Reactive System MB

4/2/2012
BalancesonReactiveSystems
Materialbalancenolonger g takestheform
INPUT=OUTPUT
Mustaccountforthedisappearanceofreactantsand
appearanceofproductsthroughstoichiometry.
Stoichiometric Equations
Thestoichiometric equation ofachemicalreactionisastatement q
oftherelativeamountsofreactantsandproductsthat participateinthereaction.
2SO2 +O2 2SO3

q yifthenumberofatomsof Astoichiometric equation isvalidonly eachatomicspeciesisbalanced.
2S 2S 4O+2O 6O
4/2/2012
Thestoichiometric equation ofachemicalreactionisa q
statementoftherelativeamountsofreactantsand productsthatparticipateinthereaction. 2SO2 +O2 2SO3 Astoichiometric ratio oftwomolecularspecies participatinginareactionistheratiooftheir stoichiometric coefficients: 2molSO3 generated/1molO2 consumed 2molSO3 generated/2molSO2 consumed
C4H8 +6O2 4CO2 +4H2O Isthisstoichiometric equationbalanced?
Whatisthestoichiometric coefficientofCO2? Whatisthestoichiometric ratioofH2OtoO2? HowmanylbmolO2 reacttoform400lbmolCO2?

400lbmol CO2 6lbmolO2 = 600 lbmol O2 4 lbmol lb l CO2
100lbmol/minC4H8 isfedand50%reacts.Atwhatrateiswater
formed?
lbmol C 4H8 lbmolH2O 4lbmolH2O 0.50 = 200 100 min 1lbmolC 4H8 min
4/2/2012
LimitingandExcessReactants
Tworeactantsaresaidtobeinstoichiometric p proportion ifthe p
ratio(molesApresent/molesBpresent)equalsthe stoichiometric ratiofromthebalancedreactionequation.
2SO2 +O2 2SO3

thefeedratiothatwouldrepresentstoichiometric proportionis
nSO2/nO2 =2:1
If freactantsarefed f dinstoichometric h proportion,and dthe h reaction
proceedstocompletion,allreactantsareconsumed.
Stoichiometric Proportion Reactantsarep presentinaratio p
equivalenttotheratioofthestoichiometric coefficients.
A +2B 2C
4/2/2012
Limiting greactant Areactantislimiting gifitispresent p
inlessthanstoichiometric proportionrelativetoevery otherreactant. A +2B 2C
Excessreactant Allotherreactantsbesidesthe
limitingreactant.
f fractionalexcess(fXS) ratiooftheexcesstothestoichiometric proportion. (n ) (n A )stoich fXS = A feed (n A )stoich
A +2B 2C
5 4 = 0.25 4
4/2/2012
fractionalconversion(f) ratiooftheamountofa
reactantreacted,totheamountfed. A +2B 2C
f=
(n A )reacted (n A )fed
fA =
0 = 0.0 5
fB =
0 = 0.0 8
f fractionalconversion(f) ratiooftheamountofareactant
reacted,totheamountfed.
f=
A +2B 2C
fA =
1 = 0.2 5
fB =
2 = 0.25 8
4/2/2012
f=
A +2B 2C
fA =
2 = 0.4 5
fB =
4 = 0.5 8
A +2B 2C
f=
3 fA = = 0.6 5
fB =
6 = 0.75 8
4/2/2012
A +2B 2C
f=
fA =
4 = 0.8 5
fB =
8 = 1.0 8
ExtentofReaction
extentofreaction() anextensivequantitydescribingthe
progress p g ofachemicalreaction. stoichiometric coefficients:A =1,B =2,C =2 n i = n i0 + i A +2B 2C
=0
n A = n A0
n B = n B0 2
nC = nC0 + 2
4/2/2012
ExtentofReaction
progressofachemicalreaction. stoichiometric coefficients:A =1,B =2,C =2
n i = n i0 + i
A +2B 2C
=0
nA = 5 = 5
n B = 8 2 = 8
nC = 0 + 2 = 0
ExtentofReaction
n i = n i0 + i
A +2B 2C
=1
nA = 5 = 4
n B = 8 2 = 6
nC = 0 + 2 = 2
4/2/2012
ExtentofReaction
n i = n i0 + i
A +2B 2C
=2
nA = 5 = 3
n B = 8 2 = 4
nC = 0 + 2 = 4
ExtentofReaction
progress ofachemicalreaction. p g stoichiometric coefficients:A =1,B =2,C =2 n i = n i0 + i =4 A +2B 2C
nA = 5 = 1
n B = 8 2 = 0
nC = 0 + 2 = 8
4/2/2012
2C2 H 4 + O2 2C2 H 4O
Assumeanequimolar reactantfeedof100kmol:
Whatisthelimiting greactant?
Areactantislimitingifitispresentinlessthanstoichiometric proportionrelativetoeveryotherreactant.
n C2H4 nO 2 nC2H4 nO 2
2 = 1 stoich =1 feed 1
ethylene
2C2 H 4 + O2 2C2 H 4O
Assumeanequimolar reactantfeedof100kmol: q
Whatisthepercentageexcessofeachreactant?
fXS ,O2 = =
(n ) (n ) (n )
O2 feed O2 stoich
O2 stoich
100 50 = 1.00 = 100% 50
10
4/2/2012
2C2 H 4 + O2 2C2 H 4O
Ifthereactionproceedstocompletion: (a)howmuchoftheexcess
o n O2 = n O + O2 2
reactantwillbeleft?
o n C 2H 4 = n C + C 2H 4 2H 4
0 = 100 + ( 2)
n O2 = 100 + ( 1)50 n O2 = 50
(b)How H much hC2H4O
willbeformed?
n C2H4O = 0 + (2)50 n C2H4O = 100
= 50 o n C 2H 4O = n C + C2H4O 2H 4O
(c)Whatistheextentofreaction?
2C2 H 4 + O2 2C2 H 4O
Ifthereactionp proceedstoap pointwherethefractional
(n ) f= (n )
f= n
o C 2H 4
conversionofthelimitingreactantis50%,howmuchofeach reactantandproductispresentattheend?Whatis?
C2H 4 reacted C2H 4 fed
= 0.5
= 0.5
100 50 = 100 + ( 2) = 25
o n O2 = n O + O2 2
o n C 2H 4 = n C + C 2H 4 2H 4
n C 2H 4
o C 2H 4
o n C 2H 4O = n C + C2H4O 2H 4O
n C2H4O = 0 + (2)25 n C2H4O = 50
100 n C2H4
n O2 = 100 + ( 1)25
= 0.5 100 n C2H4 = 50
n O2 = 75
11
4/2/2012
2C2 H 4 + O2 2C2 H 4O
Assumeanequimolar reactantfeedof100kmol: Ifthereactionproceedstoapointwhere60molofO2 is left,whatisthefractionalconversionofC2H4?Whatis?
n O2 = n + O2
o O2
o n C 2H 4 = n C + C 2H 4 2H 4
60 = 100 + ( 1) = 40
n C2H4 = 100 + ( 2)40 n C2H4 = 20
f=
(n ) (n )
C2H 4 reacted C2H 4 fed
100 20 = 0.8 100
ReactionStoichiometry
Acrylonitrile producedbyreactionofammonia,propylene,andO2 at
30%conversionoflimitingreactant:
determinelimitingreactant
limiting
C3 H6 + NH3 + 3 O3 C3 H3 N + 3H 2O
2
(nNH (nNH (nO (nO

