MUKESH PATEL SCHOOL OF TECHNOLOGY MANAGEMENT AND ENGINEERING

SVKMS NMIMS

A REPORT

ON

CHALLENGES OF MAKING CHLORINATION PRODUCTS

SUBMITTED IN PARTIAL FULFILMENT

OF THE REQUIREMENTS FOR THE DEGREE OF

MBA Tech (CHEMICAL)

BY

TANUJ JOSHI

( L017)

UNDER SUPERVISION

OF

(SANKET GUDEKAR)

YEAR OF GRADUATION (2018)

1
 INDEX

I. Introduction...3
II. Chlorinated derivatives 4
a.Chlorinated hydrocarbons..4
b Chlorinated solvents..4
III. Polyvinyl chloride.7
IV. Chlorobenzene..8
V. Harmful byproducts..9
a. phosgene...9
b. hydrogen chloride.9
VI. Phosgene mitigation11
a.caustic spray tower..12
b.caustic packed tower...15
c.dispersion stack...19
VII. Hydrogen chloride mitigation system ...22
a.ejector venture gas scrubber...22
b.countercurrent packed tower..22
c.multi stage system..23
VIII. Phosgene and hydrogen chloride mixture .27
IX. Scale up problem...28
X. References32

2
INTRODUCTION

Chlorine, an exceptional agent in synthesis, is essential to the chemical industry in

the same way that salt, from which it is obtained, is essential to life. Among
halogens, the most active class of chemical elements, chlorine is by far the most
abundant in nature and is also the easiest to produce and to use. This explains its
predominant and irreplaceable role in the chemical industry, in all industrial sectors
and in our day-to-day life:

Forty million tonnes of chlorine were produced in the world in 1995.

More than 85% of all pharmaceuticals and more than half the products
marketed by the chemical industry are derivatives of chlorine chemistry.
1500 of these products have been listed: they are used in all industrial and
economic sectors such as health, agro-food, building, textiles, transport,
leisure activities, cosmetics, etc,

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CHLORINATED DERIVATIVES

PVC, polyvinyl chloride

The presence of chlorine contribute to its specific properties:

resistance to fire: PVC is classified as a difficultly flammable material, just

after concrete.
excellent resistance to bacteriological contamination.

Other chlorinated polymers

Polyvinylidene chloride- multi layer films for food packaging

Polychloroprene- high resistance to fire and oils and its excellent weathering
characteristics. It is used in cable coverings and gaskets.

Chlorinated solvent.

Chloroethylenes Perchloroethylene (PERC) is a dry cleaning solvent and metal

degreasing agent. With repeated exposure, headaches, drowsiness, vertigo, and
fatigue have been reported in humans; impairments of short-term memory and
psychomotor function have also been reported. Another chloroethylene is
trichloroethylene (TCE), which is used as a dry cleaning agent, degreaser of
metallic parts, cleaning fluid, and paint remover. Longer term exposure has been
reported to result in impaired visual performance

Chlorinated hydrocarbons

Hydrocarbon whose some or most hydrogen atoms have been replaced by chlorine
atoms. Chemically and thermally stable, chlorinated hydrocarbons are used mainly
in the manufacture of synthetic solvents and insecticides.

Application

Chlorinated hydrocarbons have many industrial applications, including the

manufacture of nonstick cookware, industrial solvents and pesticides. Some
organochlorides are naturally occurring, although most useful chlorinated
hydrocarbons are synthesized in a lab or chemical plant.

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Biosynthesized organochlorides include alkaloids, terpenes, amino acids, fatty
acids and steroids. Special organochlorides called dioxins are produced in the high-
temperature reactions that occur in forest fires. Vinyl chloride is an organochloride
that can be polymerized to produce polyvinylchloride, abbreviated PVC. This
polymer is used to produce piping and nonstick coatings. A specialized layer of a
closely related cousin to PVC, called poly-tetrafluroethane, is patented as the
nonstick coating Teflon.

Other chlorinated hydrocarbons are used as solvents, pesticides, coatings,

precursors and synthetic rubber.

Adverse effect

Chlorinated hydrocarbons may pose a threat to human and environmental

health

The negative effects of chlorinated hydrocarbons is the pesticide DDT,

which devastated bird populations by weakening the outer structure of eggs.

