Pgina87
120
INGENIERAQUMICA
6.Stream3requiresmoreheattobringittothepinchtemperatureamountneeded:
HD2.0802090D30kW
Thiscanbeprovidedfromstream2,asthematchwillnowbeawayfromthepinch.
Theriseintemperatureofstream3willbegivenby:
TD H/CP
Sotransferring30kWwillraisethetemperaturefromthesourcetemperatureto:
20C30/2.0D35 do
andthisgivesastreamtemperaturedifferenceontheoutletsideoftheexchangerof:
9035D55 do
Sotheminimumtemperaturedifferencecondition,10C,willnotbeviolatedbythis
match.
7.Stream2willneedfurthercoolingtobringittoitstargettemperature,soacooler
mustbeincludedcoolingrequired.
H fro D1.0903030D30kW
Whichistheamountofthecoldutilitypredictedbytheproblemtable.
TheproposednetworkformaximumenergyrecoveryisshowninFigure3.27.
180C
90C 80C
?H
CP
kW/C kW
60C 3.0 360
64/74
16/11/2015
1
segundo
150C
LA
2
Calentador
135C
LA
140C 50kW 60kW
segundo
270kW Pinch
do
re
Enfriador
30C
120
1.0
30kW
20C 2.0
re
do
3
90kW 30kW
80C 4.5
4
230
270
do
Figure3.27.Proposedheatexchangernetwork
minD10T
Streamsplitting
Iftheheatcapacitiesofstreamsaresuchthatitisnotpossibletomakeamatchatthepinch
withoutviolatingtheminimumtemperaturedifferencecondition,thentheheatcapacity
canbealteredbysplittingastream.Dividingthestreamwillreducethemassflowrates
ineachlegandhencetheheatcapacities.ThisisillustratedinExample3.16.
GuiderulesforstreammatchingandsplittingaregivenintheInstitutionofChemical
EngineersGuide,IChemE(1994).
Pgina88
121
Resumen
Theheuristics(guiderules)fordevisinganetworkformaximumheatrecoveryaregiven
abajo:
1.Dividetheproblematthepinch.
2.Designawayfromthepinch.
3.Abovethepinchmatchstreamsadjacenttothepinch,meetingtherestriction:
CP caliente
CP fro
4.Belowthepinchmatchstreamsadjacenttothepinch,meetingtherestriction:
CP caliente
CP fro
5.Ifthestreammatchingcriteriacannotbesatisfiedsplitastream.
6.Maximisetheexchangerheatloads.
7.Supplyexternalheatingonlyabovethepinch,andexternalcoolingonlybelowthe
pinch.
3.17.4.Minimumnumberofexchangers
ThenetworkshowninFigure3.27wasdesignedtogivethemaximumheatrecovery,and
willthereforegivetheminimumconsumption,andcost,ofthehotandcoldutilities.
Thiswillnotnecessarilybetheoptimumdesignforthenetwork.Theoptimumdesign
willbethatwhichgivesthelowesttotalannualcosts:takingintoaccountthecapital
costofthesystem,inadditiontotheutilityandotheroperatingcosts.Thenumberof
exchangersinthenetwork,andtheirsize,willdeterminethecapitalcost.
InFigure3.27itisclearthatthereisscopeforreducingthenumberofexchangers.
ExchangerDcanbedeletedandtheheatloadsofthecoolerandheaterincreasedto
bringstreams2and3totheirtargettemperatures.Heatwouldcrossthepinchandthe
consumptionoftheutilitieswouldbeincreased.Whethertherevisednetworkwouldbe
better,moreeconomic,woulddependontherelativecostofcapitalandutilities.Forany
networktherewillbeanoptimumdesignthatgivestheleastannualcost:capitalcharges
plusutilityandotheroperatingcosts.Theestimationofcapitalandoperatingcostsare
coveredinChapter6.
Tofindtheoptimumdesignitwillbenecessarytocostanumberofalternativedesigns,
seekingacompromisebetweenthecapitalcosts,determinedbythenumberandsizeof
theexchangers,andtheutilitycosts,determinedbytheheatrecoveryachieved.
ForsimplenetworksHolmann(1971)hasshownthattheminimumnumberof
exchangersisgivenby:
ZminDN 0 1
3.41
dondeZminDminimumnumberofexchangersneeded,includingheatersandcoolers
0 Dthenumberofstreams,includingtheutilities
norte
65/74
16/11/2015
Pgina89
122
INGENIERAQUMICA
Forcomplexnetworksamoregeneralexpressionisneededtodeterminetheminimum
numberofexchangers:
ZminDN 0CL 0 S
3.42
whereL0 Dthenumberofinternalloopspresentinthenetwork
SDthenumberofindependentbranches(subsets)thatexistinthenetwork.
Aloopexistswhereaclosepathcanbetracedthroughthenetwork.Thereisaloopin
thenetworkshowninFigure3.27.TheloopisshowninFigure3.28.Thepresenceofa
loopindicatesthatthereisscopeforreducingthenumberofexchangers.
segundo
1
2
do
LA
re
LA
do
re
segundo
3
4
Pinch
Figure3.28.Loopinnetwork
Forafulldiscussionofequation3.42anditsapplicationsseeLinnhoffetal.(1979),
andIChemE(1994).
Insummary,toseektheoptimumdesignforanetwork:
1.Startwiththedesignformaximumheatrecovery.Thenumberofexchangersneeded
willbeequaltoorlessthanthenumberformaximumenergyrecovery.
2.Identifyloopsthatcrossthepinch.Thedesignformaximumheatrecoverywill
usuallycontainloops.
3.Startingwiththeloopwiththeleastheatload,breaktheloopsbyaddingor
subtractingheat.
4.Checkthatthespecifiedminimumtemperaturedifference T min nohasido
violated,andrevisethedesignasnecessarytorestorethe Tmin.
5.Estimatethecapitalandoperatingcosts,andthetotalannualcost.
6.Repeattheloopbreakingandnetworkrevisiontofindthelowestcostdesign.
7.Considerthesafety,operabilityandmaintenanceaspectsoftheproposeddesign.
Importanceoftheminimumtemperaturedifference
Inaheatexchanger,theheattransferarearequiredtotransferaspecifiedheatloadis
inverselyproportionaltothetemperaturedifferencebetweenthestreamsseeChapter12.
Pgina90
123
Thismeansthatthevaluechosenfor T min willdeterminethesizeoftheheat

