COKE FORMATION INTO EDC CRACKER IN VINYL

CHLORIDE PLANTS

VCM (Vinyl Chloride) is produced in furnace crackers where EDC (Ethylene

Dichloride) is fed to thermally break the molecule to generate vinyl
monomer and hydrogen chloride.

Fig 1 Balanced VCM Process

The chemical reaction occurs as follows:

0
𝐶𝑙𝐶𝐻2 − 𝐶𝑙𝐶𝐻2 → 𝐶𝐻2 = 𝐶𝐻𝐶𝑙 + 𝐻𝐶𝑙 ∆𝐻298 71 𝐾𝑗/𝑚𝑜𝑙

𝐸𝐷𝐶 → 𝑀𝑉𝐶 + 𝐻𝐶𝐿

he conversion of EDC to VCM is related to cracker temperature in a range

of 45 - 52 % depending on the licensor and the cracking furnace design.
The reaction temperature is between 480 - 510 °C, operating pressures
are between 20 - 22 bars, there is 99 % VCM selectivity, and the resident
time is 10 - 30 sec. If the furnace conversion is increased to values above
55%, more VCM will be produced, but the furnace operating cycle will be
reduced due to increased carbon generation, which is deposited in the
pipe in the radiation zone, mainly. The actual design conversion is limited
to 50 – 52 % to get a longer running time for the cracker.

EDC crackers receive purified EDC (99,96 % minimal for the actual process
license) from a storage tank or directly from the EDC purification unit. The
technologies differ in the way the EDC is preheated before being fed to the
furnace cracker. Geon/Ineos preheats the EDC by means of the direct
chlorination reactor outlet stream and the quench column overhead
gases; vapor EDC is fed to the convection zone of the cracker. Vinnolit(1)
preheats with steam generated in the oxychlorination unit and feeds the
EDC in the form of vapor through an EDC evaporator heat exchanger,
which exchanges heat with stream leaving from the radiation zone of the
cracking furnace; subsequently the EDC is fed to the convection section
and passes to the radiation zone, where, by the burners, the temperature
is raised to 500°C for thermal cracking, to produce vinyl monomer (VCM)
and hydrogen chloride (HCl).

Coke formation into the crackers tubes is a process condition that must be
reduced or avoided, because it will plug the coil, increasing the pressure
drop (in liquid feed systems, the discharge pressure becomes to increase
and the flow control valve opens above the normal value) and eventually a
shutdown of the furnace to clean the tubes. In general, a decoking
shutdown time for the cracking unit takes around 4 – 6 days with an
economic loss. The designers calculated the decoking time every 18
months as a standard adopted; some licensors reached that their furnaces
could run 2 and a half years without loading reduction of the cracker.
 Fig 2 VCM Cracking Furnace vapor Feed

Carbon formation in cracking furnaces can be classified into 2 primary

causes:

- Furnace operating variables.

- EDC Quality

Furnace Operating Variables

Cracker operating variables have a major influence on carbon formation
rates in coils. Control room operators must keep continuous monitoring of
operating temperature conditions, operating pressure, skin temperature,
feed EDC flow rate, and EDC quality. Startup procedures must be reviewed
carefully to avoid operational pitfalls that increase the trend to coke
formation in the coils.
The actual VCM plants are implementing as standard, into the DCS system,
Advanced Process Control (APC) which is a multivariable control system
that takes multiple inputs that are processed with algorithms, process
models, and mathematical models to generate multiple outputs to the
process controllers in the distributed control system (DCS). Therefore,
models are developed to simulate and control the cracking process,
avoiding those deviations of the controlled variables that imply a
premature coking into the coils in normal operations, upset operations,
and startup or shutdown procedures.

1. Conversion Rate
The conversion rate should be limited to 52% as a maximum, because
higher conversions imply accelerated carbon formation into the coil.
Furnace conversion is inversely related to selectivity; at a temperature of
500 °C, the selectivity of EDC to MVC conversion is in the order of 99%. As
the conversion increases, the selectivity decreases, and more
unsaturated, saturated, and coke impurities are generated. See fig. 2,
where it is shown that at a furnace temp of around 505 °C, the mass
fraction of impurities is around 0.9% (2).
·10−2
460
1.2
Temperature [°C]

420 1.1
Mass fraction [-]

1
380
0.9
340 0.8

300 0.7

Tf = 1170 K 0.6
260
Tf =1160 K 0.5
0 0.2 0.4 0.6 0.8 1 1.2 1.4 0 0.2 0.4 0.6 0.8 1 1.2 1.4
z [-] z [-]

Fig 2 Conversion (left) and selectivity (right) as a function of cracker, z, for flue gas
temperature (2).
The secondary reactions in the formation of unsaturated compounds are
as follows (4):

𝐶𝐻2 = 𝐶𝐻𝐶𝑙 → 𝐶𝐻 ≡ 𝐶𝐻 + 𝐻𝐶𝑙 Acetylene from VCM

𝐶𝑙𝐶𝐻2 − 𝐶𝑙𝐶𝐻2 → 𝐶𝐻2 = 𝐶𝐻2 + 𝐶𝐿2 Ethylene/Chlorine from EDC

𝐶𝐻2 = 𝐶𝐻2 + 𝐶𝐻2 = 𝐶𝐻𝐶𝑙 → 𝐶𝐻2 = 𝐶𝐻 − 𝐶𝐻 = 𝐶𝐻2 Butadiene

𝐶𝐻2 = 𝐶𝐻𝐶𝑙 + 𝐶𝐻 ≡ 𝐶𝐻 → 𝐶𝐻2 = 𝐶𝐶𝑙 − 𝐶𝐻 = 𝐶𝐻2 Chloroprene

Unsaturated organochlorine compounds formation are highly undesirable

because these compounds polymerize and create Coke in the furnace
tubes. This is minimized by operating at cracking temperatures as low as
possible to maintain the conversion rate at design conditions, and the APC
will handle the furnace variables to maximize the conversion rate at the
desired output temperature.

