Methyl Chlorine Plant 1 Instruction Manual

Methyl Chloride
Production:
General:Methyl Chloride is a solvent or Chemical Reagent (e.g. use as an alkylating
agent). It is also used as a refrigerant.
Generally methyl chloride is a gas under atmospheric pressure and
ambient temperature (30 C). Some of its characteristics are:
Chemical Formula
Molecular Weight
Melting Point
Boiling Point
Colour
Flammability
Flammable Limit
Odour
Solubulity
Health Hazard

CH3Cl
50.49
-97.7
-23.8
Gas : colourless
Liquid: transparent
Flammable gas
Lower: 10.7 % in air
Upper: 17.4% in air
Faintly sweet
Soluble in water; very soluble
in alcohol, chloroform, mineral oils etc
Threshold limit: 100 ppm

Methyl Chloride can be produced in the following process:

a) Direct chlorination of methane gas
b) Reaction of gaseous HCl and vapour methanol
For our process, we produce it by the reaction of gaseous HCl and
vaporized methanol. One of the raw material for the above process, i.e.
hydrochloric acid, is readily available from our existing Chloro-Soda plant.
Introduction to the Process
Methyl Chloride (CH3Cl) is produced by combination of gaseous HCl and
vapour methanol in a glass-lined reactor (G100) using zinc chloride
solution as the reaction catalyst. Thus,
ZnCl2

CH3OH + HCl

CH3Cl + H2O + h
145 C

The reaction is exothermic i.e. heat h is generated.

For the same reactor and at the same reaction conditions and
consequences, Methyl Oxide formation (CH3 O CH3) through methanol
own molecules reaction also take place as side reaction is:
ZnCl2

CH3OH + CH3OH

145 C

CH3OCH3 + H20

The side reaction can be suppressed to a very small extent (only 0.1%) by
an excess HCl atmosphere in the reactor. The most economic and optimal
HCL excess is 25% more than what requires for the reaction.
The products which is then coming out from the reactor is called the
crude products which contain: 1.
2.
3.
4.
5.
6.

Methyl Chloride (CH3Cl)

Excess and or Unreacted HCl
Water vapour (a reaction product)
Methyl Oxide (0.1 %)
Unreacted Methanol (in Trace)
Traces of ZnCl2 due to foaming

This hot crude is then condensed in a condenser E101 leading to the gasliquid phase separation inside a knock down drum D101 where:1. HCl and water vapour is condensed as the liquid phase product as
31% HCl solution which is pumped back to the process for
reutilisation.
2. The gas phase products still contains the same material as
described above but with lesser amount of HCl which has been
condensed.
It is then send for purification process called the Gas Treatment Unit (GTU)
where all the impurities, HCl, CH3-O-CH3, trace of ZnCl2 and methanol,
water vapour, are removed leaving only a very pure product of methyl
chloride.
Pure methyl chloride is then compressed in a two stage compressor P105
the Crepelle compressor, to a Pressure of 9 bar. The temperature of this
compressed gas is usually 110 C. When this cooled down to below 40 C
in the liquefactor E104, methyl chloride becomes liquid and has a vapour
pressure of about 7 bars.
Liquified methyl chloride is then stored in the storage tank. It is then filled
into ISO Container (International Standard Organisation) and dispatch to
individual customer.

Process Flow Diagram

From the above description, a process flow diagram can be computes as
below:
HCl
Distillation
Unit

Gaseous
HCl

Reactor

Crude CH3Cl
135 C

G100

Condenser
E101

Methanol
Evaporator

Knock Down
Drum
D101

Vapour
Methanol

Liquid CH3Cl
35 C
7 bar
Pure
CH3Cl

Liquefactor
E104
Liquid CH3Cl
35 C
7 bar

Remove CH3-O-CH3 &

Water Vapour

CH3Cl
105 C
8 bar

Remove water vapour

completely

P105

98%
H2SO4
Column
C102B

78 %
H2SO4
Column
C102A

84 % Full

Soda
Wash
Column
C101

Remove Methanol & ZnCl2

& HCl

Brink Mist
Separator
R107

Remove HCl Completely

40 C
0.3 bar

Water
Wash
Column
C100

CH3Cl Storage
R130

Tanker
P130

Methyl Chloride
Detail Description of the reaction Process and Important Control
Parameters
The reaction to produce methyl chloride (CH3Cl) is performed by
introducing gaseous HCl ( 96%) and vapour methanol ( 99%) into the
base of a glass-lined reactor G100 which contains a Zinc Chloride solution
(acts as the reaction catalyst) at its bottom.

E101
Condenser

Gaseous
Product
Crude CH3Cl
etc

G100
D101
Knock Down
Drum

ZnCl2

HCl
Distilling
Column

HCl Gas

1m

Methanol
Vapour

Methanol
Evaporator

Liquid Product
(31% HCl)

In 25%
Excess

Reaction Conditions:
Reaction Pressure
: 0.5 1 barG
Reaction Temperature
: 145 C
Catalyst Concentration
: 68 70% (SG 1.96)
Catalyst Boiling Point
: 150 C
HCl Gas Concentration
: 96 %
Methanol Vapour Concentration
: 99 %
Excess HCl
: 25 %

The whole reaction process (until final product in storage) takes place in a
closed atmosphere inside the glass lined reactor G100 in the absence of air
and other impurities especially oxygen which can form an explosive
mixture with methyl chloride. Therefore, it is necessary to purge out all
the air, especially oxygen from all the process equipments using nitrogen
gas before reaction is carried out.
Catalyst
The zinc chloride solution inside the reactor has a level of 1 meter in height
measures from the injecting point of the raw materials. The bottom part of
the reactor which contains the zinc chloride solution is called catalyst
bath
of
the
reactor.
Gaseous HCI and methanol vapor will only react inside ZnCl solution
catalyst bath. Out of the ZnCl solution boundary, reaction will not take
place. Therefore, a sudden flush of raw material inside the reactor should
always be avoided. This is to prevent:
a.) Wasteful of raw materials, unreacted HCI and methanol
b.) Flooding of the reactor
c.) More importantly: Pressure rise
Pressure Factor
The most important factor to note in raw materials feeding is that a sudden
flush of methanol and HCI inside the reactor will produce an abundance
yield of methyl chloride gas which gives a sudden pressure rise in the
reactor. If this high pressure rise exits the Rupture Pressure Limit of the
Safety Rupture Disc on top of the reactor, this disc will blow off leading to a
complete shutdown of the plant for maintenance replacement of a new
disc- In any case, this would be prevented from happening.
Side Reaction
It is important to note that, in this process methanol will tend to react in the
catalyst bath with its own molecules to form methyl oxide (CH-0-CH) in
the following way:
CHOH + CHOH
CH-O-CH + HO
Methanol

Methanol

Methyl Oxide

Water

Methyl chloride, being a side reaction product without much usefulness,

will not only affects the quality of the main product methyl chloride, but
also will:
5

a.) Increase consumption of sulphuric acid which is used to absorb it

(methyl oxide) in this gas treatment unit. Thus increase the production
cost.
b.) Affects the production rate of the main reaction to yield CHCl in the
reactor and thus give a poor production efficiency.
c.) Methanol is wasted for its formation of methyl oxide. It is a burden for
the unit production cost of methyl chloride.
Fortunately this side reaction can be suppressed to a very small extend (
0.1% by weight under normal operation condition) by an excess amount of
HCI feeding into the reactor. The excess HCI (25% extra of require for the
reaction) atmosphere will not only increases the frequencies and chances
of the HCI molecules and methanol molecules collision leading to a
favorable chemical formation of methyl chloride but also that this excess
can be easily recovered for reutilization in the process.
Excess HCI
When there is an excess HCI atmosphere inside the reactor, the reaction
environment will change. As soon as the methanol is injected into the zinc
chloride catalyst bath, its molecules will be surrounded by more HCI
molecules, with its aids of the catalysts, favorable reaction for producing
CHCl take place. Methyl oxide formation is thus suppressed.
But through experience, it is not possible and not practical also to control
the reaction process in such a way that gives zero production of methyl
oxide.
By experiment and by experience, the most economic way of the operation
is by feeing a 25% excess HCI into the reactor. By doing this, methyl oxide
formation through the process reaction is only 0.1% under normal optimal
operation condition.
This small amount of methyl oxide can be treated in the gas treatment unit
by absorption of the sulphuric acid and is get rid of easily.
It will be described in later pages about the excess HCI atmosphere in the
reactor, and why a 25% excess is required and not more.
Therefore, with a 25% excess HCI feeding, the reaction is 99.9% in favor of
methyl chloride production and 0.1% in favor of methyl oxide formation
only.
*This is an important control parameter of the reaction.*

Catalyst Dilution
ZnCl

Reaction Formula:

CHOH

HCI

CHCl

HO

Catalyst

Molecular Weight:

32

36.5

50.5

18

ZnCl2

Reaction Formula:

CHOH

CHOH

CH-O-CH + HO
Catalyst

Molecular Weight:

32

32

46

18

From the above reaction equation, it is noticed that water, HO, is one of
the products from the main reaction:
18
__________
Quality of water produced, H0 =
=

100%

50.5 + 18
26.3% of total product

Actually, this reaction produced water is in vapor state at 145% reaction

temperature. It will come out from the reactor together with the main
product CHCl, excess HCI etc. This is then condensed together with the
major part of the excess HCI in Crude Condenser E 101 and is separated
from the gaseous products (CHCI etc) in a knock down drum D 101 to give
a 31% HCI solution. Therefore, the zinc chloride solution, which has a
boiling point of 150c will retain its concentration without being affected by
the water generated through the main reaction.
Therefore, as far as the catalyst is concerned, there is no dilution problem,
no loss quantity, unless the reactor or the reaction process has been
operated in a wrong way for a long time. (Foaming of ZnCI inside the
reactor will cause only negligible lost of catalyst only.)
By wrong operation, this means:
a.) Low catalyst temperature during start up
b.) Low HCI excess during start up
c.) Feed CHOH, methanol first before HCI feeding during start up
d.) Low reaction temperature
The DOGMA of Reaction Operation
As it was mentioned above, that formation of methyl oxide (CH-O-CH)
should be avoided or reduced to a minimum extent for economic reason, it
is important to observe during any start up operation or increases in
7

production rate. Raw material feeding should be carried out in the following
way:
Always feeds HCI gas into the Reactor G 100 first
Methanol feeding should follow only if it is 100% sure and confirmed
through testing at the down stream side of the process that HCI has
already been introduced into the reactor and is in EXCESS.
Therefore, we can say in this way, for this process, the DOGMA of the
operation is Always feeds HCI gas into the reactor first.
Control Parameter of the Reaction Process
It is mentioned above that, by experience and by experiment, 25% excess
HCI feeing is an economic operation process that gives only 0.1% methyl
oxide formation in the reactor and that this amount of methyl oxide is
easily and quite economically get rid of in the Gas Treatment Unit (GTU)
through Sulphuric acid absorption.
Operation wise, it is quite impossible to measure the exact flow rate of HCI
gas and methanol vapor that is being fed into the reactor, In order to decide
and to determine an optimal operation condition, the 31% HCI
concentration in the knock down drum D 101 after a liquid and gas phase
separation of the reaction products ia an IMPORTANT CONTROL
PARAMETER of this process.
From the reaction formula:
Reaction Formula: CHOH
Molecular Weight:
32

HCI
36.5

ZnCl2

CHCl
50.5

HO
18

We know that, if 32 grams if methanol reacts with 36.5 grams of HCI, the
reaction will produce 50.5 grams of methyl chloride and 18 grams of water.
If HCI is in 25% excess, total HCI gas feed into the reactor will be
36.5

______
125
= 45.625 grams
100

Amount in excess is (42.625 36.5) grams or 9.125 grams.

