Process Design Development

BTE 4417 PROCESS PLANT DESIGN AND SAFETY
Process Design Development
Level 1 Decision
Level 2 Decision
Semester 1 2016/17 1
CONTENT
0 Input Information
1 Batch versus Continuous
2 Input- Output Structure
3 Recycle structure of the Flowsheet
4 Separation System
5 Heat Exchanger Network
Level 0. Input Information
• Introduction (Chapter 1)
– Background of the design project
– Reasons of selection (i.e. product and process)
– Objective (i.e. product, production volume)
– Range/scope of work (i.e. product volume using selected
process)
– Problem statement
• Why to produce the product (i.e. to meet demand - new
product? Existing product requires retrofitting? or
expansion of existing process? Etc.)
• Literature Survey (Chapter 2)

1. Process background
2. Market survey
3. Feed and product properties
4. Possible site location that may lead to a more
profitable design
5. Reaction path analysis using EP 1
1. Process Background
– Overview of product
• Molecular Path Synthesis - Identify chemical pathway(s)
– Overview of processes for the product
• from journal papers or patent search - reference design
only
• Process Background Information
– Complete existing design
– Modification of or use of part of an existing design.
– Generation of completely new design

1. Process Background - Patent search
2. Market survey
– Market demand (current and future)
– Application of product
– Product price (current and future)
3. Feeds, product and byproducts properties.

Example of information required;
– Chemical formula
– Molecular weight
– Specific gravity
– Normal boiling point
– Normal melting point
– Solubility
– Toxicity
– Biological hazard
Price
Semester 1 2016/17 10
4. Plant Location
i. Raw materials availability
ii. Markets
iii. Energy availability
iv. Climate
v. Transportation facilities
vi. Water supply
vii. Waste disposal
viii. Labor supply
ix. Taxation and legal restrictions
x. Site characteristics
xi. Flood and fire protection
xii. Community factors
Semester 1 2016/17 11

Gather important informations required on the reaction needed for the process.
What Informations are needed ?
Info. 1 Reaction path selected for the production of the desired products.
Q. How do we select the most desirable reaction path ?
Economic Potential !
Info. 2 Types of reaction system involved
Multiple Reactions in series

Single Reaction
producing byproducts
Feed(s) -----> Product + Byproduct(s)
Multiple Reactions in parallel Product -----> Byproduct(s)
Mixed Parallel and Series Reactions
Feed(s) -----> Byproduct(s)
Polymerisation Reaction Feed(s) -----> Byproduct(s)
Semester 1 2016/17 Product -----> Byproduct(s) 12
Example
Develop information on potential reaction pathways and physical
and operational properties involved in the production of vinyl
chloride, C2H3Cl.
Solution:
- Several patented process such as in USA and other countries..
- 23,000,000 t (metric)was produced worldwide in 1997.
- 26% produced in USA
- Average plant capcity is about 500,000 t (metric)/yr (5x108
kg/yr)
Example (cont.) -Assess Primitive Problem
• Process design begins with a primitive design problem that

expresses the current situation and provides an opportunity to
satisfy a societal need.
• Normally, the primitive problem is examined by a small design team,
who begins to assess its possibilities, to refine the problem
statement, and to generate more specific problems:
– Raw materials - available in-house, can be purchased or need to be
manufactured?
– Scale of the process (based upon a preliminary assessment of the
current production, projected market demand, and current and
projected selling prices)
– Location for the plant
• Refined through meetings with engineering technical management,
business and marketing.
• Brainstorming to generate alternatives

Example (cont.) - Eliminate differences in molecular types
Chemicals participating in VC Manufacture:
Molecular Chemical Chemical
Chemical weight formula structure
Acetylene 26.04 C2H2 H- CC- H
Chlorine 70.91 Cl2 Cl-Cl
Cl Cl
| |
H-C-C-H
1,2-Dichloroethane 98.96 C2H4Cl2 | |
H H
H H
C=C
Ethylene 28.05 C2H4 H H
Hydrogen chloride 36.46 HCl H-Cl

