CHAPTER 1

1.0 INTRODUCTION

1,3-butadiene is a simple conjugated diene with the formula C4H6. It is a synthetic,

colourless, noncorrosive gas with mild aromatic odour at room temperature and
atmospheric pressure, and it is practically insoluble in water but soluble in ethanol,
ether, acetone and benzene (PubChem Compound Database , 2017).

Butadiene is commonly produced by four processes which are production from

Propylene, steam cracking of paraffinic hydrocarbons, catalytic dehydrogenation of n-
butane and oxidative dehydrogenation of n-butene. (White, Butadiene production
process overview , 2007)

Finished butadiene is traded globally with the largest exporters being Canada,
Western Europe, Saudi Arabia and Korea. The largest net importers are Mexico, United
States and China. (Chemical Marketing Associates Inc. (CMAI), 2005).

1.1 Supply and Demand for Butadiene

1.1.1 Importance and Uses of Butadiene

Petrochemical industry produces a major product such as Butadiene in their field

of production. Its simple chemical composition combined with its high chemical
reactivity and low molecular weight makes it a very useful building block in the
creation of other materials. Some of the major uses and applications of butadiene are
shown in the Table 1.1.

1
 Table 1.1 Importance and uses of Butadiene Based on 2 Major Groups

POLYMER USAGE INTERMIDIATE USAGE

Styrene-Butadiene Rubber (SBR) Process in making Adiponitrile to
Applications: Hexamethylen-diamine (HMDA).
-Tire Products
Applications:
-Adhesives
-Sealants -Nylon Resins and Fibers
-Coatings
-Rubber Articles (e.g., Footwear)
-Chewing Gum Base
Polybutadiene (PB) Process in making Chloropropene to
Applications: Neoprene.
-Tires Applications:
-ABS Resins
-Gloves
-Intermediates
-Belts and Footwear
-Impact modifiers
Acrylonitrile Butadiene Styrene (ABS) Use in intermediate process of 1,4-
Applications: hexadiene to Ethylene-Propylene
-Automotive parts Terpolymer (EPDM).
-Telephones
Applications:
-Office machines
-Computers -Coated Fabrics
-Appliances
-Automotive Parts
-Safety Bumpers
-Wire & Cable Coating
-Resin Modifier
-Footwear
-Mechanical Rubber Products
-Gaskets
-Tire Tubes
Styrene-Butadiene Latex (SBL) Use in intermediate process of sulfolane
Applications: to produce extraction solvent.
-Foam Rubber (Carpet Backing Cushions
Pads, Sponges, etc.)
-Adhesives
-Sealants
-Paper Coatings

2
 Nitrile Butadiene Rubber (NBR) Use in intermediate process of 1,5,9-
Applications: Cyclordecatriene to produce nylon fibers
-Hoses Fuel and resins.
-Lines Auto
-Parts Latex
-Adhesives
-Oil-Resistant
-Clothing/Article
-Gloves -Footwear
Styrene Butadiene Block Copolymers
(SBS, SEBS)
Applications:
-Automotive
-Applications
-Asphalt
-Extender
-Lubricating Oil
Methyl Methacrylate Butadiene Styrene
(MMBS)
Applications:
-Impact Modifiers Used in:-
 Auto Parts

 Food Packaging

 Bottles

Based on the analysis, butadiene is very useful in many ways. In facts, it is

mostly used as a monomer in the production of a wide range of polymers and
copolymers. For instance, the applications from production of polymer are asphalt, lines
auto, parts latex, adhesives and etc. Furthermore, Butadiene can be importance to some
of the chemical industry as the companies used it as intermediate chemicals. For
examples, used in intermediate process of 1,4-hexadiene to Ethylene-Propylene
Terpolymer (EPDM) and in process of sulfolane to produce extraction solvent.Other
than that, butadiene also consists of its strength and constraint.

3
 Table 1.2 Fragment between the strength and constraint of butadiene.

STRENGTH CONSTRAINT
 Flame Retardant : Superior low  Limited weathering resistance
temperature flexibility  Moderate heat and moisture
 Heat resistance and very good heat-  Flammable with high smoke
aging qualities generation
 Chemical resistance
 Impact resistance : High and Good
 Low cost alternative material to
natural rubber
 Has a variety of market applications
Table 1.2 shows that, butadiene consists of more strengths or advantages than
constraints or disadvantages. The advantages are flame retardant as it is superior low
temperature flexibility, heat resistance and very good heat-aging qualities, chemical
resistance, cheap alternative material to natural rubber and many market applications.
The disadvantages are limited weathering resistance, has moderate heat and moisture.
It is also flammable with high smoke generation. Thus, it is worth to be produced.
(Ashraf, http://textileinsight.blogspot.my, 2014)

1.1.2 Butadiene Producer

1.1.2.1 Plant Capacities in Malaysia

Since the demand of butadiene keep increase, Malaysian Synthetic Rubber

Sdn. Bhd. a joint venture between Ube Industries, Ltd. with, LOTTE CHEMICAL
CORPORATION Lotte Chemical Titan Holding Sdn. Bhd and Mitsubishi Corporation
located in Pasir Gudang, Johor, Malaysia. With all the shareholders holds about 40%
for LOTTE CHEMICAL CORPORATION, 10% for Lotte Chemical Titan Holding
Sdn. Bhd, 40% for Ube Industries, Ltd and 10% Mitsubishi Corporation, Malaysian
Synthetic Rubber Sdn. Bhd is responsible to support the manufacturing and marketing

4
of butadiene so that, the supply and the demand can be kept stable to each other. The
joint venture has 77,000 tons/year production capacities while Lotte Chemical Titan
Holding plant in Malaysia has capacity of butadiene 100,000 tons/year. LOTTE
CHEMICAL maintains its own global butadiene production (Ube Establishes Joint
Venture for Synthetic Rubber Production in Malaysia, 2013).

1.1.2.2 Plant Capacities in Asia

The demand of the butadiene is expected to increase by 6-7% while Asian

market will be the bigger market for butadiene due to the increasing of the tire,
rubber and other manufacturer. (Ube Establishes Joint Venture for Synthetic
Rubber Production in Malaysia, 2013) Among asian regions, India is the larger
butadiene producer as compared to China. There are two companies of butadiene
production located in India which are Indian Oil and ONGC Petro-additions Ltd
(OPaL). Butadiene capacities in Indian Oil is 120,000 tons/year while in ONGC
Petro-additions Ltd (OPaL), the capacity is 95,000 tons/year. Other than that,
there are also Reliance Industries Limited (RIL) and India’s Haldia Petrochemicals
Ltd (HPL) which has 72,000 tons/year and 100,000 tons/year of butadiene
respectively. These companies are producer of butadiene which export the
product to synthetic rubber producers, normally in northeast and south -east Asia
(Yan, 2011)

Figure 1.1 shows that the largest capacity of butadiene obtained from India is
31% from Indian Oil while the lowest capacity is about 19% from Reliance Industries
Limited (RIL). Capacities of butadiene from India’s Haldia Petrochemicals Ltd
(HPL) and ONGC Petro-additions Ltd (OPaL) almost equal, 26% and 24% each.
The capacities are varies from each other because of the facilities, types of
feedstock and types of process in order to produce butadiene. (Yan, 2011)

5
 BUTADIENE CAPACITY IN ASIA

26%
31% Indian Oil

ONGC Petro-additions Ltd

(OPaL).
Reliance Industries Limited
(RIL)
19% India’s Haldia Petrochemicals
Ltd
24%

Figure 1.1 Butadiene Capacities in Asia

1.1.2.3 Plant Capacities in World

Since automobile demand increases, manufacture of automobile tyres in the

production of styrene rubber (SBR) is one of the largest single applications
for butadiene. Hence, the demand towards butadiene production and consumption
increase. First of all, butadiene capacities in European markets are 310,000 million
tons/year in 2015. There are three common butadiene producers in Europe, Hungarian
MOL Petrochemical, German Evonik and Austrian OMV.

