PRINSIP DESAIN DAN SINTESA PROSES

INTRODUKSI

Annasit
198106012006041001

POLITEKNIK ENERGI DAN SUMBER DAYA MINERAL AKAMIGAS

2022
 Introduksi
• Desain proses: aktivitas meng-kreasi sebuah proses kimia untuk
mengkoversi bahan baku menjadi produk yang diinginkan
– pembuatan ethylene dengan oksidasi-dehidrogenasi ethane,
– pembuatan asam terepthalat,
– natural gas to liquid,
– pencairan gas alam,
– pembuatan bahan bakar liquid dari batubara, dll

Raw material Chemical process Chemical product

Menemukan proses yang sustainable untuk mengkonversi

bahan baku menjadi produk yang diinginkan
Sustainable: ekonomis, dampak lingkungan kecil, rendah
emisi, minim limbah dan buangan, efisien, ...
masnasit 2
 The chemical industry value chain

masnasit 3
 Produk migas dan petkim
• Produk-produk migas dan petrokimia sangat penting bagi kehidupan
modern
• Hampir semua aspek dalam kehidupan sehari-hari ditopang dengan
produk-produk tersebut.
• Produk-produk olahan minyak dikelompokkan menjadi tiga kategori:
– light distillates (LPG, gasoline, naphtha),
– middle distillates (kerosene, jet fuel, diesel),
– heavy distillates and residuum (heavy fuel oil, lubricating oils, wax, asphalt).
• Refinery dapat memproduksi berbagai produk olahan minyak,
bergantung pada komposisi minyak dan permintaan konsumen.
• Produk-produk kimia:
– fine,
Small volume, high added value
– specialty,
– Commodity : large volume, low added value

masnasit 4
 Tahapan-tahapan desain proses
A. Formulation of
The Design Problem

B. Preliminary
process synthesis

D. Detailed E. Plant-wide
Process Synthesis C. Development Controllability
-Algorithmic of Base-case Assessment
Methods

Detailed Design, Equipment

sizing, Cap. Cost Estimation,
Profitability Analysis, Optimization

masnasit 5
 Design problems
Permasalahan desain harus mencerminkan situasi terkini dan memberi
peluang untuk memenuhi kebutuhan masyarakat
•Keinginan untuk menghasilkan produk dengan spesifikasi tertentu.
– petrochemicals, polymers, bio chemicals
– petroleum products, industrial gases
– foods, pharmaceuticals
•Peningkatan mutu/kualitas produk sesuai tuntutan pelanggan
•Peningkatan kapasitas kilang eksisting
– Kenaikan demand produk-produk eksisting

•Meningkatnya kesadaran publik terhadap lingkungan:

– Desain proses untuk memecahkan masalah lingkungan serta mematuhi standar
keselamatan yang lebih ketat
•Ketersediaan bahan baku yang murah dan melimpah
•Ditemukannya pasar baru, terutama di negara berkembang
masnasit 6
 Information gathering
• Information gathering
– Bisa diperoleh dari literatur (internet), data proyek
– Detail produk-produk kimia: nilai penting, kegunaan, properties, produsen,
– Alternatif bahan baku,
– Prinsip reaksi kimia
– Byproduk dan intermediate
Contoh pemenuhan kebutuhan LPG
Saat ini Indonesia masih mengimpor LPG sekitar 6-7 juta ton per tahun untuk memenuhi
konsumsi dalam negeri dan masih akan meningkat. Di beberapa wilayah mengalami
kekurangan pasokan LPG. Bagaimana solusi untuk mengatasi kebutuhan LPG?

