Group design project

Professor: Mohammed Shahir

Sadek

Students:

Abdelftah saad

Ahmed Saad

Hassan Shehata

Mohammed Nassrat

Yousab Gerges

1
Table of Contents

History of acrylonitrile ...................................................................................................................... 4

USES AND APPLICATIONS: ................................................................................................................. 6

Physical and chemical properties of acrylonitrile ............................................................................. 8

Economic analysis .......................................................................................................................... 13

Consumption of acrylonitrile. ......................................................................................................... 15

Cost estimation................................................................................................................................ 18

Methods of preparation ................................................................................................................... 20

Acrylonitrile from propylene ...................................................................................................... 20

Acrylonitrile from hydrogen cyanide and acetylene ................................................................... 23

Acrylonitrile from propene.......................................................................................................... 26

Environmental Impact Of Acrylonitrile .......................................................................................... 28

Effect of Acrylonitrile on Humans and Environmental levels .................................................... 28

Environmental Levels............................................................................................................ 28

Ambient Air ............................................................................................................................. 28

Indoor Air ................................................................................................................................ 28

Food ......................................................................................................................................... 28

Effects on Laboratory Mammals ................................................................................................. 28

Irritation and sensitization ....................................................................................................... 28

Irritation of Skin ...................................................................................................................... 28

Irritation of Eye ....................................................................................................................... 29

Respiratory irritancy ................................................................................................................ 29

Effects on Humans................................................................................................................... 29

2
 Effects on Aquatic Organisms ................................................................................................. 29

How to be safe from Acrylonitrile .............................................................................................. 29

References ....................................................................................................................................... 31

3
 History of acrylonitrile
Acrylonitrile is considered to be the key ingredient in the acrylic fibre as it is used to make
clothing and carpeting also acrylonitrile-butadiene-styrene (ABS) is a durable material used in
automobile components such as telephone and computer casings, and sports equipment.
Moreover, nitrile tuber which is used in the manufacture of hoses for pumping fuel is also made
from acrylonitrile. However, Acrylonitrile is used to produce plastics that are impermeable to
gases and are ideal for shatterproof bottles which hold chemicals and cosmetics and packaging for
many other products. It is also a component in plastic resins, paints, adhesives, and coatings. The
acrylonitrile was made by a process discovered and modified in the 1950s by scientists and
engineers at The Standard Oil Company which became part of British Petroleum (BP) in 1987.
The process is a single-step direct method for manufacturing acrylonitrile from propylene,
ammonia, and air over a fluidized bed catalyst. (Hance, 1991)

Acrylic Fibres
ABS/SAN
Carbon Fibre Sweaters Carpet
Pipe
Sweats Blankets
Space Shuttle
Auto Bumpers, Socks Draperies
America's Cup
Dashboards Appliances Shirts Industrial yarns
Sailboat suits Dye receptor
T.V. Computer Casings

Polyols
Latex
Specialty Products
Caulking
Seat Cushions
Paints
Head Rest
Silicones
Packaging
Acrylamide Speciality
Clear Coat on Auto
Blister Packs
4
Water Soluble for Wastewater Coupling Agent for chemicals
Treatment Fiber Glass Gas Impermeable &
Shatterproof Containers
Acrylonitrile was first synthesized in 1893 by a scientist whose name is Charles Moorea, but
unfortunately it did not become important till the end of 1930s as many industries began to use it
in new applications such as acrylic fibres for textiles and synthetic rubber. Furthermore, by the
late 1940s the utility of acrylonitrile was unclear as many existing manufacturing methods were
expensive, multistep processes an according to these factors’ acrylonitrile could well have
remained little more than an interesting, low-volume specialty chemical with limited applications.
However, In the late 1950s, Sohio's research into a selective catalytic oxidation led to an entering
in acrylonitrile manufacture. Not only does using the catalytic oxidation had shown such a
dramatic lowering of process costs that all other methods of producing acrylonitrile,
predominantly through acetylene, became more popular, but it also has increased the Worldwide
consumption of acrylonitrile o be 52% between 1976 and 1988, from 2500 to 3800 thousand
tonnes per year. Since the 1960s, acrylic fibres have remained the major outlet for acrylonitrile
production in the United States and especially in Japan and the Far East. Also, they have been
classified as Fibres containing 85 wt% or more acrylonitrile is usually referred to as ‘acrylics’ and
fibres containing 35–85 wt% acrylonitrile is called ‘modacrylics’. Now a days, Acrylic fibres are
playing a main role in many industries as they are used primarily for the manufacture of apparel,
including sweaters, fleece wear and sportswear, and home furnishings, including carpets,
upholstery and draperies. (langvardt, 1985) (Brazdil, 1985)