2 2
)0 = (0.120 100 0.100 100)= 1.20 nC H ) =( 1 1)= 1 stoich nC H ) = ( 0.780 0.21 100 0.100 100)= 1.64 0 nC H ) =( 1.5 1)= 1.5 stoich
nC 3 H 6
3 6 3 6 3 6
12
4/2/2012
determinefractionalexcesses
limiting
f XS = 0.20 0 20
C3 H6 + NH3 + 3 O C3 H3 N + 3H2O 2 3
f XS = 0.093
1 mol NH = 10.0 mol NH3 (n NH )stoich = 10.0 mol C3 H6 1 mol C H NH NH ( ) = 12.0 10.0 = 0.20 (f XS )NH = ( () 10.0 NH ) 1.5 mol O = 15.0 mol O2 (nO )stoich = 10.0 mol C3 H6 1 mol C H (O ) (O ) = 16.4 15.0 = 0.093 (f XS )O = (O ) 15.0
3 3 3 6 3 0 3 stoich 3 3 stoich 2 2 3 6 2 0 2 stoich 2 2 stoich
limiting
f XS = 0.20
C3 H 6 + NH3 + 3 O3 C3 H 3 N + 3H2O
usefractional conversiontodetermine amountofpropylene thatleavesthereactor
f XS = 0.093
nC 3 H 6 = 1 f nC 3 H 6
( )(
)0 = (1 0.30)(10.0 mol C3H6 )= 7.0 mol C3H6
13
4/2/2012
C3 H6 + NH3 + 3 O C3 H3 N + 3H2O 2 3
determine extent of reaction by applying mole balance to propylene
limiting
f XS = 0.20
f XS = 0.093
= 3 mol
n i = n i0 + i
nC 3 H 6 = 7.0 mol C3 H6
nC3 H 6 = nC 3 H 6
7.0 mol = 10.0 mol = 3 mol
)0 + (1)
Acrylonitrile producedbyreactionofammonia,propylene,
andO2 at30%conversionoflimitingreactant:
f XS = 0.20
f XS = 0.093
applymolebalanceto allremainingspecies
C3 H 6 + NH 3 + 3 2 O2 C3 H 3 N + 3 H 2 O
= 3 mol n i = n i0 + i
nC 3 H 6 = 7.0 mol C3 H 6
nNH 3 = (0.12)(100 ) + ( 1)(3) = 9 nC3 H 3 N = (0) + (+ 1)(3.0) = 3 nH 2O = (0) + (3)(3.0) = 9
)(3) = 11.9 nO2 = (0.21)(0.78)(100) + ( 3 2

nN 2 = (0.79)(0.78)(100 ) + (0 )(3) = 61.6
14
4/2/2012
Fuel for motor vehicles other than gasoline are being eyed because they generate lower levels of pollutants than does gasoline. gasoline Compressed propane has been suggested as a source of economic power for vehicles. Suppose that in a test 22 kg of C3H8 is burned with 400 kg of air to produce 44 kg of CO2 and 12 kg of CO. a. What was the percent excess air? b. The components in the product stream.
29
C3H8 +5O2
Component C3H8 Air O2 N2 CO2 CO H2O. Total 44 12 Amount (kg) 22 400
3CO2 +4H2O
Molecular weight 44 29 Input (kg-mol) 0 50 0.50 13.80 0.21*13.80 =2.90 0.79*13.80 =10.9 44 28 18 29.87 Output (kg-mol) ? ? ? ? 1 0.43 ? ?
Percentexcessair=(O2 in O2 used)/(O2 theory) =(2.90 5*0.5)/(5*0.5)=16%