Figure 1.2 shows that Hungarian MOL Petrochemical plant in Tiszaujvaros has
the highest capacity of about 130,000 mt/year of butadiene. Then, it is followed by
German Evonik plant in Antwerp which producing 100,000 mt/year butadiene while
Austrian OMV plant in Burghausen has the lowest butadiene producing capacity of
80,000 mt/year .(Petrochemicals Special Report, 2016).

6
 BUTADIENE CAPACITY IN WORLD
140,000
120,000

Butadiene Cpacity
100,000
80,000
(mt)
60,000
40,000
20,000
0
Hungarian MOL German Austrian OMV’s
Petrochemicals’ Evonik’s
company

Figure 1.2 Butadiene Capacities in world

1.1.3 Projected Supply and Demand for Next 10 Years in Global

1.1.3.1 Global Market Supply for Butadiene from 2010 - 2025

There are two sources of butadiene in this world which are extractive distillation
and “on-purpose”. In the extractive distillation, the butadiene is obtained from the
ethylene production where the butadiene is produced as co-product from crude C4
stream. However, “On-purpose” butadiene production is obtained from the
dehydrogenation of n-Butane or n-Butene. “On-purpose” production is higher
compared to extractive distillation based on some aspects as shown in Figure 1.2.
(Chemicals & Petrochemicals Manufacturers' Association, India, 2012)

7
 BUTADIENE PRODUCTION BY RPOCESS VS
YEAR
15000
Butadiene Production by Process

10000 "ON-PURPOSE"
Million tons

EXTRACTIVE
5000 DISTILLATION

0
2010 2015 2020 2025
YEAR

Figure 1.3 Butadiene Productions by Process VS Year

(Global Petrochemical Overview:, 2014)

Figure 1.3 shows that the butadiene productions in 2010 to 2025 in world have
been increases from time to time. Based on the statistics data from 2010 to 2015, there
were 10650 and 11250 Million tons/year of “on-purpose” and 10000 and 10625 Million
tons/year of extractive butadiene that has been supply. For expected data from 2020 to
2025 are about 12550 and 14950 Million tons/year of “on-purpose” butadiene and
11450 and 13700 Million tons/year of extractive distillation butadiene are expected to
be supply in the world (Global Petrochemical Overview:, 2014). These increasing data
may due to the demand of the butadiene and its derivatives such as Styrene Butadiene
Rubber and Styrene Butadiene Latex. Focusing on “on-purpose” butadiene, from 2010
to 2015, there is only small increasing in the demand of the butadiene which is 600
Million tons/year which may due to the high feedstock price and economic downturn.
However, from 2020 to 2025, the demand is predicted to increase rapidly from past
years as about 10% of “on-purpose” butadiene will be produced by 2025.

1.1.3.2 Global Demand of Butadiene

8
 Both Europe and Middle East is a large market of butadiene among other
countries which responsible for about 34% of the global butadiene demand. Recently,
the demand in Middle East is growing while the demand in Europe is slow down as
Europe economy has been facing an economic recession. However, the demand growth
in Europe is still higher than in Middle East and the butadiene demand in Europe is
expected to grow faster than is past after that had recovered from recession. Among
these countries, Germany is the largest consumer of butadiene followed by French,
Saudi Arabia, Russia, Italy and Iran which hold a share of 28.7%, 25.5%, 21.4%,
11.1%, 7.7% and 2% respectively (Butadiene Market in Europe and Middle East To
2020 - European Demand Expected To Recover While Exports Drive Middle East
Production, 2017).

Figure 1.3 shows the demand for butadiene globally from 2015 to 2020. The
global demand in 2015 has been approximately to 11 million tons/year (Plotkin, 2016)
and increase to 11.66 million tons/year in 2017. The market demands are expected to
rise 3% per year (Butadiene, 2016), which is up to approximately 12.65 million
tons/year in 2020. This analysis is made based on the prediction of a double or triple
increment of automobile sales in emerging markets over the next 10 to 15 years.

GLOBAL DEMAND OF BUTADIENE FROM

2015-2020
13
12.5
Butadiene Demand
Million tons

12
11.5
11
10.5
10
2015 2016 2017 2018
2019
2020
Year

Figure 1.4 Demand of Butadiene in Global from 2015-2020

9
1.2 Process alternatives

Based on studies, there are several processes that are applicable on production
of butadiene: (1) Production from steam cracking process (SCP) of hydrocarbons , (2)
Production from propylene to butadiene (PTB) , (3) Catalytic dehydrogenation (CAD)
of n-butanes and (4) Oxidative dehydrogenation (OXD) of n-butene.

1.2.1 Steam Cracking Process (SCP)

Steam cracking (pyrolysis) of hydrocarbon is a non-catalyzed process of

thermal decomposition of hydrocarbon and can be represented as process in which the
saturated hydrocarbons are broken down into smaller, unsaturated hydrocarbons. In this
process, hydrocarbons feedstock such as ethane, propane, butane, naphtha, gas
condensate and gas oil are converted into α -olefin such as ethene, propene, isobutene
and butane, butadiene and aromatic hydrocarbons such as benzene, toluene and xylene.
However, the product obtained depends on the feed composition, hydrocarbon-to-steam
ratio, cracking temperature and residence time (Jukic, Production Of Olefin - Steam
Cracking Of Hydrocarbon).

Olefins plants are commonly designated either gas crackers or liquid crackers.
Gas crackers, also called as light crackers use ethane and propane as feedstock produce
very low quantities of C4s, about 2lb of butadiene per 100 lb of ethylene. Liquid
crackers, also called heavy crackers use naphtha, condensates or gas oil as feedstock
can produce higher quantities of butadiene and heavier co-products, about 16 lb per 100
lb of ethylene (White, Butadiene production process overview, 2007). Therefore, we
are focused more on naphtha cracking.