Moreover, the production of Acrylonitrile-Butadiene-Styrene and Styrene acrylonitrile resins

consumes the second largest quantity of acrylonitrile as ABS resins are produced by grafting
acrylonitrile and styrene onto polybutadiene or a styrene–butadiene copolymer that contain about
25 wt% acrylonitrile which are used to make components for automotive and recreational
vehicles, pipe fittings, and appliances. The purity of SAN resin allows it to be used in automobile
instrument panels, for instrument lenses and for houseware items. One of the growing specialty
applications for acrylonitrile is the manufacture of carbon fibres that are produced by pyrolysis of
oriented polyacrylonitrile fibres and are used to reinforce composites for high-performance
applications in the aircraft, defence and aerospace industries. On the other hand, one of the minor

5
specialty applications of acrylonitrile are in the production of fatty amines, ion exchange resins
and fatty amine amides used in cosmetics, adhesives, corrosion inhibitors and water-treatment
resins. (Brazdil, 1985)

Table 1 Worldwide acrylonitrile uses and consumption (thousand tonnes)

use 1976 1980 1985 1988

Acrylic fibres 1760 2040 2410 2520
Acrylonitrile– 270 300 435 550
butadiene–
styrene resins

Adiponitrile 90 160 235 310

Other (including 420 240 390 460
nitrile rubber,
styrene–
acrylonitrile
resin,
acrylamide, and
barrier resins)

USES AND APPLICATIONS:

Acrylonitrile:
Acrylonitrile is used mainly as a monomer to make polyacrylonitrile, a homopolymer, or some
important copolymers, such as styrene-acrylonitrile (SAN), acrylonitrile butadiene styrene (ABS),
acrylonitrile styrene acrylate (ASA), and other artificial rubbers such as acrylonitrile butadiene
(NBR). Dimerization of acrylonitrile gives adiponitrile, used in the production of certain
polyamides. Small amounts are moreover used as a fumigant. Acrylonitrile and derivatives, such
as 2-chloro-acrylonitrile, are dienophiles in Diels-Alder reactions. Acrylonitrile is also a pioneer
in the developed manufacture of acrylamide and acrylic acid. (Brazdil J. F., 1983)

6
Acrylonitrile methyl acrylate:
Acrylonitrile methyl acrylate affords one of the best single layer oxygen barriers of all packing
materials. Products made from acrylonitrile methyl acrylate show first-rate strength and chemical
resistance.

Acrylonitrile methyl acrylate can be used to make a variety of polymeric products such as films,
sheets and bottles. These products can be produced using processes such as extrusion, injection
molding, calendaring and thermoforming.
Characteristics of products made out of acrylonitrile methyl acrylate:
• Rigid vessels and flexible films are extremely hard
• Good chemical resistance to acids, bases and other corrosive compounds
• High shine and sparkle

The main application for acrylonitrile methyl acrylate is in packaging. Examples of packaging
where acrylonitrile methyl acrylate are used include:
• Medical and pharmaceutical products
• Flasks for chemicals
• Packing for personal care, hygiene and cosmetic products
• Foods
(Serkov & Radishevskii, 2008)

Poly acrylonitrile:
Homopolymers of polyacrylonitrile have been used as fibers in hot gas separation systems,
outdoor blinds, sails for yachts, and fiber-reinforced concrete. Copolymers containing
polyacrylonitrile are often used as fibers to make woolen clothing like socks and sweaters, as well
as outdoor products like tents and similar items.
The advantages of the use of these acrylics is that they are low-cost compared to natural fiber,
they offer better sunlight resistance and have superior resistance to attack by moths.

7
Poly acrylonitrile absorbs many metal ions and aids the application of absorption materials.
(Delong, 2011)

Acrylonitrile-Butadiene-Styrene (ABS):
It has a good effect resistance with toughness and rigidity, metal coats have brilliant adhesion
to ABS, formed by straight thermoplastic methods, light-weight plastic. These are some of the
advantages of using the ABS. It has some application such automotive hardware, application
cases, pipe, plated items. ABS's light weight and ability to be injection molded make it useful
in developed products such as drain-waste-vent pipe systems, musical instruments (recorders,
and pianos), and golf club heads (Hammond & Jones, 2008). ABS plastic is an average
diameter of less than 1 micrometer is used as the color in some tattoo inks. Tattoo inks that
use ABS are very bright. When extruded into a string, ABS plastic is a common material used
in 3D printers. (Kennedy & al, 2010)

Physical and chemical properties of acrylonitrile

Acrylonitrile is a volatile, flammable, water-soluble liquid at room temperature. The vast majority
of acrylonitrile in Canada is used as a feedstock or chemical aid in the production of nitrile
butadiene rubber and in acrylonitrile-butadiene-styrene and styrene-acrylonitrile polymers. in
1993 the Estimated world capacity was about 4 million tonnes. the European Union which
produce 1.25 million tonnes per year, the USA that produce approximately 1.5 million tonnes per
year and Japan that produce 0.6 million tonnes per year are considered to be the major areas of
production. Acrylonitrile is released into the environment primarily from chemical production and
plastic products industries There are no known natural sources, but they actually released to
nature as Acrylonitrile is distributed largely to the environmental compartments to which it is
principally released with movement to soil, sediment, or biota as it is being limited reaction, so
advection is the major removal mechanism. Acrylonitrile is rapidly absorbed via all routes of
exposure and distributed throughout examined tissues. Acrylonitrile is also known as acrylic acid
nitrile, acrylon, carbaryl, cyanoethylate, fumigant, propenenitrile,2-propenenitrile, propanoic acid