30
15
4/2/2012
C3H8 +5O2 C3H8 +7/2O2

Component Input (kg-mol) 0.50 Consumed [1] [ ] (kg-mol) 0.33
3CO2 +4H2O 3CO+4H2O

Consumed [2] [ ] (kg-mol) 0.43/3=0.14 3.5*0.14= 0.49 Generated [1] [ ] (kg-mol) 1 4*0.33= 1.32
[1] [2]
Total Output (kg-mol) 0.03 0.76 10.9 1 0.43 1.88 15
Generated [2] [ ] (kg-mol) 0.43 4*0.14= 0.56
C3H8 O2 N2 CO2 CO H2O. Total
0.21*13.80 5*0.33= 1.65 =2.90 0.79*13.80 =10.9 29.87 -
31
Example
A gas stream containing 80 mol% C2H6 and 20 mol% O2 is burned in an engine with 200% excess air. If 80% of the ethane goes to CO2, 10% goes to CO and the remaining unburned, determine the amount of the excess air per 100 moles of the feed gas.
C2H6 +7/2O2 C2H6 +5/2O2
2CO2 +3H2O[1] 2CO+3H2O[2]
32
16
4/2/2012
Basis=100molefeedgas
C2H6 +7/2O2
2CO2 +3H2O
Component Input Gas Stream 80 20 + 0.21*Gair= 799.7 Gair= 4.76*780 = 3,712.8 0.79*Gair= 2,933.1
[1]
Output (kg-mol)
Percentexcessair(basedonair): (O2 in O2 used)/(O2 theory)=2 O2 theory (Eq 1) = 3.5*80=280 O2 used (air) =O2 theory (Eq 1)-20=260 moles (O2 in (air)-260)/(260)=2 O2in (air)=260+(2*260)=780moles N 780 ,93 .8 N2 in = 3.76 3.76*780=2,932.8 Air stream=2,932.8 + 780=4.76*780=3,712.8
C2H6 O2 Air N2 CO2 CO H2O. Total
33
C2H6 +7/2O2 C2H6 +5/2O2

Component Input (mol) 80 799.7 2,933.1 3812.8 Consumed [1] [ ] (mol) 64 224 -
2CO2 +3H2O[1] 2CO+3H2O[2]

Consumed [2] [ ] (mol) 8 20 192 Generated [1] [ ] (mol) 128 Generated [2] [ ] (mol) 16 24 Total Output (mol) 8 204 2933.1 128 16 216 3,505.1
C2H6 O2 N2 CO2 CO H2O. Total
34
17
4/2/2012
ChemicalEquilibrium
Given asetofreactivespecies,and reactionconditions Determine 1. thefinal(equilibrium)compositionofthereaction mixture 2. howlongthesystemtakestoreachaspecifiedstate shortofequilibrium
ChemicalEquilibrium
Irreversiblereaction reactionproceedsonlyinasingledirectionA B concentrationofthelimitingreactanteventually approacheszero(timedurationcanvarywidely)
Equilibriumcompositionofanirreversiblereactionis thatwhichcorrespondstocompleteconversion.
18
4/2/2012
ChemicalEquilibrium
Reversiblereaction reactionproceedsinbothdirectionsA B netrate(forward backward)eventuallyapproaches zero(again,timecanvarywidely)
Equilibriumcompositionofareversiblereactionisthat whichcorrespondstotheequilibriumconversion.
EquilibriumComposition
Anequilibriumreactionproceeds
K(T ) =
yi =
y CO2 y H2 y CO y H2O
ni ntotal
toanextentattemperatureTbased ontheequilibriumconstant,K(T).
whereyi isthemolefractionofspeciesi
ni = ni0 + i
CO(g ) + H2O(g ) CO2 (g ) + H2 (g ) Watergasshiftreaction: Assume1moleCOand2moleH2O K(1105K)=1.00
19
4/2/2012
CO = (nCO )0 + ( 1) = (1 ) n
nH2O = nH2O 0 + ( 1) = (2 )
CO2 0
nCO2 nH2
( ) = (n ) + (+ 1) = = (n ) + (+ 1) =
H2 0
K(T ) =
yi =
ni = ni0 + i
ni ntotal
ntotal = nCO + nH2O + nCO2 + nH2 = 3
nCO = 1 = 0.333 nH2O = 2 = 1.333 nCO2 = = 0.667 nH2 = ntotal = 3
()() =1= (1 )(2 )

= (1 )(2 )
2
K(T ) =
yi =
ni ntotal
= 0.667
2 = 2 2 + 2 = 0.667mol
ni = ni 0 + i
20
4/2/2012
EquilibriumComposition ( )( ) = 1 (1 )(2 ) y = 0.333 / 3 = 0.111

CO
K(T ) =
y CO2 yH2 y CO y H2O

ni ntotal
y H2O = 1.333 / 3 = 0.444 y CO2 = 0.667 / 3 = 0.222 y H2 = 0.667 / 3 = 0.222 ntotal = 3
2 = (1 )(2 ) 2 = 2 2 + 2 = 0.667mol
yi =
ni = ni0 + i
y CO = 0.333 / 3 = 0.111 y H2O = 1.333 / 3 = 0.444 y CO2 = 0.667 / 3 = 0.222 y H2 = 0.667 / 3 = 0.222 ntotal = 3
limitingreactantisCO equilibrium atequilibrium,

= 0.667mol
ni = ni0 + i
nCO = 1 + ( 1)(0.667) = 0.333mol
fractionalconversionatequilibrium
0.333 f = 1.001 = 0.667 .00
21
4/2/2012
MultipleReactions
C2 H 4 + 1 O2 C2 H 4O C2 H 4 + 3O2 2CO2 + 2H2O
forj reactionsofi species, molebalancebecomes
2
ni = (ni )0 + ij j
j
nC2H4 = nC2H4 nO2 = nO2 nC2H4O

