8/15/16

LEVEL I Decision: Batch vs. Continuous

Hierarchy of decisions Favor batch operation, if

1. Batch versus continuous 1. Production rate

2. Input-output structure of the flowsheet a ) less than 10×10 6 lb/yr (sometimes)
Ch. 4
3. Recycle structure of the flowsheet b ) less than 1×10 6 lb/yr (usually)
4. General structure of the separation system Ch.5 c ) multi-product plants
2. Market force
a. Vapor recovery system
a ) seasonal production
b. Liquid recovery system
b) short production lifetime
5. Heat-exchanger network Ch.6, Ch.7, Ch.16
3. Scale-up problems
a ) very long reaction times
b ) handling slurries at low flow rates
c ) rapidly fouling materials.

Hierarchy of decisions
1. Batch versus continuous Heuristics:
2. Input-output structure of the flowsheet
Ch. 4 Recover more than 99% of all valuable materials.
3. Recycle structure of the flowsheet
assume
4. General structure of the separation system Ch.5

a. Vapor recovery system

b. Liquid recovery system
Completely recover and recycle all
5. Heat-exchanger network Ch.6, Ch.7, Ch.16 valuable reactants

LEVEL 2 DECISIONS:

DECISIONS FOR THE INPUT/OUTPUT STRUCTURE 1 ) Should we purify the feed streams before they enter the process?
2 ) Should we remove or recycle a reversible by-product?
• Flowsheet Alternatives
3 ) Should we use a gas recycle and purge stream?
(1) 4 ) Should we not bother to recover and recycle some reactants?
Feed streams Products 5 ) How many product streams will there be?
Process
by-products
no reactants 6 ) What are the design variables for the input/output structure?
(2) What economic trade-offs are associated with these variables?
Purge
Products
Products • •
&
Feed streams Process Feeds
•
• PROCESS •
•
By-Products By products
reasons:
OR
a. inexpensive reactants, e.g. Air, Water. Purge
b. gaseous reactants + (inert gaseous feed impurity or inert gaseous • •
Products
reaction by-product) Feeds •
• PROCESS •
• &
By products

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1 ) Purification of Feeds (Liquid/Vapor)

Heat Compressor
H2, CH4 Purge
1 ) If a feed impurity is not inert and is present in significant quantities,
remove it. H2 CH4
Heat
1150° ~ 1300° 95°F
2 ) If a feed impurity is present in large amount, remove it. Reactor Coolant Flash

3 ) If a feed impurity is catalyst poison, remove it. Toluene 500 psia

Heat Heat
4 ) If a feed impurity is present in a gas feed, as a first guess, process the Benzene H2, CH4
impurity.

Recycle

Product
5 ) If a feed impurity is present as an azeotrope with a reactant, often it is Toluene
better to process the impurity.
6 ) If a feed impurity is inert, but it is easier to separate from the product than
the feed, it is better to process the impurity. Dipheny1

7 ) If a feed impurity in a liquid feed stream is also a byproduct or a product

Toluene
component, usually it is better to feed the process through the separation
system.

A HIERARCHICAL APPROACH

3 ) Gas Recycle and Purge

“Light” reactant +
“Light” feed impurity, or
“Light” by-product produced by a reaction

Whenever a light reactant and either a light feed impurity or a light by-
product boil lower than propylene (-55ºF), use a gas recycle and purge
stream.

