Pontificia Universidad Javeriana

Departamento de Ingenierı́a Industrial

PROCESO DE PRODUCCIÓN DEL CPVC TOMADO LITERALMENTE DE ”ELEMENTARY PRINCIPLES

CPVC is produced by reacting suspension PVC resin with chlorine. The reaction is initiated by decomposing
diatomic chlorine dissolved in water into highly unstable and reactive chlorine atoms,

Cl2 → 2Cl

with either high heat or ultraviolet radiation. Once this initiation step has taken place, a chlorine atom attacks a PVC
chain at a random location and replaces a hydrogen atom at the attack position. The liberated hydrogen atom reacts

with a chlorine molecule to form a molecule of hydrogen chloride and another chlorine atom:

H · +Cl2 → HCl + Cl·

The new chlorine atom attacks a polymer molecule and replaces another hydrogen atom, and this chain propagation
sequence continues as long as both chlorine gas and hydrogen atoms on polymer chains remain in the system. If enough
chlorine is added to the reactor, a structure similar to the following one might be obtained (the added chlorines are
circled): When the polymer has this structure (which requires replacing roughly one out of every five hydrogen atoms

on the PVC chains with chlorine atoms) it contains between 67 and 68 wt % chlorine and its softening temperature
is about 110 ºC, high enough for the material to be used for hot water piping. If the chlorine content rises above 70
wt % Cl, the polymer becomes too difficult to process. In this case study, we analyze a process for producing CPVC
from PVC.

PROCESS DESCRIPTION:

Step 1.Solid PVC resin is combined with water in a stirred tank to make a slurry (a suspension of solid particles in
a liquid) containing about 10 wt % PVC. The slurry is pumped to a continuous chlorine absorber, a vessel equipped
with an impeller that keeps the contents agitated. A stream of chlorine vapor at 25º C also enters the absorber. The
absorber operates at 25º C. The chlorine absorber is enclosed by a jacket through which a hot or cold fluid can be
pumped to maintain the absorber contents at any desired temperature. A pressure relief pipe emerging from a point
near the top of the absorber is equipped with a rupture disk, a thin metal membrane designed to break if the absorber
pressure rises above a certain value. If this happens, gas flows from the absorber through the relief pipe to a surge
tank,lowering the pressure in the absorber while containing the released gas.

Step 2. The chlorine that will eventually be fed to the absorber is stored in a tank as a liquid under pressure at 22
ºC. Liquid is pumped from this tank through a chlorine flow control valve chlorine vaporizer,a tall tank about half of
which is filled with chlorine liquid and the other half with chlorine vapor. The liquid and vapor are in equilibrium at 5
ºC. Saturated steam at 2 bar absolute is fed through a steam flow control valve into a coil submerged in the liquid that
is in the vaporizer, and the heat transferred through the coil wall vaporizes chlorine. Chlorine vapor flows from the top
of the vaporizer. The pressure and liquid level in the chlorine vaporizer are controlled automatically. As vapor flows out
the top, the pressure in the tank begins to decrease.Apressure sensor detects the drop and sends a signal to the steam
flow control valve. The valve opens and feeds more steam to the coil, causing more liquid chlorine to evaporate and rai-
sing the pressure back to the desired value.As the liquid evaporates, the liquid level in the tank begins to drop. A liquid
level sensor detects the drop and sends a signal to the liquid chlorine flow control valve. The valve opens, and more
liquid enters the tank to replace the liquid that evaporated, raising the liquid level back to the set-point (desired) value.

Step 3. The chlorine vapor leaving the vaporizer passes through an adiabatic expansion valve,then through a chlo-
rine vapor heat exchanger. In the exchanger, the vapor comes in thermal contact with a hot flue gas from a furnace to
be described in Step 15. The heat transferred from the flue gas is used to raise the temperature of the chlorine vapor
to 25 ºC. The heated vapor is the chlorine feed to the absorber mentioned in Step 1.

