R-22 Final

DEPARTMENT OF CHEMICAL ENGINEERING
PROJECT :- UNDERSTANDING THE REFRIGERANT GAS MANUFACTURING PROCESS
INTRODUCTION
Chlorodifluoromethane (R-22)
Chlorodifluoromethane
or
difluoromonochloromethane
is
hydrochlorofluorocarbon (HCFC). This colorless gas is better known as HCFC-22, or R22. It is commonly used as a propellant and refrigerant. These applications are being
phased out in developed countries due to the compound's ozone depletion potential
(ODP) and high global warming potential (GWP), although global use of R-22
continues to increase because of high demand in developing countries. R-22 is a
versatile intermediate in industrial organofluorine chemistry, e.g. as a precursor to
tetrafluoroethylene. R-22 cylinders are colored light green.
Chlorodifluoromethane
IUPAC name-Chlorodifluoromethane
Other nameDifluoromonochloromethane,
Monochlorodifliuoromethane, HCFC-22, R-22,
Genetron 22, Freon 22, Arcton 4, Arcton 22, UN
1018,

PROPERTIES
Molecular formula CHClF2
Molar mass
86.47 g/mol
Appearance
Colorless gas
Density
3.66 kg/m3 at 15C, gas
Melting point
175.42 C (283.76 F; 97.73 K)
Boiling point
40.7 C (41.3 F; 232.5 K)
Solubility in water 0.7799 vol/vol at 25 C; 3.628 g/L

log P
1.08
Vapor pressure
908 kPa at 20 C
kH
0.033 mol.kg-1.bar-1
Structure
Molecular shape
Tetrahedral
Hazards
R-phrases
R59
S-phrases
S23 S24 S25 S59
Main hazards
Dangerous for the environment (N), Central

nervous system depressant, Carc. Cat. 3
Autoignition
temperature
632 C
PHYSICAL PROPERTIES

Property
Value
Density () at -69 C (liquid)
1.49 g.cm3
Density () at -41 C (liquid)
1.413 g.cm3
Density () at -41 C (gas)
4.706 kg.m3
Density () at 15 C (gas
3.66 kg.m3
Specific gravity at 21 C (gas)
3.08 (air = 1)
Specific volume () at 21 C (gas)

Density () at 15 C (gas)
0.275 m.kg1
Triple point temperature (Tt)
-157.39 C (115.76 K)
Critical temperature (Tc)
96.2 C (369.3 K)
Critical pressure (pc)
4.936 MPa (49.36 bar)
3.66 kg.m3
0.9384 MPa (9.384 bar)
Vapor pressure at 21.1 C (pc)

Critical density (c)
6.1 mol.l1
1
Latent heat of vaporization (lv) at 233.95 kJ.kg
boiling point (-40.7 C)
1
1
Heat capacity at constant pressure 0.057 kJ.mol .K
(Cp) at 30 C (86 F)
Heat capacity at constant volume (Cv) 0.048 kJ.mol1.K1
at 30 C (86 F)
Heat capacity ratio () at 30 C (86 1.178253
F)
Compressibility factor (Z) at 15 C
0.9831
Acentric factor ()
0.22082
Viscosity () at 0 C
12.56 Pa.s (0.1256 cP)

R-22 is prepared from chloroform:
HCCl3 + 2 HF HCF2Cl + 2 HCl

An important application of R-22 is as a precursor to tetrafluoroethylene. This
conversion involves pyrolysis to give difluorocarbene, which dimerizes
2 CHClF2 C2F4 + 2 HCl

The compound also yields difluorocarbene upon treatment with strong base and is
used in the laboratory as a source of this reactive intermediate.
The pyrolysis of R-22 in the presence of chlorofluoromethane gives
hexafluorobenzene.

APPLICATION OF R-22
Refrigerent in
Room air conditioners
Central chillers
Packaged airconditioners
Commercial and industrial
refrigeration units
Returnables: 5 kg, 61
kg, 825kg
Net cylinders, isotanks
Non-returnables:13.6
kg and 22.7 kg
Net cylinders
HCFC 22
PTEF grade
Raw material in the manufacture of
fluoropolymer resins
Isotanks

PROCESS DESCRIPTION
Products Manufactured :
Name plate capacity
Floron-22
F-22
This plant is divided into to 6 sections.
Feed section
Reaction section
Low Pressure System
Distillation section
Intermediate Tank form
Main Tank Form
36 TPD

BLOCK DIAGRAM OF PLANT
T10
2
T-101
REACTOR
T-103
T-104
P.CAUSTIC
E10
4
R-22
SEC.
TOWER
CAUSTIC
HOLD
TANK
T-133
COLUMN
T-112
MINI
T-105
C
O
L
U
M
N
DRYER
H2SO4
BIG
TOWER
Compressors
ALUMINA
DRYER

F-22 operation Brief Process Description

Chemistry:
F-22 is produced by the liquid phase Catalytic reaction of Chloroform (CHCl3) and
Anhydrous Hydrofluoric acid (AHF) at 10Kg/cm2 pressure and 58C temperature.
The catalyst used is Antimony pentachloride.
Chemical Reactions:
1) Catalyst preparation:
SbCl3 + Cl2 SbCl5
(Antimony pentachloride)
2) HF + SbCl5 SbCl4F + HCl
(Antimony Monofluorotetrachloride)
3) SbCl4 F+ CHCl3 SbCl5 + CHCl2F
(Dichloro Monofluoromethane) F-21
4) SbCl4F+ CHCl2F SbCl5 + CHClF2
(Monochloro Difluoromethane) F-22
5) SbCl4F + CHClF2 SbCl5 + CHF3
( Trifluoromethane) F-23

Reaction products (F-23, F-22 and HCl) stream from the reaction system
enters into low pressure system after pressure let down.
The gas stream first enters into HCl absorption system where HCl gas gets absorbed
into water and produces 30% HCl. Then the gas stream passes through a two stage
Caustic scrubbing system where residual acidity in the gas stream gets removed. Gas
stream from the outlet of Caustic scrubbing system enters into H2SO4 scrubbing
system, where moisture from the gas stream is removed. Finally, gas stream from
the outlet of H2SO4 scrubber passes through two stage Alumina dryer, where H2SO4
mist gets removed. The gas stream is compressed and fed into two stage distillation
section for products separation. In the first distillation column F-23 gets separated
and bottoms of first distillation flows into second distillation column. High boiling
compounds are separated and F-22 product is taken out from top of the column as
product.