H Cl
C=C
Vinyl chloride 62.50 C2H3Cl H H
PROCESS INFORMATION- Example 4.1

Selection of pathway to VCM (1)
1. Hydrochlorination of acetylene:
C2H2  HCl  C2H3Cl (2.2)
Advantages:
– This exothermic reaction. It provides a good conversion (98%) of C2H2 to
VC in the presence of HgCl2 catalyst impregnated in activated carbon at
atmospheric pressure.
– These are fairly moderate reaction conditions, and hence, this reaction
deserves further study.
Disadvantages:
– Flammability limits of C2H2 (2.5 100%) – Flammable gas

2. Direct chlorination of ethylene:
C2H4  Cl2  C2H3Cl  HCl (2.1)
Advantages:
– Occurs spontaneously at a few hundred oC.
Disadvantages:
– Does not give a high yield of VC without simultaneously producing large
amounts of by-products such as dichloroethylene (EDC).
– Half of the expensive chlorine is consumed to produce HCl by-product,
which may not be sold easily.

3. Thermal cracking of C2H4Cl2 from chlorination of C2H4:
C2H4  Cl2  C2H4Cl2 (2.3)
C2H4Cl2  C2H3Cl  HCl (2.4)
C2H4  Cl2  C2H3Cl  HCl (2.1)

Advantages:
– Conversion of ethylene to 1,2-dichloroethane in exothermic reaction (2.3) is
98% at 90 oC and 1 atm with a Friedel-Crafts catalyst such as FeCl3. This
intermediate is converted to vinyl chloride by thermal cracking according to
the endothermic reaction (2.4), which occurs spontaneously at 500 oC with
conversions as high as 65% .
Disadvantage:
– Half of the expensive chlorine is consumed to produce HCl (by-product),
which may not be sold easily.

4. Thermal Cracking of C2H4Cl2 from Oxychlorination of C2H4:
C2H4  2HCl  21 O2  C2H4Cl2  H2O (2.5)
C2H4Cl2  C2H3Cl  HCl (2.4)
C2H4  HCl  21 O2  C2H3Cl  H2O (2.6)
Advantages:
– Highly exothermic reaction, achieves a 95% conversion to C2H4Cl2 in the
presence of CuCl2 catalyst, followed by pyrolysis step (2.4) as Reaction
Path 3.
– Excellent candidate when cost of HCl is low
Disadvantages:
– Economics dependent on cost of HCl

5. Balanced Process for Chlorination of Ethylene:
C2H4  Cl2  C2H4Cl2 (2.3)
C2H4  2HCl  21 O2  C2H4Cl2  H2O (2.5)
2C2H4Cl2  2C2H3Cl  2HCl (2.4)
2C2H4  Cl2  21O2 2C2H3Cl  H2O (2.7)
Advantages:
– Combination of Reaction Paths 3 and 4 - addresses Alternative 2.
– All Cl2 converted to VC
– No by-products!
INPUT/OUTPUT STRUCTURE- Example 4.2

Evaluation of Alternative Pathways
Chemical Bulk Prices
Reaction path, kg/kg vinyl chloride

Species Price, 1 2 3 4 5
$/kg
Cl2 0.03 0.00 -1.13 -1.13 0.00 -0.57
HCl 0.22 -0.58 0.58 0.58 -0.58 0.00
C2H2 1.39 -0.42 0.00 0.00 0.00 0.00
C2H4 0.45 0.00 -0.45 -0.45 -0.45 -0.45
C2H3 Cl 0.45 1.00 1.00 1.00 1.00 1.00
O2 0.04 0.00 0.00 0.00 -0.26 -0.13
EP ($/kg VC) -0.26 0.34 0.34 0.11 0.23
INPUT/OUTPUT STRUCTURE- Example 4.2