This excess will come out from the reactor together with all the gaseous
products of the reaction, i.e. methyl chloride, water vapor etc.

At 40c condensation temperature, a major part of the excess HCI will

condense together with almost all the water vapor in a condenser to form
31% HCI in the knock down drum D 101.

If the amount of condensate is X,

Then
X
_______
= 0.31
X+ 18
X = 8.087 grams
This leaves (9.125 8.087) grams or 1.038 grams of uncondensed HCI to be
treated in the gas treatment unit.
Under optimal operation condition, a 31% HCI condensate in the knock
down drum D 101 is an indication that the reactor is operated at 25% HCI
excess and that methyl oxide formation is suppressed to a very small
extend of only 0.1%.
Therefore: 31% HCI condensate in the knock down drum is an important
control parameter of the whole reaction process.
This control parameter is important because it guarantees smooth
production process and also it is the Base of Trouble Shooting Works if
things have gone wrong with the process.
Trouble Shooting of the Reaction Process
In case there is a change in the knock down drum, HCI condensate
concentration (normally 31%), for example a low% HCI condensate and at
high temperature, the methyl chloride crude products condenser E 101
must be check of fouling. Its efficiency of condensing should be rectified
and maintained.
The same checking should be carried out on the concentration of the HCI
that is being fed into the HCI distilling column C 201 also.
Higher HCI excess
For this process, it is possible, of course, to feed HCI into the reactor G 100
at a higher excess rate, but generally, this is not economically favorable
because of the following reason.

1. Methyl oxide formation is already very small (0.1% only) at 25% HCl
excess will not give very obvious suppression result of methyl oxide
formation.
2. There will be more uncondensable HCl in the knock down drum
which will
a) increases the work load of the GTU
b) requires more waste treatment effort and thus increases the
production cost
3. HCl is wasted.
Conclusion
For this reaction process, it is important to note:
1. DOGMA : Always feed HCl gas into the reactor first.
2. EXCESS: 25% HCl in excess feeding is important.
3. CONTROL PARAMETER: 31% HCl in knock down drum is an
important control parameter of the reaction.

10

METHYL CHLORIDE
Process Description (an outline)
Process Flow Diagram
C Valve 203b

Cooling H2O
Crude CH3Cl

E101
Condenser
C Valve 203a
32% HCl
Feed

C201
HCl
Distillation
Column

G100
Reactor

E203

HCl
Gas

E204
HCl
Reboiler

Azeotropic HCl

D101
Knock
Down
Drum
CH3OH Vapour

Liquid Product
31% for
reutilization

E102
Methanol
Evaporator

R100
Catalyst Tank

Steam Condenser
Methanol Feed

Pure CH3Cl

R107
Brink
Mist
Separator

P105

C100B

C102A

C101

C100

98%
H2SO4
Wash
Column

78%
H2SO4
Wash
Column

Casutic
Soda
Wash
Column

Water
Wash
Column

Compressed CH3Cl
P103B

P103A

P102

CH3Cl Storage
R130

P101

Filling (ISO or Cylinders)

E104 Liquefactor

11

Process Description (Outline)

1.) The Raw Materials Preparation Unit
To produce methyl chloride, the raw materials requires for the reaction
are
a.) GASEOUS HCI of > 96% concentration and
b.) METHANOL VAPOR of > 99% concentration
2.) The Reaction Unit
Both the raw materials, i.e Gaseous HCI, methanol vapor are injected
into the base of a glass-lined reactor G 100 which at its bottom contains
liquid Zinc Chloride Solution (70% in concentration) which acts as a
catalyst for the following reaction:
ZnCl2

CHOH

HCI

CHCI + HO

145C

For the same reactor and at the same reaction conditions and
consequences, another side reaction will also take place; ie. the
formation of methyl oxide through own molecules reaction of the
methanol:
CHOH

CHOH

ZnCl2

CH-O-CH

+ HO

Fortunately this side reaction can be suppressed to a very small extend

(0.1% under normal operation condition) by creating an excess HCI
atmosphere inside the reactor. The excess HCI feed is 25% (in extra)
After the reaction, the products contain:
1) Methyl Chloride
(main product of the reaction)
2) HCI Gas
(Excess upon feeding and or unreacted)
3) Water Vapor
(a product of the reaction)
4) Methanol
(Unreacted: in very small quantity)
5) Methyl Oxide
(Side reaction product : about 0.1%)
6) ZnCI
(in traces only, due to foaming)
This crude products will pass through a condenser E 101 where upon
cooling will lead to a liquid-gas phase separation of the product in a
knock down drum D 101 where
a) The liquid phase product is a 31% HCI solution which is pumped
back to the process for reutilization

12

b)

The gas phase product which contains the same materials as in

the original crude with the most of its water vapor and HCI gas
condensed in (a).

The gas phase crude will then send for purification process. The whole
purification facility is called the Gas Treatment Unit
3.) Gas Treatment Unit (G.T.U)
Gas treatment unit is a very important section of the whole production
process, because the quality of the product CHCI totally depends on a
proper control of the operation of this whole unit.
It mainly consists of four gas wash columns and a brink filter called the
Brink Mist Separator.
In all the four wash columns, the gas always takes the upward stream
flow and the wash solution take a downward flow. They are termly:
a) The water wash column C 100 :
where all the unreacted methanol trace of ZnCI are completely
removed and most of the uncondensed HCI are also removed.
b) The soda wash column C 101:
which acts as a safety precaution Wash Column using 20%
caustic solution to remove any trace of HCI not removed by the
previous column.
c) The 78% sulphuric acid wash column C 102 A:
where all the methyl oxide and most of the water vapor are
removed.
d) The strong sulphuric acid (98%) wash column C 102 B
where all trace of water vapor are removed.
e) The brink mist separator:
This only allows dry and pure methyl chloride to pass through.
Mist of sulphuric acid is filtered by the Brink candle.
4.) Compression, Liquefaction, Storage
Methyl Chloride gas up to this state is totally pure and free of any
previously mentioned impurities except that there might be some inert
gases like N, O, in a very small quantity.
It is then compressed by a two stages compressor P 105 up to a
maximum pressure of < 9 bars (Temperature: 110C after the
compression). This compressed gas is then passed through a
liquefactor E 014 where upon cooling, it is liquefied and send into
storage tank R 130 A and R 130 B and store as a liquid product.

13

METHYL CHLORIDE
Detail Process Description and Unit Operation
The process of methyl chloride production consists mainly the following
four major sections, namely:
1.) Raw Material Preparation Unit includes:
a.
b.
c.

HCI Distillation Unit

Methanol Evaporator
Catalyst Preparation Tank

C 201, E 204, E 201, E 202, E 203, R 201 & R 202

E 102
R 100

2.) Reaction Unit, which include:

a.
b.
c.

Reactor
Crude Methyl Chloride Condenser
31% HCI knock down drum

G 100
E 101
D 101

3.) Gas Treatment Unit, which include:

a.
b.
c.
d.
e.

Water wash column

Caustic wash column
Weak sulphuric acid wash column
Strong sulphuric acid wash column
Brink mist separator

C 100
C 101
C 102 A
C 102 B
R 107

4.) Compression and Liquefaction Unit, which include:

a.
b.

The Crepelle Compressor

Methyl chloride liquefactor
Storage tank

P 105
E 104
R 130 A & R 130 B

All these four sections have their unique roll for functions and are equally
important in the course of methyl chloride production.
A detail description of each section is given below which include:
i.) Name of equipments
ii.) Equipment description and functions
iii.) Detail process description
iv.)
Operation Condition
v.)
Operation Procedures ( Individual Unit)

14

DETAIL PROCESS DESCRIPTION

Raw Materials Preparation Unit
a.) HCI Distillation Unit
FLOW DIAGRAM: HCI DISTILLATION UNIT
95 C

E203
Reflux
Condenser

34%
Feed HCl
FV211

Reflux
Condensate

HCl Distilling Column

C201

Steam

75 C, 32% HCl

E204
Reboil
er

Condensate
E201
Heat
Exchanger

Graphite
Jacket

Steam

HCl, 85C

96% HCl

160 C, 5.2 bar

FV221

Cooling
Water

130 C

E202
Azeo
Cooler

HV203a
To Reactor
G100

HV203b
To HCl
vent
absorption
unit

LV211
20% HCl,
35C

Azeo HCl, 90C

Cooling
Water
R202
R201
LV201
L

20%
Azeo
HCl
Storage

32%
Strong
HCl
Storage

LV202

P201

P202

15

HCI DISTILLATION UNIT

I.) Name of Equipments:
No
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15

Code
C 201
E 204
E 201
E 202
E 203
R 201
P 201
R 202
P 292
HV 203a & HV 203b
LV 211
LV 201
FV 211
LV 202
FV 221

Name
HCI Distilling Column
HCI Reboiler
Feed HCI Heat Exchanger
Azeo HCI Cooler
Reflux Condenser
Strong HCI Buffer Storage Tank
ROPAC HCI Feed Pump
Azeo HCI Storage Tank
ROPAC Azeo HCI Pump
Inter-operating Valves
Column Liquid Level Control Valves
Make up HCI Control Valve
Feed HCI Control Valve
Azeo HCI Flow Control Valve
Steam Flow Control Valve

II.) Equipment Description and Functions

1.) C 201: HCI Distilling Column
Dimension
Material
Internal Packing
Facilitated with
Function

Height 7039mm, Outside Diameter 310mm

Graphite
Packed with 3 layers of PVDF pall rings
Bottom liquid level control and recording system
To generate gaseous HCI of more than 96% concentration
for process reaction.

2.) E 204: HCI Reboiler

Dimension
Material
Service Fluid
Function

Height 3800mm, Outside Diameter 300mm

Graphite, outer surface insulated
Steam for HCI Distillation
To heat up HCI solution for distillation

3.) E 201: Feed HCI Heat Exchanger

Dimension
Material
Function

Height 605mm, Outside Diameter 460mm

Graphite, outer surface insulated
Using heat obtains from the Azeotropic HCI solution to
preheat the Stromg Feed HCI Solution (32%) before entering
HCI Distilation Column C 201

16

4.) E 202: AZEO HCI Cooler

Dimension
Material
Function

Height 620mm, Outside Diameter 660mm

Made of graphite
To cool down Azeo HCI solution to below 40C before
entering Azeo HCI solution enter its storage tank R 202

5.) E 203 : HCI Reflux Condenser

Dimension
Material
Function

Height 1499mm
Made of graphite
To condense water vapor coming out from top of HCI
distilling column. Thus, enriches gaseous HCI
concentration.