8
nitrile. Its Chemical Abstracts Service (CAS) number is 107-13-1, its molecular formula, C3H3N,
and its relative molecular mass, 53.06. (Martin, 1996)

The molecular structure of acrylonitrile is presented below

Figure 1 chemical structure of acrylonitrile

The physical and chemical properties of acrylonitrile are presented in Table 2. At room
temperature, acrylonitrile is a volatile, flammable, colourless liquid with a weakly pungent odour.
Acrylonitrile has two chemically active sites, at the carbon–carbon double bond and at the nitrile
group, where it undergoes several reactions. It is a polar molecule because of the presence of the
(CN) group. It is soluble in water (75.1 g/litre at 25 °C) and miscible with most organic solvents.
The vapours are explosive, with cyanide gas being produced. Acrylonitrile may polymerize
spontaneously and violently in the presence of concentrated caustic acid, on exposure to visible
light, or in the presence of concentrated alkali Hence, it is stored accordingly, often as an
acrylonitrile–water formulation that acts as a polymerization inhibitor. (Kirk, 1983)

9
Figure 2 acrylonitrile process

Table 2 physical and chemical properties of acrylonitrile

property value

molecular weight 53.06 g/mole

density 0.806 g/mL

melting point 0.806 g/mL

boiling point 0.806 g/mL

refractive index 1.3888

solubility in water 7.30 weight %

solubility of water in acrylonitrile 7.30 weight %

10
viscosity 7.30 weight %

dielectric constant 38

dipole moment 3.88 Debye

vapor density 1.83

critical pressure 2.6524 x 104 mm Hg

critical temperature 245.8°C

critical volume 3.790 mL/g

surface tension 27.76 dynes/cm

ionization potential 10.75 eV

heat of combustion 10.75 eV

11
flambility limits

lower 3.0 volume %

upper 17.0 volume %

free energy of foramtion 46.7 kcal/mole

enthalpy of formation 43.0 kcal/mole

enthalpy of vaporization 35.16 kcal/mole

heat of polymerization 17.3 ± 0.5 kcal/mole

molar heat capacity liquid 26.53 cal/mole •°K

molar heat capacity vapor 15.3 cal/mole •°K

molar heat of fusion 1.58 kcal/mole

entropy 65.5 kcal/mole •°K

flash point 0°C

12
thermal conductivity 397 cal/cm sec °C

(Martin, 1996) (Nagel, 1988) (AEL, 1996)

Economic analysis
The most affected factor in the price of acrylonitrile is the price of propylene feedstock and what
is the future price of it. So, let's take a look on the decreasing of the acrylonitrile sale price and
compare it with the price of the propylene. After taking a look and doing some researches on the
capital and operating costs of producing acrylonitrile, the following was discovered:

First, propylene control about 35-45% of acrylonitrile selling price. Second, average capacity
utilization, plant space and petrochemicals are very important factors affected the selling price of
acrylonitrile. By taking this economics in consideration, it also has to observe how much this
consider will affect or make a change in environment or error in our assumption. As a good
example for it, " if a plant designed with capacity of 440 Ib/year, when it works with 90% of this
capacity, the costs would be lower than 1 cent/Ib. but if the plant work with just 75% of this
capacity, this will increase the cost by 0.7 cent/Ib." (said by U.S. Tariff Commission). So, it's very
important to choose the right size and operating capacity of the plant to serve available
markets.Invalid source specified.

There is another environmental factor affected the price of acrylonitrile, as the increasing of the
cost of the required energy and hydrocarbons raw material. Also, the increasing of the selling
price of the natural gas in the gulf coast will lead to direct increasing in the acrylonitrile selling
cost. In addition, the indirect increasing of ammonia prices will affect the price of acrylonitrile.
Even though, propylene is the most important and complex material that affect the price of
acrylonitrile, so, it's required a detailed analysis due to its natural as a by-product to produce
olefins and refining materials. There are many articles have been published about propylene, most
of them said that the selling price of propylene either decrease or at least not increase as fast as
other petrochemicals. In other side, a lot of propylene used in making alkylate gasoline containing

13
lead. propylene alkylate is inferior to butylene alkylate in a nonleaded gasoline pool. There is a
problem for us, when the capacity of both isobutane and alkylate is allocated to put the butylene
in place, there will be no available capacity to expand the use of propylene in refineries. But now
there is a solution to fix this problem, that’s by instead the using of ethane and propane that was
fed in past, with using steam crackers that used to handle heavier feed stocks. Because it is the
feed stock produce 0.4-0.6 kg propylene for each kg of ethylene higher than ethane feed stocks,
the olefins markets will get an un-symmetrical increasing in the available propylene that they
have. Although that the markets of propylene are spreading around the world, but there is no one
expected this rapidly expanding and growing of it as the ethylene shops. In addition, the cost of
propylene which is little lower than ethylene will make high statistics of growing rates of it by
changing propylene derivatives with ethylene derivatives and this will make a big competition
between both of them in the markets. At the end this will help to decrease the cost of acrylonitrile,
mostly when Sohio catalyst application combined with it.Invalid source specified.