These dioxins are toxic and mutagenic, having deleterious effects on the
immune, nervous and reproductive systems of forest animals.

Their danger to the environment comes from their toxicity, great stability
(persistence in the environment), and propensity to evaporate with water into the
atmosphere. CHCs become concentrated in animal fat and attack heart and liver;
some have anesthetic or narcotic effect. Action of sunlight on chlorinated
hydrocarbons forms chlorine monoxide which contributes to breaking-down of the
ozone-layer, causing wide 'holes' through which cancer-causing ultraviolet (UV)
rays can reach the earth's surface.

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6
POLY VINYL CHLORIDE

H2C=CH2 + Cl2 ClCH2CH2Cl

Cl-CH2-CH2-Cl H2C=CH-Cl + HCl

The hydrogen chloride can be re-used in the production of more 1,2-dichloroethane

via the oxychlorination route

2 H2C=CH2 + 4 HCl + O2 2 ClCH2-CH2Cl + 2 H2O

Characteristics

Toughness, strength.
Ease of blending, ease of processing
Flame resistant and fire prevention properties
For example PVC is difficult to ignite and in the absence of a
powerful external flame will not continue to burn. This is due
to its chlorine compound. This makes it an ideal construction and cable
material.
It is compatible with other additives that can provide PVC clear or colored,
rigid or flexible, etc..
Excellent electrical insulation properties. This makes it ideal to be use in
cables.
Impact strength and resistant to bad weather conditions (i.e. it does not
corrode and is very durable), appropriate to be used as a
construction material
Resistance to grease, oil and chemicals
PVC is chemically stable and does not de-polymerize
Density: 1.32-1.42 g/cc

7
CHLOROBENZENE

There are different ways in which the chlorination of benzene can be brought
about and these form the different processes for the manufacture of
Chlorobenzene. The first is called the Raschig Process. In this process, benzene is
chlorinated by chlorine that has been produced in situ in the reactor by the catalytic
oxidation of hydrogen chloride. A pre-heated mixture of benzene vapour, air,
steam, and HCl, at ordinary pressure, is brought into contact at 220 - 260C with a
catalyst of copper oxide. 2% of the total benzene combusts, giving rise to about
one quarter of the total heat output of the process. The disadvantage of this process
is that the high temperature greatly favours high combustion rates of benzene and
the reaction may become uncontrollable. Moreover the high costs of this vapour
phase chlorination process in comparison with other available processes, allows it
to be highly uneconomical for Chlorobenzene manufacture and thus renders it
obsolete. In another process, chlorination of benzene is carried out in a quartz tube
at 400 - 500C. Here the principal product obtained is Chlorobenzene along with
minor amounts of dichlorobenzene. Benzene has also been chlorinated in the
gaseous phase at 425C by means of nitrosylchloride. The process of Loeser and
Schmidt, in which a mixture of benzene vapour, HCl, and air is reacted at 150
300C in contact with a copper hydroxide-alumina catalyst (in the form of a
fluidised mass), may be regarded as a variant of Raschigs Process. The
disadvantages of all these processes are low efficiency and high temperature,
which may make the reaction uncontrollable leading to formation of higher
Chlorobenzene. Based on all the above considerations, the continuous liquid phase
chlorination of benzene at a temperature of about 40C is best suited for production
of large amounts of monochlorobenzene in the industry.

The reactions involved in the process are as follows:

1. C6 H6 + Cl2 -> C6H5Cl + HCl

2. C6H5Cl + Cl2 -> C6H4Cl2 + HCl

8
BYPRODUCTS

Harmful by-products from chlorination

-phosgene

-HCL

Phosgene

It is a highly toxic gas that has been used as a chemical warfare agent. It is an
insidious poison as it is not irritating immediately, even when fatal concentrations
are inhaled.

Phosgene is a colorless gas or very low-boiling, volatile liquid (b.p. 8.3C, 48F)
with an odor of new-mown hay or green corn. Extremely toxic. Warning properties
of the gas inhaled are slight, death may occur within 36 hours. Prolonged exposure
of the containers to intense heat may result in their violent rupturing and rocketing.