6. R 201: Strong HCI Buffer Storage Tank (HCI Feed Tank)

Dimension
Material
Function

Height 2800mm, Internal Diameter 1250mm

Carbon Steel Tank, internally rubber lined.
As 32% HCI Feed tank.

7. P 201: ROPAC HCI Feed Pump

Power
Material
Maximum Del.Rate
Function

4kW
Graphite Pump
3
5m /hr
Feeding strong HCI solution into distilling column

8. R 202: Azeo HCI Storage Tank

Dimension
Material
Function

Height 2800mm, Internal Diameter 1250mm

Carbon Steel Tank, internally rubber lined.
Store Azeo HCI from Distilling Column before sending it
for reabsorption ( reconcentration in HCI plant

9. P 202: ROPAC Azeo HCI Transfer Pump

Power
Material
Maximum del.rate
Function

4kW
Graphite Pump
3
7m /hr
To transfer Azeo HCI solution

10. HV 203a & HV 203b: Inter operating Control Valves

Service

CONTROL VALVES

HV 203a

Open when reactor G100 is ready to accept > 96% HCI

gas for reaction. Remain open when reaction is in
progress. Close when plant trip or shut down.

HV 203b

Open to HCI vent absorption unit during S/U of distilling

column or when after plant trip or shut down.

17

The above valves HV 203a and HV 203b are inter-operating ie.

When HV 203a is opened to feed gaseous HCI (> 96%) into the
reactor, HV 203b is cvlosed from sending HCI gas to HCI vent
absorption unit or otherwise: when HV 203a is closed, then at the
same instance HV 203b is opened.
11. LV 211: Distilling Column Level control valve
Service
Function

CONTROL VALVES
Controls and maintains liquid HCI level at
bottom of distilling column at 750 mm. This is a
Level Control Valve.

12. LV 201: Make up HCI control valve

Service
Function

CONTROL VALVES
To control make up HCI flow rate so as to
maintain Feed HCI tank R 201 AT HALF. This is a
level control valve.

13. FV 211: Feed HCI Control Valve

Service
Function

CONTROL VALVES
To control HCI flow rate feeding into Distilling
Column. This is a Flow Control Valve.

14. LV 202: Azeo HCI Flow rate Control Valve

Service
Function

CONTROL VALVES
To control Azeo HCI flow rate from Azeo HCI
storage tank R 202 that is being sent for
reconcentration process. Also maintains R 202
level at half. This is a Level Control Valve.

15. FV.221: Steam Flow Control Valve

Service
Function

CONTROL VALVES
To control steam flow rate into reboiler E 204.
This is a Flow Control Valve.

18

III.) Detail Process Description

HCI Distillation Unit is installed in order to generate gaseous HCI of
more than 96% concentration for methyl chloride reaction process.
In normal operation, the whole unit functions in the following ways:
1. Steam is fed onto reboiler E 204 for heating up HCI solution inside
the reboiler.
Note: In the case of start up follows a short shut down, steam
should be fed in slowly at first in order to avoid flooding of
distilling column.
2. Pump (P 201) pumps strong HCI (32%) under a well determined rate
from the strong HCI feed storage tank (R 201) and feed
continuously into the distilling column C 201.
Before entering top of distilling column, strong HCI solution is
preheated by the Azeotropic HCI solution coming out from the
bottom of distilling column from 35C to 80C in the heat exchanger
E 201.
Strong HCI solution enters side way into distilling column top at
space between the column top packing and middle packing.
3. On entering the distilling column, liquid HCI will flow downwards
and reaches the bottom of the distilling column and maintains a
height of 750 mm by Level control valve LV 211 situated at the
down stream pipe line of HCI Azeotropic solution. At this state,
reboiler is operated under totally immersed condition which has
its best efficiency.
4. Inside the Reboiler, HCI solution is heated up to 130C by process
steam and boils and evaporates. When hot HCI solution on top of
reboiler evaporates into the distilling column, azeotropic HCI
solution from bottom of the distilling column comes in to replace
the space: This phenomenon is called Thermosyphoning effect of
the reboiler.
5. Inside the distilling column, HCI being more volatile than water is
separated from its solution and travels up the column. On its path,
it comes into contact with the freshly feed HCI from R 201. Using
the heat it carries, it evaporates HCI gas out from the fresh feed HCI
solution. Thus as this hot gas travels up, its concentration is
enriches continuously until when it reaches the top of distilling
column, gaseous HCI concentration will be > 96%.

19

6. At the same instance that gaseous HCI traveling up the column and
enriches its concentration, liquid HCI solution will travel
downwards the column and decreases in HCI concentration. When
it reaches the bottom of distilling column, its concentration will
decreases from 32% to about 20%. The weak HCI solution is called
the Azeotropic HCI solution.
7. As the distillation process goes on, HCI gas exerts a pressure of
1.3 bars in the column.
8. Azeotropic HCI solution at the bottom of the Distilling Column will
either
a) Acted by the column pressure fo 1.3 bars, flow through Heat
Exchanger E 201 where it preheats the fresh feed HCI solution
to 80C and is cooled down in Azeo HCI cooler to 40C before
it enters Azeo HCI storage tank R 202 where pump P 202
pumps it away for reconcentration process in HCI plant or
send for vent absorption unit.
b) By the thermo-Syphoning effect of reboiler E 204, enters the
reboiler proceeding for distillation process.
9. During start up period of HCI Distillation Unit, gaseous HCI of less
than 96% concentration has to be sent to HCI vent absorption unit
by way of opening inter-operating valve HV 203b.
10. Azeo HCI solution sampling and Test (130C 30% concentration)
and Reflux condensate sampling and Test (75C, 32.3% HCI) will
provide information of gaseous HCI coming out from the top of the
dstilling column.
On top of that, the following control parameter is also important for
us to attain an optimal operation condition of distilling column.
Reboiler Temperature = 130C (Increases steam flow rate if temperature is below 130C)
Distilling Column Top Temperature = 90C
Reflux Condensate Temperature = 75C

11. An experienced person will need 20 or 30 minutes to bring distilling

column under optimal operation condition and provide > 96%
gaseous HCI for methyl chloride reaction process.
Note: Azeotropic solution
Physical Chemistry Terms: which mean a solution through boiling
and distillation process to separate out one of its component out
from it, when reaches its Azeotropic Boiling point will give its gas
phase product in equivalent concentration to the liquid phase
solution.

20

IV Process Operation Conditions

Description
Service Steam for Reboiler
Liquid HCI in Reboiler
Distilling Column Top
Distilling Column Bottom
Reflux Condenser Gas
Reflux Condenser Liquid
Feed HCI from R 201
Feed HCI entering C 201
Azeo HCI Before E 201
Azeo HCI After E 201
Azeo HCI Before E 202
Azeo HCI After E 202

Temperature
160C
130C
90C
130C
90C
75C
< 35C
80C
130C
89C
89C
< 40C

Pressure
5.3 bars
1.3 bars
1.3 bars
-

Concentration
Steam
20%
> 96% HCI gas
20% Liquid HCI
> 96% HCI Gas
< 32.3% Liquid Gas
32% Liquid Gas
32% Liquid Gas
20% Liquid HCI
20% Liquid HCI
20% Liquid HCI
20% Liquid HCI

V Operation Procedures
Before start up HCI Distillation Unit, check and make sure that:
a) HCI vent absorption unit in operation
b) Inter-operating valves HV 203b is opened and HV 203a is closed
c) Pumps P 201 and P 202 are functioning
d) Cooling water are on for E 202 and E 203
e) Make up HCI is available from General Storage Tank
VI Operation and Controls
1. Feed steam onto the Reboiler E 204
Regulates Regulator FIC 221 to control steam flow rate feeding
onto the reboiler. Set control valve FV 221 at requires value of
steam flow rate.
Note: In the case of start up after a short shut down of the plant, steam
should be fed in slowly to avoid flooding of distilling column.

2. Start up pump P 201 to feed 32% HCI into HCI Distilling Column 201
Regulates Regulator FIC 211 to control HCI flow rate feeding into C
201. Set control valves FV 211 at requires value of HCI flow rate.
3. Check Level of R 201
Regulates Regulator LIC 201 to maintain HCI liquid level in R 201 at
half tank position, This will induce the control on the control valve
LV 201 which controls the make up HCI flow rate from the general
storage.
Check and compare HCI flow rate recorded by Flow Recorder FR
201 and FR 211:
a) FR 201 flow rate = FR 211 flow rate during start up operation of HCI Distilling Column.
b) FR 201 flow rate + HCI flow rate from D 101= FR 211 flow rate after reactor G 100 in

21

operation

4. Set level control valve LV 211 to give 750 mm liquid HCI level at
bottom
of HCI Distilling Column.
5. Start up pump P 202 as soon as Azeotropic HCI solution reaches
down to R 202.
6. Regulates Regulator LIC 202 to maintain HCI liquid level in R 202 at
half tank position- This will induce control on the control valve LV
202 which controls the Azeotropic HCI pumping rate to:
a) Azeotropic HCI solution general storage tank
b) E 210 in HCI vent absorption unit.
7.

Actions to be taken
Check Reflux Condensate Temperature TJR 203
Check Reflux Condensate Concentration
Check Azeotropic HCI Temperature TJR 201
Check Azeotropic Concentration
Check gaseous HCI Temperature at Distilling Column Top TJR
211

75C
32.30%
130C
20%
95C

8. When above conditions are met, interchange operation of valves HV

203a and HV 203b.That is:
a) Open HV 203a and send > 96% gaseous HCI into reactor G 100
reaction
b) Close HV 203b to the HCI vent absorption unit.
9. Increase steam flow rate and maintains its temperature and
pressure whenever HCI Feeding rate into C 201 is increased.
10. It takes about 20 or 30 minutes to attain an optimal condition in the
distilling column.
Remark: Study P&I of HCI Distillation Unit

22

METHYL CHLORIDE
THE RAW MATERIALS PREPARATION UNIT
0.7 bar
To Reactor
G100

Pressure induce control valve

V4

PV102

3 bar

V3

HAP

30% Level

HV122
V2

LV102
E102

Steam from
Boiler

V6 Steam
Condensate ByPass Valve
FV112
R120
Methanol
Storage
Tank

Methanol
Feeding
Pump

V5
Methanol
Drain Valve

7 Pipes

Steam Trap

P120

23

Methanol Evaporator
I. Name of Equipments
Code
E 102
FV 112
HV 122
PV 102
LV 102
P 120
V1
V2
V3
V4
V5
V6
S
P
HAP
LV 102

II.