Table 1.3 Product yields (%) by mass from steam cracking depend on hydrocarbon
feedstock.
Product Feedstock
Raw Material Ethane Propane Naphtha Gas Oil
Hydrogen 5 2 1 1
Methane 9 27 15 8

10
 Ethene 78 42 35-25 23-15
Propene 3 19 16 14
Butene 5 5
Butadiene 2 3 5 6
RPG* 3 7 19-29 20
Fuel Oil 4 23-31
*RPG (raw pyrolysis gasoline) is a mixture of C5 - C8 hydrocarbons

By focusing on product of butadiene, the tabulated (Table 1.3) data shows that
heavy (liquid) hydrocarbon feedstock such as naphtha and gas oil produce higher
number of production compared to light (gaseous) hydrocarbon feedstock such as
propane and ethane. (Jukic, Production Of Olefin - Steam Cracking of Hydrocarbons,
2013)
The steam cracking process performed at: very high temperature: 750 - 900 °C,
approximately normal pressure: 2-4 bar, water vapour: ≥ 40%, retention time: 1s and
conversion per pass: 60-80%. This process consists of three main sections which are A)
pyrolysis, B) primary fractionation/compression and C) product recovery/separation
(Tao, Martin, & Kornelis, 2006):

Section (A) pyrolysis:

The processes are carried out with the addition of water vapor in the volume
share (%) which increases with increasing molecular weight of raw material. For
instance ethane, propane / butane, naphtha and gas oil with (25%), (30%), (35%) and
(50%) respectively. Naphtha fed to a pyrolysis furnace and preheated to 650 °C. Then,
naphtha is vaporized with superheated steam and is passed into tubes that made of
chromium nickel alloys. Pyrolysis takes place in the radiant section of the furnace,
where tubes are externally heated to 750–900 °C by fuel oil. Naphtha is cracked into
smaller molecules by free-radical mechanism without catalysts depending on the
severity. After leaving the furnace, the hot gas mixture is quenched in the transfer line
exchangers (TLE) to stop the reaction.

Section (B) Primary fractionation/compression:

Gasoline and fuel oil streams have been condensed and fractionated. When
liquid fraction extraction occurs, the gaseous fraction is de-superheated by a circulating

11
oil or water stream and then passed through five stages of gas compression at 15–100
°C. Then, cool and clean up to remove acid gases, carbon dioxide and water. Most of
the dilution steam is condensed, recovered and recycled. Products that produced are
fuel oil and aromatic gasoline. Water steam are used to reduce fouling or decrease the
formation of coke as build-up of polymers on the rotor and other internals results in
energy losses as well as mechanical problems.

Section (C) product recovery/separation:

It is a separation process through a series of distillation, refrigeration and
extraction, leaving the crude C4s or crude butadiene. Equipment involves are chilling
trains and fractionation towers, refrigeration, de-methanizer, de-ethanizer and others.
Separation of C2 compounds or ethylene and ethane need large distillation columns up
to 180 trays and high reflux ratios while undesired acetylene can be removed through
catalytic hydrogenation or extractive distillation. Similarly to C3 compounds and
propylene which are re-boiled with quench water at 80 °C and separated in the C3
splitter. Ethane and propane are recycled back as feedstock while methane and
hydrogen are separated at cryogenic temperatures. Butadiene, other C4 compounds and
aromatic gasoline are separated in the end.

Figure 1.5 Steam Cracking Process of Naphtha (JoulesBurn, 2011)

12
1.2.2 Production of Butadiene from Propylene

The plant for production of butadiene from propylene is divided into four
sections: (1) Metathesis, (2) Distillation, (3) Oxidative dehydrogenation and (4)
Extractive distillation. The co-products for this process included gasoline and ethylene.
Solvent such as N-methyl-2-pyrolidone (NMP) are required in this process in order to
achieve high purity of 95.95% of butadiene throughout the separation by extractive
distillation column.

Metathesis of Propylene to 2-butene

The first step involves a process known as metathesis. Two propylene molecules
are reacted to produce ethylene and 2-butene. Other co-products as a result of side
reactions are 1-butene, pentenes and hexenes. In order to make this process to be more
selective and only produce ethylene and 2-butene, a suitable catalyst is required.
However, there is no such catalyst in operation today. Since 1966-1972, Phillips
Petroleum ran this method using W03/SiO2 as a catalyst and in the last 40 year, there
has been a great deal of advancement in catalyst development techniques, therefore a
new catalyst needs to be explored. Ethylene and gasoline are distilled and separated and
then sold as co-products. Once 2-butene is produced, it is converted to butadiene via
oxidative dehydrogenation. The flow of metathesis process is shown in Figure
1.17. .

Figure 1.6 Flow Diagram of Metathesis Process (Nestlerode, Victor , & Safia, 2015)

13
Distillatin

The second step of the process is to recover the butene that were produced in
the metathesis reactions. This process is done using three distillation columns with
pumps in between each column to make up for losses in pressure. Ethylene will be
separated and sold off at an industry specified purity of at least 99.5% in the distillate
of the first distillation column. In the second column, propylene will be recovered in
the distillate and recycled back into the metathesis feed. Finally, the butene products
will be separated from the side products, C5 and C6, in order to undergo the oxidative
dehydrogenation.

Figure 1.7 Flow Diagram of Distillation Process

(Recovery of butenes)

Oxidative Dehydrogenation
Oxidative dehydrogenation is a well-known industrial process, often used for
converting 2-butenes to butadiene. The reaction mechanism works by utilizing oxygen
to facilitate the removal of two hydrogen atoms from 2-butene in order to form an
additional double bond, resulting in a molecule of butadiene and a molecule of water.
This process has a large advantage over the non-oxidative process where it could
achieve 100% conversion of 2-butenes and high yields of butadiene, all at relatively
lower temperature (Nestlerode, Victor , & Safia, 2015).

14
 In order to achieve these high conversions and yields, a catalyst must be used to
facilitate the reaction. A variety of catalysts will work for this, with the traditional
option being a ferrite catalyst, and over recent years a number of catalysts have been
developed to achieve even higher yields of butadiene. Recent patent research uses
multi-metal oxide catalysts to achieve yields of butadiene above 90% (Josch et al.,
2014). Two primary reactions occur inside this reactor, one being the desired oxidative
dehydrogenation of 2-butenes to butadiene, and the second being the undesired
combustion reaction of 2-butenes to produce CO2 and water. The stoichiometry of these
reactions is as below:
1. Oxidative dehydrogenation of 2-butenes (cis and trans) to butadiene:
C4H8-2 + 1/2 O2 C4H6 + H2O
2. Combustion of 2-butenes:
C4H8-2 + 6 O2 4 CO2 + 4 H2O

The reaction specifications for the oxidative-dehydrogenation process are shown in

Table 1.4:
Table 1.4 Conversion Mechanisms and Heat of Reaction
( (Nestlerode, Victor , & Safia, 2015)
Reaction Conversion Heat of Reaction (Btu/lbmol)
C4H8-2 (cis) + 1/2 O2  C4H6-4 + H2O 95% -53,881
C4H8-3 (trans) + 1/2 O2  C4H6-4+ H2O 95% -52,333.5
C4H8-2 (cis) + 6 O2  4 CO2 + 4 H2O 5% -1,089,600
C4H8-3 (trans) + 6 O2  4 CO2 + 4 H2O 5% -1,088,050

The combustion reaction in which either cis- or trans-2-butene reacts with

oxygen to form carbon dioxide and water is an undesired side reaction, and while the
catalyst yields greater selectivity for the primary reaction in which butadiene is
produced, it cannot entirely eliminate the side reactions.

15
 .