HF FEED SYSTEM
Fresh HF is fed from the HF storage tank located adjacent to the process structure via
positive displacement diaphragm Pump (P101 A, B & C). One pump can deliver 12Kg/
minute (max) flow. Depending up on plant capacity another pump to be operated. A
remote shut-off valve (XCV-30) is located at the HF tank out let which can be
operated from the Control Room or in the field nearby. This valve is to be activated
by the operator in case of emergency to stop flow to the diaphragm pump (valve fails
closed in power failure).
Flow control of the diaphragm pump is done by pneumatic stroke length adjuster
operated form the Control Room. The flow measurement is accomplished by a Mass
Flow meter (FE-60).
The fresh HF feed flows into an Inconel-600 jacketed vaporizer (E-103). The
vaporizer is operated with 6barg steam to boil the incoming HF and convert it to
vapor. A pressure transmitter (PT-51) indicates the vaporizers pressure and a
temperature transmitter (TE-55) indicates the vapor outlet temperature. Both are
displayed in the Control Room.
The vapour flow of HF continues to the Reactor through a TFE lined pipe.
10

AHF Feed
Storage Tank
( U -281C )
Steam
E
1
0
3
Drain XCV
Steam
R-22
Reactor
XCV 30
FIG:- HF FEED SYSTEM
11

CHLOROFORM FEED
CHCl3 is fed separately from storage tank U-202 of 130MT capacity using pumps
102A/B or P-102C/D. At a time one set of pumps will be in operation and they work
in series.
Flow measurement of CHCl3 feed is accomplished by a Mass Flow Meter (FE-52) and
is controlled through FIC-52. The feed is first preheated through a steam pre-heater
(E-108) and comes out at 135o C before injecting into the reactor feed line. 3barg
steam is used in the pre-heater for heating organics.
Steam
Micromotion
Micro
Organic
Filter
U-202
Pre heater
Condensate
P-102 A/B & C/D
R-101
XCV 58
FIG:- CHLOROFORM FEED SYTEM
12
FCV 52

CHLORINE FEED SYSTEM

Chlorine is fed into the Reactor to maintain Antimony Catalyst Tri-valent to less than
5%. Chlorine is fed form a ton-cylinder using the cylinder bottom outlet (as liquid).
For R-22 operation, high pressure Nitrogen is used for padding of tonner at about
10barg will be required. Chlorine should continuously be fed to the Reactor at about
2 -3Kg/hr.
Every Tuesday Catalyst is analyzed for trivalency and Chlorination is discontinued if
trivalency is reported less than 5%. Chorination is resumed after lapse of two days.
The chlorine cylinder is weighed on a scale (W101) and the weight value will be used
in determining and adjusting the feed rate. A chlorine leak monitor is located nearby
and an alarm would be sounded if it detects a leak. An emergency chlorine cylinder
repair kit is provided to temporarily stop the leak (within the capability of the repair
kit see chlorine cylinder repair kit manual for detail and instruction).
13

Nitrogen from CMS

Plant
FCV 59
Padding Tube
XCV
CHLORINE TONNER
To XCV-57
PT
WI 53
FIG:- CHLORINE FEED SYSTEM
14

REACTOR AND CATALYST STRIPPER SYTEM

FOR F-22 PRODUCTION
The Reactor (R101) is 4 6 I.D x 8 6 T/T, Inconel 600, and has a carbon steel steam
jacket. The Reactor is designed to operate with the following quantity of catalyst:
Weight of SbCl3
charged
Catalyst weight after

chlorine activation
3.2 MT
4.2MT
Expected operating weight

with organic
6.0MT
The reactor content weight (load cells) is displayed in the Control Room.
Fresh HF vapour and CHCl3 liquid are premixed in the TFE lined feed pipe before
entering the Reactor at the bottom. The outlet stream from the Reactor is a vapour
containing F-22, F-23, HCl, HF, Cl2, and Antimony Catalyst.
For F-22 production, the reactor level and weight are essentially constant with the
reactor content rich in organics. 6 bar steam is fed to the reactor jacket to maintain
the reactor content between 58C - 60C. The steam flow is controlled and displayed
in the Control Room. For reactor cool down or shutdown, cooling water valves from
the Control Room (power is needed to remotely operate these valves).
15

Product vapor form the reactor proceeds to the catalyst stripper (T-101) for
catalyst removal. The catalyst stripper is 18 diameter & 64 tall. The upper
2/3 section is carbon steel with stainless packing and the lower third
section is Inconel 600 with stainless packing. The Catalyst stripper has three packed
beds. Top bed has 1 S.S pall rings, middle bed has 2 S.S pall rings and bottom
bed has No # 2 S.S pall rings. The catalyst is removed by refluxing with organics
generated from the Catalyst Stripper Condenser (E-101). The condenser is operated
with -10C R-30 circulating brine and the brine flow is displayed and regulated in the
Control Room. Catalyst along with high boiling organics flows into the Reactor.
For F-22 production, Reboiler is isolated and not used. Recirculation catalyst in F-22
operation traditionally does not provide any improvement in HF utilization.
In order to maintain the catalyst activity, chlorine is periodically fed into the Reactor
to maintain SbCl3 to the active SbCl5. The catalyst activity is determined
analytically by withdrawing a sample from the reactor. Catalyst fumes at the time of
sampling is absorbed into CAS (Central Absorption System) gets scrubbed.
16