0
( ) + ( ) + ( 3) ) + (+ 1) = (n
1 2 1 C 2H4 O 0 1
+ ( 1)1 + ( 1)2
2
nCO2 = nCO2 nH2O
( ) + (+ 2) = (n ) + (+ 2)
0 H2O 0
MultipleReactions
C2 H 4 + 1 O C2 H 4O 2 2
forj reactionsofi species, molebalancebecomes
C2 H 4 + 3O2 2CO2 + 2H2O
ni = (ni )0 + ij j
j
yield =
molesdesiredproductformed molesformed at 100% conversion with no side reactions

molesdesiredproductformed molesundesiredproductformed
selectivity =
22
4/2/2012
MultipleReactions
100molesAfedtoabatchreactor productcomposition:10molA,160B,10C
Whatis 1. fA? 2. YB? 3. SB/C? 4. 1,2
A 2B AC
fA =
100 10 = 0.9 100
MultipleReactions
Whatis 1. fA? 2. YB? 3. SB/C? 4. 1,2
A 2B AC
YB = 160 = 0.889 (100 10 )( 2 1)
23
4/2/2012
Whatis 1. fA? 2. YB? 3. SB/C? 4. 1,2
A 2B AC
SB /C =
160 = 16 10
100molesAfedtoabatchreactor
A 160B, B 10C productcomposition:10molA,
Whatis 1. fA? 2. YB? 3. SB/C? 4. 1,2
A 2B A C
nB = nBo + B11 160 = 0 + 21 1 = 80
nA = nAo A + A 1 1 + A 2 2 10 = 100 1 2 2 = 90 1 = 10
24
4/2/2012
BalancesonReactiveProcesses
Continuous, of ethane , steady ystate dehydrogenation y g Total mass balance still has INPUT = OUTPUT form Molecular balances contain consumption/generation Atomic balances (H and C) also have simple form
C2H6 C 2H4 + H2
Continuous,steadystatedehydrogenationofethane Firstconsidermolecularbalances: MolecularH2 balance:generation=output generationH2 =40kmol H2/min C2H6 balance:input=output+consumption 100kmol C2H6/min=n1 +(C2H6 consumed) C2H4 balance:generation=output (C2H4 generated) t d)=n2
C 2H6 C 2H4 + H2
25
4/2/2012
Continuous,steadystatedehydrogenationofethane
At i Cb l i t=output t t Atomic balance: input
C 2H6 C 2H4 + H2
100molC2H6
2molC 1molC 2H6
& ( )= n
2molC 1 1molC 2H6
& ( )+ n
2molC 2 1molC 2H4
)
)
AtomicHbalance:input=output
100 mol C2 H 6
6 mol H 1 mol C 2 H 6
) = 40(
2 mol H 1 mol H 2
&( )+ n
6 mol H 1 1 mol C 2 H 6
& ( )+ n
4 mol H 2 1 mol C 2 H 4
IndependentEquations
To understand the number of independent species balances in a
reacting system requires an understanding of independent algebraic equations. Algebraic equations are independent if you cannot obtain any of them by adding/subtracting multiples of the others.
x + 2y = 4[1] 3x + 6y = 12[2]
x + 2y = 4 [3] 2x z = 2 [4] 4 y + z = 6[5]

2[3] [4]=[5]
3[1]=[2]
26
4/2/2012
IndependentEquations
To understand the number of independent species balances p p
in a reacting system requires an understanding of independent algebraic equations. Algebraic equations are independent if you cannot obtain any of them by adding/subtracting multiples of the others.
x + 2y = 4[1] 3x + 6y = 12[2]
3(4 2y ) + 6y = 12
(12 6y ) + 6y = 12
12 = 12
IndependentSpecies
If two molecular or atomic species are in the same ratio to p
each other where ever they appear in a process and this ratio is incorporated in the flowchart labeling, balances on those species will not be independent equations.
&1 = n &3 n & 1 = 3.76n &3 3.76n
27
4/2/2012
IndependentChemicalReactions
When using balances or extents of g molecular species p
reaction to analyze a reactive system, the degree of freedom analysis must account for the number of independent chemical reactions among the species entering and leaving the system.
IndependentChemical Reactions
Chemical reactions are independent if the stoichiometric p
equation of any one of them cannot be obtained by adding and subtracting multiples of the stoichiometric equations of the others.
A 2B [1] B C[2] A 2C[3]

2[2]+[1]=[3]
28
4/2/2012
SolvingReactiveSystems
There are 3 possible methods for solving balances around a reactive
system: 1. Molecular species balances require more complex calculations than the other methods and should be used only for simple (single reaction) systems. 2. Atomic species balances generally lead to the most straightforward solution procedure, especially when more than one reaction is involved 3. Extents of reaction are convenient for chemical equilibrium problems.
MolecularSpeciesBalances
Tousemolecularspeciesbalancestoanalyzeareactivesystem,the
balancesmustcontaingenerationand/orconsumptionterms.
Thedegreeoffreedomanalysisisasfollows:
#unknownlabeledvariables +#independentchemicalreactions #independentmolecularspeciesbalances #other relating h equations i l i unknown k variables i bl #ofdegreesoffreedom
29
4/2/2012
C 2H6 C 2H4 + H2
atsteadystate
2unknownlabeledvariables +1independentchemicalreactions 3independentmolecularspeciesbalances 0otherequationsrelatingunknownvariables 0degreesoffreedom
atsteadystate
C2 H 6 C2 H 4 + H 2
H2 Balance:generation=output
genH 2 = 40 kmol H 2
C2H6 Balance:input=output+consumption
C2 H 6 H2 &1 + 40 kmol 1000 kmol =n min min C2 H 6 &1 = 60 kmol n min
)(
1 kmol C 2 H 6 1 kmol H 2
C2H4 Balance:generation=output
H2 & 2 = 40 kmol n min
)(
1kmolC 2H4 1kmolH2
C 2H4 & 2 = 40 kmol n min
30
4/2/2012
AtomicSpeciesBalance
C 2H6 C 2H4 + H2
Allatomicspeciesbalancestaketheform
INPUT=OUTPUT
Degreeoffreedomanalysis,ndf =
#unknownlabeledvariables #independent p atomicspecies p balances #molecularbalancesonindependentnonreactivespecies #otherequationsrelatingunknownvariables
Allatomicspeciesbalancestaketheform
INPUT=OUTPUT
Degreeoffreedomanalysis,ndf =0=
2unknownlabeledvariables 2independentatomicspeciesbalances 0molecularbalancesonindependentnonreactive species 0otherequationsrelatingunknownvariables
31
4/2/2012
C 2H6 C 2H4 + H2
CBalance:input=output
(100
kmol C 2 H 4 min
)(
2 kmol C 1 kmol C 2 H 6
&( )= n
2 kmol C 1 1 kmol C 2 H 6
& ( )+ n
2 kmol C 2 1 kmol C 2 H 4
&1 + n &2 100 kmol = n
HBalance:input=output
(100
kmolC2H4 min
)(
6kmolH 1kmolC2H6
) = (40 & ( +n
kmolH2 min
)(
2kmolH 1kmolH2
6kmolH 1 1kmolC2H6
) & ( )+ n
4kmolH 2 1kmolC2H4
& 1 + 4n &2 600kmol = 80kmol + 6n
C 2H6 C 2H4 + H2
Solvesimultaneously
&1 + n &2 C :100kmol = n & 1 + 4n &2 H :600kmol = 80kmol + 6n & 1 = 60kmolC2H6 / min n & 2 = 40kmolC2H4 / min n
32
4/2/2012
ExtentofReaction
The3rd methodbywhichtodeterminemolarflowsinareactivesystem
isusingexpressionsforeachspeciesflowrateintermsofextentsof reaction (). ni = (ni )0 + ij j