Figure 1.8 Process Flow of Oxidative Dehydrogenation

(Nestlerode, Victor , & Safia, 2015)

Extractive Distillation

Once butadiene is produced, it needs to be separated out via extractive

distillation. N-methyl-pyrrolidone (NMP) is used as a solvent. Butadiene needs to be
separated from water, non-condensable, cis- and trans-butenes and NMP.

The reactor effluent from the oxidative dehydrogenation reaction contains a

large amount of side products as well as inert nitrogen that was initially used for heat
distribution in the highly exothermal reaction. As a result, stream S-308 in Figure 1.10
entering extractive distillation is only about 30% butadiene by mass, and 48% nitrogen.
There is also a significant amount of water, carbon dioxide, and 1-butene that must be
removed in order to purify the butadiene. This system produces high-purity of 99.5%wt
butadiene. In order to achieve this high purity, an extractive distillation train will be
used to recover the butadiene.

16
 Figure 1.9 Process Flow of Extractive Distillation
(Nestlerode, Victor , & Safia, 2015)

1.2.3 Catalytic Dehydrogenation (CDP) Process

As shown in the Figure 1.10, the n-Butane which is the feedstock will be first
pre-heated in a furnace alongside with unreacted gases that have been recovered to get
the actual desired temperature. Gases enter the catalytic packed bed reactors loaded
with the chromium oxide catalyst. All of the products that have been withdrawn and
the stoppage of the feed flow to the reactor unit are carried out by using valves.

When this reaction is subjected to run with the catalyst, there will be coke
formation during the process. Therefore, the coked catalyst is subjected to combustion
using preheated air. Then, the air preheating will be done using steam in an extended
area at the utility unit which is a heat exchanger. Consequently during regeneration, the
preheated air will allow to enter by another set of valves and enable the product
withdrawal after the combustion. The pre-heated air not only removes the coke as
carbon dioxide (CO2), somehow it increases the reactor temperature to 650°C. Then,
flue gases will not be released to the environment, but it will be sent to a waste heat
recovery boiler so as to generate steam from water. The whole operation of a feed entry,

17
product withdrawal, pre-heated air entry and combustion gases withdrawal from the
packed bed reactor corresponds to one single cycle.

Batch operation is used in the above process. Hence, to ensure the operation
continuously working in a specified time and manner, two reactors are used in this
plant. These two reactors are operated in cyclic fashion in example, when the first
reactor is subjected to reaction to run the process, another reactor will be subjected to
run the catalyst regeneration and vice-versa. Outlets gases from the hot reactor are sent
to a quenching tower to cooled down and stop the reactions.

After the production of gases from the quenching tower have been compressed
and cooled, it then will flow and eventually enter to an absorber. Absorbent that used
in this absorber is naphtha. This naphtha is functioning to absorb all hydrocarbons
except fuel gas. The absorbent will mix with the hydrocarbons that then will eventually
flow to a stripper that produces fresh naphtha and hydrocarbon mixture. The mixture of
the hydrocarbons consists of the unreacted feed stock and butadiene with some heavy
ends. Then, these mixture will be directly enters a fractionator to separate the crude
butadiene and heavy ends. Eventually, the crude butadiene undergoes purification
process. Due to the components with almost similar boiling points, distillation process
is not suitable while solvent extraction is commonly used in the purification of
butadiene.

Figure 1.10 Process Flow Diagram of Catalytic Dehydrogenation (Vidya Mitra, 2017)

18
1.2.4 Oxidative dehydrogenation of n-Butene (OXD) Process

Oxidative dehydrogenation of n-butene is one of the processes that

commercially used in production of butadiene. There are several processes and catalysts
developed for the oxydehydrogenation of n-butanes and n-butene feedstock to produce
butadiene. However, butene are more reactive as compared to butanes due to their
unsaturated structure. Moreover, production plant for n-butene required less severe
operating conditions than for n-butanes to produce equivalent amount of product.
Therefore, n-butene is more preferable raw materials for butadiene production than n-
butanes.

Generally, in an oxydehydrogenation process, a mixture of n-butene, air and

steam is passed over a catalyst fix bed reactor at low pressure and approximately 930-
1110 °F (500-600 °C).The heat from the exothermic reaction can be removed by
circulating molten heat transfer salt, or by using the stream externally for steam
generation. An alternate method is to add steam to the feed to act as a heat sink. The
heat can then be recovered from the reactor effluent .Reaction yields and selectivity can
range from 70-90%, making it unnecessary to recover and recycle feedstock.

As shown in Figure 1.11, a mixture of air, steam, and n-butene is passed over
the dehydrogenation catalyst in a continuous process. The air feed rate is such that an
oxygen over n-butene molar ratio of approximately 0.55 is maintained, and the oxygen
is totally consumed. However, a ratio of 10:1 of steam to n-butene has been reported as
necessary to absorb the heat of reaction and to control the temperature rise.

19
 Figure 1.11 Process Flow Diagram of Oxidative Dehydrogenation
(Product Stewardship Guidance Manual, 2010)

The production line is followed by the purification of crude butadiene produced.

In order to obtain a high purity of butadiene, recovery of butadiene via extractive
distillation is commonly used. There are four recovery processes available: Butadiene
Purification via Acetylene Hydrogenation and Extractive Distillation using aqueous
methoxy-proprio-nitrile (MOPN) (Figure 1.12); Extractive and Conventional
Distillation Process using Aqueous n-methyl-2-prryolidone (NMP) (Figure 1.13);
Dimenthylformamide (DMF) Solvent Extraction Process (non-aqueous) (Figure 1.14);
Aqueous Separation and Acetonitrile (ACN) Extraction (Figure 1.15). (BUTADIENE,
2010).

Figure 1.12 Process Flow of Butadiene Purification via Acetylene Hydrogenation and
Extractive Distillation with Aqueous methoxy-proprio-nitrile (MOPN)/Furfural

20
Figure 1.13 Process Flow of Extractive and Conventional Distillation Process with Aqueous
n-methyl-2-prryolidone (NMP)

Figure 1.14 Process of Dimenthylformamide (DMF) Solvent Extraction Process (non-

aqueous)

21
 Figure 1.15 Process Flow of Aqueous Separation and Acetonitrile (ACN) Extraction

1.2.5 Comparisons of Process Alternatives

Based on the research, the process alternatives for butadiene production are
analysed in the aspect of raw material, catalyst, operating conditions, safety factors,
economics and market analysis, flexibility and controllability, environmental impact,
green chemistry and sustainability and yield as shown in Table 1.5.

Table 1.5 Comparisons between the Alternative Processes.

