PROCESS DESCRIPTION

Allyl chloride is produced by the thermal chlorination of propylene at elevated temperatures and
relatively low pressures. Along with the main reaction, several side reactions also take place. These are
shown below.

Main Reaction
C3H6 + Cl2 → C3H5Cl + HCl ΔHreac,298K = −112 kJ/mol
allyl chloride
Side Reaction
C3H6 + Cl2 → C3H5Cl + HCl ΔHreac,298K = −121 kJ/mol
2-chloropropene
Side Reaction
C3H6 + 2Cl2 → C3H4Cl2 + 2HCl ΔHreac,298K = −222 kJ/mol
dichloropropene
Side Reaction
C3H6 + 3Cl2 → 3C + 6HCl ΔHreac,298K = −306 kJ/mol
The propylene feed is heated in a furnace, fired by natural gas, and brought up to reaction
temperature (design conditions are given in Table 1.1). The chlorine is mixed with the hot propylene in a
mixing nozzle and then fed to the reactor. During the thermal chlorination process, a significant amount
of carbon can be produced, and it has a tendency to deposit on equipment that operates at temperatures
greater than 400°C. For this reason, the reactor chosen for this process is a fluidized bed with an inert
solid, sand, on the reaction side. The sand provides a large surface area on which the carbon can deposit.
It also acts as a scouring agent on the immersed heat transfer tubes in the reactor and prevents the
buildup of carbon on the heat transfer surfaces. The carbon, which deposits preferentially on the sand, is
removed by combustion in the solids regeneration unit. The regenerated sand is sent back to the reactor,
thus maintaining a constant inventory of solids in the reactor. The heat produced in the reactor, by the
exothermic chlorination reactions, is removed via the heat transfer tubes through which is circulated a
heat transfer medium. The heat transfer fluid is a commercially available coolant called Dowtherm A.
Physical properties of this fluid are included in the table. The gases leaving the reactor contain unreacted
propylene along with the reaction products These hot gases are cooled in a waste-heat boiler and a trim
cooler prior to being sent for further processing, including the refining of the allyl chloride and the
separation and recycle of unused propylene. Crude allyl chloride, Stream 5, from the reaction section of
Unit 600 enters the allyl product cooler, E-604, at 50°C and 2.1 bar. This stream is cooled to −50°C using
the circulating liquid propylene refrigerant. The two-phase mixture leaving E-604 is fed to V-601, where
the liquid stream is taken off and is fed to the HCl column, T-601.

The HCl column removes essentially all the HCl and propylene from the cooled crude allyl chloride
feed as overhead product at approximately −57°C. This stream is mixed with the vapor coming from V-
601 and is fed to E-T-60607, where it is heated with low-pressure steam. The bottoms product from T-601
contains essentially all the chlorinated hydrocarbon derivatives and a small amount of propylene. This
stream is fed to T-603, where the remaining propylene is removed as the overhead product at
approximately −40°C. The bottoms product from T-603 is fed to column T-604, where 95 mol%
chloropropene is removed overhead at approximately 30°C. The bottom product from T-604 is fed to the
Table 1.1. Flow Summary Table for Unit 600: Allyl Chloride Production Facility
Steam Number 1 2 3 4 5
Temperature (˚C) 25 25 511 400 50
Pressure (bar) 11.7 2.09
Vapor fraction 1.0 1.0
Mass flowrate (tonne/h) 3.19
Molar Flowrate (kmol/h)
Propylene 75.89 --- 58.08 --- 58.08
Chlorine --- 19.70 --- --- ---
Allyl chloride --- --- 15.56 --- 15.56
Dichloropropene --- --- 0.46 --- 0.46
Dichloropropene --- --- 1.81 --- 1.81
Hydrogen Chloride --- --- 19.70 --- 19.70
Carbon --- --- * --- ---
Dowtherm A --- --- --- 4.62 kg/s ---
Total mole flow (kmol/h) 75.89 19.70 95.61 4.62 kg/s 95.61

Equipment Fuel gas (std Cooling Water bfw Steam

m3/h) (kg/s) (kg/s)
H-601 131+ --- --- ---
E-601 --- 14.5
Tin= 30˚C ---- ---
Tout= 40˚C
E-602 --- --- 0.333 0.333
(90˚C) (sat. at 6 bar)
E-603 --- 6.82
Tin= 30˚C --- ---
Tout= 40˚C

* Carbon is formed but at a rate does not affect the material balance
+ Actual gas

allyl tower, T-605, where 99.9% by mole pure allyl chloride is removed as overhead product at 55°C and
sent to storage. The bottoms product from T-605 contains 95 mol% 1,2, dichloropropene, and this stream
is sent to storage after being cooled in an offsite heat exchanger

The stream leaving E-607 is fed to T-602, where it mixes with water at 20°C. The flow of water is
controlled to give an aqueous solution of hydrochloric acid with 31.5 wt% HCl. This concentration of acid
is equivalent to a liquid density of 20° Baumé. The use of degrees Baumé is the common method by which
hydrochloric acid is specified. The vapor stream leaving T-602 contains all the propylene and small
amounts of water and HCl. This stream is sent to one of a pair of acid traps, V-603 A and B, where the
water and HCl are removed (by adsorption onto activated carbon). The vapor stream leaving the absorbers
is pure propylene. This propylene stream is sent to a two-stage compressor, C-601 A and B, with
intercooler E-408 and condenser E-409. The stream leaving the condenser is a liquid at 45°C and is recycled
to the propylene storage tank for Unit 600. Four of the exchangers in Unit 600 (E-604, E-606, E-611, and
E-613) require heat to be removed from the process stream at temperatures less than 35°C. In order to
do this, a refrigeration system is required. In Unit 600, this is achieved by circulating a stream of cold
(−62°C) propylene through these exchangers. The refrigeration loop is shown in the second PFD for Unit
600. The refrigeration is achieved by taking a high-pressure (20 bar) stream of liquid propylene (45°C) and
flashing it down to low pressure (0.5 bar). Cooled liquid and vapor propylene streams (−62°C) are sent to
the four process exchangers, where they provide the necessary cooling. The warmed propylene vapor
(−46°C) is recycled back to the refrigeration loop compressors C-602 A&B, the intercooler E-616, and the
condenser E-617. A makeup propylene stream is provided to account for minor system leaks.