exchangersinanetwork.Reducing T minwillincreasetheheatrecovery,decreasing
theutilityconsumptionandcost,butattheexpenseofanincreaseintheexchangersize
andcapitalcost.
Foranynetworktherewillbeabestvaluefortheminimumtemperaturedifference
thatwillgivethelowesttotalannualcosts.Theeffectofchangesinthespecified Tmin
needtobeinvestigatedwhenoptimisingaheatrecoverysystem.
66/74
16/11/2015
3.17.5.Thresholdproblems
Problemsthatshowthecharacteristicofrequiringonlyeitherahotutilityoracold
utility(butnotboth)overarangeofminimumtemperaturedifferences,fromzeroupto
athresholdvalue,areknownasthresholdproblems.Athresholdproblemisillustratedin
Figure3.29.
Hotutlity
DT =Threshold
MIN
Latemperatura
Coldutility=zero
Enthalpy
Figure3.29.Thresholdproblem
Todesigntheheatexchangernetworkforathresholdproblem,itisnormaltostartat
themostconstrainedpoint.Theproblemcanoftenbetreatedasonehalfofaproblem
exhibitingapinch.
Thresholdproblemsareencounteredintheprocessindustries.Apinchcanbeintroduced
insuchproblemsifmultipleutilitiesareused,asintherecoveryofheattogeneratesteam.
Pgina91
124
INGENIERAQUMICA
TheprocedurestofollowinthedesignofthresholdproblemsarediscussedbySmith
(1995)andIChemE(1994).
3.17.6.Multiplepinchesandmultipleutilities
Theuseofmultipleutilitiescanleadtomorethanonepinchinaproblem.Inintro
ducingmultipleutilitiesthebeststrategyistogenerateatthehighestlevelanduseatthe
lowestlevel.ForadetaileddiscussionofthistypeofproblemrefertoSmith(1995)and
IChemE(1994).
3.17.7.Processintegration:integrationofotherprocessoperations
Theuseofthepinchtechnologymethodinthedesignofheatexchangernetworkshasbeen
outlinedinSections3.17.1to3.17.6.Themethodcanalsobeappliedtotheintegration
ofotherprocessunitssuchas,separationcolumn,reactors,compressorsandexpanders,
boilersandheatpumps.Thewiderapplicationsofpinchtechnologyarediscussedinthe
InstitutionofChemicalEngineersGuide,IChemE(1994)andbyLinnhoffetal.(1983),
andTownsendandLinnhoff(1982),(1983),(1993).
Someguiderulesforprocessintegration:
1.Installcombinedheatandpower(cogeneration)systemsacrossthepinchver
Captulo14.
2.Installheatengineseitheraboveorbelowthepinch.
3.Installdistillationcolumnsaboveorbelowthepinch.
4.InstallheatpumpsacrossthepinchseeSection3.16.7.
Thetechniquesofprocessintegrationhavebeenexpandedforuseinoptimisingmass
transferoperations,andhavebeenappliedinwastereduction,waterconservation,and
pollutioncontrol,seeDunnandElHalwagi(2003).
67/74
16/11/2015
Example3.18
Determinethepinchtemperaturesandtheminimumutilityrequirementsforthestreams
setoutinthetablebelow,foraminimumtemperaturedifferencebetweenthestreamsof
20C.Deviseaheatexchangernetworktoachievethemaximumenergyrecovery.
Corriente
nmero
1
2
3
4
Escribe
caliente
caliente
fro
fro
Heatcapacity
kW/ do
40.0
30.0
60.0
20.0
Fuente
Objetivo
Calor
do
do
temperatura
temperatura
loadkW
180
40
5600
150
60
2700
30
180
9000
80
160
1600
Solucin
Theconstructionoftheproblemtabletofindtheminimumutilityrequirementandthe
pinchtemperatureisfacilitatedbyusingaspreadsheet.Thecalculationsineachcellare