The vapors of chlorinated solvents exposed to high temperatures have been known
to produce phosgene

SYMPTOMS OF POISONING

Coughing

Burning sensation in the throat and eyes

Watery eyes

Blurred vision

Difficulty breathing or shortness of breath

9
 Nausea and vomiting

ADVERSE EFFECTS

Phosgene is extremely toxic by acute (short-term) inhalation exposure.

Severe respiratory effects, including pulmonary edema, pulmonary
emphysema, and death have been reported in humans.
Severe ocular irritation and dermal burns may result following eye or skin
exposure.
Chronic (long-term) inhalation exposure to phosgene has been shown to
result in some tolerance to the acute effects noted in humans, but may also
cause irreversible pulmonary changes of emphysema and fibrosis.
EPA has classified phosgene as a Group D compound, not classifiable as to
human carcinogenicity.

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 PHOSGENE NEUTRALIZATION SYSTEMS

DISPERSION STACK
CAUSTIC PACKED TOWER
CAUSTIC SPRAY TOWER

Caustic Scrubbers

Caustic (sodium hydroxide solution) scrubbers provide a method for mitigation of

a phosgene release. Within the category of caustic scrubbers, there are several
different types of scrubbing towers. The basic caustic scrubbing system is
comprised of a caustic source feeding a scrubbing tower. The tower is either an
open- contact type tower or a packed tower.

Key operating parameters for operation of a caustic scrubber include:

the maximum flow rate of phosgene expected from the process; the
maximum duration of the release to the scrubber;
the concentration of caustic available for scrubbing;
and the circulation or flow rate of caustic into the scrubbing tower.

Many systems are run with 10 to 20% caustic strength. If it's less than 10% there
may not be enough caustic to neutralize efficiently. If it's greater than 20% then
there is the risk of not enough heat sink from water and the neutralization solution
can boil. This also presents the possibility that salts may precipitate out and foul or
plug up the scrubber system.

All process emissions from phosgene production and utilization are typically
routed to a caustic scrubber. The caustic scrubber is the control of choice because
phosgene is rapidly and completely destroyed by aqueous sodium hydroxide, as
shown in the following reaction: COCl2 + 4NaOH 2NaCl + Na2CO3 + 2H2O.
The sodium hydroxide concentration should be maintained at between 3 and 8
weight percent, and the sodium chloride and sodium carbonate must not precipitate
and clog the reactor. It should be noted that the solubility of these components is
appreciably lower in caustic solution than in water. These requirements are met by

11
continually replacing the solution in the scrubber with fresh caustic solution.
Phosgene control is severely reduced if

1) the phosgene flow to the scrubber exceeds the design capacity of the scrubber,
or

2) the caustic concentration in the scrubber is not maintained between 3 and 8

weight percent.

The design of the scrubber therefore must be such that it can accommodate any
phosgene surge. Control can be achieved with a single caustic scrubber.

Figure 1: Source Stephen Kistner , Daniel Lillian , John Ursillo , Norval Smith ,
Kenneth Sexton , Michael Tuggle , George Esposito , George Podolak & Steven
Mallen (1978) A Caustic Scrubber System for the Control of Phosgene Emissions:
Design, Testing, and Performance, Journal of the Air Pollution Control
Association, 28:7, 673-676, DOI: 10.1080/00022470.1978.10470644
Caustic Spray Towers

In a spray tower, the caustic supply is sent to the tower at several locations from
the bottom to near the top of the tower. Spray-rails are installed to control the spray
pattern of the caustic into the tower. Phosgene would be introduced near the
bottom of the tower and as the gas rises it is neutralized with the caustic spray. A
drawback to this type of scrubber is any change in the caustic spray pattern will
affect the scrubbing efficiency of the scrubber. Phosgene would still have a chance
to break through the scrubber.

12
Spray scrubbers consist of empty cylindrical or rectangular chambers in which the
gas stream is contacted with liquid droplets generated by spray nozzles. A common
form is a spray tower, in which the gas flows upward through a bank or successive
banks of spray nozzles. Similar arrangements are sometimes used in spray
chambers with horizontal gas flow. Such devices have very low gas pressure drops,
and all but a small part of the contacting power is derived from the liquid stream.
The required contacting power is obtained from an appropriate combination of
liquid pressure and flow rate

Spray towers do not suffer from restrictions to gas flow by accumulated residues
commonly found in packed bed scrubbers. However, spray towers have the least
effective mass transfer capability and thus, are generally limited to use for PM
removal and with high-solubility gases.