In cost expectation studies, prof. Robert Stobaugh did a lot of statically about these issues, one of
them is about four factors decreased in the past due to the decreased of the costs of the
petrochemicals. There are two of them are the most affected factors in decreasing the costs of
about 82 petrochemical materials during last 17 years,

1- the increasing in the scale economies of ever-large production facilities.

2- the efficiencies resulting from accumulating production experience.
These two factors will always help to decrease the cost of acrylonitrile.

3- Unified products.
4- Many producers.
The importance of the big volume of acrylonitrile and its cost refers to that the petroleum
companies may join to Sohio application in acrylonitrile production, with decreasing of the
produced acrylonitrile. This will end coinciding with the life time of the product as applied on
petrochemicals, with growing, a lot of petrochemicals attract petrol companies and showed the
real decreasing manufacturing costs, while other petrochemicals will opposite this direction in the
next period of time.

Acrylonitrile has a good position help it to be in the trend of declining real price. There are four
important points can help to decrease the cost of acrylonitrile:

14
(1) improve the technologies

(2) do the possible to reduce propylene prices

(3) using some huge plants for production

(4) and get some new producers which they will make competitive threats

All of these points should overcome increases in other production costs to reduce real
Acrylonitrile prices. According to these costs of the competitive monomers, will help to
accomplish a huge spread of the acrylonitrile products through next years.

Consumption of acrylonitrile.
acrylonitrile is used in production of acrylonitrile butadiene styrene (ABS), nitrile butadiene
rubber, styrene acrylonitrile and acrylic fibers. Polyester fibers are the main competitors to acrylic
fibers. Global ACN market is expected to grow at 4% per year, driven mainly by ABS resins
industry. The next figure shows the acrylonitrile demand by application.

Figure 3 Acrylonitrile demand by application

Acrylonitrile demand is cyclic because it's associated with the general world economics. Most of
acrylonitrile markets are cyclic and affected by economic down-stream. The demand for
acrylonitrile is almost come from the emerging world, as a lot of chemicals and chemical
intermediate. Where the increasing in the living standard lead to increase the demand for products

15
as electronics, textile, clothes, cars and the development of infrastructure. In 2016, china markets
alone accounted for 32% of the global acrylonitrile market.Invalid source specified.

The growth of acrylonitrile is expected to increase in 2021. Also, it's expected that Northeast Asia
will have more than half of the world demand of acrylonitrile through next five years with a
percent of 55%. In September-2008, during the global recession, the percentage of acrylonitrile
decreasing to about 12% in just 1 year, this is the best evidence of the dependence of acrylonitrile
on the general world economics.Invalid source specified. Production of ABS resins is the
essential usage of acrylonitrile in the world, it' represent about 34% of the total demand. Due to
its excellent properties in strength, hardness and heat resistance, ABS is a majoring resin in the
market and these characteristics make it also a major polymer for technical applications. ABS is
mainly used in appliances such as vacuum cleaners, refrigerators, hair dryers and others.
Appliances account for about 40% of ABS demand globally. The market for electricity and
electronics is one of the major markets for ABS resins. Accounting for 25% of demand. Also, the
market of cars representing about 11% of global consumption of ABS resin. The following figure
shows the world consumption of ABS resins in 2017.

Figure 4 world consumption of ABS resins

It's expected that the Middle East and Africa ABS resins markets record a better percentage in
compare with the world market. Also expected that the market is going to register a CAGR of
around 3% during 2018 to 2023. Middle East & Africa accounted for around 3% of the global
market share in 2017.Invalid source specified. Figure (3) shows the consumption of ABS resins
in Middle East and Africa.

16
Figure 5 Consumption of ABS resins in Middle East and Africa

In 2000's, acrylic fiber was one of the largest outlets for acrylonitrile, accounting for about half of
the market. However, over the last ten years, it has suffered fierce competition with cheap
polyester fibers, which has reduced the demand for acrylic fiber. Several factors have made
polyester fibers the preferred fibers in the textile industry including their physical properties,
versatility, cheap price and recyclability. Over the past decade, the acrylonitrile volumes used to
produce acrylic fiber have contracted at an average rate of 3.3% annually, and now account for
about 29% of acrylonitrile demand.Invalid source specified.