repetitiveandtheformulacanbecopiedfromcelltocellusingthecellcopycommands.
Pgina92
125
ThespreadsheetASEASYAS(TRIUSInc)wasusedtodevelopthetablesforthis
problema.
Firstcalculatetheintervaltemperatures,for TminD20do
hotstreamsTintDT acto 10do
coldstreamsTintDT acto
C10do
Actualtemp. do
Intervaltemp. do
Corriente Fuente
Objetivo Fuente
Objetivo
1
180
40
170
30
2
150
60
140
50
3
30
180
40
190
4
80
160
90
170
Nextranktheintervaltemperatures,ignoringanyduplicatedvalues.Showwhich
streamsoccurineachintervaltoaidinthecalculationofthecombinedstreamheat
capacities:
190C
170
140
Interval1
2
180C
1 180C
160C
2 150C
90
50
40
4
5
6
30
4 80C
60C
40C
3 30C
Figure3.30.Intervalsandstreams
Nowsetouttheproblemtable:
Intervalo
1
2
3
4
5
6
Intervalo
do
temperatura
190
170
140
90
50
40
30
T
do
20
30
50
40
10
10
CP do
CP marido H
kW/ do
kW
60.0
40.0
10.0
10.0
20.0
40.0
1200
1200
500
400
200
400
Cascada
0
2900
1200
1700
2400
500
2900
0
2500
400
2700
200
2300
600
Inthelastcolumn2900kWofheathavebeenaddedtoeliminatethenegativevalues
inthepreviouscolumn.
So,thehotutilityrequirementis2900kWandthecold,thebottomvalueinthecolumn,
is600kW.
DO.
Thepinchoccurswheretheheattransferrediszero,thatisatintervalnumber3,90
68/74
16/11/2015
Pgina93
126
INGENIERAQUMICA
Soatthepinchhotstreamswillbeat:
90C10D100do
andthecoldat:
9010D80 do
Todesignthenetworkformaximumenergyrecovery:startatthepinchandmatch
streamsfollowingtherulesonstreamheatcapacitiesformatchesadjacenttothepinch.
Whereamatchismade:transferthemaximumamountofheat.
TheproposednetworkisshowninFigure3.31.
100C80C
1800kW
3200kW
180C
1
150C
1500kW
1200kW
600kW
40C
60C
1.300kW
180C
30C
3
160C
1600kW
80C
4
Pinch
Figure3.31.Network,example3.17
Themethodologyfollowedindevisingthisnetworkwas:
Abovepinch
1.CP caliente
CP fro
2.Canmatchstream1and2withstream3butnotwithstream4.
3.Checktheheatavailableinbringingthehotstreamstothepinchtemperature.
stream1 HD40.0180100D3200kW
4.Checktheheatrequiredtobringthecoldstreamsfromthepinchtemperatureto
theirtargettemperatures.
5.Matchstream1with3andtransfer3200kW,thatsatisfies(ticksoff)stream1.
6.Matchstream2with3andtransfer1500kW,thatticksoffstream2.
7.Includeaheateronstream3toprovidethebalanceoftheheatrequired:
H caliente
D60004700D1300kW
8.Includeaheateronstream4toprovideheatloadrequired,1600kW.
Pgina94
127
Belowpinch
9.CP caliente
CP fro
10.Notethatstream4startsatthepinchtemperaturesocannotprovideanycooling
belowthepinch.
11.Cannotmatchstream1or2withstream3atthepinch.
12.So,splitstream3toreduceCP.Anevensplitwillallowbothstreams1and2to
bematchedwiththesplitstreamsadjacenttothepinch,sotrythis:
13.Checktheheatavailablefrombringingthehotstreamsfromthepinchtemperature
totheirtargettemperatures.
69/74
16/11/2015
14.Checktheheatrequiredtobringthecoldstreamsfromtheirsourcetemperatures
tothepinchtemperature:
stream4isatthepinchtemperature.
15.Notethatstream1cannotbebroughttoitstargettemperatureof40 Cbyfull
C,so T
interchangewithstream3asthesourcetemperatureofstream3is30