Evaluation of Alternative Pathways
VC reaction path comparison using long-term average prices
Reaction path, kg/kg vinyl chloride
Species Price, 3 4 5
$/kg
Cl2 0.21 -1.13 0.00 -0.57
HCl 0.27 0.58 -0.58 0.00
C2H4 0.53 -0.45 -0.45 -0.45
C2H3 Cl 0.41 1.00 1.00 1.00
O2 0.04 0.00 -0.26 -0.13
EP ($/kg VC) 0.09 0.00 0.23
INPUT/OUTPUT STRUCTURE
C2H4  Cl2  C2H4Cl2

2C2H4
C2H4  2HCl  21 O2  C2H4Cl2  H2O 2C2H3Cl
Cl2 2C2H4Cl2  2C2H3Cl  2HCl
½ O2 2C2H4  Cl2  21O2 2C2H3Cl  H2O H2O

Choice of Reaction Path- example
Choice of reaction path for the production of vinyl chloride
Raw material and product data

Path 1
Material Formula MW Value
C2H2 + HCl  C2H3Cl
($/kg)
Path 2 Acetylene C2H2 26 0.94
C2H4 + Cl2  C2H4Cl2 Chlorine Cl 71 0.21

C2H4Cl2  C2H3Cl + HCl
1,1-Dichloroethane Ethylene C2H4 28 0.53
Hydrochloric HCl 36 0.35

Path 3
acid
C2H4 + ½ O2 + 2HCl  C2H4Cl2 + H2O
Vinyl chloride C2H3Cl 62 0.42
C2H4Cl2  C2H3Cl + HCl
Semester 1 2016/17 25

Path 1:
EP = 62 kg/kmol  $0.42/kg – 26 kg/kmol  $0.94/kg – 36 kg/kmol  $0.35/kg
= -$11.0/kmol VCM
Path 2:
Assume the byproduct HCl may be sold
EP = 62 x 0.42 + 36  0.35 – (28 x 0.53 + 71 x 0.21) = $8.89/kmol VCM
Assume HCl cannot be sold

EP = 62 x 0.42– (28 x 0.53 + 71 x 0.21) = -$3.71/kmol VCM
Path 3:
EP = 62 x 0.42– (28 x 0.53 + 36 x 0.35) = -$1.40/kmol VCM
Semester 1 2016/17 26
Hierarchy of decisions
0 Input Information
4 Separation System
Semester 1 2016/17 27
1. Batch versus continuous
2. Input-output structure of the flowsheet
3. Recycle structure of the flowsheet
4. General structure of the separation system
a. Vapor recovery system
b. Liquid recovery system
5. Heat-exchanger network
Level 1: Batch vs. Continuous Operation
– Continuous Operation
• Preferred mode operation in production commodity chemicals,
petroleum products, plastics, paper, solvent etc.
• Reduced labor cost, improved process control and more uniform
product quality.
– General Guideline
• Production rate greater than 10 X 106 kg/h
• Single product
• No severe fouling
• Good catalyst life
• Proven process design
• Establish market
Semester 1 2016/17 29
Level 1: Batch vs. Continuous Operation
– Batch Operation
• When production rates are small eg. Pharmaceuticals, or when
product demand is intermittent.
– General Guideline
• Production rate less than 1 X 106 kg/h
• A range of products or product specification
• Severe fouling
• Short catalyst life
• New Product
• Very long reaction time
• Uncertain design
Semester 1 2016/17 30
0 Input Information
4 Separation System
Semester 1 2016/17 31
Level 2. Input-Output Structure
Heuristics:
Recover more than 99% of all valuable materials.
but #1: might be cheaper to lose inexpensive reactants (e.g.,
air, water etc.)
but #2: recycle gaseous reactant and purge a gaseous impurity
or by-product
Remarks: If the cost of separation is cheap, the gas recycle and
purge might not be necessary.
Assume:
Completely recover and recycle all

valuable reactants
32
Semester 1 2016/17
Level 2: Decisions For The Input/Output Structure

 Flowsheet Alternatives
(1)
Feed streams Process Products
by-products
no reactants
(2) Purge
Products
Feed streams Process
By-Products
reasons:
1. inexpensive reactants, e.g. Air, Water.
2. gaseous reactants + (inert gaseous feed impurity or inert gaseous
reaction by-product)
33
Semester 1 2016/17

LEVEL 2 DECISIONS:
1 ) Should we purify the feed streams before they enter the process?
2 ) Should we remove or recycle a reversible by-product?
3 ) Should we use a gas recycle and purge stream?
4 ) Should we not bother to recover and recycle some reactants?
5 ) How many product streams will there be?
6 ) What are the design variables for the input/output structure?
What economic trade-offs are associated with these variables?
 