Name of Equipments
Methanol Evaporator
Total Methanol Flow Control Valve
Liquid Methanol Flow Control Valve
Vapor Methanol Flow Control Valve
Steam Flow Control Valve
Methanol Feeding Pump
Evaporator Feed Methanol Isolation Valve
Reactor Liquid Methanol Isolation Valve
Reactor Vapor Methanol Isolation Valve
Reactor Feed Methanol Isolation Valve
Evaporator Methanol Drain Valve
Evaporator: Steam by pass valve
Evaporator Safety Blow Valve
Vapor Methanol Pressure Gauge
Vapor Methanol High Pressure Alarm System
Evaporator Methanol Levl Indication and Recording System
Steam Trap

Equipments Description and Its Function

1. E 102: Methanol Evaporator
Dimension
Material
Facilities

Length 1.2m, Internal Diameter 0.5m, cylindrical bomb

shape like
Made of carbon steel. Internally fixed with seven Ushaped steel tubes for steam passing.
a.) Level alarm and recording system
b.) Pressure alarm and recording system

Function

a) Service: Tube side: Steam at 160 and 5.2 bars to heat

and evaporate methanol into its vapor.
b.) Shell side: contains liquid methanol to be evaporated
for reaction purpose

Other
Accessories

S: Safety Blow Valve

P: Vapor Methanol Pressure Gauge

2. FV 112: Total Methanol Flow Rate Control Valve

Service

Control Valve. Incorporated with Flow Rate Recorder

Function

To control total methanol flow requires for the reaction

and recording hourly methanol feeding rate.

24

3. HV 122: Liquid Methanol Flow Control Valve

Service
Function

Control Valve. Hand regulates

To feed cool liquid methanol into the reactor if reaction
temperature is too high.
(Reason: The reaction is exothermic)

4. PV 102: Vapor Methanol Flow Control Valve

Service
Function

Control Valve. This is a pressure induced control valve.

Open only when methanol vapor pressure is > 3 bars
To control flow of vapor methanol feeding into the reactor

5. LV 102: Steam Flow Control Valve

Service
Function

Control Valve.
To control flow rate of steam in order to provide enough
heat for methanol evaporation.

6. P 120: Methanol Feeding Pump

Power
RPM
Maximum del. rate
Maximum del. pressure
Function

3 kW
2900 rpm
3
7m /hr
5 bars
To pump liquid methanol from its storage ( R
120) and feed into methanol evaporator or
reactor.

7. V1: Evaporator Feed Methanol Isolation Valve

Function

To isolate liquid methanol from going into evaporator

when methanol evaporator is not in use.

8. V2: Reactor Liquid Methanol Isolation Valve

Function

Isolation valve before HV 122. Open when after E 102 is in

operation and let HV 122 to be regulated for reaction
temperature adjustments.

9. V3: Reactor Vapor Methanol Isolation Valve

Function

Isolate methanol vapor from going into reactor after a

plant shut down.

10. V4: Reactor Feed Methanol (Liquid and Vapor) Isolation Valve
Function

Total methanol feed isolation valve.

25

11. V5: Evaporator Methanol Drain Valve

Function

To drain evaporator empty after a plant shut down and to

avoid a sudden pressure rise in the evaporator when reshut up.

12. V6: Evaporator Steam By Pass Valve

Function

To by pass steam from evaporator steam tube and to

purge steam condensate directly after a plant shut down.

13. Steam Trap

Function

To purge steam condensate out from the evaporator when

it is in operation.

III. Detail Process Description

Methanol Evaporator E 102 is installed in order to generate vapor
methanol and feed this into the reactor to react with gaseous HCI to
produce methyl chloride.
When Reactor G 100 is ready to accept vapor methanol for reaction,
steam ( at 160C, 5.2 bars steam pressure) is fed into the
evaporator E 102. Methanol pump P 120 feeds the evaporator
with liquid methanol from its storage tank R 120.
When liquid methanol level in the evaporator rises and immerses
the steam U-tubes, the heat from the steam will heat up the liquid
methanol and vaporize it. When methanol vapor reaches 3 bars or
more, valve PV 102 is induced to open. Vapor methanol will be fed
into the reactor by the differential of pressure between the
evaporator (higher pressure at 3 bars) and reactor ( lower pressure
at 1 bar).
Methyl chloride reaction is exothermic. ie. heat is generated during
the reaction, If the reaction temperature is too high, it is necessary
to divert some the liquid methanol and feed them directly into the
reactor in order to regulate the reaction temperature. This diversion
is achieved through manipulation on the control of valve HV 122.
Methanol evaporator will cease its operation when:
a) Reactor is operated at very high pressure.
b) Evaporator is operated at own high pressure.

26

IV. Process Condition

No
1
2
3
4
5
6
7
8
9
10

Description
Total Methanol Flow Rate
Methanol Flow Rate for Evaporation
Vapor Methanol Temperature
Vapor Methanol Pressure
Steam Flow Rate
Steam Pressure
Steam Temperature
Vapor Methanol High Pressure Alarm
Vapor Methanol Very High Pressure
Alarm (Tripping)
Level of Methanol Inside Evaporator

Start Up
100 kg/hr
100 kg/hr
110C
3 bars
30 kg/hr
5.2 bars
160C

Normal Condition (Max)

200 kg/hr
100 kg/hr
110C
3 bars
60 kg/hr
5.2 bars
160C
4.5 bars gauge
5 bars gauge

half

half

V. Operation Procedures
To operate methanol evaporator safely and smoothly, it is
important to
observe the followings:
a.) After a plant shut down:
1. Always drain evaporator empty of methanol
2. Always open steam by pass valve
3. Close isolation valves V1, V2, and V3.
b.) Before start up evaporator:
1. Make sure there is no methanol inside
2. Check and make sure that isolation valves V1, V2 and V3 are
all at close position as yet.
Procedures:
1. Feed steam into evaporator slowly.
Regulates regulator LIC 102 to pen control valves LV 102
Set steam flow rate at 30 kg/hr during S/U
Check steam pressure and temperature at 5.2 bars & 160C
2. Close steam by pass valve V6 at steam condensate outlet
3. Close methanol drain valve V5
4. Start up methanol feeding pump P 120
Regulates regulator FIC 112 to open control valve FV 112
Set FIC 112 to open FV 112 at minimum operating position
5. Open isolation valve V1 to feed liquid methanol into Evaporator
E 102
6. Wait until the level builds up and immerses the steam tubes.

27

Check level of methanol in evaporator through level recoreder

LR 102.
Set LIC at .
Keep close watch on methanol vapor pressure at Local
pressure gauge on top of methanol evaporator.
7. When methanol vapor pressure is 3 bars or more, open valve
V3. At the same time open also valve V2 for stand by.
Communicate with control room and informs all the above
information:
That is: a.) Methanol vapor pressure is at 3 bars now
b.) Valves V2 and V3 are opened.
8. Open valve V4 to feed vapor methanol into Reactor G 100 for
reaction with gaseous HCI.
Note: As soon as V4 is opened a strong bubbling sound is heard
from inside the reactor. Reaction is taking place now.
The above 2,3,4,5,6,7,8 are on site operation.
9. Pass control of methanol evaporator to Control Room.
10. Increases reaction rate by regulating FIC 112.
Regulates Control Valves FV 112 opening position to increase
methanol flow rate slowly.
11. Keep close watch on methanol evaporator pressure and also
reactor pressure.
12. Increases methanol feeding rate in accordance with HCI
(Excess) flow rate for the reaction, Keep close watch on
Compressor (P 105) performance while reaction rate is
increased.
13. When reaction temperature is too high, ie.> 145C,
Regulate HIC 122 to open HV 122 to feed in liquid methanol for
adjustment on reaction temperature.
Note: Total methanol flow rate is not affected.
14. Always: proceeds to increase total methanol flow rate into
reactor SLOWLY
This is to avoid a sudden pressure rise in the reactor due to an

28

abundance yield of Methyl Chloride which will cause the rupture

disc on top of Reactor G 100 to blow off leading to a plant shut
down.

29

DETAIL PROCESS DESCRIPTION AND UNIT OPERATION

REACTION UNIT- FLOW DIAGRAM OF REACTION UNIT
135C

CH3Cl

135C
Cooling
Water

E101
Condenser
Rupture
Disc
(graphite)
2.7 bar

Rupture
Disc

High Pressure
Alarm
System

35C
Tripping
Pressure
Alarm
System

Crude
CH3Cl

G100
Reactor
HCl Injectors
1.3 bar

HCl
Distillation Unit

CH3OH Injectors
1.3 bar

D101
Knock
Down
Drum

145C,
ZnCl2

LV101

To R201,
31% HCl

Steam

PV102

Catalyst Tank
R100

P202B

HV122
Methanol
Evaporator

30

Reaction Unit
I.) Name of Equipments
Reaction Unit of Methyl Chloride plant mainly consists of the
following equipments:
Code
G 100
E 101
D 101
P 202B
FR 100
PV 101
LV 101
PAH 101
PAHH 101

Name of Equipments
Methyl Chloride Reactor
Hot Crude Condenser
31% HCI Knock Down Drum
31% HCI Solution Pump
Gaseous HCI Flow Rate Recorder
Crude CHCI Pressure Induced Control Valve
31% HCI Levl Induced Control Valve
Reactor High Pressure Alarm Circuit
Reactor Very High Pressure Alarm and Tripping Circuit

II.) Equipments Description and Functions

1. G 100: Methyl Chloride Reactor
Dimension
Material

Description

Function

Outside Diameter 1.4m, Height 5.3m

Internally glass lined carbon steel cylinder
a.) Cylindrical in shape, vertically installed
b.) Three HCI injectors and three methanol injectors, enter Reactor at
600mm position measures from its base at opposite direction and
directly pointing at one another
c.) Bottom of reactor is a Zinc Chloride solution catalyst bath. Its level
is 1m measures from the raw material injection points. This level
can be check through a level indicator LI 100 installed on the reactor.
d.) On top of reactor are
(1) Outlet for reaction products
(2) A safely rupture disc which leads to catalyst tank if blow off.
e.) Temperature Detect Element TE 120 installed on top of reactor
measure gaseous product and indicates by TJR 120 in control room
f.) Temperature detect element TE 120 installed on top of reactor
measure gaseous products temperature and indicates by TJR 120 in
control room
g.) Near the bottom, there is a man-hole for visual inspection of reactor
internal glass lining or if required enter for spark test.
For reaction of gaseous HCI and vapor methanol to take place in
catalyst bath inside this reactor

2. E 101: Hot Crude Condenser

Dimension
Material
Description

Function

6.88m in height installed vertically

Graphite
a.) This is a graphite heat exchanger. Hot crude enters from top, travel
downwards and come out from bottom. Water enters from side way
at bottom and comes out side way from top.
b.) Internally baffled
To condense excess HCI gas from the reactor together with the
reaction produced water to form 31% HCI solution

31

3. 31% HCI Knock Down Drums

Dimension
Material

Description

O.D 1.2M, height 1.4m, bottle shape drum

Internally glass lined carbon steel
a.) Bottom part of this glass lined drum receives 31% HCI solution
condensed by E 101.
b.) Level transmitter LT 101 coordinates with regulator LIC 101 of
control valve LV 101 to maintain drum 31% HCI level at 60% height
of drum.
c.) On top is flanged outlet of crude Methyl Chloride and uncondensed
vapor and gas and recycles HCI inlet through HCI solution pump
P 202B.