min
wouldbeviolated.Sotransfer1800kWtoonelegofthesplitstream3.
16.Checktemperatureatexitofthisexchanger:
1800
TempoutD100
D55C,satisfactory
40
17.Providecooleronstream1tobringittoitstargettemperature,coolingneeded:
H fro D24001800D600kW
18.Transferthefullheatloadfromstream2tosecondlegofstream3thissatisfies
bothstreams.
Notethattheheatingandcoolingloads,2900kWand600kW,respectively,match
thosepredictedfromtheproblemtable.
3.18.REFERENCIAS
segundo
,JA(1975)Inst.Mech.Ing.ConferenceonEnergyRecoveryintheProcessIndustries,London.
ARLOW
Energyrecoveryinapetrochemicalplant:advantagesanddisadvantages.
segundo
,J.andM
,CP(1982)Hyd.Proc.61(July)117.Heatpumpcutsenergyuse.
ARNWELL
ORRIS
segundo
,HP,C AMERON
,JA,D ANOWSKY
,FM,J AMES
,R.,SWEARINGEN
,JSandW EIGHTMAN
,ME
LOCH
(1982)CompressorsandExpanders:SelectionandApplicationsfortheProcessIndustries(Dekker).
segundo
,D.andL
,B.(1979)Chem.Engr,LondonNo.343(April)222.Thepreliminarydesignof
OLAND
INNHOFF
networksforheatexchangersbysystematicmethods.
segundo
,F.(1981)Chem.Eng.,NY88(Jan26th)113.Usingcentrifugalpumpsashydraulicturbines.
USAR
do
,N.(1984)Chem.Eng.,NY91(July23rd)57.Useofhydraulicturbinestorecoverenergy.
HADA
reOUGLAS
,JM(1988)ConceptualDesignofChemicalProcesses(McGrawHill).
reRYDEN
,I.(ed.)(1975)TheEfficientUseofEnergy(IPCScienceandTechnologyPress).
reUNN
,KSandTOMKINS
,AG(1975)Inst.Mech.Ing.ConferenceonEnergyRecoveryintheProcessIndus
tries,London.Wasteheatrecoveryfromtheincinerationofprocesswastes.
reUNN
,RFandE LMARIDO
,MM(2003)J.Chem.Technol.Biotechol.78,1011.Processintegration
ALWAGI
technologyreview:backgroundandapplicationsinthechemicalprocessindustry.
mi
,WC(1948)Pet.Ref.27(Nov.)129(609).Applicationsofthermodynamicstohydrocarbon
DMISTER
processing,partXIII
heatcapacities.
Pgina95
128
INGENIERAQUMICA
GRAMO
,T.andN
,L.(1988).Comp.andChem.Eng.,12,No.6,503.Thesynthesisofcostoptimal
UNDERSEN
AESS
heatexchangernetworks
anindustrialreviewofthestateoftheart.
MARIDO
,DM(1995)BasicPrinciplesandCalculationsinChemicalEngineering,6thedn(Pearson).
IMMELBLAU
MARIDO
,P.(1975)Inst.Mech.Ing.ConferenceonEnergyRecoveryintheProcessIndustries,London.Residuos
INCHLEY
heatboilersinthechemicalindustry.
MARIDO
,EC(1971)PhDThesis,UniversityofSouthCalifornia,Optimumnetworksforheatexchangers.
OLMANN
MARIDO
,FAandDEVOTTA
,S.(1986)Chem.Engr,London,No.425(May)61.Prospectsforheatpumps
OLLAND
inprocessapplications.
YAVEO
E(1994)UserGuideonProcessIntegrationforEfficientUseofEnergy,revisededn(Institutionof
HEM
ChemicalEngineers,London).
JENETT
,E.(1968)Chem.Eng.,NY75(April8th)159,(June17th)257(intwoparts).Hydraulicpowerrecovery
sistemas.
KENNEY
,WF(1984)EnergyConversionintheProcessIndustries,AcademicPress.
LINNHOFF
,B.andF
,JR(1978)AIChEJI24,633(2parts)synthesisofheatexchangernetworks.
LOWER
LINNHOFF
,B.,MASON
,DRandW ARDLE
,I.(1979)Comp.andChem.Eng.3,295,Understandingheat
exchangernetworks.
LINNHOFF
,B.,DUNFORD
,H.andS
R
.(1983)Chem.Ing.Sci.38,1175.Heatintegrationofdistillation