Alternative 1: meningkatkan produksi LPG dari kilang-kilang gas alam dan kilang minyak.
Produksi gas alam terus mengalami penurunan, kilang eksisting tidak mampu menambah
produksi LPG

Alternative 2: menambah import LPG. Fasilitas terminal LPG di beberapa wilayah belum
tersedia

Alternative 3: mengusahakan bahan bakar pengganti LPG, misal DME. Terdapat sejumlah opsi
proses produksi DME
masnasit 7
 Information gathering
• Environmental and safety data
– Flash point, LFL, UFL, auto ignition temperature, toxicity
– Toxicity: TRI (toxic chemical release inventory)
http://www.epa.gov/tri/chemical/index.htm
– NFPA : data for process design and engineering practice (woods, 1995)

masnasit 8
 Information gathering
• Chemical prices
– Salah satu sumber data untuk komoditas kimia : ICIS chemical business
(chemical market report)
http://www.icis.com/StaticPages/Students.htm
– Untuk beberapa kasus diperlukan estimasi harga utilitas seperti steam, air dll

masnasit 9
 Targeting
• Identifikasi target / performa desain (berkorelasi dengan penentuan kondisi)
– Maximum yield of desired product or byproduct
– Minimum usage of raw material
– Minimum usage of utilities
– Minimum discharge of pollutant and waste streams

Raw material Process flowsheet Desired product

Mass Targeting

masnasit 10
 Targeting
• Strategi yang digunakan:
1) Perhitungan stoikiometri/neraca massa sederhana: jika data dan
informasi proses sangat terbatas
2) Integrasi massa: jika ada data detail desain proses

Targeting dengan neraca massa sederhana

Bisa ditambahkan
• Assay based calculation estimasi keekonomian
• Composition based calculation awal (EP: economic
• Stoichiometric based calculation potential)

masnasit 11
 Targeting
• Skema targeting
– Theoretical

– Assay, Composition, Stoichiometric (ACS) based calculation

Separation
feedstocks Theoretical target
Assay calc. Assuming max yield
Comp. Calc. Assuming max yield
With full product recovery

Byproducts and wastes

Reaction Separation
feedstocks Theoretical stoichiometric target
Stoichiometric calculation
Full recovery products
Assuming max yield
With full product recovery

Recycle Byproducts and wastes

masnasit 12
 Targeting
• Skema targeting
– Actual

– Assay, Composition, Stoichiometric (ACS) based calculation

Separation
feedstocks Actual target
Assay calc. With actual yield
Comp. Calc. With actual yield
With full product recovery

Byproducts and wastes

Reaction Separation
feedstocks Actual stoichiometric target
Stoichiometric calculation
Full recovery products
With actual yield
With full product recovery

Recycle Byproducts and wastes

masnasit 13
 Targeting
• Skema targeting
– Aktual dengan losses

– Assay, Composition, Stoichiometric (ACS) based calculation

Separation
feedstocks Actual target
Assay-Comp calc. with actual yield and
accounting product losses
With product losses

Lost product, Byproducts and wastes

Reaction Separation
feedstocks Actual stoichiometric target
Stoichiometric calculation Accounting for product
With actual yield losses
With full product recovery

Recycle Lost product,

Byproducts and wastes

masnasit 14
 Economic potential

masnasit 15
 Stoichiometric targeting
• Contoh: methanol plant
• Sebuah perusahaan sedang mencoba untuk mengkonversi gas
alam menjadi methanol berdasarkan reaksi kimia sebagai berikut:
– Steam reforming methane untuk memproduksi syngas
CH4 + H2O  CO + 3H2 (1)
– Reaksi sintesa methanol
CO + 2H2  CH3OH (2)

– Karena sintesa metanol memerlukan rasio stoikiometri CO:H 2 sebesar 1:2, maka
terdapat ekses hidrogen. CO2 diinjeksikan ke dalam reaktor dimana akan
bereaksi dengan methane melalui reaksi “dry reforming”.
CH4 + CO2  2CO + 2H2 (3)

• Diharapkan dapat memproduksi methanol sebesar 1 juta ton per

tahun

masnasit 16
 Stochiometric targeting
• Penyelesaian
– Kombinasi reaksi 1 dan 3 (steam dan dry reforming) menghasilkan:
3CH4 + 2H2O + CO2  4 CO + 8 H2 ......... (4)
– Dari reaksi sintesa methanol, reaksi 2, diperoleh
3CH4 + 2H2O + CO2  4 CO + 8 H2  4CH3OH ......... (5)
– Reaksi akhir
3CH4 + 2H2O + CO2  4CH3OH ......... (6)