Process Propylene to Catalytic Oxidative Steam Cracking

Butadiene Dehydrogenati Dehydrogenatio Of Hydrocarbon
(PTB) on (CDP) n (OXP)
Process Process Process
Raw Material Propylene n-butane n-butene Naphtha
Catalyst - Chromium Zinc Iron Oxide -
Oxide
Operating -temp: 300- -temp :500- -temp :500- -temp : 750-
Condition 400 °C 600°C 600°C 900◦C
-minimal heat -Pressure: 300- -Pressure: 1atm -Pressure : 2-4atm
generation 350atm -Retention time :
1s

22
 -endothermic
reaction
Safety Factor -face with many - high temp to - low pressure Need very high
flammable
optimize operation temperature to
substance and
hence results production reduced the prevent the
toward a more
increased the operating risk. formation of
risk and safety coke.
measures to be
done
Economic and -ratio of -Commercial - Commercially -not profitable
Market propylene to availability and available butene process because
Analysis butadiene in relatively low -high yields of the fluctuate
production is price of alkanes makes this and increasing
2:1 -Catalyst used is production more price of naphtha
- Not profitable available in profitable
due to the price market
of propylene is
currently high.
Flexibility and -low flexibility -Not flexible -Not flexible -High flexibility
Control Ability due to metathesis because the raw because the raw because many
process which material and material and type of feedstock
responsive to catalyst used catalyst used can be used.
catalyst must be must be specific. -Low
-low specific. -High controllability
controllability -Low controllability because it is
due to controllability due to the difficult to control
complicated due to the production of the yield of
process process higher yield and desired product
required. purity of
butadiene.
Environmental -more waste -emission of -emission of -emission of CO2
impact water produced CO2 CO2 and N2 can cause global
and warming

23
 -water treatment Ammonium
for waste water Hydroxide
required
Green -waste water is -do not emit -heat is produced -the process is not
Chemistry
produced and CO2 as coke and removed by green chemistry
&
Sustainability treatment is catalyst prevent circulating as it emit CO2
required the coke molten heat
formation transfer salts
Yield ~90% ~40% 70-90% <5%
-as co-product
from production
of ethylene

1.2.6 Process Chosen among the Alternatives

Based on the analysis, steam cracking of hydrocarbon is not chosen as the best
process among the four alternative processes listed in Table 1.5 because butadiene is
produced as co-products. This process is the most energy consuming process. Based
on this process, it is not green chemistry as there will be high carbon dioxide emissions
up to 200 million tons. (Tao, Martin, & Kornelis, 2006) This situation may leads to
global warming and climate changes. Last but not least, deposited coke at inner
cracking pipes surface causes negative impact towards process economy. It can increase
the pressure drop, reducing of heat transfer, hot spots and corrosion by carbonization.
It also able to change the process kinetics and give bad effect on desired products yield
(Jambor & Elena , 2015). For these reasons, we are strongly agreed that steam cracking
of hydrocarbon is not a good process.

Other than that, the production of butadiene from propylene through this process
making a significantly high negative return on investment (ROI) value of 202% due to
the high cost material used. (Smock, 2013) Hence, this process is reported to be not
profitable at current prices of butadiene and propylene. However, it is predicted to be
profitable in the future 20 to 30 years based on the trending of prices. Therefore, this
process plant is currently unavailable. (Nestlerode, Victor, & Safia, 2015)

24
 Next, catalytic dehydrogenation of n-butane is not a good choice for production
of butadiene. The maximum yield of the butadiene production from this process is only
40%. On the other hand, there is another way that can increase the yield of the
production up to 46%. For instance, by adding small amounts of nickel and lithium to
a commercial catalyst, yields of butadiene of about 46% per pass were obtained in
comparison to yields of about 40% per pass for the reaction of catalyst without the
added nickel and lithium. However, the consuming of this added chemical is not
profitable to the production. Therefore, this process is not chosen as the best alternative
process.

Last but not least, oxidative dehydrogenation process from n-butene is the most
suitable choice to produce butadiene as this process producing highest amount (70%-
90%) of yield. Hence, it could be profitable production. Moreover, this process using
n-butene as raw material is predicted to be less energy consuming as compared to
process initiate with n-butane. This process does not require high pressure condition
whereas most of the equipment and streams work under atmospheric pressure.
However, few modifications and designs on the currently exist plant is required in order
to minimize the production of waste to reduce risks and environmental impacts, and
optimize the butadiene recovery and production in order to increase the profits.
According to the reported sources, a plant for butadiene production is designed and
assessed in this project.

1.3 Critical Assessment of the Process Chosen

1.3.1 Capacity of the Plant

According to the research, the demand of the butadiene increase continuously

from year to year. It is predicted to exceed the supply of butadiene. For example, from
the demand and supply analysed in section 1.1.3, the demand of the butadiene is about
100 million ton/year beyond the butadiene supply. Based on literature background of
production capacities of butadiene in Malaysia, Asia and World, the best production
capacity of this plant is 100,000 tons/year. With this production capacity, it is possible

25
to increase the production capacities in Malaysia, Asia and World by 36%, 21% and
24% respectively.

1.3.2 Process Descriptions

The plant designed for the production of butadiene initiates from n-butene as
the raw material by using oxidative dehydrogenation process due to the reported high
yields as compared to other alternative processes.

Air is pumped into the catalysed fixed bed continuous flow reactor (R-101)
(attachment 1) together with the preheated raw material, n-butene and water in vapour
or steam phase. The catalyst used is Zinc Ferric Oxide due to its high selectivity to
butadiene in this process. (J. A. Toledo, et al., 1995)

The steam to butene input ratio is set to be 10:1 while the air feed rate is
maintained at oxygen/butene molar ratio at approximately 0.55. Under these input
conditions, oxygen is totally consumed. (Product Stewardship Guidance Manual, 2010)

The products produced in the reactor are predicted to be the reported typical
composition of n-butene oxidative dehydrogenation reactor effluent (Table 1.6)
including the main product, butadiene, the co-products of n-Butane, Cis-2-Butene and
Trans-2-Butene together with gases such as Nitrogen, Carbon Dioxide. (Organic
Chemical Manufacturing volume 10: Selected Processes, 1980)

Table 1.6 Typical composition of n-Butene Oxidative Dehydrogenation

Reactor Effluent

Component Composition
(wt%)
Main Product Butadiene 10.8
Co-product Cis-2-Butene 1.4
Trans-2-Butene 1.7
n-Butane 0.4
1-Butene 1.9
Nitrogen 15.8
Carbon dioxide 3.0

26
 Water 65.0

The effluent from the reactor is then pass through a heat exchanger (E-100) to
cool the mixture products and to condense the steam (gas phase) into water (liquid
phase). Then, the mixture products are further cooled down by entering a quench tower
(V-100) in order to completely stop the reactions among the hydrocarbons mixture. At
the same time, condensed water is separated from the mixture and effluent out from the
quench tower as water disposal.

As water is removed, the gas mixture is then entering a hydrocarbons adsorption

column (V-101). The hydrocarbons in the mixture would be extracted out where as
Nitrogen and Carbon Dioxide would be vent out. By passing through a stripper (V-
102), the solvent is recovered and recycle while the mixture hydrocarbons stream is
vent to the downstream.

As the boiling points of the C4 hydrocarbons are relatively closed to each other,
solvent extraction would be the most effective separation method to apply in this
process. By using aqueous methoxy-proprio-nitrile (MOPN) furfural as a solvent, the
C4 hydrocarbons would be separated whereas n-Butane, 1-Butene and Trans-2-Butene
would be vent out from the top of the extractive column and recycled.

Meanwhile, the butadiene and Cis-2-Butene rich MOPN solvent is removed

from the bottom and sent to the downstream, a butadiene fractionator. Eventually, the
purification steps to obtain butadiene from the products produced ended in the
fractionating column whereas the butadiene is concentrated in the overhead products.
However, the remaining Cis-2-Butene is recycled back to the furnace as fuel. Hence,
the purified butadiene is thus sent to the storage tank.