MITH
columnsintooverallprocesses.
LINNHOFF
,B.(1993)TransIChemE71,PartA,503.PinchAnalysis
astateoftheartoverview.
METRO
,AHandRUDD
,DF(1969)AIChEJl15,10.Thesynthesisofsystemdesign:heuristicstructures.
ASSO
METRO
,A.(1990)Chem.Ing.Prog.86(6)60.Heatpumpsfordistillationcolumns.
EILI
METRO
,FD(1961)NitricAcidManufactureandUses(OxfordUP)
ILES
METRO
,R.(1968)Chem.Eng.,NY75(May20th)130.Processenergysystems.
ILLER
METRO
,F.andS
,H.(1985)HeatPumpsinIndustry(Elsevier).
OSER
CHNITZER
norte
,N.,LIU,YAandL APIDUS
,L.(1977)AIChEJl23,77.Studiesinchemicalprocessdesignand
ISHIDA
sntesis.
PERRY
,RHandCHILTON
,CH(eds)(1973)ChemicalEngineersHandbook,5thedn(McGrawHill).
PERRY
,RHandGREEN
,DW(eds)(1984)Perry'sChemicalEngineersHandbook,6thedn(McGrawHill).
PORTON
,JWandDONALDSON
,RAB(1974)Chem.Ing.Sci.29,2375.Afastmethodforthesynthesisof
optimalheatexchangernetworks.
REAY
,DAandMACMICHAEL
,DBA(1988)HeatPumps:DesignandApplication,2ndedn(Pergamon
Press).
SANTOLERI
,JJ(1973)Chem.Ing.Prog.69(Jan.)69.Chlorinatedhydrocarbonwastedisposalandrecovery
sistemas.
SIIROLA
,JJ(1974)AIChE76thNationalMeeting,Tulsa,Oklahoma.Studiesofheatexchangernetwork
sntesis.
SINGH
,J.(1985)HeatTransferFluidsandSystemsforProcessandEnergyApplications,MarcelDekker.
STERBACEK
,Z.,BISKUP
,B.andT
,P.(1979)CalculationofPropertiesUsingCorrespondingstateMethods
AUSK
(Elsevier).
SHULTZ
,JM(1962)Trans.ASME84(JournalofEngineeringforPower)(Jan.)69,(April)222(intwoparts).
70/74
16/11/2015
SMITH
Thepolytropicanalysisofcentrifugalcompressors.
,R.(1995)ChemicalProcessDesign(McGrawHill)
TOWNSEND
,DWandLINNHOFF
,B.(1983)AIChEJl29,742.Heatandpowernetworksinprocessesdesign.
TOWNSEND
,DWandLINNHOFF
,B.(1982)Chem.Engr.,London,No.378(March)91.Designingtotalenergy
systemsbysystematicmethods.
3.19.NOMENCLATURA
la
Constantinspecificheatequation(equation3.13)
segundo Constantinspecificheatequation(equation3.13)
CP
Streamheatcapacity
dop
Specificheatatconstantpressure
dopla
Specificheatcomponenta
dopsegundo
Specificheatcomponentb
dopdo
Specificheatcomponentc
dopmetro Meanspecificheat
dop1
Specificheatfirstphase
Dimensiones
inMLTq
L2T 2q 1
L2T 2q 2
ML2T 2q 1
L2T 2q 1
L2T 2q 1
L2T 2q 1
L2T 2q 1
L2T 2q 1
L2T 2q 1
Pgina96
dop2
Specificheatsecondphase
dov
Specificheatatconstantvolume
Idealgasstatespecificheat
doo
p
do
Constantinspecificheatequation(equation3.13)
CPdo Sumofheatcapacitiesofcoldstreams
CPmarido
Sumofheatcapacitiesofhotstreams
mi
Efficiency,electricmotors
mi
mi
Polytropicefficiency,compressorsandturbines
p
F
Fuerza
gramo Gravitationalacceleration
MARIDOEnthalpy
MARIDO
Specificenthalpyofcomponenta
la
MARIDO
segundoSpecificenthalpyofcomponentb
Enthalpytopproductstream(Example3.1)
MARIDO
re
MARIDO
Enthalpyfeedstream(Example3.1)
F
MARIDO
SpecificenthalpyattemperatureT
T
MARIDO
Enthalpybottomproductstream(Example3.1)
w
Changeinenthalpy
H
Hfro Heattransferfromcoldutility
Hex
Heattransferinexchanger
Hcaliente
Heattransferfromhotutility
Hnorte Heatavailableinnthinterval
Hm,t Heatofmixingattemperaturet