P r o d u c t s
Feeds 

PROCESS 

By products
OR Purge
  Products
Feeds  PROCESS 
 
Semester 1 2016/17 B y p ro d u c t s 34

1 ) Purification of Feeds (Liquid/Vapor)
1 ) If a feed impurity is not inert and is present in significant quantities,
remove it.
2 ) If a feed impurity is present in large amount, remove it.
3 ) If a feed impurity is catalyst poison, remove it.
4 ) If a feed impurity is present in a gas feed, as a first guess, process the
impurity.
5 ) If a feed impurity is present as an azeotrope with a reactant, often it is
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.
7 ) If a feed impurity in a liquid feed stream is also a byproduct or a product
component, usually it is better to feed the process through the separation
system.
Semester 1 2016/17 35
2) Recover or recycle by-products
Produce Benzene from toluene (Hydrodealkylation of Toluene

(HDA Process))
Toluene + H2  Benzene + CH4

2 Benzene  Diphenyl + H2
recycle: oversize all equipment in the recycle loops

remove: increase raw material costs
 No simple design guideline is available to make the
decision.
Semester 1 2016/17 36

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, -48oC)), use a gas recycle and
purge stream.
Lower boiling components normally cannot be condensed at high pressure

with cooling water (i.e. both high P and refrigeration would be required)
Semester 1 2016/17 37
4 ) Do not recover and recycle some reactants which are

inexpensive, e. g. air and H2O.
We could try to make them reacted completely, but often we feed them as an excess
to try to force some more valuable reactant to completion.
Semester 1 2016/17 38

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.None Reactants-if complete conversion or unstable reaction intermediates
5.Excess - vent Gaseous reactant not recovered or recycles
6.Excess - vent Liquid reactant not recovered or recycled
7.Primary product Primary product
8.Fuel By-products to fuel
9.Waste By-products to waste treatment should be minimized
A ) List all the components that are expected to leave the reactor. This list includes all
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
39
number of product streams.
Toluene + H2  Benzene + CH4

Purge : H2 , CH4
H2 , CH4 Benzene
Toluene Process
Diphenyl
40
Possible Design Variables For Level 2

For complex reactions:
Reactor conversion (x), reaction temperature (T) and pressure (P).
If excess reactants are used, due to reactant not recovered or gas recycle and purge, then
the excess amount is another design variable.
Design Variables, Overall Material Balances and Stream Costs
Semester 1 2016/17 41

Procedures For Developing Overall Material Balance
1 ) Start with the specified production rate.
2 ) From the stoichiometry (and, for complex reactions, the correlation for product
distribution) find the by-product flows and the reactant requirements (in terms of the
design variables).
3 ) Calculate the impurity inlet and outlet flows for the feed streams where the reactant are
completely recovered/recycled.
4 ) Calculate the outlet flows of reactants in terms of a specific amount of excess for streams
where reactants are not recovered and recycled (recycle and purge, or air, or H2O)
5 ) Calculate the inlet and outlet flows for the impurities entering with the reactant streams
in Step 4).
Normally, it is possible to develop expressions for overall MB in terms of design

variables without considering recycle flows.
Semester 1 2016/17 42
CONVERSION (x)
REACTANT CONSUMED IN THE REACTOR
SINGLE PASS
REACTANT FED TO THE REACTOR
REACTANT CONSUMED IN THE PROCESS