Lower boiling components normally cannot be condensed at high pressure

with cooling water.
Toluene + H2 ® Benzene + CH4
2 Benzene Diphenyl + H2
1150 ° F ～ 1300 ° F
500 psia

5 ) Number of Product Streams

TABLE 5.1-3
Destination codes and component classifications

Destination code Component classifications

1. Vent Gaseous by-products and feed impurities
2. Recycle and purge Gaseous reactants plus inert gases and/or gaseous by-products
3. Recycle Reactants
Reaction intermediates
Azeotropes with reactants (sometimes)
Reversible by-products (sometimes)
4 ) Do not recover and recycle some reactants which are 4.None
5.Excess - vent
Reactants-if complete conversion or unstable reaction intermediates
Gaseous reactant not recovered or recycles
inexpensive, e. g. air and H2O. 6.Excess - vent
7.Primary product
Liquid reactant not recovered or recycled
Primary product
8.Fuel By-products to fuel
9.Waste By-products to waste treatment should be minimized
We could try to make them reacted completely, but often we feed them as an excess A ) List all the components that are expected to leave the reactor. This list includes all
to try to force some more valuable reactant to completion. the components in feed streams, and all reactants and products that appear in every
reaction.
B ) Classify each component in the list according to Table 5.1-3 and assign a destination
code to each.
C ) Order the components by their normal boiling points and group them with
neighboring destinations.
D ) The number of groups of all but the recycle streams is then considered to be the
number of product streams.

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EXAMPLE 5 Purge
b.p. A Waste
A + B to waste ① H2 , CH4
B Waste H2 , CH4
C Recycle 1 3
Process Benzene
D Fuel 2 4
D + E to fuel stream # 1 ② Toluene Diphenyl
E Fuel
F Primary product F to primary product ③ Production rate = 265

G Recycle (storage for sale) Design variables: F E and x

Component 1 2 3 4 5
H Recycle
H2 FH2 0 0 0 FE
I Valuable By-product I to valuable by-product (storage for sale) ④ CH 4 FM 0 0 0 F M + P B/S
J Fuel J to fuel stream # 2 ⑤ Benzene 0 0 PB 0 0
Toluene 0 P B/S 0 0 0
EXAMPLE Diphenyl 0 0 0 P B(1 - S)/(2S) 0
Temperature 100 100 100 100 100
b.p. Pressure 550 15 15 15 465
-253°C H2 Recycle and Purge
-161 CH4 Recycle and Purge ① where S = 1 - 0.0036/(1 -x) 1.544 F H2 = F E + P B(1 + S)/2S
80 Benzene Primary Product F M = (1 - y FH)[F E + P B(1 + S)/S]/ y FH F G = F H2 + F E
111 Toluene Recycle ②
253 Diphenyl Fuel ③ FIGURE 5.2-1
Stream table
.
① Purge : H2 , CH4
H2 , CH4 ② Benzene
Process
Toluene
③ Diphenyl

REACTOR PERFORMANCE
Conversion (x)
Alternatives for the HDA Process
= (reactant consumed in the reactor)/(reactant
1. Purify the H2 feed stream.
fed to the reactor)
2. Recycle diphenyl
Selectivity (S)
3. Purify H2 recycle stream. =[(desired product produced)/(reactant
consumed in the reactor)]*SF
Reactor Yield (Y)
=[(desired product produced)/(reactant fed to
the reactor)]*SF

Material Balance of Limiting Reactant in Reactor

STOICHIOMETRIC FACTOR
(SF) Toluene
unconverted recycle
(1-x) mole

The stoichiometric moles of reactant Toluene Benzene

feed produced
required per mole of product (1 mole) Toluene
Sx mole
converted
x mole
Diphenyl
produced
(1-S)x / 2

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Gas recycle Purge

H2 , CH4
Toluene 1 x POSSIBLE DESIGN VARIABLES FOR LEVEL 2
Benzene Sx
1
Diphenyl (1 S) x Benzene
H2 , CH4 Reactor 2
Separation Sx For complex reactions:
system system Reactor conversion (x), reaction temperature (T) and pressure (P).
Toluene
x Dipheny1
1 If excess reactants are used, due to reactant not recovered or gas recycle and purge, then
(1 S)x
2 the excess amount is another design variable.
1 x
Toluene recycle
Material Balance of the Limiting
Reactant (Toluene)
Assumption: completely recover and recycle the limiting reactant.