Hr,t Heatofreactionattemperaturet
Hdo Standardheatofcombustion
Standardenthalpyofformation
HF
HmetroStandardheatofmixing
H Standardheatofreaction
L r
Numberofauxiliarystreams,heatexchangernetworks
L0
Numberofinternalloopsinnetwork
l
Distancia
METRO Numberofhotstreams,heatexchangernetworks
METRO Molecularmass(weight)
metro Polytropictemperatureexponent
metro Masa
metro Massflowrate
norte
Numberofcoldstreams,heatexchangernetworks
0
norte
Numberofstreams
Expansionorcompressionindex(equation3.30)
norte
P
Presin
Pyo
Interstagepressure
Reducedpressure
Pr
P1
Initialpressure
P2
Finalpressure
Q
Heattransferredacrosssystemboundary
QsegundoReboilerheatload(Example3.1)
Qdo
Condenserheatload(Example3.1)
Qp
Heatadded(orsubtracted)fromasystem
Qr
Heatfromreaction
Qs
Heatgeneratedinthesystem
R
Universalgasconstant
S
Numberofindependentbranches
Scj
Coldstreams,heatexchangernetworks
SHola Hotstreams,heatexchangernetworks
SReinoUnido
Auxiliarystreams,heatexchangernetworks
T
Temperature,absolute
Tacto
Actualstreamtemperature
129
L2T 2q 1
L2T 2q 1
L2T 2q 1
L2T 2q 3 oL2T 2q 2.1
ML2T 2q 1
ML2T 2q 1
MLT2
LT 2
ML2T 2
L2T 2
L2T 2
ML2T 3
ML2T 3
L2T 2
ML2T 3
ML2T 2
ML2T 3
ML2T 3
ML2T 3
ML2T 3
L2T 2
L2T 2
L2T 2
L2T 2
L2T 2
L2T 2
L
METRO
1
MONTE
ML 1T 2
ML 1T 2
ML 1T 2
ML 1 T 2
2T 3
ML2T 2 orML
ML2T 3
2
3
MLT
2T 3
ML2T 2 orML
2T 3
ML2T 2 orML
2T 3
ML2T 2 orML
L2T 2q 1
q
q
71/74
16/11/2015
Pgina97
130
INGENIERAQUMICA
Tre
Datumtemperatureforenthalpycalculations
Tint
Intervaltemperature
Tnorte Temperatureinnthinterval
Tp
Phasetransitiontemperature
Reducedtemperature
Tr
Ts
Sourcetemperature
Targettemperature
Tt
Tmin Minimumtemperaturedifferenceinheatexchanger
Tnorte Internaltemperaturedifference
t
Temperature,relativescale
t
Hora
tr
Referencetemperature,meanspecificheat
tF
Inletstreamtemperatures,heatexchangernetworks
to
Outletstreamtemperatures,heatexchangernetworks
U
Internalenergyperunitmass
u
Velocidad
V1
Initialvolume
V2
Elvolumenfinal
Volumeperunitmass
v
X
Compressibilityfunctiondefinedbyequation3.33
Distancia
X
Xla
Molfractioncomponentainamixture
Xsegundo Molfractioncomponentbinamixture
Xdo
Molfractioncomponentcinamixture
Y
Compressibilityfunctiondefinedbyequation3.34
W
Workperunitmass
Wyo
Heatcapacityofstreamsinaheatexchangernetwork
Z
Compressibilityfactor
z
Heightabovedatum
Minimumnumberofheatexchangersinnetwork
Zmin
q
q
q
q
q
q
q
q
q
T
q
q
q
L2T 2
LT 1
L3
L3
1L3
METRO
L
L2T 2
ML2T 3q 1
L
3.20.PROBLEMAS
3.1.Aliquidstreamleavesareactoratapressureof100bar.Ifthepressureisreduced
to3barinaturbine,estimatethemaximumtheoreticalpowerthatcouldbe
obtainedfromaflowrateof1000kg/h.Thedensityoftheliquidis850kg/m3.
3.2.Calculatethespecificenthalpyofwateratapressureof1barandtemperatureof
200 C.Checkyourvalueusingsteamtables.Thespecificheatcapacityofwater
canbecalculatedfromtheequation:
3twheretisin CyC
dop D4.2210
p inkJ/kg.
TaketheotherdatarequiredfromAppendixC.
3.3.Agasproducedasabyproductfromthecarbonisationofcoalhasthefollowing