j
Degreeoffreedomanalysisforsuchanapproach:
ndf =#ofunknownlabeledvariables +#independentreactions #independentnonreactivespecies #otherrelationshipsorspecifications
IncompleteCombustionofCH4
Methaneisburnedwithairinacontinuoussteadystatereactortoyield
amixtureofcarbonmonoxide,carbondioxide,andwater.
CH4 + 3 O2 CO + 2H2 O
2
CH 4 + 2O2 CO2 + 2H2 O Thefeedtothereactorcontains7.80mol%CH4,19.4mol%O2,72.8 mol%N2.Methaneundergoes90.0%conversion,andtheeffluentgas contains8molCO2 permoleCO.
33
4/2/2012
fCH4 =0.9
CH4 + 3 O2 2
CO + 2H2 O
CH4 + 2O2 CO2 + 2H2 O

mol%N2.Methaneundergoes90.0%conversion,andtheeffluentgas contains8molCO2 permoleCO. ndf =5unknowns p reactions +2independent 5expressionsfor(CH4,O2,CO,CO2,H2O) 1nonreactivespeciesbalance(N2) 1specifiedmethaneconversion =0
Thefeedtothereactorcontains7.80mol%CH4,19.4mol%O2,72.8
CH4 + 3 O2 CO + 2H2 O
2
fCH4 =0.9
CH4 + 2O2 CO2 + 2H2 O
N2 balance:nonreactivespecies,INPUT=OUTPUT
N2 nN2 = 0.728 mol mol (100mol ) = 72.8molN2
CH4 conversionspecification:
CH4 nCH4 = (1 0.900 ) 0.0780 mol l) = 0.780 mol l CH4 mol (100 mol
34
4/2/2012
CH 4 + 3 2 O2 CO + 2 H 2 O CH 4 + 2 O2 CO2 + 2 H 2O
Extentofreactionmolebalances:
nCH4 = nCH4
( )
nCO = (nCO )0 + (+ 1)1 nCO2 = nCO2 nH2O nO2