• Price
– Natural gas = $5/1000 SCF = $0.213/SCM
– Steam (MP) = $7/1000 lb = $15.3/1000 kg
– CO2 from carbon capture = $15 – 25/ton
– Methanol = $700/ton

masnasit 17
 Assay targeting
• Contoh: attaka crude refinery (API gravity = 42.3)

HGO

LGO

Kerosene

Heavy naphtha
Light
naphtha

masnasit 18
 Assay targeting
• Intermediate product cost

Unit cost from

reference
2020 cost by
Nelson Farrar
Index
Power law of
capacity

End product prices – Downstrem cost

Refence: Maples, R. Petroleum Refinery Process Economics, 2nd ed.; Pennwell Corp.: Tulsa, OK, 2000

masnasit 19
 Crack spread
• Harga satu barel minyak mentah dan berbagai harga produk
olahannya tidak selalu sinkron.
– Tergantung pada waktu tahun, cuaca, pasokan global, dan banyak faktor lainnya,
– Penawaran dan permintaan untuk hasil olahan tertentu dapat berubah sehingga
mempengaruhi margin keuntungan pada satu barel minyak mentah yang
disuling.
• Untuk mengurangi risiko harga, penyuling menggunakan kontrak
berjangka berdasar nilai crack spread.
• Pedagang juga menggunakan crack spread untuk berspekulasi
tentang potensi perubahan harga crude dan produk olahan.
• Crack spread = commodity spread, rasio feed crude menjadi
produk komoditas yang paling kompetitif (gasoline dan heating oil)
– 3 : 2 : 1 crack spread
– 5 : 3 : 2 crack spread

masnasit 20
 Crack spread
• 3:2:1 crack spread
Menggunakan rasio 3 crude menjadi 2 gasoline + 1 heating oil
Gross cracking margin dapat dihitung sebagai berikut:
– Asumsi harga gasoline = 57.50¢ per gallon,
– Heating oil = 54.50¢ per gallon,
– Crude oil = $18.50 per barrel.

Sehingga:
– 57.50¢ per gallon x 42 = $24.15 per barrel of gasoline x 2 barrels = $48.30
– 54.50¢ per gallon x 42 = $22.89 per barrel of heating oil x 1 barrel = $22.89
– Jumlah total revenue dari produk = $48.30 + $22.89 = $71.19
– Tiga barrel crude ($18.50 x 3) = $55.50
– Dengan demikian gross cracking margin sebesar $71.19 - $55.50 = $15.69
– 3:2:1 crack spread sebesar $15.69/3 barrels = $5.23 per barrel (margin)

masnasit 21
 EXERCISE-1
Buatlah konsep pendahuluan rancangan unit proses pengolahan migas /
petrokimia / nabati yang meliputi:
– Detil produk yang ingin dibuat (spesifikasi/properties, kegunaan, produsen
di dunia & Indonesia saat ini, demand di dunia & Indonesia)
– Bahan baku yang diolah (alternatif bahan baku, ketersediaan, karakteristik)
– Alternatif proses yang digunakan
– Prinsip reaksi kimia yang diaplikasikan untuk proses pengolahannya (jika
pengolahan hanya berupa proses pemisahan fisik, poin ini bisa dilewati)
– Byproduct (jika ada), % konversi reaksi (jika ada)
– Harga produk, byproduct (jika dapat dijual), dan bahan baku
– Data keselamatan dan lingkungan untuk produk, byproduct dan bahan baku
– Estimasi Gross Economic Potential/economic targeting menggunakan
skema 1,2 dan 3 (slide 12, 13, 14) dan buat analisis apakah rancangan
yang anda buat layak untuk dilanjutkan (contoh perhitungan dapat dilihat di
slide 47)
– Tugas dibuat berkelompok dengan anggota @ 3-4 mahasiswa
masnasit 22
 Preliminary process synthesis
• Initial process flowsheet.
– Untuk mengkonversi bahan baku potensial menjadi produk tidak
dapat dilakukan dengan satu tahapan proses
– Menggunakan berbagai variasi unit proses untuk reaksi kimia
serta unit operasi pemisahan produk dengan byproduk dan
unreacted material
– Proses merangkai unit operasi menjadi flowsheet disebut
sintesa proses