If we talk about the third use of acrylonitrile in the world, acrylamide will be considered.
Acrylamide represents about 13% of the acrylonitrile market. About 90% of acrylamide is used in
the production of polyacrylamide, which is commonly used in wastewater treatment and in
industrial processes such as pulp and paper mills.Invalid source specified.

The demand for acrylonitrile over the next five years is expected to increase at an annual rate of
3.2 percent. Also, it's expected that the largest demand for acrylonitrile will be in Northeast Asia
to be around 55% from the world demand, followed by the Middle East and North America. The
following figure shows world consumption of acrylonitrile in 2018.

17
Figure 6 world consumption of acrylonitrile

Cost estimation
In industry, a costing specialist is the main production specialist specialized in basic cost data. Its
primary responsibility is to ensure that all components of production costs are taken into account
when it starts in a new product or changes an existing product. Elements of production costs
include raw materials, direct labor, variable and fixed incremental equipment, equipment,
production equipment, workplace, non-productive facilities.

Cost details for a new or improved product are available from manufacturing personnel,
production, production processes, plant layout, material handling, road and time measurements.
The function of the cost estimator is to coordinate information and to express an opinion as to the
validity of cost estimates and to investigate any dropped elements.

If the cost estimate is in doubt in any of the costing elements it receives, it will contact the
relevant production specialists, and if the original cost is verified, the discussion brings about
convergence of ideas on the subject. However, sometimes the review may show aspects of
product requirements that have not been fully evaluated by specialists.

The cost estimator, to fulfill its primary responsibility, should establish a library of past
experience on costs. It should prepare a catalog of cost information related to materials, direct

18
labor and additional costs. To be used in comparison between old and new. Such a library
provides greater consensus and reliability in its estimates.

The cost estimate, prepared for a detailed cost-of-operation assessment, links manufacturing and
accounting. And draws attention to the inter-relations of different costs. He analyzes the costs of
manufacturing and explains to the accounting professional how to treat the cost
vocabulary.Invalid source specified.

19
Methods of preparation
The organic compound “Acrylonitrile” which is having the formula (CH2=CHCN) consisting
of vinyl group where it was attached to nitrile.

Acrylonitrile maybe prepared by three methods:

Firstly, by propylene ammoxidation in the presences of ammonia and oxygen.

Secondly, by the catalyzed reaction between hydrogen cyanide (HCN) and acetylene (H-C=C-
H).

Thirdly, ammoxidation of propene by (BiMoOx).

Acrylonitrile from propylene

Preparation of acrylonitrile with the ammoxidation of propylene method in the presence of
ammonia and oxygen depends in the contacting on the catalyst system which is mainly
composed of three components which are:

- Molybdenum (Mo) which is not found as a free metal on the earth. The catalyst
contains (Mo) with percentage range from 5-60%
- Bismuth (Bi) which is found on the earth more than the gold. The catalyst contains
(Bi) with percentage range from 25-70%
- Antinomy (Sb) which is not found in an abundant range on the earth but it is mostly
found in sulfide stibnite (Sb2S3). The catalyst contains (Sb) with percentage range from
5-70% (yamada, 1966)

But, the main problem for using this catalyst was that it’s accompanied by side reactions with
high ratios which result in lowering the yield and that’s is not the aimed result. The by-
products which is resulted in the side reactions are (acetonitrile, hydrogen cyanide and carbon
dioxide).

20
The reactions which is happened in the preparation of acrylonitrile as the following:
- the main reaction

2 C3H6 + 2 NH3 + 3 O2 → 2 C3H3N (Acrylonitrile) + 6 H2O

- the side reactions

2 C3H6 + 3 NH3 + 3 O2 → 3 C2H3N (Acetonitrile) + 6 H2O

C3H6 + 3 NH3 + 3 O2 → 3 HCN (Hydrogen cyanide) + 6 H2O

2 C3H6 + 9 O2 → 6 CO2 (Carbon dioxide) + 6 H2O

Then, due to the side reactions which is happened in this method the catalyst needed to be
changed with another one in order to prevent the occurrence of the side reaction and in the
same way to obtain acrylonitrile with high yield and selectivity.