0
+ ( 1)1 + ( 1)2
0.78 = 7.80 1 2 nCO = 1 nCO2 = 8nCO = 2 nH2 O = 21 + 22 nO 2 = 19.4 3 1 22 2
( ) + (+ 1) = (n ) + (+ 2) + (+ 2) = (n ) + ( ) + ( 2)
2 H2O 0 1 O2 0 3 2 1 2
ProductSeparationandRecycle
Twodefinitionsofreactantconversionareusedintheanalysisof
chemicalreactorswithproductseparationandrecycleofunconsumed reactants.
overall conversion sin glepass inputtoprocessoutputfromprocess = reactant inputtoprocess
input to reactor output from reactor = reactant conversion inputtoreactor
35
4/2/2012
overall 75molA/min0 = 100% = 100% conversion 75molA/min sin glepass 100molA/min25molA/min = 100% = 75% conversion 100molA/min
CatalyticPropaneDehydrogenation
C 3H8 C3H6 + H2
95%overall conversion
36
4/2/2012
C 3H8 C 3H6 + H2
Overall Process
ndf =3unknowns(n6,n7,n8) 2independentatomicbalances(CandH) 1relation(overallconversion) =0 considern6,n7,n8 knownforfurtherDOFanalyses
ndf =2
C 3H8 C 3H6 + H2
Mixing point
ndf =4unknowns(n9,n10,n1,n2) 2balances(C3H8 andC3H6) =2
37
4/2/2012
ndf =3 ndf =2
C 3H8 C 3H6 + H2
reactor
ndf =5unknowns(n3,n4, n5, n1,n2) 2balances(CandH) =3
ndf =3 ndf =0 ndf =2
C 3H8 C 3H6 + H2
separator
ndf =5unknowns(n3,n4, n5, n9,n10) 3balances(C3H8,C3H6,andH2) 2relations(reactantandproductrecoveryfractions) =0
38
4/2/2012
C 3H8 C 3H6 + H2
overall
conversion relationship
n6 = (1 0.95)(100 mol l) = 5 mol l C 3H8
n6 = 5 mol C3H8
C 3H8 C 3H6 + H2
overall
Catomicbalance
3molC (100mol)(1mol C H
3 8
) = (5molC H )(
3 8
3molC 1molC 3H8
)+ n (
3molC 7 1molC 3H6
n7 = 95molC 3H6
39
4/2/2012
n6 = 5 mol C3H8 n7 = 95 mol C3H6
C 3H8 C 3H6 + H2
overall
Hatomicbalance
8molH (100mol)(1mol C H
3 8
) = (5molC H )(
3 8
6molH + (95molC 3H6 ) 1mol C 3H6 + n8
8molH 1molC 3H8
) (
2molH 1molH2
n8 = 95mol H2
n6 = 5 mol C3H8 n7 = 95 mol C3H6 n8 = 95 mol H2
C 3H8 C 3H6 + H2
separator
givenrelations
n6 = (0.00555)n3 n3 = 900 mol C 3H8
n10 = (0.0500 )n7 n10 = 4.75molC 3H6
40
4/2/2012
n3 = 900 mol C 3H8
C 3H8 C 3H6 + H2
separator
n10 = 4.75 molC 3H6
propanebalance
n3 = n6 + n9 n9 = 895 molC 3H8
n3 = 900 mol C 3H8
C 3H8 C 3H6 + H2
mixer
n9 = 895 molC 3H8 n10 = 4.75 molC 3H6
propanebalance
100 + n9 = n1 n1 = 995 molC3H8
41
4/2/2012
n1 = 995molC3H8
n3 = 900 mol C 3H8
C 3H8 C 3H6 + H2
mixer
n9 = 895 molC 3H8 n10 = 4.75 molC 3H6
propylenebalance
n10 = n2 n2 = 4.75 molC3H6
n1 = 995 molC 3H8 n2 = 4.75 molC 3H6
n3 = 900 mol C 3H8
C 3H8 C 3H6 + H2
reactor
n9 = 895 molC 3H8 n10 = 4.75 molC 3H6
Catomicbalance
3mol C 3 mol C (995mollC3H8 )(1mol 75 mol l C 3H6 )(1mol C H C H ) + (4.75 3molC 3molC = (900molC3H8 )(1molC H ) + (n4 )(1molC H )
3 8 3 8 3 6
3 6
n4 = 99.75molC 3H6
42
4/2/2012
n1 = 995 molC 3H8 n2 = 4.75 molC 3H6
n3 = 900 mol C 3H8
n4 = 99.75 mol C 3H6
C 3H8 C 3H6 + H2
reactor
n9 = 895 molC 3H8 n10 = 4.75 molC 3H6
Hatomicbalance
8molH 6molH (995molC3H8 )(1mol C H ) + (4.75molC 3H6 )(1molC H ) 6molH 8molH = (900molC 3H8 )(1mol C H ) + (99.75molC 3H6 )(1molC H
3 8 3 6 3 8
3 6
)+ n (
2molH 5 1molH2
n5 = 95molH2
n1 = 995 molC 3H8 n2 = 4.75 molC 3H6
n3 = 900 mol C 3H8 n4 = 99.75 mol C 3H6 n5 = 95 mol H2
C 3H8 C 3H6 + H2
n9 = 895 molC 3H8 n10 = 4.75 molC 3H6
singlepass conversion
fsingle pass =
(995 mol C3H8 ) (900 mol C3H8 ) 100% = 9.55% (995molC3H8 )
43
4/2/2012
n1 = 995 molC 3H8 n2 = 4.75 molC 3H6
n3 = 900 mol C 3H8 n4 = 99.75 mol C 3H6 n5 = 95 mol H2
fsingle pass = 9.55%
C 3H8 C 3H6 + H2
n9 = 895 molC 3H8 n10 = 4.75 molC 3H6
Recycleratio
R=
n9 + n10 (895mol) + (4.75mol) molrecycle = = 9.0 mol freshfeed (100molfeed) (100mol)
Purging
Necessarywithrecycletopreventaccumulationofaspeciesthatisboth
presentinthefreshfeedandisrecycledratherthanseparatedwiththe d product.
mixedfreshfeed andrecycleisa convenient basisselection
f single pass = 60% CO + 3H2 CH3 OH + H2 O 2
44
4/2/2012
MethanolSynthesis
ndf =7unknowns(n0,x0C,np,x5 5C,x5 5H,n3,n4)+1rxn
5independentspeciesbalances=3
f single pass = 60% CO2 + 3H2 CH3 OH + H2 O
MethanolSynthesis
ndf =4unknowns(n1,n2,n3,n4)+1rxn
4independent species balances p p 1singlepassconversion=0
45
4/2/2012
ndf =3unknowns(n5,x5C,X5H)
3independentspeciesbalances =0
ndf =3unknowns(n0,x0C,nr)
3independentspeciesbalances =0
46
4/2/2012
ndf =1unknowns(np)
1independent p species p balance =0
investigate molebalancesand theirsolutionin thetext
CombustionReactions
Combustion rapid p reactionofafuelwithoxygen. yg Valuableclassofreactionsduetothetremendousamount
ofheatliberated,subsequentlyusedtoproducesteamused todriveturbineswhichgeneratesmostoftheworlds electricalpower. Commonfuelsusedinpowerplants:

coal fueloil(highMWhydrocarbons) gaseousfuel(naturalgas) liquified petroleumgas(propaneand/orbutane)
47
4/2/2012
CombustionChemistry
Whenafuelisburned
CformsCO2 (complete)orCO(partialcombustion) HformsH2O SformsSO2 NformsNO2 (above1800C)
Airisusedasthesourceofoxygen.DRYairanalysis:
78.03mol%N2 20.99mol%O2 0.94mol%Ar 0.03mol%CO2 0.01mol%H2,He,Ne,Kr,Xe
usually ll safe f toassume: 79mol%N2 21mol%O2
CombustionChemistry
Stack(f (flue) gas p productg gasthatleavesafurnace. )g Compositionanalysis:
wetbasis waterisincludedinmolefractions drybasis doesnotincludewaterinmolefractions
Stackgascontains(mol)onawetbasis:
60.0%N2,15.0%CO2,10.0%O2,15.0%H2O Drybasisanalysis:

