DESIGN PROJECT 2023

Refining of cracked Bio-naphtha

PROJECT BRIEF

Introduction

This project concerns the design of a complete processing train for the
products of a Catalytic Cracker. Naphtha, used as main feedstock for the
petrochemical industry, is classified into the light naphtha, whose boiling
point is 35 to 130°C; heavy naphtha, whose boiling point is 130 to 220°C;
and full-range naphtha, containing both these types. Naphtha is used as
feedstock for pyrolysis to produce ethylene, propylene, butadiene, benzene,
toluene and xylene that are basic feedstocks for petrochemistry. They are in
turn used to make a wide range of products including synthetic resins,
synthetic rubber, synthetic fibre, dye and medicine. Naphtha is mostly
composed of mixtures that have 5 to 12 carbons.

Feed

The Naphtha Cracker product stream is high in ethylene and light gases. A
proprietary catalyst augments the feed-stream to that shown in Table 1

In addition, you can assume that fuel oil, 50% caustic, air, hydrogen,
ammonia and sulphuric acid are readily available from outside battery
limits (OSBL) at a cost (which is separately listed),

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 Table 1 - Feed entering the plant (T=500 oC; P=107 kPag)

ASPEN NOMENCLATURE Mass Flow kg/h

Hydrogen H2 404
Nitrogen N2 1557
Carbon Monoxide CO 24
Carbon Dioxide CO2 559
Methane CH4 4836
Ethylene C2H4 17756
Ethane C2H6 3366
Propylene C3H6 27009
Propane C3H8 4330
1,3-Butadiene 13BD 336
1-Butene 1-BUTENE 7336
iso-Butylene ISOBUTYL 4602
N-Butane N-BUTANE 778
iso-Butane I-BUTANE 778
Cyclopentane CYLPENTA 594
1,4-Pentadiene 297
1-Pentene 1PENTEN 1897
N-Pentane N-PENTAN 594
N-Hexane C6NA 1878
Benzene BENZENE 4169
N-Heptane C7NA 1445
Toluene TOLUENE 11568
N-Octane C8NA 63
0-Xylene XYL-EB 5935
1, 2,4-Trimethylnapthalene C9AR 1703
1,2,3,4-Tetrahydronaphthalene C10AR 895
N-Pentylbenzene Cll+ 292
Water H20 5799
TOTAL 110800

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Process Overview

The process has been broken down into six areas, as follows:
• Area 1- Feed Conditioning
• Area 2 - Depropaniser and Debutaniser (including Hydrogenation)
• Area 3- Demethaniser, De-ethaniser and C2 Splitter
• Area 4- C3 Splitter and Refrigeration
• Area 5 -Gasoline Production (including Hydrogenation) and Benzene
Purification
• Area 6 -Acrylonitrile Production.

For groups having only five people, Acrylonitrile Production (Area 6) can be
omitted. For the specialist function, groups of five may also neglect the layout
function.

PFD's of the process, including area demarcations, are shown in Figures 1,

2, 3 with brief descriptions of the areas.

In area 1, The process gas from the Naphtha Cracker is rapidly quenched and
then compressed (to 6-9 barg). It is treated to remove oxygen, acetylene and
acid gas then dried and sent forward for product separation.

The first separation step in area 2 is a depropaniser and the liquid product is
sent to a separate unit to remove C4 fractions in a debutaniser.

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Figure 1: PFD for Feed Conditioning (Area 1) and Depropaniser/Debutaniser
(Area 2)

Area 3 concerns demethanisation and deethanisation using the lights product

from area 2: Demethanisation separates methane as an overhead component
from C2 and heavier bottom components. These bottoms product are sent to
a deethaniser which separates acetylene, ethylene, and ethane as overhead
components from C3+ bottom components. The C2 products are then further
separated in a C2 splitter

Area 4 concerns a C3 splitter or propylene fractionation which takes the C3

stream from area 3 and separates propylene as a chemical grade overhead
product. This is then cooled to a liquid product in unit(s) along with the
ethylene stream from area 3. The bottoms product from the C3 splitter is a
propane stream.

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Figure 2: PFD's of demethanlser/de-ethaniser/C2-splitter (Area 3) and C3-
splitter/refrigeration (Area 4)

In Area 5, the C5+ stream from area 2 is hydrogenated in a gasoline

hydrogenation unit to remove dienes and produce benzene and gasoline. In this
area, the benzene is also removed and purified, using extractive distillation.

In Area 6, propylene from area 4 is reacted with air and ammonia to form
acrylonitrile. This is then purified with acetonitrile and cyanide as by-products.
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Figure 3 : PFD's of Gasoline Production/Benzene Purification (Area 5) and
Acrylonitrile Production (Area 6)

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PRODUCTS AND SPECIFICATIONS

The main products from this plant are gasoline (hydrogenated to remove pentadiene to
zero; temperature < 30 "C; pressure 200 kPag), ethylene, propylene, benzene and
acrylonitrile. The specifications of the latter three/four products at battery limits (incl.
temperatures and pressures) are given in Tables 2, 3, 4 and 5.