Many trials had been made concerning in discovering a catalyst which helps in obtaining the
acrylonitrile in high yield and preventing the formation of the by-products. So, a little change
had been made in the ranges of the three components which the catalyst is mainly depend on.
Firstly, the ranges were MO (5-60) %, BI (25-70) % and Sb (5-70) %. For increasing the yield
of the acrylonitrile and reduce the formation of the by-products the new percentage ranges
are: MO (5-45) %, BI (50-70) % and Sb (5-45) %. The catalyst which will have this
composition will provides the best selectivity and yield of the acrylonitrile and will decrease
the formation of the by-products to the lowest level possible. (E., 2008)

The following figure shows the flowsheet of the process of ammoxidation of propylene to
obtain acrylonitrile:

21
 Figure 7 Flow sheet for the production of acrylonitrile from propylene

Firstly, the reactants (ammonia, propylene and air) are being controlled to the needed pressure
for making the reaction achieving the aim and then enter the catalytic reactor where the
spherical catalyst (Mo-Bi) is the catalyst which is used in this reaction. Inside, the fluid bed
reactor a cyclone separator is kept inorder to separate the products from the catalyst after the
fluidization which happens in seconds. Then, the product gases enter a water scrubber inorder
to absorb the propane and nitrogen and take them off from the top of the tower and the other
products (acrylonitrile, acetonitrile and other heavy products) is then sent to enter a product
splitter. Where, the acrylonitrile, HCN, heavy products and light products are existing as a top
product after being separated. While, acetonitrile, water and heavy products are existing the
splitter as a bottom product.

22
Top product stream which had left the splitter is then entering an azeotrope column with
water as an extractant. Where, three layers will be obtained (vapor, organic and aqueous)
layer. The vapor layer consists of HCN with light products as shown in the above flowsheet.
While, the organic layer consisting of acrylonitrile and heavy products which is sent to a
purification column inorder to obtain the clear product acrylonitrile. Finally, the aqueous layer
is used as a reflux for the azeotropic column.

Note: the oxalic acid which is added for the stream which is entering the purification is
essentially as cyanhydrins is produced as a by-product which is known for the formation of
the volatile compounds which is mainly a polluting compound. When, the oxalic acid is added
it form which cyanhydrins a complex compound which enter the heavy products.

Bottom product stream which had left from the bottom of the splitter is also then being sent to
another azeotropic column where the water exist from it as a bottom product and the
acetonitrile with some heavy products (the organic layer) is also the same sent to a
purification column inorder to being able to purify the acetonitrile from the traces for the
heavy products and obtain acetonitrile as a pure product.

Acrylonitrile from hydrogen cyanide and acetylene

In order to improving the preparation method for the acrylonitrile a catalytic liquid phase
reaction takes place between hydrogen cyanide (HCN) and acetylene (C2H2). Many catalysts
had been tested on this reaction for obtaining the best result.

H-C=C-H + HCN → H2C=CHCN

The best result is obtained in the presence of cuprous chloride as a catalyst for this reaction
(in an anhydrous medium) it usually prepared as an aqueous solution but with some additives

23
which are hydrochloric acid and ammonium chloride or alkali metal which are working as a
solubilizer for it.

The problem which results from this reaction is having also by-products such as the
acetaldehyde (CH3CHO) and lacto-nitrile (C3H5NO). Where, the lacto-nitrile may be
dissociated into the acetaldehyde and hydrogen cyanide. As a result of that the cuprous
chloride preferred to be used in an anhydrous medium or using carboxylic acid chain amides
in order to prevent the formation of acetaldehyde completely.

As this seems to be a good solution for overcoming the problem of formation of the
acetaldehyde but it also affects the activity of the catalyst and the yield of the obtained
acrylonitrile.

Later, it was invented that using cuprous bromide (BrCu) in an anhydrous medium will be
better than using cuprous chloride as it is having low activity in the water. The solvent which
maybe used with the cuprous bromide maybe compound which must be having lactam
structure (pyrrolidone or piperidone) or amide straight chain (N-methyl or N-ethyl).

Using cuprous bromide, the by-products maybe mono and di-viniyl acetylene while, using
cuprous chloride the by-product maybe vinyl chloride. So, increasing the acidity maybe able
to prevent the formation of both mono and di-vinyl acetylene and the acidity maybe increased
by the addition of (HBr) (christopher, 1955)

24
The following flowsheet shows the process of the production of acrylonitrile from acetylene
and hydrogen cyanide:

Firstly, the reactants (acetylene, hydrogen cyanide and the catalyst cuprous chloride) feed into
the reactor to start the process. Where two streams is obtained one is recycle for the catalyst
which pass through catalyst regeneration after leaving the reactor inorder to recover the
catalyst. The other stream enters a scrubber after leaving the reactor inorder to separate the
traces of the reactants from the acrylonitrile where two streams is obtained also. One stream
which contains Lacto nitrile is then recycled to the feed stream as it maybe dissociated into
acetaldehyde and HCN. The other stream enters a separator to purify the stream from the
wastes then the stream is passed into the product column where the final clean acrylonitrile is

25
obtained after purifying it again from the waste for the second time after leaving the separator.
Steam and water which is added as a fresh stream in the scrubber and distillation column
inorder to make the separation happens more effectively. (E., 2008)

Acrylonitrile from propene

Nowadays, 25% of the chemicals which is used in the industrial fields or consumed as
products are made by the catalytic oxidation of the lower alkene to un-saturated aldehydes
and then ammoxidation to nitriles. According to this process (catalytic oxidation) the
acrylonitrile maybe obtained from propene. Through the following reaction:

CH3CH=CH2 + 3/2 O2 + NH3400- → CH2=CHCN + 3 H2O

460
Cat.

In this method the acrylonitrile was produced in the presence of molybdenum oxide and
bismuth. But, with combination with other metals the yield increased (+80) %. Then, this
method hadn’t been classified as the optimal method. Many mechanical studies for the
different steps for converting the allyl-activated intermediate into acrylonitrile through the
molybdenum oxide inorder to describe the partial pressure of the ammonia feed

26
 Figure 8 mechanism of propene ammoxidation over bismuth molybdates

Firstly, ammonia had been activated on the molybdenum sites inorder to form MO=NH group
as shown. Then, propene had been activated by surface oxide which is linked with bismuth to
obtain allyl intermediate. In the fourth step the allyl is being binding to the MO=NH inorder
to form C-N bond on the molybdenum as shown and this happened by breaking the double
bond of (NH). After that, hydrogen abstraction happened through the bond (Mo=NH) or
(Mo=O) inorder to obtain the acrylonitrile. Lattice oxygen helps in the re-oxidation of the
active sites as the empty position maybe filled with gaseous di-oxygen (pudar, 2010)

27
Environmental Impact Of Acrylonitrile
Effect of Acrylonitrile on Humans and Environmental levels

Environmental Levels

Ambient Air
There are predicted rates of the emission of acrylonitrile during every half-hour where in the
maximum value it was predicted to be 0.003 , 0.018 and 0.028 g/s for stacks which is 11 , 14 and
17 meter high. these values were measured near the site of largest user in Canada. Also Six
samples were taken in two different days around a nitrile-butadine rubber production plant and
acrylonitrile was not detected above the ground by 2 meters and 5 meters outside the fence of the
plant (Sparks, 1997)

Indoor Air
As known that acrylonitrile appears in indoor air from the tobacco smoke where it is considered
to be the source of acrylonitrile in indoor air.

Food
Also acrylonitrile is introduced in food stuffs resulting from the acrylonitrile based polymer
which is used mainly in food packing. Average concentration of acrylonitrile which is measured
in three different samples of food packaging ranged from 8.4 to 38.1 ng/g.

Effects on Laboratory Mammals

Irritation and sensitization
It is known from the available data that acrylonitrile is irritant on skin , respiratory and eye.

Irritation of Skin
Three studies were held to identify the data on irritancy of acrylonitrile on skin, where it was held
on a rabbit with shaved skin. In the first 15 min little vasodilatation and oedema were observed
but after a long while of time the effect was more stronger and more harsh. (McOmie, 1949)

28
Irritation of Eye
Some investigations were done to test the irritation of acrylonitrile on eye were results of these
investigations was saying that 0.1 ml of undiluted acrylonitrile was placed in the right
conjunctival sac of each of two albino rabbits. After 20 seconds tap water is used to wash one of
these treated eyes of one rabbit of them and keep washing for one minute and as a result moderate
corneal clarity, moderate iritis and harsh conjunctival irritation in the unwashed eye, while in the
washed eye it was slightly less in irritation than that of unwashed one. (McOmie, 1949)

Respiratory irritancy
Although it is not examined directly, but in a studies of repeated dose toxicity, it was discovered
that the upper respiratory tract is affected by irritation including nasal discharge in rats extremely
exposed. (Food and Drug Research Laboratories , 1985).

Effects on Humans
As the acrylonitrile affects animals, air and water it also affect humans where it affect the workers
in acrylonitrile plants production by some physical diseases in some of their organs. Few studies
were held to study the effect of acrylonitrile on humans including liver function tests and lung
cancers on workers. The cursed disease which is called Cancer is considered to be an end point
for risk characterization for acrylonitrile. A primarily studies proved that human lungs are
affected by cancer " All tumors ". (Zhou & Wang, 1991). Also not only lung cancer but colorectal
cancer (Mastrangelo et al., 1993).

Effects on Aquatic Organisms

Wide range of studies were held also on acrylonitrile related to the aquatic organisms which are
affected from waste water getting out through acrylonitrile plants production. These studies
discussed the effect of acrylonitrile on 34 different species of aquatic organisms (Fish).