composition,molpercent:carbondioxide4,carbonmonoxide15,hydrogen50,
methane12,ethane2,ethylene4,benzene2,balancenitrogen.Usingthedata
giveninAppendixC,calculatethegrossandnetcalorificvaluesofthegas.Dar
youranswerinMJ/m3,atstandardtemperatureandpressure.
3.4.Inthemanufactureofaniline,liquidnitrobenzeneat20 Cisfedtoavaporiser
whereitisvaporisedinastreamofhydrogen.Thehydrogenstreamisat30 DO,
andthevaporiseroperatesat20bar.Forfeedratesof2500kg/hnitrobenzeneand
366kg/hhydrogen,estimatetheheatinputrequired.Thenitrobenzenevapouris
notsuperheated.
Pgina98
131
3.5.Anilineisproducedbythehydrogenationofnitrobenzene.Thereactiontakes
placeinafluidisedbedreactoroperatingat270Cand20bar.Theexcessheatof
reactionisremovedbyaheattransferfluidpassingthroughtubesinthefluidised
cama.Nitrobenzenevapourandhydrogenenterthereactoratatemperatureof
260 C.Atypicalreactoroffgascomposition,molpercent,is:aniline10.73,
cyclohexylamine0.11,water21.68,nitrobenzene0.45,hydrogen63.67,inerts
(takeasnitrogen)3.66.Estimatetheheatremovedbytheheattransferfluid,for
afeedrateofnitrobenzenetothereactorof2500kg/h.
Thespecificheatcapacityofnitrobenzenecanbeestimateusingthemethodsgiven
inChapter8.TaketheotherdatarequiredfromAppendixC.
3.6.Hydrogenchlorideisproducedbyburningchlorinewithanexcessofhydrogen.
Thereactionishighlyexothermicandreachesequilibriumveryrapidly.los
72/74
16/11/2015
equilibriummixturecontainsapproximately4percentfreechlorinebutthisis
do
rapidlycombinedwiththeexcesshydrogenasthemixtureiscooled.Below200
theconversionofchlorineisessentiallycomplete.
Theburnerisfittedwithacoolingjacket,whichcoolstheexitgasesto200 DO.
Thegasesarefurthercooled,to50C,inanexternalheatexchanger.
Foraproductionrateof10,000tonnesperyearofhydrogenchloride,calculate
theheatremovedbytheburnerjacketandtheheatremovedintheexternalcooler.
Taketheexcesshydrogenas1percentoverstoichiometric.Thehydrogensupply
contains5percentinerts(takeasnitrogen)andisfedtotheburnerat25C.El
chlorineisessentiallypureandisfedtotheburnerasasaturatedvapour.los
burneroperatesat1.5bar.
3.7.Asupplyofnitrogenisrequiredasaninertgasforblanketingandpurgingvessels.
Aftergeneration,thenitrogeniscompressedandstoredinabankofcylinders,
atapressureof5barg.Theinletpressuretothecompressoris0.5barg,and
3/marido.
temperature20C.Calculatethemaximumpowerrequiredtocompress100m
Asinglestagereciprocatingcompressorwillbeused.
3.8.Hydrogenchloridegas,producedbyburningchlorinewithhydrogen,isrequired
atasupplypressureof600kN/m2,gauge.Thepressurecanbeachievedbyeither
operatingtheburnerunderpressureorbycompressingthehydrogenchloride
gas.Foraproductionrateofhydrogenchlorideof10,000kg/h,comparethe
powerrequirementofcompressingthehydrogensupplytotheburner,withthat
tocompresstheproducthydrogenchloride.Thechlorinefeedwillbesuppliedat
therequiredpressurefromavaporiser.Boththehydrogenandchlorinefeedsare
essentiallypure.Hydrogenwillbesuppliedtotheburneronepercentexcessof
overthestoichiometricrequirement.
Atwostagecentrifugalcompressorwillbeusedforbothduties.Takethepolytro