4. P 202B: 31% solution pump

Dimension
Material
Motor
Normal Discharge Rate
Maximum Discharge Rate
Suction Pipe
Discharge Pipe
Function

O.D 1.2M, height 1.4m, bottle shape drum

Graphite pump. ROPAC type
2.2kW, 3 phases, 440 volts, 1450 rpm
0.15 m/hr
2 m/hr
50 mm I.D
32 mm I.D
To transfer 31% HCI solution receives by D 101 into R
201 of HCI Distillation Unit.

5. FR 100: Gaseous HCI Flow Rate Recorder

Service
Function

Gas Flow Rate Recorder

To record hourly gaseous HCI flow rate into Reactor G 100.

6. PV 101: Crude CHCI Pressure Induced Control Valve

Service
Function

Control Valve
Set to maintain reactor pressure at 0.5 or 1 bar gauge

7. LV 101: 31% HCI Level Induced Control Valve

Service
Function

Control Valve
To control pumping rate of 31% HCI from D 101 and maintain level
inside D 101 at 60% height.

8. PAH 101: Reactor High Pressure Alarm

Service
Function

Alarm
Signal reactor high pressure. Comes out when PR 101 is more than 1.5
bars

32

9. PAHH 101: Reactor Very High Pressure Alarm & Tripping Circuit
Service
Function

Alarm & Tripping

Shut down of plant when reactor is working at very high pressure of >
1.75 bars. This will shut off methanol flow control valve FV 112 and
steam valve of evaporator LV 102. Signals reverse operation of HV 203a
& HV 203b.

III.) Detail Process Description of Reaction Unit

In normal operation, reaction proceeds in the following ways:
1.

Hot Zinc Chloride solution forms a catalyst bath at the bottom of

glass-lined reactor G 100 and immerses HCI gas injectors and
methanol vapor injectors with a level of 1 meter above these
injectors.

2.

96% above HCI gas feeds into reactor catalyst bath through HCI
injectors. 99% or above methanol vapor feed into reactor
catalyst bath through methanol injectors.
Both these raw materials feeds into catalyst bath at opposite
direction pointing directly at one another. As they bubbles
through the Zinc Chloride solution, with the help of this catalyst,
HCI & methanol reacts to form Methyl Chloride thus:
HCI

3.

CHOH

ZnCl2

CHCI + HO +

Catalyst

The reaction products bubbles out from the catalyst solution

and goes into space at reactor top where they find their outlet
into that crude Condenser E 101.
Note: HCI gas feed was in 25% Excess for the reaction.

4.

As this hot crude enters condensers E 101, it travels downwards

through tubes of 10 mm diameter. At the outer surface of these
tubes, cooling water passes at upward direction though baffles
and cools the hot crude down from 135C to 40C.

5.

When this hot crude is being cooled down, the excess fed HCI
condenses together with water vapors produced through the
reaction to form a 31% HCI solution.
The condensed 31% HCI solution (liquid) is received by knock
down drum D 101.
Inside knock down drum D 101, gas phase products and liquid
phase products of the reaction are separated with:

6.

33

a. The liquid phase product, ie. 31% HCI solution being

pumped away from the pump P 202B to R 201 for process
utilization again.
b. The gas phase products which contain:
i.) CHCI
ii.) Uncondensed Water Vapor
iii.) Uncondensed HCI gas
iv.)
Trace of Methanol
Find their outlet on top of knock down drum D 101 to the Gas
Treatment Unit on the process where all impurities are removed
from Methyl Chloride gas before sending for compression and
liquefaction.
7.

Until just at the outlet of knock down drum D 101, the reaction
unit works on a pressure of 0.5 or 1.0 bar gauge pressure.
a. On top of knock down drum D 101, high pressure alarm
system of reaction unit which include PT 101, PR 101, PSH
101, PAH 101 will provide information of reaction pressure
and signals alarm of high pressure if this unit works on high
pressure.
Code
PT 101

Components
Pressure Transmitter
installed on D 101
CHCI outlet line

PR 101

Pressure Recorder

PSH 101

High Pressure Switch

PAH 101

High Pressure Alarm

Functions
Transmit pressure signal of reaction
unit to PR 101 in control room
Records pressure signals transmit
by PT 101 in control room
Signals high pressure alarm PAH 101
Alarm comes in when reaction unit
pressure is more than 1.5 bars gauge

b. Reactor very high pressure alarm & Tripping Circuit installed

before (a) which includes
1.
PSHH 101
2.
PAHH 101
if comes in will:
i.) Shut feed steam control valve LV 102 of methanol
evaporator
ii.) Shut feed methanol control valve FV 112
iii.) Inter-operate HV 203a to HV 203b

34

The above will result and bring a shut down of the plant for
investigation on faults.
Under normal operation, PAH 101 setting is 1.5 bars gauge &
PAHH setting is 1.75 bars gauge.
IV. Operating Conditions
A. Temperature
No
1
2
3

Description
Reaction Temperature (catalyst bath)
Product Temperature ( Gas on Reactor
Top)
31% Condensed HCI at D 101 bottom

Recorder
TJR 110

Temperature
145C

TJR 120

135C

TJR 101

Below 40C

Recorder
PR 101
PR 102
(ALARM)
PAH 101
PAHH 101
PAH 102
PAHH 102

Bars
0.5 or 1 bar
3 bars
(SETTING)
1.5 bars
1.75 bars
4.5 bars
5 bars

B. Pressure
No
1
2
3
4
5
6

Description
Reaction Pressure
Methanol vapor (Feed) Pressure
(PRESSURE ALARM STSTEM)
Reactor High Pressure
Reactor Very High Pressure
Methanol Evaporator High Pressure
Methanol Evaporator Very High Pressure

C. Level
No
1
2
3

Description
Reactor Catalyst Level (1m above injector)
D 101 31% HCI Level
Methanol Liquid Level in Evaporator

Recorder
LI 100
LI 101
LR 102

Setting
1600mm
600mm
250mm

V. Operation Procedure:
Commissioning of the reaction unit brings the whole of Methyl
Chloride plant to its total momentum. Before reaction can actually
starts in the reactor, the following operation had to be carried out
first.
1. Start-up the cooling water network and make sure sufficient
cooling water are supplied to all coolers, condensers,
liquefactor,etc.
2. HCI vent absorption unit is in operation.
3. Gas treatment unit is in operation.
4. Steam network is started for HCI Distillation Unit & methanol
evaporator.
5. Compressor is running with minimum operation suction pressure.

35

6. Reactor had already been filled with minimum operation suction

pressure.
7. Reactor had already been filled with Zinc Chloride catalyst
solution
( > 80C)
When all these are ready or in operation, then actual functioning if
the reaction unit can be achieved through the following operation:
1. Inter-operate HV 203a and HV 203b, that is by opening HV 203a to
feed HCI gas into the reactor and close HV 203b from sending HCI
gas to HCI vent absorption unit.
2. Regulates regulator PIC 101 to keep HCI Distilling Column top at
1.3 bars. Check this pressure through HCI Distlling Column Top
Pressure Recorder PR 211.
Note: Wait for few seconds after each regulation of PIC 101 allow
response from PT 211 to be reflected to PR 211 and shows
on the recorder.
3. Check Gas Treatment Unit water wash column C 100 outlet pH to
justify HCI gas practical for justification.
Note: During S/U period, D 101 sampling to test for HCI gas
presence is not practical for justification.
Reason: Reaction not yet started, no water produced. E 101
couldnt condense pure HCI gas into liquid HCI solution.
4. Once C 100 outlet shows presence of HCI gas in the reaction unit
system, Methanol Evaporator E 102 can be started to introduce
methanol vapor into the reactor for the reaction to progress.
5. Immediately after reaction started:
a) Check reaction pressure, increases compressor P 105
suction rate to keep reactor pressure at 0.5 or 1 bar
b) Increase reaction rate slowly especially the feeding of
methanol into reactor G 100
c) Keep close watch on reaction temperature.
6. When reaction is in progress, and if reaction temperature is too
high, HV 122 can be opened to introduce liquid methanol into
reactor G 100 in order to control the reaction temperature.
Opening of HV 122 will not effects the total flow rate of methanol

36

being injected into the reactor as this flow rate is control by FV

1112.
Note: Regulates steam flow rate into E 102 after opening HV 122
liquid methanol feeding valve, in order to keep E 102
methanol vapor pressure at 3 bars only. Too high pressure
in E 102 may lead to a shut down of plant.
7. Performance of compressor must be keep close watch after
reaction unit is in operation. Adjust suction rate of compressor to
keep reactor pressure all times as at (a) of 5.
8. When reaction unit is under well control, check D 101 condensed
HCI to justify HCI excess of 25%.
a) Increase HCI feed to HCI distillation unit if D 101 condensed
is below 31%.
b) Increased methanol flow rate if D 101 condensate is more
than 31% or else decrease HCI feed to HCI distilling column
if reactor is at its full capacity.
9. Starts pump P 202B once methanol is added into the reactor for
reaction. Regulates LIC 101 to control pumping rate and to
maintain D 101 level at 600mm all times.

37

GAS TREATMENT UNIT

I. Name of Equipments
No
1
2
3
4
5
6
7
8
9
10
11

Code
C 100
C 102
C 102 A
C 102 B
R 107
E 103
E 105
P 101
P 102
P 103 A
P 103 B

Name
Water Wash Column
Caustic Soda Column
78% HSO Column Washing
98% HSO Column Washing
Brink Mist Separator
Recycle 78% HSO Cooler
Recycle Caustic Cooler
C 100 Recycle Pump
C 101 Recycle Pump
C 102 A Recycle Pump
C 102 B Recycle Pump

Instrument
No
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15

Code
TJI 130
LR 110
LAL 110
LAH 110
TJI 141
LR 111
LAH 111
TJI 152
LR 112
LAL 112
LAH 112
LR 122
LAH 122
PDR 107
PDAH 107

Name
C 100 Outlet CHCI Gas Temperature Indicator
C 100 Bottom Drum Level Recorder
C 100 Bottom Drum Low Level Alarm
C 100 Bottom Drum High Level Alarm
C 101 Outlet CHCI Gas Temperature Indicator
C 101 Bottom Drum Level Recorder
C 101 Bottom Drum High Level Alarm
C 102 A Outlet CHCI Gas Temperature Indicator
C 102 A Bottom Drum Level Recorder
C 102 A Bottom Drum Low Level Alarm
C 102 A Bottom Drum High Level Alarm
C 102 B Bottom Drum Level Recorder
C 102 B Bottom Drum High Level Alarm
R 107 Pressure Drop Recorder
R 107 High Pressure Drop Alarm

38

II. Equipments Description and Functions

1.) C 100 Water Wash Column
This unit consists of:
a) An internally glass-lined carbon steel column section
b) An internally glass-lined bottom drum
c) A glass-lined bobbin neck flanged to the column and drum.
Column section
Dimension

Bottom Section
Bobbin Neck

Outside Diameter
Height of column
Outside Diameter
Height of column
Top Flange
Bottom Flange
Height

300mm
4000mm
1200mm
1500mm
300mm
500mm
620mm

The bottom part of the column section is packed with 35mm

PPH pall rings of a length of 2500mm. This is called packed
column section.
A demister is installed on top of the column. A level transmitter
is installed at the bottom drum.
Crude Methyl Chloride Gas Inlet
Crude Methyl Chloride Gas Outlet
Recycle Wash Water Inlet
Recycle Wash Water Outlet
(to recycle pump)
Function

At the bobbin neck

Right on the column top
500 mm above the packed column
section
Right at the bottom

Water is used in this column to absorb methanol vapor,

ZnCI and HCI gas carried by the crude methyl chloride gas.

