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Assignment

Chemical and process design

Title of Project: Plant Design for alkylation reaction between iso butane and iso-
butene to produce branched octanes (2,2,4-trimethylpentane)

Submitted by

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Submitted to

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Dated

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TABLE OF CONTENTS

1. Title page…...…………………………………………………………………….1
2. Table of contents……...………………………………………………………….2
3. Objective……...………………………………………………………………….3
4. Introduction …....…….……….…………………………………….……………3
5. Physical and chemical properties ………....………..……………………………4
6. Process used……….. ……………………………………………………………5
7. Production capacity in world ……………………………………………………7
8. Site selection……………………………………..…….…………………………7
9. Production capacity….…………………………..…….…………………………8
10. Material balance…………………………………..…….………………………..8
11. Energy balance ..…….……………….………………….……………………….9
12. Process flow diagram……………………………..…….……………………..…10
13. Instrumentation…….……………………………..…….………………………..11
14. References……………………………………..…………..………………….….11
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Objective:

The purpose of this report is to design a plant for the alkylation reaction between iso butane and
iso-butene in the presence of required catalyst and feed flow rate of 782 m3/year (student ID) to
form 2,24-trimethylpentane. This report covers physical and chemical properties of raw material
and products, process used, process flow diagram, material and energy balance.

Introduction:

Alkylation is one of the most common process in the refining process of converting low octane
number hydrocarbon to high octane number hydrocarbon. (Britannica, n.d.) This process was
first used in petroleum refining industry in 1930 but late during world war2, it became very
famous as the demand of gasoline was increased. In this process light gaseous hydrocarbons
combine to form high octane number hydrocarbon. The light carbon olefins are such as
isobutene, butylene and propylene. The light hydrocarbons in the presence of catalyst (H2SO4 or
HF) are fed to reactor, which resulted the formation of heavy hydrocarbons including fraction of
alkylate. Alkylates are the iso-octanes having higher octane number. The main purpose is to
increase octane number but there also other benefits of alkylation such as follow:

Benefits of alkylation:

 Little or no undesired by products

 It produces hydrocarbon for aviation
 It gives antiknock properties to gasoline
 It achieved required engine octane rating

There are other processes that can also be used to increase the octane number such as distillation
of crude oi, catalytic reforming, fluid catalytic cracking, isomerization and polymerization. But
alkylation is most preferred because it has very less undesired by-product and it has benefits as
described above. Gasoline which under goes alkylation are light and gaseous as well as they have
boiling range of 85 oC to 195 oC. 2,2,4-trimethylpentane has high octane number as compared to
light hydrocarbons, therefore, it is preferred. Followings are octane number of some
hydrocarbons:
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Compounds Octane number

Iso-pentane 93
n-pentane 61.8
2,2,4-trimethylpentane 100
n-hexane 24.8
2,2-dimethylbutane 91.8

Catalyst:

Many catalysts are used in alkylation process including solid as well as liquid catalysts such as
AlCl3, H2SO4, HF, HCl and many others. HF is the most commonly used catalyst and we also
used HF for our process because it produces hydrocarbon with 100 octane number. Other benefit
of using HF is that olefins are soluble in HF and it has low viscosity.

Physical and chemical properties product, raw material and catalyst:

Raw material:

 Iso-butane
 Iso-butene

Catalyst:

 Hydrogen fluoride

Product:

 2,2,4-trimethylpentane

There are other products formed but they are all considered as other alkylate. (control, n.d.)

Physical Isobutane Isobutene HF 2,2,4-

properties trimethylpentane
Molecular wt 58.12 g/mole 56.106 g/mol 20 g/mol 114.23 g/mole
Freezing point -255.3F -221 F -118.48 F -161.8 F
Density 0.563 g/ml 0.587 g/ml 0.99 g/ml 0.629 g/ml
Boiling point 10.9 F 19.6 F 67.1 F 210.74 F
Water soluble Very less Insoluble Soluble Insoluble
color colorless colorless colorless colorless
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Chemical Isobutane Isobutene HF 2,2,4-

properties trimethylpentane
flammability flammable flammable Non flammable flammable
Octane number 100 99 no 100
polarity Non polar Non polar polar Non polar

Process used:

The process used for production of 2,2,4-Trimethylpentane is by alkylation of isobutene and

isobutene in the presence of HF. Detail is given as follow;

Description;

Feed pretreatment:

The feed is pretreated by deethanizing and merox treating to saturate dienes and to decrease the
consumption of acid.

Reactor:

The isobutene and isobutene are chilled and water is removed and sent to reactor with agitator.
The first zone is cascade reaction at low temperature zone has high iso octane concentration and
high octane number produces. Agitation is continued for mixing HF and isobutene. An emulsion
is formed which is sent to further treatment.

Emulsion treating:

The alkylate and excess isobutene emulsion is treated. It is warmed and acid is removed. The
ester produced as byproduct also separated. The treating system consisted of washing with acid
and caustic soda.