R-22 REACTOR LINE UP WITH CATALYST STRIPPER
PCV 89
R-101
XCV-106 A
17

HCL ABSORBER SYTEM
The heart of the HCl Absorber system is a 440 ft2 Karbate Falling Film Absorber /
Exchanger (E104). This unit, also named Alberger, is expected to absorb up to 78% of
the incoming acid and to remove the bulk of the heats generated. The remainder of
the gas is then sent to an 18 dia x 20 ht., TFE packed with 12 thick demister Tail
Tower (T-102) where fresh water flows countercurrently to absorb the acid. This Tail
Tower operates adiabatically without any heat removal, thus the resulting acid
temperate is limited to 180F with a corresponding acid strength of about 11% HCl.
This hot and weak acid solution then flows to the Alberger where it will be used to
absorb the incoming HCl gas to make 32.5% HCl solution.
The strong acid from the Alberger into the Pump Tank (U-104) by gravity. It is then
pumped
(P-105 A&B) over to a rubber lined acid storage tank. To prevent organics
from attacking the rubber liner of the storage tank, an organic Trap Tank (U-105) is
installed ahead of the storage tank to accumulate any organics which would separate
from the acid. The Trap Tank should be bled down periodically to remain effective.
To stabilize the Alberger operation against periodical feed upsets and turn down
operations, strong acid from the pump tank is circulated over the Alberger. This
mode of operation improves the heat removal but lowers the acid absorption
capacity. The Alberger has been sized to take account of this sized to take account of
this mode of operation.
18

TO LP
Water
PCV-89
T10
1
E104
HClA
bsor
Water
Water
U104
HCl MTF
U203/204/
LCV 127
P-105A P-105B
FIG:- HCL absorbing system
19
T1
0
2

CAUSTIC SCRUBBER SYSTEM

The caustic scrubber system is designed to remove the remainders of the acid and
chlorine which were not absorbed in the HCl Absorption system.
The system consists of two packed towers in series. The primary Caustic Scrubber is
18 dia. x 16 ht, carbon steel with 3 SNOWFLAKES polypropylene packing ; the
secondary caustic scrubber is 18 dia x 19 ht., carbon steel with 3 SNOWFLAKES
polypropylene packing and a 12 thick demister. The acid removal is done by
circulating (P-106 A, B & C) 5% caustic solution in F-11/12 production and 3% caustic
solution in F-22 production over the scrubbers, counter currently to the Refrigerant
gas flow.
In F-22 production, higher concentration of caustic would lead to precipitation of
NaF (Sodium Fluoride) and choke packing / pipe lines.
The heats generated in the absorption is removed by double pipe heat exchangers
(E-105, E-106), one for each scrubber. The Heat exchangers operate with -5C CaCl2
brine. Brine circulation through the cooler is kept opening F-22 production. During F11/12 production, brine supply & return valves are kept closed to prevent F-11
condensation in Caustic solution.
When the caustic strength has reached below 1%, the spent caustic solution is
drained out from the pump Tanks (U-106, U-107) and refilled with a new batch of
caustic. The operation is done manually approximately twice a shift for the
primary, and once a shift for the secondary.
20

Level sight glasses mounted on each pump tank will be used to gauge the
make-up operation..
DIAGRAM OF CAUSTIC SCRUBBING SYSTEM
Dilute
Caustic
Preparation
Tank
T
1
0
3
( U - 129 )
T10
4
brine
brine
T-
brine
U-106
P-106A
U-107
P-106C
E
1
0
6
P-106B
21
To
H2SO4 TOWER

SULFURIC ACID SCRUBBER AND ALUMINA

DRYER SYSTEM
The sulfuric Acid and Alumina Drying system is designed to remove the moisture and
trace of acidity from the crude Refrigerant gas. The sulfuric scrubber tower (T-105) is
18 dia x 19 HT, carbon steel with 2 polypropylene pall rings as packing and a 12
thick demister. The scrubber is followed by an mini Alumina Dryer and a big Alumina
dryer (T-106),
24 dia x 10 ht, filled with approximately 500Kgs of Alumina
desiccants.
The bulk of the moisture removal is done by circulating (P-107 A& B) 98% sulfuric
acid solution over the scrubber counter currently to the incoming Refrigerant gas.
Acid circulation rate through the tower is 8m3 / hr. The heat generated in the drying
process is removed by a water cooled heat exchangers (E-107). When the sulfuric
acid has diluted to 92% strength, the spent acid is pumped out from the pump tank
(U-108) and refilled with a new batch of fresh acid. The operation is done manually
approximately once a shift. Level sight glass mounted on the pump tank will be used
to gauge the make-up operation. The pump tank also contains a high level switch to
automatically stop the fresh acid flow if overfill has occurred.
The crude Refrigerant gas from the sulfuric acid scrubber is sent to the Alumina
dryer to remove any residual moisture and acidity that have gotten through. Under
normal operation, each desiccants charges in mini Alumina dryer should last more
than two months and in big Alumina dryer should last more than six months.
22

VENT
H2SO4
KNOCK
OUT POT
MINI ALUMINA
DRYER
BIG ALUMINA
DRYER
GAS
COMPRESSO
FROM
SECONDARY
CAUSTIC TOWER
C.W O/L
ACID COOLER
H2SO4
PUMP
TANK
C.W I/L
P - 107A/B
23
CRUDE

CRUDE GAS COMPRESSOR SYSTEM

The crude Refrigerant gas, free of moisture and acidity, is compressed from near
atmospheric condition to about 6.5Kg / cm2 in F-11/12 operation before sending
over to T-112 column for final purification operation. 9Kg / cm2 in F-22 operation
before sending over to T-113 column for final purification operation.
The Refrigerant gas first flows into a 5 dia x 6 L crude gas surge tank
(U-109)
before going to the compressor. The surge tank provides a 1 minute surge capacity to
enable handling of process upset. The compressor (P-110A / B) is a reciprocating,
positive displacement, and non-lubricated oil free compressor. Because of the
limited turndown capability of this type of compressor, partial capacity control is
accomplished by recirculation the hot discharge gas back to the suction of the
compressor (via the surge tank ) using PV-199.
For F-22 operation, the compressed gas is passed through a de-super heater and
condenser and gets condensed in the crude gas condenser (E-109) using -5C CaCl2
brine. This step is necessary in order for the downstream distillation column to
separate F-23 from the product. Crude gas compressors;
24