1.3.3 Process Chemistry and Reactions

In order to produce butadiene, chosen process is oxidative dehydrogenation of

n-butenes. The raw materials for this process are 1-butene and 2-butene while by-
product are oxygen, nitrogen, carbon dioxide, water, trans-2-butene and cis-2-butene.
Catalyst that been used in this process is Zinc Iron Oxide. .

27
 Figure 1.16 Chemical Reaction of Butadiene Production

The reaction is between one mole of 1-butene or 2-butene with half mole of
oxygen that reacts together and one mole of butadiene and one mole of water will be
produced. This process is exothermic reaction. (Organic Chemical Manufacturing
volume 10: Selected Processes, 1980)

1.3.4 Kinetics, Themordynamics Data, Physicals and Chemicals Properties

Data.

Refer the following tables for kinetics (Table 1.7), thermodynamic data (Table
1.8), physicals and chemical properties data (Table 1.9) for the reactants and products
that involve in the oxidative dehydrogenation process:

Table 1.7 Kinetics of the Chemicals

CHEMICAL KINETICS
OXYGEN Ideal gas Gibbs energy of formation: 0
Heat of formation: 0
Absolute entropy : 205 J/mol.K (Yoder, 2017)
Specific heat at constant pressure : 0.918 kJ/kg.K (at 300
K)
Specific heat at constant volume : 0.658 kJ/kg.K (at 300 K)
Equilibrium constant, K : 1.395
Gas constant, R : 0.2598 kJ/kg.K
(K. A. Kobe and R. E. Lynn, 1953)
NITROGEN Ideal gas Gibbs energy of formation: 0
Heat of formation : 0

28
 Absolute entropy : 191.6 J/mol.K (Yoder, 2017)
Specific heat at constant pressure : 1.039 kJ/kg.K (at 300
K)
Specific heat at constant volume : 0.743 kJ/kg.K (at 300 K)
Equilibrium constant, K : 1.400
Gas constant, R : 0.2968 kJ/kg.K
(K. A. Kobe and R. E. Lynn, 1953)
CARBON DIOXIDE Ideal gas Gibbs energy of formation: -394.6 kJ/mol
Heat of formation : -393.3 kJ/mol
Absolute entropy : 213.8 J/mol.K (Yoder, 2017)
Specific heat at constant pressure : 0.846 kJ/kg.K (at 300
K)
Specific heat at constant volume : 0.657 kJ/kg.K (at 300 K)
Equilibrium constant, K : 1.289
Gas constant, R : 0.1889 kJ/kg.K
(K. A. Kobe and R. E. Lynn, 1953)
WATER Ideal gas Gibbs energy of formation: -237.2 kJ/mol
Heat of formation: -285.8 kJ/mol
Absolute entropy : 69.9 J/mol.K (Yoder, 2017)
Specific heat at constant pressure : 1.8723 kJ/kg.K (at 300
K)
Specific heat at constant volume : 1.4108 kJ/kg.K (at 300
K)
Equilibrium constant, K : 1.327
Gas constant, R : 0.4615 kJ/kg.K
(K. A. Kobe and R. E. Lynn, 1953)
N-BUTANE Standard enthalpy change of fusion : 4.66 kJ/mol
Standard entropy change of fusion : 34.56 J/mol.K
Standard enthalpy change of vaporization : 22.44 kJ/mol
Standard entropy change of vaporization : 82.30 J/mol.K

LIQUID :
Enthalpy of formation : -147.6 kJ/mol

29
 Molar entropy : 229.7 J/mol.K
Heat capacity :132.42 J/kg.K (at 262oC to -3oC)
GAS:
Enthalpy of formation : -125.6 kJ/mol
Molar entropy : 310.23 J/mol.K
Enthalpy of combustion : -2877.5 kJ/mol
Heat capacity : 98.49 J/mol.K (at 25 oC)
(Butane (data page), 2014)
1-BUTENE Ideal gas Gibbs energy of formation: 71.3 kJ/mol
Heat of formation : -0.1 kJ/mol
Absolute entropies : 306 kJ/mol
(Yoder, 2017)
TRANS-2-BUTENE Ideal gas Gibbs energy of formation: 65.9 kJ/mol
Heat of formation : -7.0 kJ/mol
Absolute entropies : 301 kJ/mol
(Yoder, 2017)
CIS-2-BUTENE Ideal gas Gibbs energy of formation: 63.0 kJ/mol
Heat of formation : -11.2 kJ/mol
Absolute entropies : 296 kJ/mol
(Yoder, 2017)
BUTADIENE Ideal gas Gibbs energy of formation: 150.7 kJ/mol
Heat of formation : 110.2 kJ/mol
Absolute entropies : 279 kJ/mol
(Yoder, 2017)
AMMONIUM Standard enthalpy change of fusion : 5.653 kJ/mol
HYDROXIDE Standard entropy change of fusion : 28.93 J/mol.K
Standard enthalpy change of vaporization : 23.35 kJ/mol
Standard entropy change of vaporization : 97.41 J/mol.K
GAS:
Enthalpy of formation : -45.92 kJ/mol
Ideal gas Gibbs energy of formation : -16.6 kJ/mol
Molar entropy : 192.77 J/mol.K
(Ammonia (data page), 2014)

30
 MONOETHANOLAMINE Heat of formation : -507.5 kJ/mol
(Monoethanolamine, 2016)

Table 1.8 Physical (Toxicity and Flammability) and Chemical Properties of Chemical
Substances
Chemical Physical and chemical properties
substances
Oxygen Physical state : Gas (compressed gas)

Color : Colorless

Odor : Odorless

Molecular weight : 32 g/mole

Molecular formula : O2

Boiling/condensation point : -183.11oC (-297.6oF)

Melting/freezing point : -218.55oC (-361.4oF)

Critical temperature : -118.15oC(-180.7oF)

Vapor density : 1.1 [Air = 1]

Water solubility : 0.04 g/l

Chemical stability : The product is stable

(Oxygen (Gas) Material Safety Data Sheet, 2011)

Nitrogen Physical state : Liquid

Color : Clear Colorless

pH (1% soln/water) : Neutral

Boiling point : The lowest known value is 100oC (212oF) (water )

Specific gravity : The only known value is 1 (Water = 1 ) (water)

Vapor pressure : The highest known value is 17.535 mmHg @ 20oC (water )

Vapor density : The highest known value is 0.62 (Air = 1) (water)

Solubility : Easily soluble in cold water

Stability : The product is stable

31
 (Nitrogen Material Safety Data Sheet, 2013)

Carbon Dioxide Physical state : Gas

Appearance : Colorless gas

Color : Colorless

Odor : Odorless

Molecular mass : 44 g/mole

pH : 3.7 (carbonic acid)

Boiling point : -78.5oC (-109.3oF)

Critical temperature : 31.0oC (87.7oF)

Vapor pressure : 57.3 bar (831 psig)

Critical pressure : 73.7 bar (1069 psig)