60/(60+15+10)=0.706molN2/mol 15/(60+15+10)=0.176molCO2/mol 10/(60+15+10)=0.118molO2/mol
48
4/2/2012
CombustionChemistry
Stackgascontains(mol)onadrybasis:
65%N2,14%CO2,10%O2,11%CO
assume100moledrygasbasis 7.53moleH2O 65moleN2 14moleCO2 10moleO2 11moleCO total=107.5mole
xH2 O =
7.53 = 0.0700 107.5 65 = 0.605 xN2 = 107.5 14 = 0.130 xCO2 = 107 5 107.5 10 xO 2 = = 0.0930 107.5 11 = 0.102 xCO = 107.5
TheoreticalandExcessAir
The less expensive reactant is commonly fed in excess of stoichiometric

reactant thereby increasing ratio relative to the more valuable reactant, conversion of the more expensive reactant at the expense of increased use of excess reactant. In a combustion reaction, the less expensive reactant is oxygen, obtained from the air. Conseqently, air is fed in excess to the fuel. Theoretical oxygen is the exact amount of O2 needed to completely combust the fuel to CO2 and H2O. Theoretical air is that amount of air that contains the amount of theoretical oxygen.
49
4/2/2012
Excessairistheamountbywhichtheairfedtothe
reactorexceedsthetheoreticalair.
% excessair = molesairfed molesairtheoretical 100% molesairtheoretical
C 4H10 + 13 O2 4CO2 + 5H2 O 2
nC4H10 =100mol/hr;nair =5000mol/hr
(n )
O2 theoretica l
6.5molO2 molO2 100molC 4H10 = = 650 hr hr molC 4H10
650 mol O2 4.76 mol air mol air (nair )theoretical = = 3094 hr molO2 hr
5000 3094 100% = 61.6% 3094
% excessair =
50
4/2/2012
CombustionReactors
Procedureforwriting/solving g/ gmaterialbalancesfora
combustionreactor
1.
Whenyoudrawandlabeltheflowchart,besuretheoutlet stream(thestackgas)includes a. unreacted fuel(unlessthefueliscompletelyconsumed) b. unreacted oxygen c. waterandcarbondioxide(andCOifcombustionis i incomplete) l ) d. nitrogen(ifairisusedastheoxygensource) 2. CalculatetheO2 feedratefromthespecifed percentexcess oxygenorair 3. Ifmultiplereactions,useatomicbalances
CombustionofEthane
C2 H 6 + 7 2 O2 2CO2 + 3H 2 O C2 H 6 + 5 2 O2 2CO + 3H 2 O
fC2H6 =0.9 9
degreeoffreedom analysis
ndf =7unknowns 3atomicbalances 1nitrogenbalance 1excessairspecification 1ethaneconversionspecification 1CO/CO2 ratiospecification =0
25%oftheethaneburnedformsCO
51
4/2/2012
excessairspecification
C2 H 6 + 7 2 O2 2CO2 + 3 H 2 O C2 H 6 + 5 2 O2 2CO + 3 H 2 O
fC2H6 =0.9
(n )
O2 theoretical
100molC2H6 3.5molO2 = = 350molO2 molC2H6
0.21n0 = 1.5(350mol O2 ) n0 = 2500molair

Ethaneconversionspecification
n1 = (1 0.90 )(100 mol C2H6 ) = 10.0 mol C2H6
n 1 = 10.0molC2H6
CO/CO2 ratiospecification
C2H6 + 7 O2 2CO2 + 3H2 O
2
n 0 = 2500molair
fC2H6 =0.9
C H + 5 O 2CO + 3H2 O 2 6 2 2
2molCOgen n4 = (0.25)(0.9 )(100molC2H6 ) 1molC H react = 45.0molCO 2 6
Nitrogenbalance
n3 = (0.79 )(2500 mol air ) = 1975 mol N2

AtomicCbalance
2molC (100molC2H6 )(1mol C H
2 6
)= n (
2molC 1 1molC 2H6
)+ n (
1molC 4 1molCO
molC ) + n5 (11 molCO
n5 = 135molCO2
52
4/2/2012
n 1 = 10.0molC2H6
C2H6 + 7 O2 2CO2 + 3H2 O

2
fC2H6 =0.9
n 0 = 2500 molair
n 3 = 1975molN2
C H + 5 O 2CO + 3H2 O 2 6 2 2
atomicHbalance
6molH (100molC2H6 )(1mol C H
2 6
n 4 = 45.0molCO n 5 = 135molCO2
) = (10molC H )(
2 6
6molH 1molC2H6
)+ n (
2molH 6 1molH2O
n6 = 270molH2O
atomicObalance
2molO 1molO molO (525molO2 )(12mol O ) = n2 (1molO ) + (45molCO )( 1molCO ) 1molO molO + (135molCO2 )(12 molCO ) + (270molH2O )(1molH O )
2 2 2 2
n2 = 232molO2
C2H6 + 7 O2 2CO2 + 3H2 O

2
C2H6 + 5 O2 2CO + 3H2 O 2
n 1 = 10.0 molC 2H6 n 3 = 1975 molN 2 n 4 = 45.0 molCO n 5 = 135 molCO2 n 6 = 270 mol H2 O
fC2H6 =0.9 9
n 0 = 2500 molair
atomicObalance
2 2
molO 2molO 1molO (525molO2 )(12mol O ) = n2 (1molO ) + (45molCO )( 1molCO ) molO 1molO + (135 mol CO2 )(12 mol CO ) + (270 mol H2O )(1 mol H O )
2 2
n2 = 232molO2
53
4/2/2012
C2H6 + 7 O2 2CO2 + 3H2 O

2
C2H6 + 5 O2 2CO + 3H2 O 2
n 1 = 10.0 molC 2H6 n 2 = 232 molO 2 n 3 = 1975 molN 2 n 4 = 45.0 molCO n 5 = 135 molCO2 n 6 = 270 mol H2 O
fC2H6 =0.9 9
n 0 = 2500 molair
stackgascomposition(drybasis)
sum = 10 + 232 + 1974 + 45 + 135 = 2396 y 1 = 10 2396 = 0.00417 molC2H6 mol y 2 = 232 2396 = 0.0970 molO2 mol y 3 = 1974 2396 = 0.824 molN2 mol y 4 = 45 2396 = 0.019 molCO mol y 5 = 135 2396 = 0.0563 molCO2 mol
270molH2 O 2396moldrystackgas molH2 O = 0.113 mol drystackgas
54

Reactive System MB

Caricato da

Informazioni sul documento

Descrizione originale:

Copyright

Formati disponibili

Condividi questo documento

Condividi o incorpora il documento

Opzioni di condivisione

Hai trovato utile questo documento?