2. C 101: Caustic Wash Column

This unit also consists of:
a) An internally glass-lined carbon steel column section
b) An internally glass-lined carbon steel bottom drum
c) A glass-lined bobbin neck flanged to the column section and
bottom drum
The unit materials, dimension, packing material, crude Methyl
Chloride gas inlet and outlet, recycle wash liquid (NaOH) inlet
and outlet are all exactly the same as the previous column C
100: Water Wash Column. The only exception is a plunging pipe
sprayer installed on top of the demister use to wash salt crystal
forms on the demister. A level transmitter is installed to the
bottom drum also.

39

Function

Using 20% caustic soda solution recycling by Pump P

102 to absorb any left behind HCI gas from the previous
column.

3. C 102 A: 78% HSO Wash Column

This unit also consists of:
a) An internally glass-lined carbon steel column section
b) An internally glass-lined carbon steel bottom drum
c) A glass-lined bobbin neck flanged to the column section and
bottom drum
The unit materials (i.e internally glass lined carbon steel vessel),
packing materials dimension of bottom drum and bobbin neck,
curde Methyl Chloride gas, recycle wash liquid ( 78% HSO)
inlet and outlet are exactly the same two previous wash column.
The differences are:
1. The column section is shorter, i.e only 3000mm but the
packed column section remains the same as 2500mm.
2. No demister is installed on column top (It is not necessary
up to (..)
The remaining of the sentence was not
printed on the paper.
Function

Using recycle 78% HSO to absorb Methyl Oxide and

most of the water vapor carries by the reaction product
Methyl Chloride gas.

4. C 102 B: 98% HSO Wash Column

Material

Carbon Steel Vessel

Column section

Dimension
Bottom Section

Outside Diameter
Column Height
Outside Diameter
Height of column

350mm
4500mm
600mm
1750mm

The packed column section is right in the middle of the

column section; the packing material is polypropylene pall
rings of 25mm diameter.
Methyl Chloride Gas Inlet
Methyl Chloride Gas Outlet
Recycle Sulphuric Acid Inlet
Recycle Sulphuric Acid Outlet
(to recycle pump)

Below the packed column section

Right on the column top
On top of the packed column section
Right at the bottom of the acid reservoir

40

Function

Using recycle 98% Sulphuric Acid to

absorb any left behind water vapor from
the previous column C 102 A.

5. R 107: Brink Mist Separator

Material

Carbon steel cylindrical vessel

Outside Diameter
500mm
Dimension
Height
2300mm
Internally fix with a Brink Type glass fibre candle
Gas Inlet
At 550mm height
Gas Outlet
Above the candle
Liquid Inlet
Same height as gas inlet
Liquid Outlet
At 400mm height
Function

"Filter" mist of sulphuric acid carries by Methyl Chloride

gas. Methyl Chloride gas coming out from this vessel is
pure

6. E 103: Recycle 78% HSO Cooler

Material
Dimension
Cooling Agent
Liquid to be cooled
Temperature of inlet cooling water
Temperature of outlet cooling water
Temperature of inlet 78% HSO
Temperature of after cooled 78% HSO
Function

Tube Side
Graphite
Shell Side
Carbon Steel
Length
1725mm
Process Cooling Water
78% HSO
31C
32C
36.7C
35C
To cool down recycle 78%
HSO before sending to the
column top, C 102 A for
absorption again.

41

7. E 105: Recycle Caustic Cooler

This is a multi-plates cooler.
Plate Material
Frame Material
Number of plates
Dimension
Cooling Agent
Liquid to be cooled
Temperature of inlet cooling water
Temperature of outlet cooling water
Temperature of inlet caustic solution
Temperature of after cooled caustic
solution
Function

Tirane
Carbon Steel
15 pieces
180mm X 585mm
Process Cooling Water
20% caustic solution
< 31C
> 32C
> 41.2C
< 40C
To cool down recycle caustic
solution before sending to C 101
column top for absorption column
again.

8. P 101: C 100 Wash Water Recycle Pump

Pump

Motor
Function

Pump Material
Graphite
Normal Pumping Rate
5m/hr
Normal Discharge
Pressure
3.7 bars
Maximum Head
21 metres
Motor
3 phase / 50Hz
Horse Power (Hp)
3kW
RPM
1450
To recycle wash water from C 100 bottom drum to the
column top for the absoprtion process.

9. P 102: C 101 Caustic Recycle Pump

Pump

Motor
Function

Pump Material
Graphite
Normal Pumping Rate
5 m/hr
Normal Discharge
Pressure
3.7 bars
Maximum Head
21 metres
Motor
3 phase / 50Hz
Horse Power (Hp)
3kW
RPM
1450
To recycle caustic solution from C 101 bottom drum to
the column top for the absorption process.

42

10. P 103 A: C 102 A 78% HSO Recycle Pump

Pump

Motor
Function

Pump Material
Hastelloy C
Normal Pumping Rate
5 m/hr
Normal Discharge
Pressure
4 bars
Maximum Head
18 metres
Motor
3 phase / 50Hz
Horse Power (Hp)
2.2kW
RPM
1450
To recycle 78% HSO from C 102 A bottom drum to the
column top for the absorption process.

11. P 103 B: C102 V 98% HSO Recycle Pump

Pump

Motor
Function

Pump Material
Hastelloy C
Normal Pumping Rate
5 m/hr
Normal Discharge
Pressure
4 bars
Maximum Head
18 metres
Motor
3 phase / 50Hz
Horse Power (Hp)
212kW
RPM
1450
To recycle 98% HSO from C 102 B acid reservoir to
the column top for the absorption process.

12. P 106: 98% HSO Feed Pump

Pump

Motor
Function

Pump Material
Nicromaz C
Normal Pumping Rate
1 m/hr
Normal Discharge
Pressure
3.5 bars
Maximum Head
Motor
3 phase / 50Hz
Horse Power (Hp)
2.2kW
RPM
2900
To feed 98% HSO storage tank into R 107 Brink Mist
separator for C 102 A & C 102 B uses.

43

GAS TREATMENT UNIT

III Detail Process Description
Gas Treatment Unit is an important section in the process of Methyl
Chloride production, as the quality of the final product totally
depends on a proper and careful control of the process conditions
of this section.
In this section, there are four chemical reagents wash columns and
a mist elimination, namely:
Code
C 100
C 101
C 102A
C 102B
R 107

Components
Water Wash Column
Caustic Wash Column
78% HSO Wash Column
98% HSO Wash Column
Brink Mist Separator

Water is used in the first wash column C 100 to dissolve methanol

vapor and trace of ZnCI completely from the crude product. A
major part of the uncondensed HCI gas is also dissolve by water in
this column.
The second wash column C 101, actually acts as a safety
precaution column. This column uses 20% caustic soda solution to
dissolves any left behind HCI gas from the first column.
In the third column C 102A, 78% HSO removes all Methyl Oxide
formed in the side reaction and most of the water from the crude
product.
The fourth column, 98% HSO Wash Column C 102B, complete the
purification process of the whole unit by removing all the moisture
from the crude product. Methyl Chloride gas comes from the top of
this column is dry and traps in the gas stream.
Pure Methyl Chloride gas comes out from R 107 is then
compressed, liquefied and stored up.
Detail Description of Flow and Process is given below:
1.) C 100: Water Wash Column Treatment Process:
Crude Methyl Chloride, after its gas-liquid phase separation in
Knock Down Drum D 101 enters through gas inlet at the bottom
of the packed column section of Water Wash Column C 100.

44

The crude gas travels up to the column top through spaces

between the pall rings packing while being washed by the water
washed down from column top. As this crude Methyl Chloride
gas comes into contact with the wash water, methanol vapor
and trace of ZnCI that it carries is completely dissolved by the
wash water. Uncondensed HCI gas from D 101 is also almost
completely dissolved.
Liquid stream wash solution then flows down to the bottom
drum of this wash column forming a 5% HCI solution dissolves
with methanol and trace of ZnCI together with it. This wash
solution is then recycled by wash water Recycle Pump P 101
and feeds at a rate of 5m/hr to the top of the wash column again
for the same washing purpose.
Fresh make-up water feeds constantly (rate = 120kg/hr under
normal operating condition, check flow rate through make-up
water rotameter F1-110) into the wash solution recycle line on
the column top in order to maintain the after washed solution at
a constant 5% HCI concentration. This after washed solution is
constantly discharged away to the waste treatment pit where it
is treated (neutralized) and disposed off. The rate of discharge is
equivalent to the make-up water flow rate feeds into this column
at normal conditions.
The discharge line, Tee-out from the Recycle Pump delivery line
is fixed with an automatic level control valve LV 110: This
enables liquid level in the bottom drum to be controlled at half
all the time. Level control of the bottom drum is important
because:
1. Recycle Pump P 101 must be assured of constant liquid
supply in order to feed the column with enough wash
water and also to avoid this pump from running dry which
may lead to its damage.
2. Crude Methyl Chloride gas must be prevented from
bubbling through wash solution in the bottom drum
(when level inside is too high) which causes a high
pressure drop across this wash column.
The Automatic Level Control Valve LV 110 accomplished its
duty of level control in the following way:
1. If liquid level in the bottom drum is low, it will close
automatically and let all wash solution to recycle back to
the column top for washing until liquid level is built up
back to half again.

45

2.

If liquid level in the bottom drum is high, it will open more

to increase the discharge rate of 5% HCI solution to the
waste treatment pit until the liquid level is brought down
to the set level of half in the bottom drum.