DIAGRAM OF CRUDE GAS COMPRESSOR
BRINE
I/L
REWORK / SUCKBACK
FROM BIG ALUMINA

DRYER
BRINE
O/L
PCV-199
SURGE
C.W I/L
TANK
TANK
CRUDE GAS
COMPRESSOR
25
DISTILLATION
COLUMN

DISTILLATION COLUMNS SYSTEM

The order of purification For F-22 Production as follows:
The crude refrigerant gas from the compressor is first condensed in the crude gas
condenser and sent to T-113 column to separate F-23 from the product. F-23 vapor
overhead containing an equilibrium amount of F-22 is purged to scavenger
condenser (E-112). This condenser lowers the F-22 content in the F-23 purge stream
before letting it exit to the T-123 column. The bottom stream from the column
containing only F-22 and a small amount of F-21 and Chloroform is pumped through
P-109 A/B and sent to T-112 column. To achieve proper pump operation , the
bottom stream is pre-cooled with a double pipe exchanger (E-117) before the pump
suction. T-112 column separates the pure F-22 product overhead . The column
bottom stream, containing mostly F-21 and chloroform is transferred to rundown
tank.
In T-112 column, reflux is provided by the condenser (E-110) operating with Cooling
water. The reflux is accumulated in reflux drum (U-110) and it is pumped through P108 A / B into column as reflux and day tank as product. The column boil up is
provided by the reboiler (E-113) operating with 6bar steam.
26

T-112 Column description: This column has five packed beds with liquid re-distributor at
every bed. Column dia is 18. Three beds from top have 1 S.S IMTP packings and
remaining two beds have 1 S.S IMTP packings
27

T-113 Column description: This column has three packed beds
with packing of 1
S.S IMTP. Each packed bed is provided with liquid distributor. Column dia is 12.
28

T-123 COLUMN ARRANGEMENT

To Surge
Tank
R-23 VENT
E-123
R-22
To T-113
Column
29

RUN DOWN TANK SYSTEM

The purpose of the run down tanks is to temporarily store in-process material from
the distillation column when the production mode is being switched over.
U-116 stores F-22 in-process material
Each respective Run Down Tank (U-115, U-116) is 5 dia. x 10 T/T and equipped with
heating panels (E-115, E-116). During switchover, the in-process liquids from the
distillation column are transferred to the run down tank. Any residual process
materials starting from the crude gas surge tank are evacuated with the Crude Gas
Compressor to about 10 Hg vacuum, condensed with crude gas condenser E-109
and then sent to the run down tank for temporary storage.
On start-up of the next operating mode, materials from the respective run down tank
are sucked back in vapor form through LP system into the distillation columns. The
heating panels are used to warm up the materials in the run down tanks to build
pressure to assist the suck back
30

DAY TANK STORAGE SYSTEM

Each product (F-22) has three day tanks (U-117 through U-125).
Product
F-22
Tanks
Dryer
U -123, U-124 & U-125
T-118 & T-119
Pump
P-119
Each set of day tanks shares a common pair of dryers and a common transfer pump.
P-117B Corken pump is used for recycling F-11 into F-11/12 Reactor for obtaining higher F12 / 11 ratio.
When a day tank is filled, the product is circulated through the dryer to remove acidity and
moisture, and to thoroughly mix the content. It is then sampled and transferred to the
MTF(Main Tank Farm) after QA approval.
In case, high moisture product or low purity material is required to be transferred to MTF,
filling to be stopped prior to transfer.
After completing the transfer product, start circulation of the tank and after four hours of
circulation, material of particular MTF to be analyzed for all the quality parameters. Material
to be released for filling after getting QA approval only.
31

VENT SCRUBBING TANK

This Tank of 20MT capacity contains 5-8% caustic solution.to 60% of its
volume. The safety relief of following system are connected with vent scrubber
tank.
L.P.System
Reactors
Catalyst Stripper Reboiler
Catalyst Hold Tank
Chlorine Tonner
HF Vapourizer
.Gases from safety relief gets into tank through sparger and bubbles through
caustic solution. Acidity gets removed and non condensable gases gets vented in to
atmosphere.
Also during regeneration of R-11/12 & R 22 catalyst , regenerated production also
routed in to this tank to trap acid compounds. Concentration of this tank is checked
periodically or as and when required and topped up accordingly.
VENT GASES
CAUSTIC SOLUTION
SPARGER
32

NATIONAL
GrAde r-22 production:
Minimise level of T-112 Reboiler and dump its contents into Rundown tank.
Bring down temperature difference between T-112 Reboiler and First bed bottom
temperature to less than 10 degree Cel. When the temperature goes beyond 10 0C,
drain the reboiler contents into a tonner / rundown tank
Increase T-112 reboiler level upto 75-80 %
Increase T-112 Reflux (normally 30-32 LPM) analyse reflux purity for NATIONAL
SPECIFICATION OF REFRIGERANT R22 (MONOCHLORODIFLUOROMETHANE (CHClF2)

(CUSTOMIZED FOR NATIONAL REFRIGERANT)
S.No.
PARAMETER
UNIT
RESULTS
PURITY, w/w, Minimum
99.9
WATER CONTENT, w/w, Maximum
Ppm
10
HIGH BOILING/NON-VOLATILE RESIDUE, v/v, Maximum
0.01
PARTICULATE/SOLIDE
Visually
No matter
clean to
Pass
5
ACIDITY, as HYDROCHLORIC ACID (HCl), w/w, Maximum
CHLORIDE IONS, as Cl , w/w, Maximum
NON-ABSORBABLE GASES IN VAPOUR PHASE, v/v, Maximum %
1.5
HCFC-31, w/w, Maximum
Ppm
HCFC-21, w/w, Maximum
Ppm
10
10
CFC-12, w/w, Maximum
Ppm
500
11
HFC-32, w/w, Maximum
Ppm
100
33
Ppm
1.0
Ppm
NIL