Emission Stream Characteristics:

a. Air Flow: Typical gas flow rates for spray tower wet scrubbers are 0.7 to 47
standard cubic meters per second (sm3 /sec) (1,500 to 100,000 standard cubic feet
per minute (scfm))

b. Temperature: In general, the higher the gas temperature, the lower the absorption
rate, and vice-versa. Excessively high gas temperatures also can lead to significant
solvent or scrubbing liquid loss through evaporation. For waste gases in which the
PM is to be controlled, the temperature range is generally 4 to 370/C (40 to 700/F),
and for gas absorption applications, 4 to 38/C (40 to 100/F).

c. Pollutant Loading: Typical gaseous pollutant concentrations range from 250 to

10,000 ppmv. Spray tower wet scrubbers are not as prone to fouling as other wet
scrubber designs, but very high liquid-to-gas ratios may be necessary to capture
fine PM

Emission Stream Pretreatment Requirements:

Precoolers (e.g., an additional spray chamber) may be needed to reduce the inlet air
temperature to acceptable levels to avoid solvent evaporation or reduced
absorption rates

13
Advantages of spray towers include:

1. Relatively low pressure drop;

2. Can handle flammable and explosive dusts with little risk;

3. Fiberglass-reinforced plastic (FRP) construction permits operation in highly

corrosive atmospheres;

4. Relatively low capital cost;

5. Relatively free from plugging;

6. Relatively small space requirements; and

7. Ability to collect PM as well as gases.

Disadvantages:

Disadvantages of spray towers include:

1. May create water (or liquid) disposal problem;

2. Waste product collected wet;

3. Relatively low mass-transfer efficiencies;

4. Relatively inefficient at removing fine PM;

5. When FRP construction is used, it is sensitive to temperature; and

6. Relatively high operating costs

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15
Packed Caustic Towers

The purpose of the phosgene scrubber unit operation is to treat acid gas from the
phosgenation section of the plant prior to discharging the resulting clean streams to
the atmosphere. A scrubber unit operation often contains: a vent header, a
disengagement vessel, the scrubber tower, caustic storage tanks, and the tower feed
and return pumps. Caustic solution from the tower feed pumps flows to the top of
the scrubber to a liquid distributor and over the top packed bed. Acid gas enters the
scrubber below the lower packed section from a gas collection header. A
disengagement vessel (knockout pot) on the vapor feed line to the tower helps
ensure that no liquid phosgene is sent to the scrubbing system. Caustic is returned
back to the feed tank supplying the scrubber tower with return pumps. A heat
exchanger on the caustic return line removes the heat generated from the
neutralization of phosgene. Vents leaving the primary scrubber are normally free of
phosgene and HCl and may be further treated to destroy any carbon dioxide or
Volatile Organic Compounds in the exit gas stream. Typical streams feeding the
scrubber system may include: emergency process vents from relief devices or
16
equipment de-pressuring, vents resulting from plant startup or shutdown, and vents
resulting from clearing process equipment in preparation for maintenance.
Phosgene neutralization with caustic is a mass transfer limited operation and is a
function of the rate of absorption of the phosgene into the caustic and the rate of
chemical reaction to neutralize the phosgene. The height of packing (HTU)
required can vary greatly depending on caustic strength and the maximum amount
of phosgene to be absorbed.

Packed-bed scrubbers consist of a chamber containing layers of variously-shaped

packing material, such as Raschig rings, spiral rings, or Berl saddles, that provide a
large surface area for liquid-particle contact. The packing is held in place by wire
mesh retainers and supported by a plate near the bottom of the scrubber. Scrubbing
liquid is evenly introduced above the packing and flows down through the bed. The
liquid (Caustic) coats the packing and establishes a thin film. The pollutant to be
absorbed must be soluble in the fluid. In vertical designs (packed towers), the gas
stream (Phosgene) flows up the chamber (countercurrent to the liquid).