High and Low Level Alarm is installed at the bottom drum to

safeguard smooth running of this washing process.
Crude Methyl Chloride gas after water washing, passes
through a demister at the column top which condenses the
moisture the gas carries and enters the second wash column
C 101: Caustic Wash Column for the complete removal of HCI
gas from this crude.
II C 101: Caustic Wash Column Treatment Process
Coming from the previous column, crude Methyl Chloride gas
enters Caustic Wash Column at its gas inlet below the packed
column section. The crude gas then travels up to the column top
through spaces between the pall rings packing of the packed
column section.
Caustic solution feeds at a rate of 5m/hr by Caustic Recycle
Pump P 102 enters the column top and flows down. As this
caustic solution comes into contacts with the crude gas in the
packed column section, any untreated HCI gas from the first
column is immediately (and effectively) absorbed by the caustic
solution.
Caustic solution then flows down to the bottom drum and
recycles back to the column top for absorption again. As the
absorption reaction of HCI gas by caustic solution generates
heat, caustic solution has to be cooled down first in Recycle
Caustic Cooler E 105 before recycling back to the column top.
Unlike the washing process in the first column, caustic solution
after washing crude Methyl Chloride is not continuously
discharged away. It is because the amount of untreated HCI gas
from the previous column C 100 is negligible if its process
condition is under well control. The initial concentration of
caustic solution uses for this column is 20%, it is replaced only
when the free 0H content drops to about 2%. Therefore this is
called a batch-wise process.
Methyl Chloride gas again passes through a demister at the
column top which condenses its moisture and comes out form
this column completely free of HCI gas. It will then enter the

46

third wash column for treatment of Methyl Oxide and water

vapor.
III C 102 A: 78% HSO Wash Column
C 102 B: 98% HSO Wash Column
R 107 : Brink Mist Separator
The working process of these equipments: i.e. C 102A, C 102B
and R 107 are inter-related. They use sulphuric acid feeds into R
107 which then flows to R 102B and R 102A for absorption of
Methyl Oxide and moisture carries by crude Methyl Chloride
gas. The after washed sulphuric acid which has a concentration
of 78% is then send to the weak sulphuric acd storage tank. The
after treatment Methyl Chloride gas which is now pure is send
for compression, liquefaction process and stores up.
Detail Description of the process is given below:
a) C 102A: 78% HSO Wash Column
Crude Methyl Chloride gas enters 78% sulphuric acid
Wash Column C 102A at the gas inlet below the packed
column section. The crude gas travels up through spaces
between the pall rings packing of this packed column
section. 78% HSO Recycle Pump P 103A pumps the acid
from the bottom drum and feed it at a rate of 5 m/hr to the
top of the wash column. This acid flows down to the
bottom drum passing through the pall ring packing and as
it comes into contact with crude Methyl Chloride gas,
Methyl Oxide carries by the gas stream is completely
adsorbed together with most of the water vapor by
sulphuric acid.
The absorption of water vapor by suphuric acid generates
heat, therefore the recycle acid has to be cooled down in
E 103, Recycle HSO before its is fed back to the column
top again.
Absorption of Methyl Oxide and water vapor by sulphuric
acid in this column attains its best efficiency and is also
economical when the washed down acid concentration is
78%. Dilution of the acid by the water vapor it adsorbed is
constantly reconcentrated by make up 98% HSO
supplies from C 102B.
In order to maintain level of sulphuric acid in the bottom
drum at half all the time, 78% HSO is constantly sent to
its storage tank at a controlled rate. Automatic Level

47

Control Valve LV 112 on Pumps P 103A delivery line

performs the duty of controlling the acid level in the
bottom drum. By doing so, Pump P 103A is prevented
from controlling the acid level in the bottom drum. By
doing so, Pump P 103A is prevented from running empty
and caused damages. And also methyl chloride can enter
this column smoothly without being forced to bubble
through the wash liquid and causes high pressure drop
across this column if level of the acid is higher than the
gas outlet.
The Level Control, Recording, and Alarm system of this
column performs exactly the same as in C 100: Water
Wash Column.
Crude Methyl Chloride gas comes out from this column
carries along with its small amount of water vapor but
completely free of methyl oxide, enters the last wash
column C 102b for complete removal of water vapor by
the 98% HSO in this column.
b) C 102B: 98% HSO Wash Column
Methyl Chloride gas enters the gas inlet below the packed
column section of 98% HSO Wash Column C 102B. As in
the previous columns, Methyl Chloride gas travels up
between spaces of the pall rings packing to the column
top. 98% HSO feeds to the column top at a rate of 5m/hr
by Recycle Pump P 103B.
As Methyl Chloride gas comes into contact with the
washed down 98% HSO, unabsorbed water vapor from
the previous column (in small quantity) is completely
absorbed. Acid then flows down to the bottom acid
reservoir and is recycled back to the column top again
continuously. Fresh supply of 98% HSO flows into the
acid reservoir from R 107 Brink Mist Separator outlet line
under a constant flow rate. Same quantity of 98%
sulphuric acid as supplied from R 107 overflows
continuously through the overflow outlet of the acid
reservoir to the bottom drum of C 102A. As there is no
acid discharge line on pump P 103B delivery, 98% HSO
Recycle Pump P 103B is assured of liquid supply.
Therefore only high level alarm is installed in order to
warn fro proper action to be taken to avoid bubbling of
Methyl Chloride gas through this wash column and
causes a high pressure drop across it.

48

Methyl Chloride gas comes out from the column top of

this last water column is considered to be pure except
that some mist of sulphuric acid traps in the gas stream
has to be lastly removed in R 107, Brink Mist Separator.
c) R 107: Brink Mist Separator Treatment Process
Methyl Chloride gas, comes out from C 102B completely
dry and free from other impurities enters the gas inlet of R
107, Brink Mist Separator together with 98% HSO feeds
at a rate of 18kg/hr into CHCI gas line at a Tee- joint
before the gas entrance to R 107.
III Detail Process Description
Methyl Chloride gas after passing through Brink Mist Separator
R 107 is pure and dry. Before its entrance into the Methyl
Chloride Compressor P 105 for compression, its flow rate is
detected (FE 105: Flow Element), measured (FT 105: Flow
Transmitter) and recorded (FR 105: Flow Rate Recorder).
It then enters a Manifold Receiving pipe (the gas reservoir) of
the Crepelle Compressor P 105. The compressor will then
compress the pure Methyl Chloride gas from 0.3 bar pressure to
2,75 bar at first stage compression. The compressed gas is hot
and the temperature is about 110C.
This hot Methyl Chloride gas is then cooled down to 40C in the
compressed gas intercooler before it is compressed in the
second stage.
Second Stage Compression gas brings the Methyl Chloride Gas
to a pressure of 8 bars (maximum=9 bars). The compressed gas
is hot at a temperature of 110C. This high pressure and hot
Methyl Chloride gas is then cooled down to below 40C by
Liquefactor 104 installed on top of the plant. At 40C, Methyl
Chloride liquefies and becomes liquid which is then flows down
by the difference of its static head into Methyl Chloride storage
tanks R 130A & R 130B.
On top of the storage tank, a chiller unit and a Methyl Chloride
Vapor Chiller E 130 is installed. This is to provide a low
temperature (5C) cooling facilities for the Methyl Chloride vapor
from the Storage Tank R 130A & B and also those uncondensed
vapor from Liquefactor E 104. The vapor after chilled will liquefy
again and flow back to the storage tank.

49

At ambient temperature of 35C, pure liquid Methyl Chloride

exerts a vapor pressure of 7 bars in the storage tank. In any
case when this vapor pressure is more than 7 bars, it is an
indication that inert gas like N, SO etc is presence in the
storage tank. Through analysis of the gas composition from the
storage tanks by laboratory, vent valve on top of E 130 may be
opened to vent off these inert gas in order to bring down the
vapor pressure inside the storage tanks back to its normal
pressure of 7 bars.
IV Compression, Liquefaction and Storage
I Name of Equipments
This unit deals with the compression, liquefaction and storage
of pure chloride. The main equipments are:
Code
P 105
E 104
R 103 A & B
P 130
E 130
PV 105

Name of Equipments
Methyl Chloride Compressor
Methyl Chloride Liquefactor
Methyl Chloride Storage Tank
Methyl Chloride Loading Pump
Methyl Chloride Vapor Condenser
Compressor P 105 By-Pass Line Control Valve

Instruments
Code
FR 105
PR 105
PAL 105
TAH 105
PR 104
PAH 104
TJR 103
SAL 116

Name of Equipments
Methyl Chloride Flow Rate Recorder
Compressor P 105 Suction Pressure Alarm
Compressor P 105 High Suction Pressure Alarm
Compressed Methyl Chloride High Temperature Alarm
Liquefactor Pressure Recorder
Liquefactor High Pressure Alarm
Liquified Methyl Chloride Temperature Recorder
Compressor Stopped Alarm

II Equipments Description and Functions

1.) P 105: Methyl Chloride Compressor (Crepelle Compressor)
Nature of Compressor
Normal Compression Rate
Maximum Compression Rate
RPM
Normal Discharge Pressure
Normal Suction Pressure
Motor Horse Power (HP)
Other Facilities

Two stages compressor

312 kg/hr
400 kg/hr
397 RPM - 875 RPM
8 bars, maximum = 9 bars
0.3 bar
30kW
1.) By Pass Gas Cooler
2.) Inter-Stage Gas Cooler

50

Function

To compress pure Methyl Chloride

gas from 0.3 bar to 8 bar

2.) E 104: Methyl Chloride Methyl Liquefactor

Nature
Material
Dimension
Tube Side
Shell Side
Function

Tube and Shell Type Heat Exchanger

Carbon Steel
Length 4.5 metres, Outside Diameter (O.D) = 0.4 metres
Internal Tubes: 4000mm X 4 pieces
24 baffles
To liquefy compressed Methyl Chloride gas using water
as the cooling agent.

3.) R 130 A and R 103 B: Methyl Chloride Storage Tank

Material
Dimension
Length
Outside Diameter
Capacity
Function

Carbon Steel
As liquid Methyl Chloride storage.

4.) P 130: Methyl Chloride Loading Pump

Material
Capacity
Normal Discharge
Pressure
RPM
Motor
HP
Function

Cast Steel (Sealess Pump)

10m/hr
9.5 bars gauge
2900
3 phase X 440 volts X 50 Hz
To load liquid Methyl Chloride from storage tank
R 130A & B into ISO container

5.) E 130: Methyl Chloride Vapor Condenser

Nature
Material
Dimension
Tube Side
Shell Side
Function

Tube and Shell Type Heat Exchanger

Carbon Steel
Length 4500mm, Outside Diameter (O.D) = 200mm
4000mm X
X
Length
36 baffles
Using chill water from the refrigeration unit to cool down
vapor of Methyl Chloride into liquid from storage tanks,
ISO container, Liquefactor. And also vent out inert gas
from the storage and liquefaction system.

6.) PV 105: Compressor P 105 By-Pass Line Control Valve

Service
Function

Control Valve: Pressure Induced

Automatic Control of Suction Pressure of Compressor
P 105

51

V Operation Procedures
Besides the cooling water network of this plant, Gas treatment Unit
is the very first section to put into operation in the process of
Methyl Chloride production. This section is not only important in
quality control of the final product; also it is equally important in
the safe running of Compressor
P 105, Liquefactor E 104 and
storages R 130 A and R 130 B, all of which depends on a good and
propel control of the process conditions of this section.
Followings is a test on operation procedures.
1. Check and make sure that cooling water is fed to Recycle
Caustic Cooler E 105 ( at 5m/hr) and recycle 78% Sulphuric
Acid Cooler E 103 ( at 4m/hr)
2.

Starts up Wash Water Recycle Pump P 101 of Water Wash

Column C 100.
Set Regulator LIC 110 to operate Automatic Level Control
Valve LV 110 to control the waste water discharge in order to
maintain C 100 bottom drum level at 700mm. Check Level
Recorder LR 110.
Feeds make-up water into C 100 column top at 500kg/hr.
Check Flow Rotameter FT 110 to assure the make-up water
flow rate.

3.

Starts up Wash Caustic Recycle Pump P 102 of Caustic Wash

Column C 101.
Check Level Recorder LR 111 of this column to assure of
enough caustic for recirculation by Pump P 102.

4.