Questo contenuto è inappropriato?

Copyright:

Formati disponibili

Reactive System MB

Caricato da

Copyright:

Formati disponibili

4/2/2012

2SO2 +O2 2SO3

Whatisthestoichiometric coefficientofCO2? Whatisthestoichiometric ratioofH2OtoO2? HowmanylbmolO2 reacttoform400lbmolCO2?

ratio(molesApresent/molesBpresent)equalsthe stoichiometric ratiofromthebalancedreactionequation.

2SO2 +O2 2SO3

inlessthanstoichiometric proportionrelativetoevery otherreactant. A +2B 2C

progress p g ofachemicalreaction. stoichiometric coefficients:A =1,B =2,C =2 n i = n i0 + i A +2B 2C

progressofachemicalreaction. stoichiometric coefficients:A =1,B =2,C =2

progressofachemicalreaction. stoichiometric coefficients:A =1,B =2,C =2

progressofachemicalreaction. stoichiometric coefficients:A =1,B =2,C =2

progress ofachemicalreaction. p g stoichiometric coefficients:A =1,B =2,C =2 n i = n i0 + i =4 A +2B 2C

100 50 = 1.00 = 100% 50

(b)How H much hC2H4O

n C2H4O = 0 + (2)50 n C2H4O = 100

n C2H4O = 0 + (2)25 n C2H4O = 50

= 0.5 100 n C2H4 = 50

n C2H4 = 100 + ( 2)40 n C2H4 = 20

C2H 4 reacted C2H 4 fed

100 20 = 0.8 100

(nNH (nNH (nO (nO

)0 = (1 0.30)(10.0 mol C3H6 )= 7.0 mol C3H6

7.0 mol = 10.0 mol = 3 mol

)(3) = 11.9 nO2 = (0.21)(0.78)(100) + ( 3 2

Percentexcessair=(O2 in O2 used)/(O2 theory) =(2.90 5*0.5)/(5*0.5)=16%

C3H8 +5O2 C3H8 +7/2O2

3CO2 +4H2O 3CO+4H2O

Generated [2] [ ] (kg-mol) 0.43 4*0.14= 0.56

C3H8 O2 N2 CO2 CO H2O. Total

0.21*13.80 5*0.33= 1.65 =2.90 0.79*13.80 =10.9 29.87 -

C2H6 +7/2O2 C2H6 +5/2O2

2CO2 +3H2O[1] 2CO+3H2O[2]

C2H6 +7/2O2 C2H6 +5/2O2

2CO2 +3H2O[1] 2CO+3H2O[2]

C2H6 O2 N2 CO2 CO H2O. Total

CO(g ) + H2O(g ) CO2 (g ) + H2 (g ) Watergasshiftreaction: Assume1moleCOand2moleH2O K(1105K)=1.00

ntotal = nCO + nH2O + nCO2 + nH2 = 3

CO(g ) + H2O(g ) CO2 (g ) + H2 (g ) Watergasshiftreaction: Assume1moleCOand2moleH2O K(1105K)=1.00

()() =1= (1 )(2 )

CO(g ) + H2O(g ) CO2 (g ) + H2 (g ) Watergasshiftreaction: Assume1moleCOand2moleH2O K(1105K)=1.00

EquilibriumComposition ( )( ) = 1 (1 )(2 ) y = 0.333 / 3 = 0.111

y CO2 yH2 y CO y H2O

y H2O = 1.333 / 3 = 0.444 y CO2 = 0.667 / 3 = 0.222 y H2 = 0.667 / 3 = 0.222 ntotal = 3

CO(g ) + H2O(g ) CO2 (g ) + H2 (g ) Watergasshiftreaction: Assume1moleCOand2moleH2O K(1105K)=1.00

limitingreactantisCO equilibrium atequilibrium,

CO(g ) + H2O(g ) CO2 (g ) + H2 (g ) Watergasshiftreaction: Assume1moleCOand2moleH2O K(1105K)=1.00

nC2H4 = nC2H4 nO2 = nO2 nC2H4O

nCO2 = nCO2 nH2O

C2 H 4 + 3O2 2CO2 + 2H2O

molesdesiredproductformed molesformed at 100% conversion with no side reactions

Whatis 1. fA? 2. YB? 3. SB/C? 4. 1,2

100 10 = 0.9 100

Whatis 1. fA? 2. YB? 3. SB/C? 4. 1,2

Whatis 1. fA? 2. YB? 3. SB/C? 4. 1,2

A 160B, B 10C productcomposition:10molA,

Whatis 1. fA? 2. YB? 3. SB/C? 4. 1,2

At i Cb l i t=output t t Atomic balance: input

2molC 1molC 2H6

2molC 1 1molC 2H6

2molC 2 1molC 2H4

x + 2y = 4 [3] 2x z = 2 [4] 4 y + z = 6[5]

&1 = n &3 n & 1 = 3.76n &3 3.76n

A 2B [1] B C[2] A 2C[3]

#unknownlabeledvariables +#independentchemicalreactions #independentmolecularspeciesbalances #other relating h equations i l i unknown k variables i bl #ofdegreesoffreedom

Percentexcessair=(O2 in O2 used)/(O2 theory) =(2.90 50.5)/(50.5)=16%

0.2113.80 50.33= 1.65 =2.90 0.79*13.80 =10.9 29.87 -