masnasit 23
 Preliminary process synthesis
• Tahapan
– Penentuan basis desain dan kondisi bahan (chemical state)
• Penentuan spesifikasi bahan baku, produk dan byproduct
• Flowrate: ditetapkan paling awal sebagai basis desain. Bisa ditentukan berdasar
proyeksi demand
• Komposisi, Fasa, Bentuk (particle size distribution, particle shape), P dan T
– Memilih unit operasi
• Memilih peralatan secara individual untuk mengolah bahan baku sesuai tahapan-
tahapan proses: reaction, separation, mixing, heating, cooling, particle size reduction
or enlargement, pressure change
– Sintesa
• Mengkoneksikan unit-unit operasi membentuk satu unit proses yang utuh dan lengkap
yang mampu mengolah bahan baku menjadi produk (direpresentasikan dg flowsheet)

Connect the individual transformation to form a

Select the individual transformation steps complete process (task integration)
masnasit 24
 Synthesis steps
• Terdapat beberapa pendekatan
– Onion Diagram
– Synthesis Tree
– Heuristic

masnasit 25
 Synthesis steps – onion diagram
• The design of the process starts with the
reactor (in the core of the onion which brings
chemical changes in the feeds)
• Once feeds, products, recycle
concentrations and flow rates are known,
the separators (the 2nd layer of the onion)
can be designed
• Based on the requirement of heat for the
reactors and separators, the HEN (the 3rd
layer) can be designed
• The remaining heating and cooling duties
are handled by utility system (the 4th layer).
• The process and utility system will also
produce effluents that will have to brought to
a suitable quality for discharge. Thus the
water and effluent treatment system must be
considered (the 5th layer)
The Onion Model, Linnhoff dkk, 1994

masnasit 26
 Synthesis steps – onion diagram
Hierarchy of process design – reactor
•When synthesizing and modelling a reactor system the designer must
consider :
– What is the reactor model (CSTR, PFR, etc)
– What are its operating conditions (isothermal, adiabatic, vacuum, etc)
– How should the product conversion and yield determined?
– Is a catalyst needed in the reactor system modelling?

Steam
FEED

REACTOR

PRODUCT
Cooling water
BYPRODUCT
UNCONVERTED FEED

masnasit 27
 Synthesis steps – onion diagram
Hierarchy of process design – separation system
Separation system can be broadly classified as liquid and vapor
separation.
• Vapor separation system
– include condensers, flash
tanks, absorbers, adsorbers,
and gas separation
membranes.
– normally used to purify a
vapor recycle streams before
it re-enters the process.
• Liquid separation system
– include distillation, solvent
extraction, stripping, filtration
(include membrane),
centrifugation etc.

masnasit 28
 Synthesis steps – onion diagram
hierarchy of process design – recycle system
• Recycling is the tricky part of
flowsheet modeling
• Modeling a recycle loop is better to
use the concept of “tear stream”
• Some suggestion to aid the recycle
simulation
1) Maintaining product specification
remains the highest priority of the
process.
2) Take note of the changes in feed Additional tip to speed up the convergence
temperature and pressure The recycle stream after unit F is considered as two
separate tear stream R1 and R2
3) Beware the accumulation of the After unit A and B are solved, the simulation moves to
unwanted pollutants in the process unit C.
loop Some initial guesses for the tear stream R1 are made
4) Increase the convergence so the simulation can proceed to units D, E, and F
After unit F converges the resulting flowrates of
tolerance at the initial stage of the stream R2 is compared to the initial guess for R1
recycling simulation (additional
tip)
masnasit 29
 Synthesis steps – onion diagram
Hierarchy of process design – HEN Heat exchanger
network design
• Design of HEN usually
done using the well
established tool of
process integration
(=pinch analysis)
• HEN design procedure Reduce the hot
is divided into two utility of steam
stages :
– Utility targeting
– Network design Reduce the cold utility
of cooling water