Table 2 - Polymer Grade Ethylene Specification (T < 45oC and P = 4000 kPag)

Components Units Guaranteed Values

Ethylene %mol 99,95 min
Methane & Ethane ppm mol/mol 500 max
C3 and Heavier ppm mol/mol 10 max
Other Olefins ppm mol/mol 10 max
Acetylene ppm mol/mol 5 max
Propadiene ppm mol/mol 5 max
Hydrogen ppm mol/mol 10 max
CO ppm mol/mol 0,2 max
CO2 ppm mol/mol 5 max
Oxygen ppm mol/mol 5 max
Nitrogen ppm mol/mol 50 max
NO ppm mol/mol 5 max
Water ppm wt/wt 1 max

Table 3 • Polymer Grade Propylene Specification (T < 45oC and P = 2100 kPag)

Components Units Guaranteed Values

Propylene %mol 99.2 min
Ethane ppm mol/mol 30 max
Ethylene ppm mol/mol 10 max
Propane ppm mol/mol Balance
C4 and Heavier ppm mol/mol 2 max (as C4s)
Butenes ppm mol/mol 2 max
Butadiene ppm mol/mol 2 max
Propadiene ppm mol/mol 10 max
Hydrogen ppm mol/mol 20 max
co ppm mol/mol 0.05 max
co, ppm mol/mol 5 max
Oxygen ppm mol/mol 2 max
Water ppm wt/wt 2 max

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 Table 4 - Benzene Specification (T < 45'C and P = 1100 kPag)

Components Units Guaranteed Values

Benzene wt% 99.90 min
Sulphur mg/kg 1 max
Toluene wt% 0.05 max
Non Aromatics wt% 0.10 max
Nitrogen wt ppm 0.3 max
Water report

Table 5 - Acrylonitrlle Specification (T < 45°C and P = 200 kPag)

Components Units Guaranteed Values

Acrylonitrile wt% 99.85 min
HCN wt ppm 10 max
Acetonitrile wt ppm 1 max
Water wt ppm 10 max

OTHER PRODUCTS
METHANE-RICH STREAM
The plant is able to produce methane-rich vapour at less than 45oC and 1600 kPag. This
is intended to be used as fuel gas.

ETHANE AND PROPANE

The ethane and propane produced from the ethylene and propylene fractionation
systems are to be used as fuel gas and can thus be sent OSBL either as gases (with
temperature less than 45oC and pressure greater than 300 kPag, or as liquids (with
temperature less than 45oC and pressures above their saturation pressures.

C4 CUT
The 1,3-Butadiene rich C4 mix from liquid cracking is hydrogenated in the C4
hydrogenation unit to remove butadiene and Is sent to OSBL and sold as industrial LPG.
OSBL conditions are temperature less than 45 oC and pressure 1600 kPag. Note: LPG
can be a mixture of C3s & C4s with a limit on the amount of propane and unsaturated
compounds allowed in the mixture. Economically it would be better to put as much
propane into LPG rather than fuel gas.

-- C7+ PRODUCT
The C7+ products from Area 5 report to the Gasoline pool OSBL. The OSBL conditions
are temperature less than 30oC and pressure less than 200 kPag as a liquid product.
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 PROJECT BRIEF

Additional requirements
The clients also request that the plant be designed to allow for a ‘relatively painless’
future expansion to twice its capacity at a point in the future – this will affect layout
mainly.

Location
The proposed plant will be constructed on a brown field site on the Wilton chemical site
in Teesside since there is significant financial incentive for new investment in the NE of
the UK. The annotated diagram shown in Figure 4 shows the elements of local
infrastructure and also a close-up of the proposed plot; the latter is centred
approximately at UK grid reference NZ 575 219.
(A) (B)
Proposed site location

500 metres

Figure 4. (A) Overview of Wilton chemical works and (B) close-up of proposed
plant plot. Centre of plot located at approximate grid reference NZ 575 219.
Data

The services below are already available onsite. Any additional services, other than grid
equipment, will have to be included in the design.

• Low pressure steam (1.77 Barg, 131 ºC)

• Intermediate pressure steam (15 Barg, 201 ºC)
• 3-phase power at 33kV with a load capacity of 10 MVA
• Towns water at 20 ºC and 5 barg
• Cooling water at 18 ºC and 5 barg
• Compressed air at 18 ºC and 7 barg
• Nitrogen at 18 ºC and 7 barg

Material Cost/Price Data

Sulphuric acid (98 %) £78 / tonne
Caustic soda (50 %) £80 / tonne
Ammonia (100 %) £200 / tonne
Hydrogen £20 / 100 nm3

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 PROJECT BRIEF

Additional chemical costs can be estimated from http://ed.icheme.org/costchem.html

Utility data
Electricity – purchase from grid £ 0.11 / KWh
Towns Water £ 1.35 / tonne
Cooling Water £ 0.07 / tonne
LP Steam £ 10.00 / tonne
IP Steam £ 16.25 / tonne
Compressed air £ 0.50 / 100 nm3
Nitrogen £10 / 100 nm3

Industrial land costs

Brown field site land £200k / hectare

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