Starts up Wash Caustic Recycle Pump P 102 of Caustic Wash

Column C 101.
Set Regulator LIC 112 to operate Automatic Level Control
Valve LV 112 to control 78% HSO discharge rate in order to
maintain bottom drum level of this column ( C 102 A) at
700mm. Check Level Recorder LR 112 to make sure of steel.

5.

Starts up 98% HSO Recycle Pump P 103 B of 98% HSO

Wash Column C 102 B.
Check Level Recorder LR 112 of this column to ensure level
of 98% HSO in the reservoir or C 102 B is at its overflow
point.
Note: Pumps P 101, P 102, P 103 A & P 103 B are started up
simultaneously at the same time.

52

6.

As soon as reaction started, Feeds R 107 Brink Mist

Separator with 98% HSO at 18kg/hr.
Check HSO Flow Rotameter FI 107, to ensure of HSO flow
rate.

7.

Check PDR 107, Pressure Drop Recorder of Brink Mist

Separator R 107. Open R 107 bottom drain valve if LAH 107
comes in.

8.

After reaction started,

a) Check C 100 waste discharge concentration (HCI) and
adjust make up water flow rate accordingly.
b) Check C 101 caustic concentration by titration method;
replace caustic solution if concentration is below 2%.
c) Check temperature of recycle caustic ( TW 151 and TW
161) and also temperature of recycle 78% HSO ( TW
142 & TW 132)
Note: Method of Replacement of Caustic Solution in C 101.
a) Open discharge line isolation valve and discharge
caustic solution to waste treatment until level in
bottom drum of C 101 is at 10%. Check LR 111.
b) Stop discharge to avoid Pump P 102 to run empty.
Close discharge isolation valve.
c) Feeds Caustic from R 101 to original position of
caustic level in bottom drum.

53

IV Gas Treatment Unit: Normal Operation Conditions of Temperature, Pressure and

Level
Column

Description

Temperature
CHCI
gas
column outlet

C 100

Instrument

of
at

Temperature Indicator
TJI 130

Normal
Set Point

40

Actions on Abnormalities
1.) If > 40C, check C 100 discharge HCI.
Increase make up water flow if necessary.
2.) Check HCI excess for reaction. Adjust
HCI to C 201 accordingly.
3.) Check D 101 HCI concentration, temperature
etc.
1.) Check LR 110 of Column C 100 bottom drum
level. Reset LIC 110 if level too high.
2.) Check pressure of other column inlet and other
Compressor P 105 performance.

Pressure of CHCL
gas at column inlet

Local Pressure Gauge

0.46 bars

Level of wash water

in bottom drum

Level Indicator LR 110

700mm

Low level alarm of

bottom drum

Alarm LAL 110

450mm

1.) Increase make-up water flow rate: check

discharge HCI concentration
2.) Reset LIC 110 to bring up level to set point

High level alarm of

bottom drum

Alarm LAL 110

950mm

1.) Increase discharge HCI flow rate.

2.) Reset LIC 110 to bring down level to set point.

Temperature Indicator
TJI 141

35

1.) Check C 100 performance

2.) Check E 105 of foiling, increase cooling water
to E 105 if necessary.

Temperature
CHCI
gas
column outlet

of
at

See Action Below: LAL 110 & LAH 110

1.) Check LR 111 of column C 101 bottom

C 101

Pressure of CHCL
gas at column inlet

Local Pressure Gauge

0.42 bars

Level of caustic
solution in bottom
drum

Level Recorder LR 111

850mm

High level alarm of

bottom drum

Alarm LAH 111

950mm

Temperature
CHCI
gas
column outlet

of
at

Temperature Indicator
TJI 152

drum level. Reset LIC 110.

2.) Check pressure of other column and also
compressor P 105 performance.
See Action Below: LAH 111
1.) Bring down level of caustic solution in
the bottom drum.

40

1.) If > 40C, check Recycle 78% HSO Cooler E

103
2.) Increase cooling water flow rate to E 103 if
necessary.
1.) Check bottom drum level, avoid flooding and
bubbling of CHCI gas
2.) Check pressure of other column and also
Compressor P 105 performance.

Pressure of CHCI
gas at column inlet

Local Pressure Gauge

0.38

Level of 78% HSO

in bottom drum

Level Recorder LR 112

700mm

Low level alarm of

bottom drum

Alarm LAL 112

450mm

1.) Reset LIC 112 to bring up level to set point.

2.) Check make-up flow rate HSO level in R 107

High level alarm of

bottom drum

LAH 112

950mm

1.) Reset LIC 112. Increase discharge 78% HSO

to bring down the level to set point

C 102A

See Action Below: LAL 112 and LAH 112

54

Description

Instrument

Normal
Set Point

Pressure of CHCI
gas at column inlet

Local Pressure Gauge

0.34 bars

1.) Check pressure drop of R 107

2.) Check HSO level in R 107

Level of 98% HSO

in acid reservoir

Level Recorder LR 122

1250mm

See Action Below on LAH 122

Alarm LAH 122

1500mm

1.) Check over flow line to C 102 A for choke or air

lock.
2.) Drain to check for sulphate deposit. (Take safety
precaution)

Pressure Recorder
PDR 107

150m HO
column

See Action Below

Alarm PDAH 107

500mm
HO
column

Clean Brink Filter after plant major shut down for

maintenance.

Column

C 102B

High level alarm of

98% HSO in acid
reservoir

R 107

Pressure
drop
across brink mist
separator
High pressure drop
alarm of brink mist
separator

Actions on Abnormalities

IV Compression, Liquefaction and storage: Operation condition, Alarm etc.

Equipments

Methyl
Chloride
Compressor
P 105

Description

Instruments

Normal Set
Point

Methyl Chloride
Compressor P 105

Flow Rate
Recorder FR
105

150 kg/hr
to
40 kg/hr

Record accordingly to actual production rate.

Suction Pressure
of Compressor

Pressure
Recorder PR
105

0.3 bar

1.) Check production rate.

2.) Check compressor performance.
3.) Check Compressor By Pass Control Valve
performance.

Compressor Low
Suction Pressure
Alarm

Alarm PAL 105

Check by pass valve operation.

Compressor High
Suction Pressure
Alarm

Alarm PAL 105

0.5 bar

1.) Check Liquefactor E 104 performance and

compressor discharge pressure.
2.) Degass inert if inert content high.
3.) Check FR 105 on Methyl Chloride flow rate.
4.) Check By Pass Control Valve performance

Compressor High
Discharge Gas
Temperature
Alarm

Alarm PAL 105

120C

1.) Check intercooler performance, i.e cooling

water temperature

Compressor Stop
Signal SAL 116

PSL 116 Oil Pressure Low

FSL 116 Cooling H0 Flow Low
PSLL 116 Suction pressure Low
PSHH 116 Discharge Pressure High
TSHH 116 Discharge Temperature
High

Liquefactor
Pressure
E 104

- 0.1 bar

Comments and Action on Abnormalities

Liquid Methyl
Chloride
temperature

Pressure
Recorder
PR 104
Temperature
Recorder
TJR 103

Top up compressor oil before start up again.

Rectify cooling water system before start up
again
Check compression and liquefraction unit
Check compressor cooling system

9 bars
(maximum)

1.) Check cooling water of E 104

2.) Degass inert if inert contact high

40C
(maximum)

Check E 104 performance

55

HCI Vent Treatment Unit

I. Name of Equipment
No
1
2
3

Code
E 210
C 210
P 210

Name
HCI Gas Isothermal Absorber
HCI Tail Gas Scubber
Vent Gas Blower

Instrument
No
1
2
3
4

Code
TR 400
TR 401
TAH 401
FI 401

Name
E 210 Product Temperature Recorder
C 210 Scrubbed Water Temperature Recorder
C 210 Scrubbed Water High Temperature Alarm
C 210 Scrubbing Feed Water Rotameter

II Equipment Description:
1. E 210: HCI Gas Isothermal Absorber
Material
Dimension

Function

a.) Absorption Tubes are made of graphite

b.) Cooling water jacket is made of carbon steel
a.) Absorption tubes: Diameter 24mm, Length 2000mm
b.) Cooling water jacket: Diameter 370mm, length: 2000mm
a.) To absorb HCI gas from HCI Distilling Column 201 (during plant
start up or shut down)
b.) To absorb HCI fume from strong HCI Buffer Storage
Tank R 201 or fume form Azeotropic HCI Receiving Tank R 202

2. C 210: HCI Tail Gas Scrubber

Material
Dimension
Function

PVC, Internally packed with 1500mm, length of PP pall rings of 25mm

PVC Pipe: Outside Diameter 150mm, length: 2000mm
To absorb unabsorbed tail gas from E 210

3. P 210: Vent Gas Blower

Material
Function

Porcelain Type Blower

To vent off waste gas from C 210

III Detail Process Description

During Methyl Chloride plant start up process before HCI Distilling
Column C 201 attains its optimal process condition to give > 96%
HCI gas for reactor, Inter-operating Valves HV 203B is opened to
send the early HCI gas from C 201 to the HCI vent Treatment Unit.
When plant shut down due to power failure or powe dip, excess HCI
gas is also sent to this unit.

56

HCI fume from HCI Buffer Storage Tank R 201 and Azeotropic HCI
Receiving Tank R 202 is also sent to HCI Vent Treatment Unit for
absorption.
The HCI gas (or fume) enters the top of Isothermal Absorber E 210.
Weak HCI (20% Azeotropic HCI) send by Pump P 202 enters
sideway to the absorber top. These gas and liquid flows down to
the bottom of E 210 through the graphite tubes at the same time for
absorption of gas by weak acid to take place. This acid will then
flow back to R 202 and pump away for further reconcentration in
the HCI plant.
Unabsorbed HCI gas is separated at the bottom separator of E 210
and flows up to the Tails Gas Scrubber, C 210. This tail gas travels
up through the packed column of C 210 and is absorbed by pure
water flows down from the top of the scrubber. The weak scrubbed
solution then flows to the top of E 210 for absorption again. Other
gases are vent off to the atmosphere by Vent Gas Blower P 120.
HCI Vent Treatment Unit Operation Condition and Alarm:
Equipments
E 210

C 210

Instruments

Normal
Set Point

Comments and Action on Abnormalities

E 210 Product
Temperature Record

35C

1. Check cooling water temperature for the absorber

2. Check weak acid temperature
3. Choke up of absorption tubes
4. Absorption liquid not enough (Increase flow rate)

C 210 Scrubbed
Solution Temperature

35C

1.) If high temperature: Increase feed water flow rate

Scrubbed Solution High

Temperature Alarm

> 40C

Increase feed water flow rate

Feed Water Rotameter

Adjust flow rate of feed water to C 210 according to

production rate.

V. Operation Procedures
1. Start up Vent Gas Blower P 210
2. Feed C 210 with pure water
Adjust water flow rate (Rotameter FI 401) in accordance to
the HCI gas rate from HCI Distilling Column C 201 during
plant start up or shut down.
3. Check TR 401 of scrubbed water temperature.
Increased scrubbing water flow rate if temperature of
scrubbed water is too high
4. Maintain E 210 product concentration at below 34%. Increase
scrubbing water feeds into C 210 if E 210 product
concentration is too high.
5. Keep observe on level of R 202.

57