Advantages: Advantages of packed-bed towers include

1. Relatively low pressure drop;

2. Fiberglass-reinforced plastic (FRP) construction permits operation in highly

corrosive atmospheres;

3. Capable of achieving relatively high mass-transfer efficiencies;

4. The height and/or type of packing can be changed to improve mass transfer
without purchasing new equipment;

5. Relatively low capital cost;

6. Relatively small space requirements; and

7. Ability to collect PM as well as gases.

Disadvantages: Disadvantages of packed-bed towers include:

1. May create liquid disposal problem;

2. Waste product collected wet;

17
3. PM may cause plugging of the bed or plates;

4. When FRP construction is used, it is sensitive to temperature; and

5. Relatively high maintenance costs.

18
Dispersion Stack

- the exit gas can be dispersed at an elevated location with the intention of
reducing the risk to personnel in the general vicinity.
- A high volume air blower can be used to elevate the gas velocity through the
stack, enhancing the dispersion capability

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PATENT- US 4493818 A

Phosgene is removed from an off gas containing phosgene by contacting the off
gas with an aqueous solution containing alkali metal hydroxide and a tertiary
amine compound having 3 to 20 carbon atoms. The concentration of the alkali
metal hydroxide can vary from 1 to 25 weight percent and the concentration of the
tertiary amine can be any amount which is effective in the contact apparatus
chosen. The amines found to be useful are trialkyl amines having 1 to 4 carbon
atoms and pyridines having 0 to 3 alkyl groups of 1 to 5 carbon atoms and
diamines such as 4-dimethylaminepyridine

It appears that the use of the above tertiary amines is more efficient because they
form a quaternary ammonium salt complex with the phosgene which appears to
catalyze the reaction between phosgene and the alkali metal hydroxide. The
advantage of this invention is that since it has a high capacity for phosgene, a

20
capital equipment savings can be made in that smaller scrubbing towers or
contactors can be used.

HCL

Hydrochloric acid is a corrosive, strong mineral acid with many industrial uses.

Environmental impact

- Hydrochloric acid has a high acute toxic effect on all forms of life.

- It contributes to the decay of limestone buildings, other structures such as

bridges, and art works.

- It also contributes to the processes that cause photochemical smog.

- may contaminate groundwater.

- forms a component of acid rain

- Hydrogen chloride is irritating and corrosive to any tissue it contacts. Brief

exposure to low levels causes throat irritation. Exposure to higher levels can
result in rapid breathing, narrowing of the bronchioles, blue coloring of the
skin, accumulation of fluid in the lungs, and even death. Exposure to even
higher levels can cause swelling and spasm of the throat and suffocation.
Some people may develop an inflammatory reaction to hydrogen chloride.
This condition is called reactive airways dysfunction syndrome (RADS), a
type of asthma caused by some irritating or corrosive substances.
- Depending on the concentration, hydrogen chloride can produce from mild
irritation to severe burns of the eyes and skin. Long-term exposure to low
levels can cause respiratory problems, eye and skin irritation, and
discoloration of the teeth.
- Swallowing concentrated hydrochloric acid will cause severe corrosive
injury to the lips, mouth, throat, esophagus, and stomach.

21
 HCL MITIGATION SYSTEM

Venturi Gas Scrubber

Under many circumstances, HCl is scrubbed using an ejector venturi gas scrubber.
An ejector venturi gas scrubber is an eductor-type design. It makes use of the
scrubbing liquid as the motive fluid to pull the gas stream into and through it
without the need of another device, such as a fan, to move the gas. The liquid and
gas streams thoroughly mix, and the HCl transfers from the gas phase to the
scrubbing liquid phase. A single-stage ejector venturi gas scrubber can typically
achieve 95 percent HCl removal.

Packed Tower Scrubber

A countercurrent packed tower is used to achieve even higher HCl removal

efficiencies, up to and exceeding 99.9 percent, if necessary. This device is a

22
vertical tower in which the scrubbing liquid flows downward countercurrent to the
upward gas flow over a bed of packing pieces that function primarily to provide a
surface area on which the two streams come into contact.

For applications in which the HCl is at relatively high levels in the gas stream and
the removal efficiency must be very high, often a combination of a firststage
ejector venturi gas scrubber and a second-stage packed tower is ideal. In those
cases, the ejector venturi gas scrubber removes the bulk of the HCl and the packed
tower polishes the remainder so that an extremely low discharge concentration
can be attained.