Fresh Catalyst preparation
Procedure for Charging of Antimony Trichloride (SbCl3) into Reactor:

Required number of Carbuoys to be arranged near reactor. Using wooden hammer,
gently tap carbuoy to break lumpy material.
Check inside the reactor for presence of any moisture / foreign substance and
ensure Reactor is clean. Close the Reactor bottom valve.
Charge required amount of Catalyst into reactor. If the carbuoy contains water or
yellow substance, isolate them. They are not to be charged into reactor. After
charging every 500Kg of SbCl3, cross check weight increase with load cell indication.
After completing charging of Catalyst, box up the Reactor without any delay to avoid
moisture entry.
Reactor to be leak checked at 10b pressure with Nitrogen.
Procedure for Chlorination of Antimony Trichloride to make it Antimony

pentachloride
Heat the reactor gradually to bring solid SbCl3 into molten stage. Stop heating after
getting Reactor temperature of 70C.
34

Charge cooling water into Reactor jacket. Start Chlorination @60Kg / hr.
Since, this reaction is highly exothermic, initially, temperature will shoot up
very fast. Reactor temperature should not be allowed to cross 80C.
Temperature to be controlled with the help of cooling water.
After passing required amount of Chlorine, Catalyst sample to be taken from the
Reactor to check the content of un-reacted Antimony trichloride. If it is in the range
of 3%, no need to add further chlorine. Otherwise, depending up on trivalency,
calculated amount of Chlorine to be added.
Cool the Reactor, and add calculated amount of organics ( CTC in case of 11/12 and
CFM in case of F-22). After adding organics dip to be taken to determine vapor space
available
ON LINE CHLORINATION OF CATALYST
R-22 Catalyst:
In R-22 operation , continuous chlorination is required to convert SbCl3
formed during reaction into SbCl3.
SbCl5 +H2O
SbOCl3 + 2 HCl
SbOCl3 + CHCl3
SbCl3 + COCl3 + HCl
SbCl3 + Cl2
SbCl5
35

Hence, continuous chlorination is required to maintain trivalency (Sb +++

~ 5%)
Chlorine requirement for R-22 Mode is 20.23(X-5) where X is the %of Sb+++
Chlorination Procedure:
Chlorine tonner padding
Ensure 15 b Nitrogen is available at ISBL

Line up Nitrogen upto PCV 59 (Nitrogen pressure control valve)
Open Nitrogen valve at tonner.
Take Nitrogen pressure through PCV 59.
Reset Padding XCV ( it is reseted when Nitrogen pressure is above 10 Kg/Cm2)
Open XCV down stream inlet valve and start Nitrogen padding into tonner.
Ensure Tonner pressure is in increasing trend(as per PT-54)
When tonner pressure reaches desired value i.e.around 14 Kg/Cm2, isolate
valve at tonner and isolate XCV down stream & close PCV-59
[ PCV 59 closes itself when PT-59 (Nitrogen line pressure transmeter) reaches
14.0Kg/Cm2
padding line XCV also gets closed.
36

CHLORINE FEED INTO REACTOR
Ensure chlorine tonner pressure is 2 Kg/ Cm2 more than HF Vaporiser/

Reactor pressure.
Line up Chlorine upto XCV-57 (Chlorine line XCV)
Start chlorination by opening downstream manual valve of XCV-57. Chlorine flow is
to be adjusted to 2-3 Kg/hr by throttling the manual valve.
Catalyst life and when to go for Catalyst replacement.
F-22 Catalyst life: International norm is 1 MT of SbCl5 (Antimony Pentachloride)

produces 1500MT of F-22.
With 3.2MT of SbCl5 (Antimony Pentachloride) available in Reactor, it can produce

6300MT of F-22.
Moisture in raw material ( Chloroform & AHF), High boiling impurities in Chloroform
and operating parameters would significantly influence the life of Catalyst.
During production process, high boiling compounds generation also takes place
which gets accumulated in the Reactor and
performance. This results in reduction in throughput.
37
temporarily impairs catalyst

To get Catalyst performance back to normal, Catalyst regeneration is taken

up periodically. As the Catalyst becomes old, Catalyst regeneration
frequency gets increased. After certain cycles of regeneration, Catalyst
stops responding and becomes defunct. Catalyst needs to be changed at this stage.
Following are the indicators asking for Catalyst change:
1) Chlorination does not takes place even after regenerating the Catalyst.
Hence, SbCl3 (Antimony Trichloride) content steadily increases
2) Increased SbCl3 restricts plant capacity and leads to increased differential

pressure across Cat Stripper.
3) Needs to operate Reactor at higher temperature ( ~65C) to sustain the

operation.
4) Presence of black and thick material in the Catalyst
Production operation under these conditions should never be continued as it would

severely corrode the Reactor and Cat Stripper.
38

Procedure to off load the Catalyst;
After observing above said indications, Plant to be shut immediately and follow the
steps in sequence.
1) Depressurize the Reactor through Cat Stripper and LP system into atmosphere
and cool it to ambient temperature
2) Add 300Kg of Chloroform to the Reactor.
3) Heat the Reactor to 100C to convert residual HF. Pressure rise in the Cat
Stripper is observed which indicates that HF is reacting with Chloroform.
Allow the pressure to go up to 4Kg/cm2.
4) Depressurize the Reactor through Cat Stripper and LP system into

atmosphere.
5) Add 150Kg of Chloroform and heat the Reactor again to 100C
6) Residual HF reacts with Chloroform and pressure rise is observed. Allow the
pressure to build up to 4Kg/cm2.
7) Depressurize the Reactor through Cat Stripper and LP system into