EXAMPLE Purge ; H2 , CH4 , PG

PROCEDURES FOR DEVELOPING OVERALL relation

FG , H2 , CH4
Process
Benzene , PB
known FFT , Toluene Diphenyl , PD
MATERIAL BALANCE SS( x )
design variable
= selectivity = given
PPBB ( mol/hr ) = production rate of Benzene =given
ÚFFT ( mol/hr ) = toluene feed to process ( limiting reactant ) = PB /S
1 ) Start with the specified production rate. given
PR , CH 4 = methane produced in reaction = FFT = PB /S
2 ) From the stoichiometry (and, for complex reactions, the correlation for product ÚPD = diphenyl produced in reaction = FFT (1 - S /2 ) = (PB /S)(1 - S /2 )
distribution) find the by-product flows and the reactant requirements (in terms of the
design variables). design Let FFEE = excess amount of H2 in purge stream= PH 2
variable
Ú FE + ( PB /S ) - [( PB /S )( 1 - S )/2] = yFH FG
3 ) Calculate the impurity inlet and outlet flows for the feed streams where the reactant are
completely recovered/recycled. purge rate disapp. in reaction FH 2
of H2
4 ) Calculate the outlet flows of reactants in terms of a specific amount of excess for streams where
where reactants are not recovered and recycled (recycle and purge, or air, or H2O) FG = make-up gas stream flowrate (unknown)
yFH =
5 ) Calculate the inlet and outlet flows for the impurities entering with the reactant streams mole fraction of H2 in FG
( known )
in Step 4).
Let PCH 4 = purge rate of CH4 methane in purge stream

Ú ( 1 - yFH ) FG + PB /S = PCH 4

methane in feed methane product in reaction

Normally, it is possible to develop expressions for overall MB in terms of design
variables without considering recycle flows.

Ú PG = total purge rate = PH2 + PCH4 = FE + (1 - yFH) FG + PB/S

= FG + ( PB/S )[( 1 - S )/2] Known : yFH
Define PB P B/S F FT(1-S)/2
S(x) FFT PD
Design Variables :
yPH = purge composition of H2 = PH2/PG = FE/PG y
x, PH PB[1-(1- yPH)(1-S)/2
design S( yFH - yPH)
variable
F E+P B(1+S)/2S
It can be derined that FCH4 FH2 FE PG FG
1- yPH (PH2) P G yPH F G+(P B/S)(1-S)/2
PB [ 1- (1- yPH)(1-S)/2 ] F CH4+P B/S yPH F H2
FG =
S (yFH - yPH) design variable PCH4
Known : Design Variable : 6 ) ECONOMIC POTENTIAL AT LEVEL 2
PB/S
yFH S (x) FFT EP2 = Annual profit if capital costs and utility costs are excluded
x
= Product Value + By-product Value - Raw-Material Costs
(PB/S)[(1-S)/2]
PB FE
[EXAMPLE] HDA process
FCH4+PB/S [(1- yFH)/ yFH]FH2 FE+[PB(1+S)/2S]
PCH4 FCH4 FH2 PD 4 ´10^6
2 ´10^6
yPH
PCH4+FE $/yr
-2 ´10^6 0.1 0.3
Î 0.5 0.1 0.1
0.7
PG FG -4 ´10^6 0.9
FN2+FCH4

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Douglas, J. M., “Process Synthesis for Waste

Minimization.” Ind. Eng. Chem. Res., 1992, 31, 238-243
If we produce waste by-products, then we have negative by-
product values.
Solid waste : land fill cost / lb
Contaminated waste water :
- sewer charge : $ / 1000 gal. (e.g. $0.2 / 1000 gal)
- waste treatment charge :
$ / lb BOD ´ lb BOD / lb organic compound (e.g. $0.25 /lb BOD)

Solid or liquid waste to be incinerated :

$ 0.65 / lb

BOD - biological oxygen demand