Multiplestage System

To neutralize the HCl, it is very common to use an aqueous sodium hydroxide

(NaOH) solution as the scrubbing fluid. The reaction between NaOH and HCl
produces sodium chloride (NaCl), otherwise known as ordinary table salt. On the
other hand, if the HCl is relatively concentrated in the gas stream, it may be
practical to recover most of the HCl in aqueous solution, which can then be reused
or sold. To accomplish this, a multiplestage system is usually required, consisting
of one or more ejector venturi gas scrubbers and a packed tower as the final stage
(Fig. 3). HCl solution is recirculated as the scrubbing fluid in the initial stages,
typically absorbing and recovering more than 90 percent of the HCl. The final
stage may then utilize aqueous NaOH to meet low-ppm discharge concentrations
exiting the packed tower. This arrangement not only saves most of the cost of the
NaOH, but also may generate a salable product.

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24
Dry Sorbent Injection

Flue gases from the plant are mixed with the sorbent material. This happens as the
materials are injected into the stream. The pollutants (Acid gas- HCl) in the plant
emissions interact with the sorbent material and become inert or non-polluting. The
stream enters an electrostatic precipitator or fabric filter and the acid gas
compounds and particulate matter are filtered out. The treated flue gases are
emitted through a stack, after they meet the emission norms.

Sorbents include hydrated lime, powdered activated carbon, sodium bicarbonate

(SBC) and trona.

low capital cost solution

can be quickly installed and started up

25
MIXTURE OF PHOGENE AND HYRDOGEN CHLORIDE

Patent- US7584629B2

Phosgene is firstly partly condensed out from the mixture of phosgeneand

hydrogen chloride. The separation is therefore usually carried out either under a
high pressure, preferably 10-50 bar, or at very low temperatures, preferably about
30 C. At high pressures, phosgene can be condensed out easily and
inexpensively, for example by use of cooling water. This is economically
advantageous, but the high pressure poses a great safety risk in the case of a
leakage. Low temperatures for separating phosgene and hydrogen chloride are
generally associated with low pressures, but considerable energy has to be
expended to produce the low temperatures. Furthermore, in accordance with
Henry's law, the solubility of hydrogen chloride in phosgene is very high, so that
recirculated phosgene contains relatively large amounts of hydrogen chloride. This
can lead to formation of amine hydrochloride in the phosgenation of the amine.

26
The phosgenation of amine hydrochlorides requires longer residence times and
higher excesses of phosgene and consequently implies a higher phosgene holdup.

A process for the partial or complete separation of a mixture comprising hydrogen

chloride and phosgene, which comprises:
firstly carrying out a partial or complete condensation of phosgene;
then distillation or stripping in a column to remove the hydrogen chloride
from the bottom product phosgene; and
subsequently a scrub of the top product hydrogen chloride by a process
solvent to absorb the phosgene in the process solvent.

27
SCALE UP PEOBLEMS

Failure to scale up properly and to take appropriate precautions may lead to the
loss of process control which in turn may result in a runaway exothermic reaction
and /or the generation or release of toxic materials. The hazards of a runaway
reaction and over pressurisation are the two greatest concerns during the scale up
process. In the past, there have been a number of failures to take these issues fully
into account which have led to multiple fatalities, severe damage to property,
environmental damage and business loss.

Other problems that have arisen from inadequate scale up procedures include for
example:

dust and vapour explosions inside vessels due to the mishandling of reactants and
solvents;

fires due to overfilling of vessels;

failure to correctly assess electrical equipment for use in hazardous areas

identifying all possible sources of ignition

auto-ignition of flammable vapours, usually resulting in a flash fire but

sometimes an explosion;

inadequate mixing of reactants and solvents.

The main factors affecting the removal of heat are the size of the reactor, stirring
and cooling. These factors cannot be over emphasised. The main factors affecting
heat production are concentration of reactants and catalysts, size and starting
temperature. These factors can be subject to change in order to achieve more
production in a shorter time. However, because of the Arrhenius dependence of
rate on temperature, small changes increase heat production more than they
increase heat removal, which hardly changes with increased starting temperature.
Therefore, an attractive production change can move the system from stable
balance to one where stability can never be achieved. Finally, a maximum stable
temperature rise within a system is usually 10 to 20 C, above that is runaway. The
first and most critical step in the scale up procedure is to undertake a risk

28
assessment of the proposed chemical process at the concept stage. Where
appropriate, this should include a study of the thermochemistry of the proposed
reaction.