atmosphere.
39

8) Cool the Reactor to ambient temperature and transfer Catalyst

either into tonners or into Catalyst hold tank.
R-22 CATALYST REGENERATION PROCEDURE
Line up the reactor to vent scrubbing tank by connecting the spool piece. Line up 3''
valve to vent scrubber and close 6'' valve of vent scrubber
Release the residual pressure into vent scrubbing tank and take reactor dip
Start heating the reactor contents to 150 oC keeping vent valve open of the reactor.
& reactor weight also to be noted.
Maintain reactor temperature at 150 oC for two hours & reactor weight also to be
noted.
Close the vent valve of the reactor and cool the reactor to 60 - 70 oC.
Charge 500 kg of CFM and again heat the reactor content to 150 oC .
Maintain the reactor temperature at 150 oC for two hours and reactor weigh to be
noted.
Close the vent valve of the reactor and cool the reactor to 60 - 70 oC. And reactor
weight to be noted.
Air flush the vent line as to flush out the catalyst residual in the vent line.
Take 6'' valve in line and close 3'' valve of the vent scrubber tank.
Take 6'' valve in line and close 3'' valve of the vent scrubber tank.
Take reactor dip ,based on the dip and weight catalyst to be charged .
Charge CFM to bring the reactor weight to ..
Take final dip and the vapour space should be 1.5 mtr from the charging nozzle.
Fix back the safety valve on the reactor.
Carry out reactor leak check after pressurise up to 8 kg/cm2.
40

R-23 STORAGE & OPERATION
Line up R-30 to Vapour condenser and R-23 compressor discharge
condensers.
2
Start R-30 pump with the guidance of Utility.
Start compressor to chill R-30 with the help of Utility.
Cool R-30 to -30C
Analyse R-23 vent for purity, if the purity is > 99.9 % it is suitable to store in R23 storage tank.
Set PIC-212B-1,C-1 and D-1 at 19 kg/cm2 and PIC212B-2,C-2 and D-2 at 20

kg/cm2 and keep them in auto mode.
Line up R-23 compressor to R-23 storage tanks via condenser. Ensure

compressor discharge valve and condenser L/R line is open to storage tank.
Line up compressor to surge tank.
41

Start R-23 compressor by switching off the lub-oil pressure by-pass
switch and take it in line after 2 minutes.
10
If R-23 purity is ok, divert R-23 vent to surge tank. Monitor surge tank
pressure with the help of PT given on surge tank. If the pressure goes up
beyond 3 Kg/cm2 automatically R-23 feed is diverted to atmosphere. Adjust
recirculation isolation valve opening to operate surge tank pressure in the
range of 0.8 to 2 kg/cm2
11
Monitor R-23 storage tanks temperature, pressure and weight on hourly basis
with the help of SCADA.
12
If the pressure goes beyond 19 kg/cm2 check the cooling system and the
control valve functioning. If the pressure goes beyond 20kg/cm2 stop R-23
feed to surge tank. If the pressure is still rising check PIC 212B-2,C-2 and D-2
control valve functioning. Do not allow the pressure to go beyond 20.5
kg/cm2. Vent the vapour to atmosphere by opening the manual venting valve.
13
If the temperature is rising above -10 C stop the R-23 feed to surge tank.
Check the chilling system.
42

UTILITIES
List of Utilities used in R.G.Plant
Cooling Water
Steam
High Pressure Steam (8.5Kg/Cm2)
Low Pressure Steam (3.5 Kg/Cm2)

Process Water
R-30 Brine
Service Water
CaCl2 Brine
Instrument Air
Plant Air
Nitrogen
43

UTILITY TREE
COOLING WATER CIRCUIT TO RG PLANT EQUIPMENTS
REACTORS(R101, R102)
CRUDE GAS COMPRESSOR

CRUDE GAS CONDENSOR
COOLING WATER
ALBERGER
H2SO4 COOLER
CATALYST HOLD TANK
44

STEAM CIRCUIT TO RG PLANT
R -101
R-102
HIGH PRESSURE STEAM
U-103(CAT. STRIPPER REBOILER)
8.5 Kg/ cm2 (Max.)

T-112 REBOILER
T-113 REBOILER
ORGANIC PRE HEATER
CATALYST HOLD TANK
LOW PRESSURE STEAM

SURGE TANK
3.5 Kg/Cm2(Max.)
RUNDOWN TANK
(R-11/12)
REWORKING HEATER
(E-118)
45

CaCl2 BRINE CIRCUIT
E-110 CONDENSOR(R11/12 MODE)
SCAVENGER CONDENSOR
E-111 CONDENSOR
CaCl2 Brine
CRUDE GAS CONDENSOR
P-109 A/B SUCTION COOLER
P.CAUSTIC COOLER (R22 Mode)
SEC.CAUSTIC COOLER (R22)
R-30 BRINE CIRCUIT IN RG PLANT
R-30 BRINE
CATALYST STRIPPER CONDENSOR (E-101)
46

EQUIPMENT LIST
1. STORAGE TANKS
AHF (U-281C)
CHCl3 (U-202)
HCl ( U-104, U-203, U-204)
CAUSTIC SCRUBBING SYSTEM (U-106, U-107)
DILUTE CAUSTIC RECIPITATION TANK (U-129)
SURGE TANK (U-109)
RUN DOWN TANK
ITF
MTF
2. PUMPS
3. PRE-HEAT VAPORIZERS
4. REACTOR
5. CATALYST STRIPPER
6. ABSORPTION COLUMN
7. DRYER
8. COMPRESSOR
9. HEAT EXCHANGER
10.
DISTILLATION COLUNN
47

OVERALL MATERIAL BALANCE

FEED DESCRIPTION NORMS
1. HF
2. CHCl3 3. R-22
0.544 MT
1.51 MT
1 MT
PLANT CAPACITY
36 TPD
MATERIAL BALANCE (PLANT CAPACITY- 88.89%)