Distillation:

The alkylate and isobutene after treatment sent to distillation column to separate all the
hydrocarbons in the stream such as isobutene, 2,2,4-Trimethylpentane, heavy alkylate and other
separated on the basis of their boiling point and more refined product is achieved.
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List of main equipment:

 CSTR reactor
 Fractionation column
 Debutanizer
 HF separator

Operation conditions:

Feed flowrate = 782 m3/year

Feed:

 Isobutene
 Isobutene

Catalyst

 Hydrogen fluoride

Product

 2,2,4-Trimethylpentane
 alkylates

Temperature of alkylation = 300 K

Pressure = 30 bars

Residence time = 20 to 40 seconds

Reactor type = CSTR

Isobutene to olefins ratio = 8

Reaction:
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Isobutene and isobutene react to form 2,2,4-Trimethylpentane in presence of HF at the

temperature of 300 K. (industry, 2014)

Block flow diagram:

Production Capacity of alkylates in the World

The production capacity of alkylate globally was 2,056,035 barrel per day in 2016. It has
increased drastically in recent years. According to the studies and researches, the global alkylate
market will react US$ 78.1 billion by the end of 2021. It is expected to reach $ 100 billion by
year 2031. The demand is growing day by day. The demand is automotive and aviation sector
has increased drastically after the opening of world transportation post pandemic of COVID-19.
Another reason of increase in demand is the investment in agri-tech in china and India. The
world expects to increase in production of alkylate by 40-50% by 2031. (Singh, 2021)

Site selection for plant:

Alkylation is the process mostly used in refineries. Where it is easy to transport and convert the
isobutene to isooctane. The site is selected on the basis of following factors:

 Recourses availability (water, land, fuel power)

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 Raw material availability (isobutane, HF and isobutene)

 Labor cost (low cost)
 Transportation facility (raw material, logistic and labor)
 Environmental impacts (low emissions, low threat of land and water)
 Skilled labor (skilled labor readily available)

Keeping these parameters in mind. The location of site for alkylation plant should be in refinery
where labor, raw material, resources, and skilled labor is already available. Refineries are mostly
away from cities or sometimes offshore. Transpiration problem can be solved by connecting the
supply line through road or train. Therefore, the perfect location will be away from cities in
dessert or drilling area.

Production capacity of process:

It is estimated that the 2,2,4-Trimethylpentane produced by the process used is 1.76% of the feed
isobutane. We are using 782 m3/year of isobutane to produce 2,2,4-Trimethylpentane. So the
capacity of plant is 13.7 m3/year.

Material balance:

The process has no reaction therefore, there is no accumulation and generation. The overall
material balance equation is given as follow (Dagde, 2014):

Input – output + generation – depletion = accumulation

As there is no accumulation, generation or depletion therefore:

Input = output

The material balance was carried out on the basis of empirical factors given as follow;
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The mass factor for given products against respective feed is listed in table above.

Overall material balance is given as follow:

feed product
components (m3/year) (m3/year)
butene 0.0171 0
isobutane 0.086 0
recovered isobutane 781.9 757.9
propane out 0 0.003
butane out 0 9.6
2,2,4-Trimethylpentane 0 13.5
total 782.0031 781.003

Energy balance:

The heat capacities for each component are calculated as follow (technology, n.d.)

Cp = A + BT + CT2 + DT3

The heat capacity of a stream is given as follow:

Heat capacity of steam = ∑ nC pi

Where n = mole fraction and Cpi is heat capacity of each component.

Heat capacity of liquid and vapor mixture stream is calculated as follow:

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Heat capacity of stream = nCpl + nCpg

Where n is mole fraction of liquid or gas and Cp is respective heat capacity.

Compounds Cp inlet (J/mol.K) Cp outlet (J/mol.K)

Iso-butane 97.5 111.03

Iso-butene 95.2 ---

Propane --- 84.201

2,2,4-Trimethylpentane --- 218.72

Heat of formation:

Heat of formation of 2,2,4-Trimethylpentane is given using the chemical reaction as -260.1

kj/mol.

Process flow diagram:

Instrumentation:
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Instrumentation is very critical part of process control. Its purpose is to increase the efficiency,
decrease risk, and increase control on the process. The instrumentation is very little used in this
project. But there is space for instrumentation. Followings will be the instrumentation of process:

 Temperature sensors
 Pressure control and relief valve
 Flow control valve
 Level meter
 Pressure sensors

References
 Britannica, T. E. (n.d.). alkylation. Retrieved from Britannica:
https://www.britannica.com/technology/alkylation-petrochemical-process

 control, C. p. (n.d.). isobutane. Retrieved from CONCOA precision gas control:

https://www.concoa.com/isobutane_properties.html

 Dagde, K. K. (2014). Numerical Simulation of an Industrial Absorber for Dehydration of Natural

Gas Using Triethylene Glycol. Journal of Engineering.

 industry, e. o. (2014, 09). Cracking and related refinery processes. Retrieved from essential of
chemcial industry: https://www.essentialchemicalindustry.org/processes/cracking-
isomerisation-and-reforming.html

 Singh, M. (2021, 10). Alkylate Market to Grow by 1.3X as Demand in Aviation Industry Gradually
Returns to the Pre-pandemic Level. Retrieved from CISION: https://www.prnewswire.com/news-
releases/alkylate-market-to-grow-by-1-3x-as-demand-in-aviation-industry-gradually-returns-to-
the-pre-pandemic-level-301391840.html

 technology, N. i. (n.d.). NIST . Retrieved from NIST Chemistry WebBook:

https://webbook.nist.gov/cgi/cbook.cgi?ID=C112276&Units=SI&Mask=4