SCALE UP PROCEDURE

The design of a commercial plant can be accomplished by scaling up from

laboratory equipment using pilot plant. In some cases several pilot plants of
increasing size may be used to effect the best design for the larger plant. During the
scale up process it is useful to develop a basis for safe operation that spells out
the key controls that avoid the development of unsafe conditions. Risk assessment
is an evolving process as scale-up progresses. At each stage of the scale up
procedure the information generated should be used to review the risk assessment
to enable a decision to be made as to whether or not to proceed to the next stage. If
the process is to proceed, the risk assessment should specify the controls and
operating conditions required. The rate of a chemical reaction is fixed at any given
temperature but temperature may be influenced by mass transfer and heat transfer,
which are in turn affected by the size and design of the reactor. It is not always
possible to theoretically assess these effects on a quantitative basis and in such
cases it is usual to carry out trials with water or inert substances in the intended
plant. If this is not feasible purpose built reactor calorimeters will be required.
Laboratory experiments, carried out in test tubes, small flasks etc., produce a
required chemical or product but do not necessarily indicate side effects of the
reaction, i.e. by-products, release of gases or vapours which may be toxic or
flammable. Heat releases may be absorbed by the equipment or surroundings and
not noticed. The chemicals used may be pure materials rather than bulk
commercial chemicals, which may contain traces of impurities. In order to
overcome these problems it is essential that the apparatus, materials and chemicals
used at all stages of the scale up accurately reflect those that will be used in the
final plant

As scale increases the time required to carry out each operation is also likely to
increase and appropriate allowance should be made for this. Pilot plant is used to
assist in the scale up of the chemical process design rather than the mechanical
design. It provides information for economic design, operating parameters, and
safety considerations. In addition, pilot plants can be used in small scale

29
production for evaluation and trial marketing. Information should be obtained from
pilot plant studies to confirm the decisions made as a result of the risk assessment
stage in relation to:

operating conditions;

design parameters;

reactor problems, design, materials of construction;

unit operations problems; materials handling and sampling problems;

thermal instability and other decomposition;

phase problems;

impurities;

corrosion;

fouling;

analytical problems;

operating procedures;

working and environment problems; and

effluent and waste disposal problems.

Laboratory chemicals are often more pure than bulk chemicals. It is important that
reactions are undertaken at an early stage with the bulk chemicals that it are
intended to be used in the final reaction process.

SCALE UP OF METHYL CHLORIDE

A hybrid finite-volume/joint composition PDF simulation code with detailed

chemistry has been used to simulate scale up of a gas-phase chlorination reactor
with different feedstream configurations. The detailed chemistry enabled the study
of the reactor based on free-radical formation and turbulent transport. The effects
of reactor scale at constant residence time on the temperature and chemical
conversion in a chlorination reactor were investigated. For the premixed case, it

30
was found that as the size of the reactor increases, the temperature decreases until
eventually extinction occurs. The latter is mainly due to the fact that the rate of
enthalpy. recirculation decreases with scale, resulting in reduced heating of the
inlet stream. Although the reactor with premixed feed tends to extinguish after
scale up, we show that the plant-scale reactor can be stabilized either by increasing
the inlet chlorine level by 2%, or by heating the reactor walls to 753.15 K. In
contrast, reactors with nonpremixed inlets are easier to scale up. Neither reactor
efficiency nor stability changes significantly with scale. However, nonpremixed
reactors yield poor selectivity to the desired product. In all cases, both the flow
structure and chemistry are important in predicting the reactor performance

31
REFERENCES

Scale up of gas-phase chlorination reactors using CFD- Ying Liua,, V.

Ramanb, R.O. Foxa,A.D. Harvey

patents/US7584629

Wet scrubbing of acidic gases -Robert J. Chironna

http://www.hugo-petersen.de/en/Technology/tabid-30/Dry-gas-cleaning/Dry-
sorption.aspx

http://www.lenntech.com/polyvinyl-chloride-pvc.htm

http://www.earlham.edu/chemical-hygiene-and-safety/safety-
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https://pubchem.ncbi.nlm.nih.gov/compound/phosgene#section=Top

https://www.google.ch/patents/US4493818

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http://citeseerx.ist.psu.edu/viewdoc/download?
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