Typical heat exchanger network design. Feed 1 is heated by reactor

effluent stream to achieve temperature target inlet reactor 1 of 180 oC
masnasit 30
 Synthesis steps – onion diagram
Hierarchy of process design – utilities
•The heating and cooling duties that cannot be satisfied by heat
recovery, dictate the need for external heating and cooling utilities
(furnace heating, use of steam, steam generation, cooling water, air-
cooling or refrigeration)
•The selection of hot and cold utilities is another well established
application of process integration
•The placement of the heat pump and heat engine

masnasit 31
 Synthesis steps – onion diagram
Example 1
•Develop a process flowsheet for n-octane (C8H18) production from ethylene
(C2H4) and i-butane (i-C4H10). Component flowrates and specifications of feed
given in table below
Components Flowrate, kgmol/h Specification
Nitrogen 0.1
Ethylene, C2H4 20 T = 30oC
n-butane, C4H10 0.5 P = 20 psia
i-butane, C4H10 10

•Ethylene and i-butane react isothermally in a stoichiometric isothermal reactor

at 93oC to produce n-octane.
2 C2H4 + C4H10 ----- C8H18
•The key component is taken as ethylene with an overall conversion of 98%.
The pressure drop across the reactor is 5 psi
masnasit 32
 Synthesis steps – onion diagram
Example 1
•Analysis - to produce n-octane, we need the spesific unit operations
as follows
– Reactor to convert feed / reactant
– Separator to separate reactor outlet stream
– Heat exchanger to increase feed temperature and decrease product
temperature
– Compressor to increase the gas pressure
•The reactor outlet stream consists of product (single product n-octane
and there is no byproduct) and unconverted material. The recycle
stream is required to return the separated unconverted reactant.

masnasit 33
 Synthesis steps – onion diagram
 Separator to separate an
• Reactor unconverted reactant and inert
with product
Heat exchanger or heater  Separation process stage 1 can
is required to increase be done by flash separation.
feed temperature from 30 Pressure drop of 2 psi is
to 93oC introduced. The volatile
Unconverted component (butane & N2) are
Feed reactant separated out through the top of
T = 30oC Inert (N2) flash tank. Small portion of
P = 20 psia Product heavier product (n-octane) may
P = 20 – 5 entrained to the top.
= 15 psia  Separation process further is
distillation column. The distillation
Reactor column is added to recover n-
Isothermal, T 93oC octane from top product stream
Conversion = 98% of flash tank.
DP = 5 psi  The unconverted material leaving
at the top distillation column is
pure enough to recycle.
masnasit 34
 Synthesis steps – onion diagram
Compressor is required to increase
• Separator recycle stream pressure up to 20 psia

Purge may be
Cooler is required to decrease required to
temperature outlet compressor release some
pressure

Feed
T = 30oC 15 psia
P = 20 psia
15 psia

13 psia
Mixer
n-octane
Equal T & P of
feed & recycle n-octane

masnasit 35
 Synthesis steps – onion diagram
Preliminary flowsheet Purge

Cooler Compressor

Distillation 15 psia

Fresh
Feed

Mixer Flash
Heater n-octane
Reactor
n-octane
masnasit 36
 Synthesis steps – onion diagram
Purge
HEN
102oC

HE Compressor
85oC Heater
30 C o

93oC Distillation
Fresh
Feed 15 psia
93oC

Mixer

Next step is performe

simulation, evaluation Flash
and optimization n-octane
Reactor
n-octane
masnasit 37
 Synthesis steps – onion diagram
Exercise
•Develop a process flowsheet for fractionation of crude oil to its
fractions: gas, naphtha, kerosene, light gas oil, heavy gas oil and long
residue

Components Flowrate, Kgmol/h Specification

Crude oil 1000 T = 35oC
P = 15 psia
o
API = 38

•Crude oil is processed by physical separation and no chemical

reaction

masnasit 38
 Synthesis step – synthesis tree
Process Operation Synthesis step
(Unit Process/Operation)
Chemical reaction Reaction
(reactor) path

Distribution
Mixing
of chemicals
(mixer/mixing tank)

Separation Separations
(separator, column, etc)

(Heat exchanger, pump, T, P and phase

compressor) changes

Integrate tasks (combine Task

tasks into unit operations) integration
masnasit 39
 Synthesis step – synthesis tree
• Example 2: proses sintesa Vinyl Chloride (Seider, Lewin)
Molecular Chemical Chemical
Chemical weight formula structure
Acetylene 26.04 C2 H2 H-CC-H