How to be safe from Acrylonitrile

As mentioned above that acrylonitrile can affect all living organisms through several ways.
whether by inhalation in air or touching the chemical compound to affect the skin and eyes, also
through ingestion by food or water. Primary studies approved the perfect ways to avoid the
harmful impact of acrylonitrile. Ventilation and closed system are required to avoid exposure by

29
inhalation, also protective gloves are required to prevent the absorption of skin to acrylonitrile
and protective cloths. Eye protection with breathing protection to avoid redness and pain for
workers in factories and if eye is harmed wash the affected eye with fresh water for several
minutes. Lastly the abdominal pain which is caused in the ingestion due to workers forget to wash
their hands before eating or drinking which affect the digestion system. (Hall, 1971,).
Acrylonitrile is a volatile organic compound which leads to make acrylonitrile flammable, where
flammability properties are defined by ; Auto ignition temp.( 481 o C) which make the compound
able to ignite without any source of ignition if temp exceeded the auto ignition temp, also the
flash point ( 0 o C ) which is the temperature when vapor above liquid is ignitable when mixed
with air. Gas phase mixtures of acrylonitrile and air contains ( 3-17 % ) flammable acrylonitrile
which has a lower flammability limit of ( 3 % ) at 25 o C and Upper flammability limit of ( 17 %)
o
also at 25 C. (Bulletin, 1952). A graph is presented to show the flammability envelope of
acrylonitrile at higher temp. than that required for flammability limits mentioned above, which is
32 o C.

(Bulletin, 1952)

As noticed here in the graph the nosed shape region are potentially flammable, where vapors
outside the region is not flammable. Therefore these concentrations should be consulted during
equipment design and conditions of operating. To prevent flammable vapor mixtures during
storage, transfer and handling a procedure is designed to such an issue which is called " nitrogen
blanketing ". This procedure " nitrogen blanketing " decreases the potential for flammability of
vapors above the surface of acrylonitrile in liquid phase. Oxygen during this procedure is purged
in the tank from vapor space, where the oxygen should be purged to be below 8 %. (Monsanto
Chem. Int. Co., Jan. 1982.).

30
References
(1985). Food and Drug Research Laboratories .

AEL, D. &. (1996). Retrieved from pubchem.ncbi.nlm.nih.gov

Brazdil. (1985, 8 22). Retrieved from pubchem.ncbi.nlm.nih.gov

Brazdil, J. F. (1983). Ullmann's Encyclopedia of Industrial Chemistry.

Bulletin. (1952). In Bulletin, “Limits of Flammability of Gases and Vapors," (p. 503). U.S.
Bureau of Mines,.

christopher, G. L. (1955). Patent No. 553,691. New york.

Delong, L. (2011). Journal of Polymer Science Part A: Polymer Chemistry.

E., D. C. (2008). outlines of chemical technology. east-west press.

Hall, H. J. (1971,). Amer. Chem. Soc.,.

Hammond, G. P., & Jones. (2008). Embodied energy and carbon in construction materials.
Proceedings of the ICE – Energy.

Hance, w. (1991). International journal of chemical kinetics. International journal of chemical

kinetics.

Kennedy, C., & al, e. (2010). 3D Printing Industry. . "The Free Beginner's Guide.

Kirk. (1983, 8 06). Retrieved from pubchem.ncbi.nlm.nih.gov

langvardt. (1985). Time/toxicity relationships. American Society for Testing and Materials.

Martin. (1996, 9 14). Retrieved from pubchem.ncbi.nlm.nih.gov

Afshar, A. A. (2014, August). Polyacrylamide. Retrieved from

http://chemplan.biz/chemplan_demo/sample_reports/PAM_Profile.pdf

Deepa H.A, A. R. (2016). evaluation on production and economics of acrylonytrile by sohio

process. Retrieved from
https://www.ijert.org/phocadownload/.../IJERTCONV4IS21002.pdf

31
Ma, Z. (2014). Financial Cost Comparison of Acrylonitrile Butadiene Styrene (ABS). Retrieved
from
http://atrium.lib.uoguelph.ca/xmlui/bitstream/handle/10214/8410/Ma_Zhaohui_201409_
Msc.pdf?sequence=4&isAllowed=y

Markit, I. (2016, May). Acrylic and Modacrylic Fibers. Retrieved from

https://ihsmarkit.com/products/acrylic-and-modacrylic-chemical-economics-
handbook.html

Qin, (. Y. (2015, May 8). Acrylonitrile – World Market Overview. Retrieved from
http://www.orbichem.com/userfiles/apic%202015/apic2015_yang_qin.pdf

Symister, O. J. (2014, May). An Analysis of Capital Cost Estimation Techniques for Chemical
Processing. Retrieved from
https://repository.lib.fit.edu/bitstream/handle/11141/797/Symister%2C%20Omar%2C%20
An%20analysis%20of%20capital%20....pdf?sequence=1&isAllowed=y

Mastrangelo et al. (1993).

McOmie. (1949).

Monsanto Chem. Int. Co. (Jan. 1982.). “Acrylonitrile Handling and Storage, ". Monsanto Chem.
Int. Co., Pub No. 162,.

Nagel, K. &. (1988, 10 03). Retrieved from Koch & Nagel

pudar, s. (2010, april 5). Retrieved from https://core.ac.uk/download/pdf/4886283.pdf

Serkov, A., & Radishevskii. (2008). Fibre Chemistry.

Sparks, B. (1997). Personal communication . Canada.

yamada, k. (1966). Patent No. 658,029. Japan.

Zhou & Wang. (1991).

32