Step 4. The chlorine enters the absorber through a pipe in the bottom that ends in a sparger (something like a
showerhead nozzle) located close to the impeller. The chlorine comes out of the sparger in thousands of tiny bubbles,
which are then dispersed by the impeller throughout the slurry in the absorber. Chlorine is soluble in water and
even more soluble in the PVC resin, and so dissolves in both the liquid and solid phases of the slurry. The feed rate
of chlorine to the absorber is automatically controlled to maintain the absorber pressure at a specified value. If the
pressure begins to fall, a pressure sensor detects the drop and sends a signal to the expansion valve described in Step
3. The valve opens, causing the flow rate of chlorine to increase and raising the absorber pressure back to the set-point
value. If the pressure rises above the set point, the pressure sensor sends a signal that adjusts the control valve to
decrease the flow rate of chlorine and the pressure comes back down to the set-point value.

Step 5: The PVC resin slurry that leaves the chlorine absorber at 25 ºC is heated to 50 ºC in the reactor preheater.
A very small amount of a chemical is added to the heated slurry leaving the preheater. The amount of initiator added
is small enough to be neglected in material balance calculations on the reactor.

Step 6: The heated slurry flows to a chlorination reactor, which is a long jacketed pipe. In the reactor, the initia-
tor—which is unstable at 50 ºC and higher—decomposes and begins the PVC chlorination chain reaction described
in the introductory section. As the slurry moves through the reactor, dissolved chlorine in the resin particles reacts
with the polymer, producing hydrogen chloride as a by-product. The HCl—which is essentially insoluble in PVC and
CPVC—diffuses out of the particles and into the liquid phase, forming hydrochloric acid (by definition an aqueous
solution of hydrogen chloride), and the chlorine that had been dissolved in the liquid phase diffuses into the particles
and reacts. All of the chlorine fed to the reactor is eventually consumed. The exit stream from the reactor is a slurry
of CPVC particles containing 67–68 wt % chlorine suspended in aqueous hydrochloric acid. The chlorination reaction
is highly exothermic. Some of the heat of reaction raises the slurry temperature to its exit value of 65 C, and cooling
water flowing through the reactor jacket removes the additional heat generated. (If the reactor temperature were to
rise above 65 C, the rate of the chlorination reaction would become extremely high, chlorine dissolved in the liquid
phase would all react near the outer surface of the particles rather than diffusing through the pores, and the quality
of the final product would suffer.)

Step 7. The CPVC slurry flows to the reactor centrifuge, a spinning horizontal drum. The solids are forced against
the circular drum wall and are compressed there. Liquid hydrochloric acid (waste liquor) collects in the drum and
overflows through an opening at one end, and the wetcake retained on the wall, which contains 90 wt % CPVC resin
and 10 % hydrochloric acid, is scraped out by a large interior screw conveyor.

Step 8. The waste liquor from the reactor centrifuge flows to a where the HCl is neutralized with a caustic soda
(sodium hydroxide) solution:
HCl(aq) + N aOH(aq) → N aCl(aq) + H2 O(l)
A stream of CO2 produced in the resin neutralizer (Step 10) also enters the neutralizer liquid through a sparger and
reacts with sodium hydroxide:
CO2 (g) + 2N aOH(aq) → N a2 CO3 (aq) + H2 O(l)
The caustic solution fed to the neutralizer, which comes from the NaOH feed drum (Step 9), contains 10 wt % NaOH
and also some dissolved NaCl and Na2 CO3 .

Step 9. The solution of sodium chloride and sodium carbonate leaving the waste liquor neutralizer is combined
with the waste liquor from the product centrifuge (Step 12). The combined solution is split into two streams. One
goes to a waste treatment facility, and the other goes to the NaOH makeup tank, an agitated jacketed batch vessel.
Solid pellets of sodium hydroxide are added to this tank to bring the NaOH concentration in the solution up to 10.0
wt %. Cooling water is circulated through the makeup tank jacket to remove the considerable heat generated by the
dissolution of NaOH. Batches of solution are pumped from the NaOH makeup tank to the NaOH feed drum (a holding
tank), and solution is pumped from the feed drum to the waste liquor neutralizer (Step 8). The feed drum always
contains enough inventory to provide a continuous feed to the neutralizer.