HF
CHCl3
(19.3392) (53.6805)
R-22 + HCl + R-23

(35.55)
All weights are in metric tonn
48

DETAILED EQUIPMENT DESIGN

DESIGN OF PRE- HEAT VAPORIZER FOR
CHCl3
PROBLEM- Chloroform (CHCl3) at the rate of 36.83 Kg/min is to be heated
from 45C to 133C using steam 23.216 Kg/min at 3 bar and 143C.
DATA
The properties of streams at their average temp are:Shell side fluid (chloroform) at 45: C .
=
0 .563 Cp
Cp=
0.000956 Ki/kg c
K=
0.13 w/m c
=
1394 kg/m^3
SOLUTION:Heat transfer co-efficient

Nu=0.027(Re)^0.8(Pr)^0.33
OR
h= 0.027(DG/m)^0.8(cm/k)^.33(k/D)
FOULING FACTOR:
Formation of scale on heat exchanger is called fouling
,and the heat transfer resistance offered by the scale is called fouling
factor, commonly denoted by Rd.
49

Log Mean Temperature Difference

For double pipe heat exchanger
For multipass heat exchanger
Q=UA Tm
Pressure Drop:
Pressure drop is proportional to square of velocity and the total length
of travel thus , when the number of tube passes is increased for a given
number of tubes and a given tubes set flow rate the pressure drop rises
to the cube of increase.
Tube side pressure drop rises steeply.
Procedure of Process designing

Process condition Required:Hot Fluid :
T1,T2,W ,, k, Cp, Rd, P
Cold Fluid:
t1,t2,w, , k, Cp, Rd,P
SHELL SIDE
TUBE SIDE
ID
Number and length
Baffle Spacing
OD, BWG and Pitch
Passes
Passes
Heat Balance:Q = w Cp (T1-T2)

Q = (36.83/60) 0.000956 (133-45)
= 51.64057kW
t2=143
(saturated steam)
Calculation of LMTD:
LMTD=(143-45)-(143-133)/Ln(143-45/143-133)=38.556:C
50

For correction factor :

R=0
S=t2-t1/T1-t1=133-45/143-45 =0.8979
=1
From graph 1-4 pass
Range of U= 250-750W/m^2:C
Assume U =260 W/ :C
Area required for heat transfer
A=Q/UTm=(51.6
)/(22538.556)
= 5.948
TUBE SPECFICATION
Carbon Steel Tube
Kw=45W/m
od=16mm
id= 12mm
length=6m
leaving 25 mm on both sides for tube sheet thickness
L=5.9m
Area of one tube=
0.30144
Number of tubes
= 5.94/0.30144
=19.7
51

DISTILLATION COLUMN DESIGN
PACKED COLUMNS
Packed columns are used for distillation, gas absorption, and liquid-liquid
extraction; only distillation and absorption will be considered in this section.
Stripping (desorption) is the reverse of absorption and the same design
methods will apply.
The gas liquid contact in a packed bed column is continuous, not stage-wise, as
in a plate column. The liquid flows down the column over the packing surface
and the gas or vapour, counter-currently, up the column. In some gasabsorption columns co-current flow is used. The performance of a packed
column is very dependent on the maintenance of good liquid and gas
distribution throughout the packed bed, and this is an important consideration
in packed-column design.
Choice of plates or packing
The choice between a plate or packed column for a particular application can
only be made with complete assurance by costing each design. However, this
will not always be worthwhile, or necessary, and the choice can usually be
made, on the basis of experience by considering main advantages and
disadvantages of each type; which are listed below:
1. Plate columns can be designed to handle a wider range of liquid and gas
flow-rates than packed columns.
2. Packed columns are not suitable for very low liquid rates.
52

3. The efficiency of a plate can be predicted with more certainty than

the equivalent term for packing (HETP or HTU).
4. Plate columns can be designed with more assurance than packed
columns. There is always some doubt that good liquid distribution can be
maintained throughout a packed column under all operating conditions,
particularly in large columns.
5. It is easier to make provision for cooling in a plate column; coils can be

installed on the plates.
6. It is easier to make provision for the withdrawal of side-streams from plate
columns.
7. If the liquid causes fouling, or contains solids, it is easier to make provision
for cleaning in a plate column; manways can be installed on the plates. With
smalldiameter columns it may be cheaper to use packing and replace the
packing when it becomes fouled.
8. For corrosive liquids a packed column will usually be cheaper than the
equivalent plate column.
9. The liquid hold-up is appreciably lower in a packed column than a plate
column. This can be important when the inventory of toxic or flammable
liquids needs to be kept as small as possible for safety reasons.
10. Packed columns are more suitable for handling foaming systems.
11. The pressure drop per equilibrium stage (HETP) can be lower for packing
than plates; and packing should be considered for vacuum columns.
12. Packing should always be considered for small diameter columns, say less
than 0.6 m, where plates would be difficult to install, and expensive.
53

Packed-column design procedures

The design of a packed column will involve the following steps:
1. Select the type and size of packing.
2. Determine the column height required for the specified separation.
3. Determine the column diameter (capacity), to handle the liquid and vapour
flow rates.
4. Select and design the column internal features: packing support, liquid
distributor, redistributors.
Types of packing
The principal requirements of a packing are that it should:
Provide a large surface area: a high interfacial area between the gas and liquid.
Have an open structure: low resistance to gas flow.
Promote uniform liquid distribution on the packing surface.
Promote uniform vapour gas flow across the column cross-section.
Many diverse types and shapes of packing have been developed to satisfy
these requirements.
They can be divided into two broad classes:
1. Packings with a regular geometry: such as stacked rings, grids and
proprietary structured packings.
2. Random packings: rings, saddles and proprietary shapes, which are dumped
into the column and take up a random arrangement.
Packing size
In general, the largest size of packing that is suitable for the size of column
should be used, up to 50 mm. Small sizes are appreciably more expensive than
the larger sizes.
54

Above 50 mm the lower cost per cubic metre does not normally
compensate for the lower mass transfer efficiency. Use of too large a
size in a small column can cause poor liquid distribution.
Recommended size ranges are:
Column diameter Use packing size
<0.3 m (1 ft) <25 mm (1 in.)
0.3 to 0.9 m (1 to 3 ft) 25 to 38 mm (1 to 1.5 in.)
>0.9 m 50 to 75 mm (2 to 3 in.)
PROBLEM
FEED FLOW RATE IN COLUMN= 100 Kg/hr