Relative vapor density at 20oC: 762

Relative gas density : 1.52

Solubility : water:2000 mg/l completely soluble

(Carbon Dioxide Safety Data Sheet, 2016)

Water Physical state : Liquid

Color : Colorless

Odor : Odorless

Molecular weight : 18.02 g/mole

pH (1% soln/water) : 7 [neutral]

Boiling point : 100oC (212oF)

Specific gravity : 1 (water = 1)

Vapor pressure : 2.3 kPa (@ 20oC)

Vapor density : 0.62 (Air = 1)

(Water Material Safety Data Sheet, 2013)

32
N-butane GHS product identifier : N-Butane

Chemical name : Butane

Physical state : Gas [Liquefied compressed gas]

Color : Colorless

Odor : Odorless

Molecular weight : 58.14 g/mole

Molecular formula : C4H10

Boiling/condensation point : -0.5oC (-216.4oF)

Melting/freezing point : -138oC (-216.4oF)

Critical temperature : 151.85oC (305.3oF)

Flash point : Closed up: -60oC (-76oC)

Flammability (solid, gas) : Extremely flammable in the presence of the

following material or conditions: open flames,
sparks and static discharge and oxidizing material

Lower and upper explosive : Lower 1.8%

(flammable) limits Upper 8.4%

Specific volume (ft3/lb) : 6.435

Gas density (lb/ft3) : 0.1554

Solubility in water : 0.061 g/l

Auto-ignition temperature : 365oC (689oF)

(N-Butane Safety Data Sheet, 2014)

1-butene Physical state : Gas

Color : Colorless

Odor : Poor warning properties at low concentrations, sweetish

Molecular weight : 56 g/mole

Boiling point : -6.47oC (at 760mmHg)

Melting point : -185oC

33
 Auto-ignition temperature : 384oC

Flammability (solid, gas) : 1.6 – 9.3vol %

Vapor pressure : 260kPa

Critical pressure : 4020kPa

Density : 0.59 g/cm3 (at 20oC)

Solubility : water

(1-Butene Safety Data Sheet, 2016)

Trans-2-butene Physical state : Gas [Liquefied gas]

Color : Colorless

Odor : Sweetish

Odor threshold : Odor threshold is subjective and inadequate to warn for

overexposure

Molecular weight : 56 g/mole

Boiling point : 0.88oC

Melting point : 105oC

Flash point : -73oC TCC

Critical temperature : 155.4oC

Auto-ignition temperature : 324oC

Flammability (solid, gas) : 1.6 – 9.7vol %

Vapor pressure : 200kPa

Critical pressure : 3985kPa

Solubility : water

(Trans-2-Butene Safety Data Sheet, 2015)

Cis-2-butene Physical state : Gas [Liquefied gas]

Color : Colorless

Odor : Poor warning properties at low concentrations, sweetish

Molecular weight : 56 g/mole

34
 Boiling point : 3.7oC

Melting point : -139oC

Critical temperature : 159.9oC

Auto-ignition temperature : 325oC

Flammability (solid, gas) : 1.6 – 9.7vol %

Vapor pressure : 180kPa

Critical temperature : 4197kPa

Solubility : water

(Cis-2-Butene Safety Data Sheet, 2016)

Butadiene Physical state : Gas [Liquefied gas]

Appearance : Gas or low boiling-point liquid

Color : Colorless

Odor : Mildly aromatic. Poor warning properties at low concentrations.

Relative evaporation rate (butyl acetate =1) : >25

Boiling point : -4.4oC

Melting point : -109oC

Flash point : -76.1oC

Critical temperature : 151.9oC

Auto-ignition temperature : 418.9oC

Flammability (solid, gas) : 2 – 11.5vol %

Vapor pressure : 240kPa

Critical pressure : 4330kPa

Density : 0.6149 g/cm3 (at 25oC)

Solubility : water

(1,3-butadiene, buta-1,3-diene Safety Data Sheet, 2016)

35
1.3.5 Environmental, Safety and Health Concerns

1.3.5.1 Butadiene

Butadiene is a gas or low boiling-point liquid that mildly aromatic warning

properties at low concentrations. Remove it to fresh air and keep at rest in comfortable
position to breathing if inhale. If not breathing, give artificial respiration and if difficult
to breathe, give the oxygen and call physician. Immediately warm frostbite area with
warm water not to exceed 41oC (105oF) for exposure to liquid when skins in contact
with butadiene. In case of massive exposure, remove clothing while showering with
warm water. If contact with eye, immediately flush eyes thoroughly with water for at
least 15 minutes and hold the eyelids open and away from eyeballs to ensure that all
surfaces are flushed thoroughly.

Butadiene is danger because it is flammable and liquefied as it can forms

explosive mixtures with air. Immediately evacuate all personnel from danger area. Use
self-contained breathing apparatus where needed and remove all sources of ignition if
safe to do so. Reduce vapors with fog or fine water spray and taking care not to spread
liquid with water and also shut off flow if safe to do so. Ventilate area or move container
to a well-ventilated area. Flammable vapors may spread from leak and could explode
if reignited by sparks or flames. Explosive atmospheres may linger. Check atmosphere
with an appropriate device before entering area especially confined areas. For
environmental precautions, try to stop release and reduce vapor with fog or fine water
spray. Prevent waste from contaminating the surrounding environment and prevent soil
and water pollution with dispose of contents or container in accordance with local or
regional or national or international regulations.

In addition, safety precaution must be applied before handling any chemical

including butadiene. The butadiene must be keep away from heat, sparks, open flame
and other ignition. No smoking, use only non-sparking tools and only explosion proof
equipment while handling butadiene. Besides that, ensure that the equipment is
adequately grounded and if leakage, check the system with soapy water and never use
a flame. Wear leather safety gloves and safety shoes when handling the cylinder and
protect the cylinder from physical damage, do not drag, roll, slide or drop. While

36
moving cylinder, always keep in place removable valve cover. Never attempt to lift a
cylinder by its cap; the cap is intended solely to protect the valve. When moving
cylinders, even for short distances, use a cart designed to transport cylinders. Never
insert an object into cap openings; doing so may damage the valve and cause a leak.
Use an adjustable strap wrench to remove over-tight or rusted caps. Slowly open the
valve. If the valve is hard to open, discontinue use and contact the supplier. Close the
container valve after each use; keep closed even when empty. Never apply flame or
localized heat directly to any part of the container. High temperatures may damage the
container and could cause the pressure relief device to fail prematurely, venting the
container contents. (1,3-butadiene, buta-1,3-diene, 2015)

1.3.5.2 Wastes

Wastes for this process are water, nitrogen and carbon dioxide. Water is non-
corrosive, non-irritant, and non-sensitizer for skin. It is also non-permeator by skin and
non-irritating to the eyes. Water is non-hazardous in case of ingestion and in case of
inhalation and non-irritant and non-sensitizer for lungs. If small spill at the ground just
mop up, or absorb with an inert dry material and place in an appropriate waste disposal
container while for large spill, absorb with an inert material and put the spilled material
in an appropriate waste disposal. (Safety Data Seheet Ultrapure Water, 2013)

Nitrogen is slightly hazardous in case of eye contact, of ingestion, of inhalation.