Step 10. The wetcake produced in the reactor centrifuge is conveyed to a resin neutralizer, another large, jacketed,
agitated vessel, where the HCl in the resin is neutralized with sodium bicarbonate in the reaction
HCl(aq) + N aHCO3 (aq) → N aCl(aq) + CO2 (g) + H2 O(l)
(Sodium bicarbonate, a weak base, is used because a strong base like sodium hydroxide can damage the resin.) A
10.0 wt % aqueous NaHCO solution at 21 ºC pumped from the NaHCO feed drum (Step 11) is augmented by a clean
water stream at 60 ºC, and the combined stream is fed to the tank. Enough bicarbonate solution is fed to neutralize
all the HCl in the wetcake, and enough additional water is added to make a 15.0 wt % CPVC slurry in the vessel. A
pH controller monitors the neutralizer vessel contents and sends a signal to a flow control valve in the bicarbonate
solution feed line if more or less solution is needed. The resin remains in the neutralizer long enough for even the HCl
trapped in the resin pores to be neutralized. The neutralizer exit stream is a slurry containing 15.0 wt % CPVC in
an aqueous sodium chloride solution at 90 ºC and pH =7. Steam fed to the vessel jacket maintains the contents at
90 ºC. At this temperature, the reaction proceeds to completion and essentially all of the carbon dioxide formed in
the reaction between HCl and NaHCO3 is driven out of the aqueous phase. The CO2 leaving the resin neutralizer is
recycled to the waste liquor neutralizer (Step 8).

Step 11. The sodium bicarbonate solution fed to the resin neutralizer (Step 10) is produced by dissolving NaHCO
powder from 25-kg bags in clean water in the NaHCO3 makeup tank,an agitated batch vessel. This makeup tank is
not jacketed like the NaOH makeup tank, as the heat of solution of sodium bicarbonate is low enough for the heat
generated in the tank to be neglected. Batches of solution are pumped from the makeup tank to the NaHCO3 feed
drum,and solution is pumped continuously from the feed drum to the resin neutralizer.

Step 12. The slurry leaving the resin neutralizer goes to the product centrifuge. The dilute NaCl solution wrung
from the resin in the centrifuge is cooled to 25 C in a heat exchanger. The cooled solution combines with the effluent
stream from the waste liquor neutralizer (Step 8).

Step 13. The wetcake from the product centrifuge, which contains 90 wt % CPVC, is conveyed to a rotary dryer.
This unit functions like a clothes dryer. The resin is tumbled down an inclined, rotating drum with hot air flowing
through the drum in the opposite direction. Heat transferred from the air vaporizes most of the remaining water in
the resin. The CPVC product resin emerges from the dryer at 120 C containing roughly 0.1 wtmoisture.

Step 14. The humid air leaving the rotary dryer at 110 C, 1.3 atm, and 20 % relative humidity is split into two
streams. Ten percent of the air is vented to the atmosphere, and the other 90 % is combined with makeup dryer
air,heated in the indirect contact furnace described in the next step, and fed back to the rotary dryer (Step 13).

Step 15. In the indirect contact furnace, natural gas containing 92.5 mole % methane, 4.8 mole % ethane, and the
remainder propane is burned completely with excess air (combustion air). The dryer air feed stream (the combination
of makeup dryer air and humid air recycled from the dryer outlet) passes through metal channels within the furnace
combustion zone and then out of the furnace to the rotary dryer air inlet. The hot gases in the furnace combustion
zone heat the metal channel walls, and the walls in turn heat the dryer air.

Step 16. The combustion products leave the furnace at 250 ºC and flow through the chlorine vapor heat exchanger
(this stream is the flue gas referred to in Step 3) and then to a flare, where any carbon monoxide and residual
hydrocarbons in the gas are burned and the products released to the atmosphere. The flare is a safety precaution: if
the furnace operates as intended, the CO and hydrocarbon content of the flue gas should be negligible.