DISTILLATE FLOW RATE = 10.7 Kg/hr
Reflux flow rate
= 25/min
Selection of packing /tray
=?
For separation gaseous product packed tower are used because of low
pressure drop.
Types of packing- random/ structured =?
Structured (IMTP 3rd generation
Pressure drop in packed tower=?
Dry bed pr drop in column is given by correlation as bellow=
P= C1 (Ug)2
Given
density of gas =
Velocity of gas
Pr drop at flooding condition= .115 (Fp).7
Given
Packing factor Fp= 79
Pr drop at flooding condition= 2.449
55

HETP is required to calculate the height of stages at which

equilibrium separation is achieved
HETP = Kp/(Fp).69
Given
Packing factor for IMTP= 79
Kp
= 198
HETP= 9.8.
DIAMETER= 18
56

CONCLUSION
In the reference of the plant design of RG gas production plant ,it is clear
that our desired product is R-22 and all the by products such as R-21,23 etc. are the
undesired.
Various separation processes are being followed for removal of these undesired
chemical gases such as striping column ,distillation column etc.
Reactions regarding the production are exothermic gaseous phase reaction which
occur in the reactor that results a difficult design process for an engineer.
Catalyst used for the reaction is usually (sbcl3+cl2 ) is not that easy to produce at
once,we recover it from the product solution using catalyst recovery unit so that
there must be enough avalibilty of catalyst in reactor.
All the chemical gases which are avoidable are separated in stepwise separation
processes according to their physical and chemical properties ,as discussed earlier.
HCFC-22 is used as refrigerant mostly in developing countries because of its negative
impact on environment as it reacts with environmental Ozone molecule .So in future
,there is a possibility of replacement with new refrigerants .
Design of plant concluded various aspects that directly or indirectly affected the
production whether it be material of construction or separation processes,these may
not be standard but surely a kind of attempt that might be cherished.
57

REFERENCE
1. Wikipedia
2. Perry's_chemical_engineers' handbook
3. CHEMICAL ENGINEERING- COULSON & RICHARDSON vol 6
4. SRF Bhiwadi plant, Rajsthan(U.P.)
5. DISTILLATION - Packed Columns - Design and Performance L. Klemas and J. A.
Bonilla etc.
58

R-22 Final

Enviado por

Dados do documento

Título original

Direitos autorais

Formatos disponíveis

Compartilhar este documento

Compartilhar ou incorporar documento

Opções de compartilhamento

Você considera este documento útil?

Este conteúdo é inapropriado?

Direitos autorais:

Formatos disponíveis

R-22 Final

Enviado por

Direitos autorais:

Formatos disponíveis

DEPARTMENT OF CHEMICAL ENGINEERING

PROJECT :- UNDERSTANDING THE REFRIGERANT GAS MANUFACTURING PROCESS

DEPARTMENT OF CHEMICAL ENGINEERING

3.66 kg/m3 at 15C, gas

175.42 C (283.76 F; 97.73 K)

40.7 C (41.3 F; 232.5 K)

Solubility in water 0.7799 vol/vol at 25 C; 3.628 g/L

S23 S24 S25 S59

Dangerous for the environment (N), Central

DEPARTMENT OF CHEMICAL ENGINEERING

Density () at -69 C (liquid)

Density () at -41 C (liquid)

Density () at -41 C (gas)

Specific gravity at 21 C (gas)

Specific volume () at 21 C (gas)

Triple point temperature (Tt)

Critical temperature (Tc)

Critical pressure (pc)

4.936 MPa (49.36 bar)

0.9384 MPa (9.384 bar)

Vapor pressure at 21.1 C (pc)

Compressibility factor (Z) at 15 C

12.56 Pa.s (0.1256 cP)

DEPARTMENT OF CHEMICAL ENGINEERING

R-22 is prepared from chloroform:

HCCl3 + 2 HF HCF2Cl + 2 HCl

2 CHClF2 C2F4 + 2 HCl

DEPARTMENT OF CHEMICAL ENGINEERING

DEPARTMENT OF CHEMICAL ENGINEERING

Name plate capacity

This plant is divided into to 6 sections.

DEPARTMENT OF CHEMICAL ENGINEERING

BLOCK DIAGRAM OF PLANT

DEPARTMENT OF CHEMICAL ENGINEERING

F-22 operation Brief Process Description

2) HF + SbCl5 SbCl4F + HCl

3) SbCl4 F+ CHCl3 SbCl5 + CHCl2F

(Dichloro Monofluoromethane) F-21

4) SbCl4F+ CHCl2F SbCl5 + CHClF2

(Monochloro Difluoromethane) F-22

5) SbCl4F + CHClF2 SbCl5 + CHF3

DEPARTMENT OF CHEMICAL ENGINEERING

DEPARTMENT OF CHEMICAL ENGINEERING

DEPARTMENT OF CHEMICAL ENGINEERING

FIG:- HF FEED SYSTEM

DEPARTMENT OF CHEMICAL ENGINEERING

FIG:- CHLOROFORM FEED SYTEM

DEPARTMENT OF CHEMICAL ENGINEERING

CHLORINE FEED SYSTEM

DEPARTMENT OF CHEMICAL ENGINEERING

Nitrogen from CMS

FIG:- CHLORINE FEED SYSTEM

DEPARTMENT OF CHEMICAL ENGINEERING

REACTOR AND CATALYST STRIPPER SYTEM

Catalyst weight after

Expected operating weight

DEPARTMENT OF CHEMICAL ENGINEERING

DEPARTMENT OF CHEMICAL ENGINEERING

R-22 REACTOR LINE UP WITH CATALYST STRIPPER

DEPARTMENT OF CHEMICAL ENGINEERING

HCL ABSORBER SYTEM

DEPARTMENT OF CHEMICAL ENGINEERING

FIG:- HCL absorbing system