Chlorine 70.91 Cl2 Cl-Cl

Cl Cl
| |
1,2-Dichloroethane 98.96 C2H4Cl2 H-C-C-H
| |
H H
H H
Ethylene 28.05 C2 H4 C=C
H H

Hydrogen chloride 36.46 HCl H-Cl

H Cl
Vinyl chloride 62.50 C2H3Cl C=C
H H

Chemical yang digunakan dalam sintesa VC

masnasit 40
 Synthesis step – synthesis tree
Selection of reaction pathway
 Direct chlorination of ethylene:

C2H4  Cl2  C2H3Cl  HCl (2.1)

Advantages:
– Attractive solution to the specific problem denoted as Alternative 2
– 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
– Half of the expensive chlorine is consumed to produce HCl by-product,
which may not be sold easily.

masnasit 41
 Synthesis step – synthesis tree
Selection of reaction pathway
 Hydrochlorination of acetylene:

C2H2  HCl  C2H3Cl (2.2)

Advantages:
– This exothermic reaction is a potential solution for the specific problem
denoted as Alternative 3. It provides a good conversion (98%) of C2H2
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%)
masnasit 42
 Synthesis step – synthesis tree
Selection of reaction pathway
 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% (Alternative 2).
Disadvantage:
– Half of the expensive chlorine is consumed to produce HCl by-product
masnasit 43
 Synthesis step – synthesis tree
Selection of reaction pathway
 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 (2.5) 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
– Solution for specific problem denoted as Alternative 3.
 Disadvantages:
– Economics dependent on cost of HCl
masnasit 44
 Synthesis step – synthesis tree
Selection of reaction pathway
 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!

masnasit 45
 Synthesis step – synthesis tree
Selection of reaction pathway
 Reaction Path  is eliminated due its low selectivity.
 This leaves four alternative paths, to be compared first in terms of Gross
Profit.

Chemical Bulk Prices

Chemical Cost (cents/lb)
Ethylene 18
Acetylene 50
Chlorine 11
Vinyl chloride 22
Hydrogen chloride 18
Water 0
Oxygen (air) 0

masnasit 46
 Synthesis step – synthesis tree
• Targeting - Computing Gross Profit
Reaction path  C2H4 + Cl2 = C2H3Cl + HCl
lb-mole 1 1 1 1
Molecular weight 28.05 70.91 62.50 36.46
lb 28.05 70.91 62.50 36.46
lb/lb of vinyl chloride 0.449 1.134 1 0.583
cents/lb 18 11 22 18

Gross profit = 22(1) + 18(0.583) - 18(0.449) - 11(1.134) = 11.94 cents/lb VC

Reaction Gross Profit

Overall Reaction
Path (cents/lb of VC)
 C2H2 + HCl = C2H3Cl -9.33

 C2H4 +Cl2 = C2H3Cl + HCl 11.94

 C2H4 + HCl + O2 = C2H3Cl + H2O 3.42

 2C2H4 + Cl2 + O2 = 2C2H3Cl + H2O 7.68

masnasit 47
 Synthesis step – synthesis tree
• Preliminary flowsheet

Cl2 HCl
113,400 lb/hr 58,300 lb/hr
C2H4Cl2
Direct HCl
Pyrolysis
Chlorination
C2H3Cl
C2H4Cl2
C2H3Cl
C2H4 C2H4 + Cl2 C2H4Cl2 C2H4Cl2  C2H3Cl + HCl
100,000 lb/hr
44,900 lb/hr

• 800 MM lb/year @ 330 days/y  100,000 lb/hr VC

• On the basis of this principal sink, the HCl sink and reagent sources can be
computed (each flow is 1,600 lbmol/h)
• Next step involves distributing the chemicals by matching sources and sinks.

masnasit 48
 Synthesis step – synthesis tree
Distribute the chemicals

A conversion of 100% of the C2H4 is assumed in the chlorination reaction.