picefficiencyforbothcompressorsas70percent.Thehydrogensupplypressure
is120kN/m2 andthetemperature25C.Thehydrogenchlorideiscooledto50do
afterleavingtheburner.Assumethatthecompressorintercoolercoolsthegasto
50 C,forbothduties.
Whichprocesswouldyouselectandwhy?
Pgina99
132
INGENIERAQUMICA
3.9.Estimatetheworkrequiredtocompressethylenefrom32MPato250MPaina
twostagereciprocatingcompressorwherethegasisinitiallyat30Candleaves
theintercoolerat30 C.SeeExample3.13.
3.10.Determinethepinchtemperatureandtheminimumutilityrequirementsforthe
processsetoutbelow.Taketheminimumapproachtemperatureas15C.Devise
aheatexchangernetworktoachievemaximumenergyrecovery.
Corriente
nmero
1
2
3
4
Escribe
caliente
caliente
fro
fro
Heatcapacity
kW/ do
13.5
27.0
53.5
23.5
Fuente
Objetivo
do
do
Temperatura.
Temperatura.
180
80
135
45
60
100
35
120
3.11.Determinethepinchtemperatureandtheminimumutilityrequirementsforthe
processsetoutbelow.Taketheminimumapproachtemperatureas15C.Devise
aheatexchangernetworktoachievemaximumenergyrecovery.
Corriente
nmero
1
2
3
4
5
Escribe
caliente
caliente
caliente
fro
fro
Heatcapacity
kW/ do
10.0
20.0
40.0
30.0
8.0
Fuente
Objetivo
do
do
Temperatura.
Temperatura.
200
80
155
50
90
35
60
100
35
90
3.12.Toproduceahighpurityproducttwodistillationcolumnsareoperatedinseries.
Theoverheadstreamfromthefirstcolumnisthefeedtothesecondcolumn.
Theoverheadfromthesecondcolumnisthepurifiedproduct.Bothcolumnsare
conventionaldistillationcolumnsfittedwithreboilersandtotalcondensers.los
bottomproductsarepassedtootherprocessingunits,whichdonotformpartofthis
problema.Thefeedtothefirstcolumnpassesthroughapreheater.Thecondensate
fromthesecondcolumnispassedthroughaproductcooler.Thedutyforeach
streamissummarisedbelow:
73/74
16/11/2015
No.
1
2
3
4
5
6
Corriente
Feedpreheater
Firstcondenser
Secondcondenser
Firstreboiler
Secondreboiler
Productcooler
Escribe
Fuente
Objetivo Duty,kW
DO. temperatura
do
temperatura
fro
20
50
900
caliente
70
60
1,350
caliente
sesentaycinco
55
1100
fro
85
87
1400
fro
75
77
900
caliente
55
25
30
Findtheminimumutilityrequirementsforthisprocess,foraminimumapproach
temperatureof10DO.
Note:thestreamheatcapacityisgivenbydividingtheexchangerdutybythe
temperaturechange.
74/74

Fundamentos de Los Balances de Materia

Enviado por

Dados do documento

Direitos autorais

Formatos disponíveis

Compartilhar este documento

Compartilhar ou incorporar documento

Opções de compartilhamento

Você considera este documento útil?

Este conteúdo é inapropriado?

Direitos autorais:

Formatos disponíveis

Fundamentos de Los Balances de Materia

Enviado por

Direitos autorais:

Formatos disponíveis

16/11/2015

IfC pr isexpressedasapolynomialoftheform:C p DaCbtCct

5 300 2 C17.610 9 300 3

5T2 C5683.510 9T3

3.910 9T3 kJ/kmolK

1.0 1.2 1.4 16 1.8 2.0

CompressionratioDP 2/P1 D15.814

dop DACBTCCT 2 CDT3

465789.30 23555.2510482.593 1045.259

Thismeansthatthevaluechosenfor T min willdeterminethesizeoftheheat

Você também pode gostar