OVERALL
SOME REACTANT FED TO THE PROCESS
ADDITIONAL
NOTE :
REACTOR
PERFORMANCE
SELECTIVITY (S)
DESIRED PRODUCT PRODUCED
STOICHIOMETRIC
x FACTOR
REACTANT CONSUMED IN THE REACTOR
REACTOR YIELD (Y)

DESIRED PRODUCT PRODUCED STOICHIOMETRIC
x FACTOR
REACTANT FED TO THE REACTOR
Semester 1 2016/17 43
STOICHIOMETRIC FACTOR (SF)
The stoichiometric moles of reactant

required per mole of product
Semester 1 2016/17 44
Material Balance of Limiting Reactant in Reactor

Toluene + H2  Benzene + CH4
Toluene
unconverted recycle
(1-x) mole
Toluene Benzene
feed produced
(1 mole) Sx mole
Toluene
converted
x mole
Diphenyl
produced
Semester 1 2016/17 45
(1-S)x / 2

Gas recycle Purge
H2 , CH4
Toluene 1  x
Benzene Sx
1
Diphenyl (1  S ) x Benzene
H2 , CH4 Reactor 2
Separation Sx
Toluene system system
x Diphenyl
1
(1  S ) x
1 x
2
Toluene recycle
Material Balance of the Limiting
Reactant (Toluene)
Assumption: completely recover and recycle the limiting reactant.
Semester 1 2016/17 46

EXAMPLE Purge ; H2 , CH4 , PG
FG , H2 , CH4 Benzene , PB
relation
FFT , Toluene Process Diphenyl , PD
known
design variable
SS( x ) = selectivity = given
PBB( mol/hr ) = production rate of Benzene =given
FFT( mol/hr ) = toluene feed to process ( limiting reactant ) = PB/S
given
PR , CH4 = methane produced in reaction = FFT = PB/S
PD = diphenyl produced in reaction = FFT (1 - S)/2 = (PB/S)(1 - S)/2
design Let FFEE = excess amount of H2 in purge stream= PH2
variable
 FE + ( PB/S ) - [( PB/S )( 1 - S )/2] = yFH
y FF
FH GG
purge rate disapp. in reaction
of H2 FH2
where
FG = make-up gas stream flowrate (unknown)
y
FH = mole fraction of H2 in FG
( known )
Let PCH4 = purge rate of CH4 methane in purge stream
 ( 1 - yFH ) FG + PB/S = PCH4
Semester 1 2016/17
methane in feed methane product in reaction 47

 PG = total purge rate = PH2 + PCH4 = FE + (1 - yFH) FG + PB/S
= FG + ( PB/S )[( 1 - S )/2]
Define
y = purge composition of H = P /P = F /P
PH 2 H2 G E G
design
variableIt can be derived that
FG = PB [ 1- (1- yPH)(1-S)/2 ]
S (yFH - yPH)
design variable
Known : Design Variable :

PB/S
y S (x) FFT
FH x
(PB/S)[(1-S)/2]
PB FE
FCH4+PB/S [(1- yFH)/ yFH]FH2 FE+[PB(1+S)/2S]
PCH4 FCH4 FH2 PD
PCH4+FE
PG
Semester 1 2016/17 FG 48
FN2+FCH4
Known : yFH
PB S(x)
PB/S
FFT
FFT(1-S)/2
PD
Design Variables :
x, yPH PB[1-(1- yPH)(1-S)/2
S(yFH - yPH)
FE+PB(1+S)/2S
FCH4 FH2 FE PG FG
1- y PH
(PH2) PG yPH FG+(PB/S)(1-S)/2
FCH4+PB/S y FH2
PH
PCH4
6 ) ECONOMIC POTENTIAL AT LEVEL 2
EP2 = Annual profit if capital costs and utility costs are excluded
= Product Value + By-product Value - Raw-Material Costs
[EXAMPLE] HDA process
4 10^6
2 10^6
$/yr y
PH
-2 10^6 0.1 0.3  0.5 0.1 0.1
-4 10^6 0.7
Semester 1 2016/17 0.9 49

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
Semester 1 2016/17 50
Alternatives for the HDA Process