masnasit 49
 Synthesis step – synthesis tree
Distribute the chemicals
•Only 60% of the C2H4Cl2 is converted to C2H3Cl with a byproduct of
HCl, according to Eqn. (2.4).
•To satisfy the overall material balance, 158,300 lb/h of C 2H4Cl must
produce 100,000 lb/h of C2H3Cl and 58,300 lb/h of HCl.
•But a 60% conversion only produces 60,000 lb/h of VC.
•The additional C2H4Cl2 needed is computed by mass balance to equal:
[(1 - 0.6)/0.6] x 158,300 or 105,500 lb/h.
•Its source is a recycle stream from the separation of C2H3Cl from
unreacted C2H4Cl2, from a mixing operation, inserted to combine the
two sources, to give a total 263,800 lb/h.

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 Synthesis step – synthesis tree
• The effluent stream from the pyrolysis operation is the source for the C2H3Cl
product, the HCl by-product, and the C2H4Cl2 recycle.

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 Synthesis step – synthesis tree
• Reactor pressure levels:
– Chlorination reaction: 1.5 atm is recommended, to eliminate the
possibility of an air leak into the reactor containing ethylene.
– Pyrolysis reaction: 26 atm is recommended by the B.F. Goodrich patent
(1963) without any justification. Since the reaction is irreversible, the
elevated pressure does not adversely affect the conversion. Most likely,
the patent recommends this pressure to reduce the size of the pyrolysis
furnace, although the tube walls must be considerably thicker and many
precautions are necessary for operation at elevated pressures.
– The pressure level is also an important consideration in selecting the
separation operations, as will be discussed in the next synthesis step.

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 Synthesis step – synthesis tree
Eliminate Differences in Composition
•The product of the chlorination reaction is nearly pure C2H4Cl2, and requires no
purification.
•In contrast, the pyrolysis reactor conversion is only 60%, and one or more
separation operations are required to match the required purities in the C2H3Cl
and HCl sinks.
•One possible arrangement is given in the next slide. The data below explains
the design decisions made.
Boiling point (oC) Critical constants

Chemical 1 atm 4.8 atm 12 atm 26 atm Tc,C Pc, atm

HCl -84.8 -51.7 -26.2 0 51.4 82.1

C2H3Cl -13.8 33.1 70.5 110 159 56

C2H4Cl2 83.7 146 193 242 250 50

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 Synthesis step – synthesis tree

There may be other, possibly better alternative configurations

masnasit 54
 Synthesis step – synthesis tree
Eliminate differences in T, P and phase

masnasit 55
 Synthesis step – synthesis tree
• Intregrated task

masnasit 56
 Tahapan-tahapan desain proses
Chemical Process Construction Operating
Business Unit
Research Engineering Company Company
Idea for new Information about Proposal for
compound/market novel compound process
strategy improvement

BU Definition of
1 objective
• Objective
• Idea of production
amount

State of the CR Preliminary PE Preliminary • Estimated costs

market 1 Study 1 Study • Estimated schedule
• Patents
• Description of synthesis path
• First process description
• Analysis methods for
BU Decision on products, product quality
2 process • First safety consideration

masnasit 57
 Tahapan-tahapan desain proses
Chemical Process Construction Operating
Business Unit
Research Engineering Company Company

BU Decision on
Schedule
2 process

Conceptual
PE
process
• Description of the process 2
design
• PFD and pre P&ID
• Mass and energy balance
• Datasheets for major units
Detailed
• Site and installation plan PE
process
3
design

Decision on
BU
project
4
continuation • P&ID
• Data sheets & equipment drawings Engineering
CC
• Mass and energy balances design and
1
• Information about process at steady state construction
• Comments on start up and shut down

masnasit 58
 Tahapan-tahapan desain proses
Chemical Process Construction Operating
Business Unit
Research Engineering Company Company
Engineering • P&ID
CC
design and • Data sheets
1
construction • Equipment
drawings
• Piping spec
• Installation plan
• Building plan

Commis- Commis-
CC OC
sioning sioning
2 1
hand-over hand-over

Commis-
• Plant OC
sioning
2
• Plant documentation hand-over

OC Decommis-
3 sioning
Course: Process design principles and methods, L1, PSE for SPEED, Rafiqul Gani

masnasit 59