It is non-corrosive and non-sensitizer for skin. In case of eye contact, immediately flush
eyes with running water for at least 15 minutes and keeping eyelids open while in case
of skin contact, rinse with water for a few minutes. For inhalation, allow the victim to
rest in a well-ventilated area and seek immediate medical attention. In case for
ingestion, do not induce vomiting but loosen tight clothing such as a collar, tie, belt or
waistband. If the victim is not breathing, perform mouth-to-mouth resuscitation and
seek immediate medical attention. If small amount of nitrogen is spill, dilute with water
and mop up, or absorb with an inert dry material and place in an appropriate waste
disposal container. For large spill, absorb with an inert material and put the spilled
material in an appropriate waste disposal. Finish cleaning by spreading water on the
contaminated surface. (Material Safety Data Sheet, 2013)

37
 Carbon dioxide is dangerous when the concentration level is above about 1%.
In case of inhalation, remove to fresh air and keep at rest in a position comfortable for
breathing. If not breathing, give artificial respiration with supplemental oxygen and if
breathing is difficult, call physician because only qualified personnel should give
oxygen. For skin contact, it may cause frostbite. For exposure to liquid, cold vapor or
solid carbon dioxide, immediately warm frostbite area with warm water and maintain
skin warming at least 15 minutes or until normal coloring and sensation have returned
to affected area. In case of eye contact, immediately flush eyes thoroughly with water
at least 15 minutes and hold eyelids opened and away from eyeball to ensure that all
surfaces is flush thoroughly. (Carbon Dioxide Safety Data Sheet, 2016)

1.3.5.3 Solvent

The Fulfural solvent is danger and may be fatal if swallowed that cause eye and
skin irritation. It also may cause target organ damage and combustible vapor may cause
flash fire. It should keep away from heat, sparks and flame. Do not ingest and do not
get on skin or clothing. Avoid contact with eyes and use only with adequate ventilation
while keep container tightly closed and sealed until ready for use. Wash thoroughly
after handling. In case of ingestion, wash out mouth with water and do not induce
vomiting unless directed to do so by medical personnel. Never give anything by mouth
to an unconscious person and call medical doctor or poison control center immediately.
For eyes contact, immediately flush eyes with plenty of water for at least 20 minutes,
occasionally lifting the upper and lower eyelids and get medical attention if symptoms
occur. In case of skin contact, immediately flush skin with plenty of water for at least
20 minutes. If small spill, stop leakage and dilute with water and mop up if water-
soluble or absorb with an inert dry material and place in an appropriate waste container.
The spark-proof tools and explosion-proof equipment is used while for large spill, stop
leak if without risk prevent entry into sewers, water courses, basements or confined
areas. Wash spillages into an effluent treatment. Contain and collect spillage with non-
combustible, absorbent material (e.g. sand, earth, vermiculite or diatomaceous earth)
and place in container for disposal according to local regulations. Use spark-proof tools
and explosion-proof equipment. Dispose of via a licensed waste disposal contractor and
contaminated absorbent material may pose the same hazard as the spilled product.
(Furfural, 2004)
38
1.4 Process Synthesis Structure and Analysis

1.4.1 Input-Output Structure with Feed and Product Specification

The inputs for the oxidative dehydrogenation process are n-butene, air and
steam while the outputs, including the main product, butadiene, co-products such as
trans-2-butene, cis-2-butene, n-butane and 1-butene and also wastes such as water,
nitrogen and carbon dioxide as shown in 1.17.

Figure 1.17 Input-Output Structures with Feed and Product Specification of the
Butadiene Production

1.4.2 Price of all Product, Co-products and Raw Material

39
 The market price of products, co-products and raw material is essential to analyse
the possible profit from a production. The price for each components are listed in Table
1.9, 1.10 and 1.11.

Table 1.9 Price for Raw Material

SUBSTANCES COST/UNIT
N-Butene RM 4260 per ton

Table 1.10 Price for Product

SUBSTANCES COST/UNIT
Butadiene RM 7580 per ton

Table 1.11 Price for Co-Products

SUBSTANCES COST/UNIT

Oxygen Pure – $0.3 @ RM 1.33 per 100 g

Bulk – $0.02 @ RM 0.09 per 100g
(Oxygen Element Facts, 2012)
Nitrogen $.45 @ RM 2.00 per pound
(Averages and Seasonality of Prices for
Nitrogen Fertilizers, 2016)
Carbon dioxide $15 @ RM 66.60 per ton
(Carbon Dioxide Price Report, 2015)
Water $1.50 @ RM 6.66 for 1000gallon
(The Story of Drinking Water; Is Water
Free ? , 2002)
N-Butane $1.22 @ RM 5.41 per gallon
(Chamberlin, 2014)
Trans-2-Butene $195.00 @ RM 866.19 for 50 g
$395.00 @ RM 1754.59 for 200 g
(Trans-2-Butene, 2010)
Cis-2-Butene unavailable
1-Butene 44-45 cents/lb @ RM 395783.00/ton

40
 (Chemical Profile : Butene-1, 2007 )

Table 1.12 Price for Catalyst

SUBSTANCES COST/UNIT
Zinc Iron Oxide RM 1.09 per gram

1.4.3 Destination Code, Component Classification and Utilities

Table 1.13 Destination Codes, Component Classification and Utilities

COMPONENT COMPONENT DESTINATION CODES

CLASSIFICATION
n-Butene Reactant (gas) Oxidative Dehydrogenation
Reactor
Air Reactant (gas) Oxidative Dehydrogenation
Reactor
Steam Reactant (gas) Oxidative Dehydrogenation
Reactor
Carbon Dioxide waste (gas) Waste Treatment
Nitrogen waste (gas) Waste Treatment
Butadiene Main product (liquid) Storage
Crude Butadiene Reaction intermediate Refinery
(liquid)
Trans-2-Butene Fuel co-product Recycle
Cis-2-Butene Fuel co-product Recycle
n-Butane Fuel co-product Recycle
1-Butene Fuel co-product Recycle
Water Waste co-product Biological Treatment
Zinc Iron Oxide Heterogeneous Catalyst Disposal
Oil Absorbent Recycle
MOPN furfural Solvent Recycle
Water Utility (liquid) Recycle

41
1.5. Process Flow Diagram (PFD)

1.5.1 Block Diagram on Process Structure

Refer next page.

42
Figure 1.18 Block Diagram on Process Structure

43
1.5.2. Process Synthesis Flow Sheet

Figure 1.19 Process Synthesis Flow Sheet Part I

44
Figure 1.20 Process Synthesis Flow Sheet Part II

45
1.5.3. PFD of the process

Refer to attachment

46
References
(n.d.).

Organic Chemical Manufacturing volume 10: Selected Processes. (1980, December).

Retrieved from National Service Center for Environment Publication:
https://nepis.epa.gov/Exe/ZyNET.exe/9101OKIA.txt?ZyActionD=ZyDocument&Client
=EPA&Index=1976%20Thru%201980&Docs=&Query=&Time=&EndTime=&SearchMe
thod=1&TocRestrict=n&Toc=&TocEntry=&QField=&QFieldYear=&QFieldMonth=&QF
ieldDay=&UseQField=&IntQFieldOp=0&ExtQFiel

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