1. Purify the H2 feed stream.
2. Recycle diphenyl
3. Purify H2 recycle stream.
Semester 1 2016/17 51
Semester 1 2016/17 52
5 Purge
H2 , CH4
H2 , CH4
1 3
Process Benzene
2 4
Toluene Diphenyl
Production rate = 265

Design variables: FE and x
Component 1 2 3 4 5
H2 FH2 0 0 0 FE
CH4 FM 0 0 0 FM + PB/S
Benzene 0 0 PB 0 0
Toluene 0 PB/S 0 0 0
Diphenyl 0 0 0 PB(1 - S)/(2S) 0
Temperature 100 100 100 100 100
Pressure 550 15 15 15 465
where S = 1 - 0.0036/(1 -x)1.544 FH2 = FE + PB(1 + S)/2S
FM = (1 - yFH)[FE + PB(1 + S)/S]/ yFH FG = FH2 + FE
FIGURE 5.2-1
Stream table .`
Semester 1 2016/17 53

Process Design Development

Încărcat de

Informații document

Drepturi de autor

Formate disponibile

Partajați acest document

Partajați sau inserați document

Opțiuni de partajare

Vi se pare util acest document?

Este necorespunzător acest conținut?

Drepturi de autor:

Formate disponibile

Process Design Development

Încărcat de

Drepturi de autor:

Formate disponibile

BTE 4417 PROCESS PLANT DESIGN AND SAFETY

Process Design Development

1 Batch versus Continuous

2 Input- Output Structure

3 Recycle structure of the Flowsheet

5 Heat Exchanger Network

Level 0. Input Information

Level 0. Input Information

• Literature Survey (Chapter 2)

Level 0. Input Information

Level 0. Input Information

Level 0. Input Information

Level 0. Input Information

Level 0. Input Information

3. Feeds, product and byproducts properties.

Level 0. Input Information

Level 0. Input Information

What Informations are needed ?

Info. 2 Types of reaction system involved

Multiple Reactions in series

Level 0. Input Information

Level 0. Input Information

Example (cont.) -Assess Primitive Problem

• Process design begins with a primitive design problem that

Level 0. Input Information

Acetylene 26.04 C2H2 H- CC- H

Chlorine 70.91 Cl2 Cl-Cl

Hydrogen chloride 36.46 HCl H-Cl

PROCESS INFORMATION- Example 4.1

C2H2  HCl  C2H3Cl (2.2)

PROCESS INFORMATION- Example 4.1

PROCESS INFORMATION- Example 4.1

C2H4Cl2  C2H3Cl  HCl (2.4)

C2H4  Cl2  C2H3Cl  HCl (2.1)

PROCESS INFORMATION- Example 4.1

C2H4Cl2  C2H3Cl  HCl (2.4)

C2H4  HCl  21 O2  C2H3Cl  H2O (2.6)

PROCESS INFORMATION- Example 4.1

2C2H4  Cl2  21O2 2C2H3Cl  H2O (2.7)

INPUT/OUTPUT STRUCTURE- Example 4.2

Reaction path, kg/kg vinyl chloride

INPUT/OUTPUT STRUCTURE- Example 4.2

C2H4  Cl2  C2H4Cl2

Level 0. Input Information

Raw material and product data

Path 2 Acetylene C2H2 26 0.94

C2H4 + Cl2  C2H4Cl2 Chlorine Cl 71 0.21

Hydrochloric HCl 36 0.35

Level 0. Input Information

Assume HCl cannot be sold

1 Batch versus Continuous

2 Input- Output Structure

3 Recycle structure of the Flowsheet

5 Heat Exchanger Network

Level 1: Batch vs. Continuous Operation

Level 1: Batch vs. Continuous Operation

1 Batch versus Continuous

2 Input- Output Structure

3 Recycle structure of the Flowsheet

5 Heat Exchanger Network

Level 2. Input-Output Structure

Completely recover and recycle all

Level 2. Input-Output Structure

Level 2: Decisions For The Input/Output Structure