The reactions that drive saturated organochlorine impurities formations

are as follows:

𝐶𝑙𝐶𝐻2 = 𝐶𝑙𝐶𝐻2 + 𝐶𝐿2 → 𝐶𝑙2 𝐶𝐻2 − 𝐶𝑙𝐶𝐻 (𝑻𝑪𝑬) + 𝐻𝐶𝑙 Tricloroetano

𝐶𝑙2 𝐶𝐻2 − 𝐶𝑙𝐶𝐻 (𝑻𝑪𝑬) → 𝐶𝐻𝐶𝑙 = 𝐶𝐻𝐶𝑙 (𝑻𝑫𝑬) + 𝐻𝐶𝑙 Dicloroetileno

1
2𝐶𝑙𝐶𝐻2 − 𝐶𝑙𝐶𝐻2 → 𝐶4𝐻8𝐶𝑙3 (ℎ𝑒𝑎𝑣𝑦 𝑐ℎ𝑙𝑜𝑟𝑖𝑛𝑎𝑡𝑒𝑠) + 𝐶𝑙2
2

In improperly operated plants will lead a premature coking. Crackers that

have been subjected to periods of 12 hours in 62% conversions (3) showed
significant increase in feed pressure, as indication of a massive coke
deposition into the coils. These events lead to shut down the cracker, 2
weeks after the event, to decoked it either by Sand Jet or Pigging and
production lost time of 7 days.
 2. Hot Spot in the Coils
Hot spots in a EDC cracker are usually caused by;

- Poor distribution of radiant heat from furnace burners.

- Burner flame flow goes directly to the coil and not to the furnace walls.

- Occasional high operating temperature events.

- Occasional impurity events in the EDC feed, especially Chloroprene, free

Chlorine, Iron or an unsaturated organic.

The hot spots generate localized high conversions rates in that zone/place
that induce the production of chloroprene or unsaturated that promote the
coke formation in the coils. Studies indicate that chloroprene and any
unsaturated organics form a pyrolytic carbon, which accumulates in very
compact layers, unlike the carbon formed by proper pyrolysis of EDC,
which is soft and does not accumulate in the 90° bends.

Fig 2 Photo of a thermographic camera showing coil without Hot Spot

 Fig 3 Photo of a thermographic camera showing a hot spot on coil

Field operators should inspect the coil during night shifts, searching
for hot spots, poor flame distributions and improper heat flow
distributions by observing the burner flame.

A hot spot is an unpleasant condition because it cannot be easily

solved; several mechanisms are used gradually and depending on
the size and location of the hot spot in order to alleviate the problem
and increased the running time. These are:

- Decrease flame of the enclosed burners

- Install a steam lance to the hot spot
- Turn off nearby burners

A hot spot will eventually promoted and accelerated coke deposit into the
coils and will cause a significant drop in pressure which will be reflected
as an increase in the feed pressure to the cracker to maintain the same
loading of EDC. In any scenario a hot spot is an indication that a furnace
shutdown for decoking should be planned.

EDC Quality
The EDC fed to the cracker must have:

- Minimum purity of 99.96 %.

- Maximum water content of 10 ppm,
- Maximum free Cl2 content of 0.5 ppm
- Maximum Fe++ content of 0.5 ppm.
- Maximum chloroprene plus unsaturated organochlorine content of
10 ppm.

The compounds that have been identified as promoters of coke formation

in EDC crackers are as follows:

Iron as ferric chloride

Unsaturated organochlorine impurities

Saturated chlorinated impurities

1. Iron impurity
Fe++ was the first compound identified in the 1960's as a promoter of coke
formation in EDC cracker coils, observed at values of 1 - 2 PPM over
periods of days causing short running times and shutdowns due to coke
accumulation in the Cracker; this is identified by a general increase in tube
skin temperatures.

Fe++ in the form of ferrous chloride is always present in EDC purification

plants because the distillation columns and equipment are made of carbon
steel, EDC always contains PPM of water and HCL, which reacts to form
ferrous chloride. Current technology allows obtaining fe++ values lower
than 0.5 PPM, so in plants built after the 90's it not usual to observe high
Fe++ events in the EDC feed to the furnace.

The dry EDC feed quality has a normal value of 0.1 ppm of Fe++, higher
values is a sign of process abnormality and shutdown values to feed EDC
is 0.5 ppm.

2. Unsaturated chlorine impurities

Organochlorine unsaturated compounds such as chloroprene, chloroform,
benzene and compounds with unsaturated bonds as promoters of
pyrolytic coke formation, generating thick layers on the surface of the
pipes, which preferentially accumulate on the 90° bends and the
thermowells installed on the bends to sense the process temperature.

Unsaturated organochlorine compounds are formed in the cracker, they

were separated in the VCM purification train. The recycle EDC which
contains the unreacted EDC and the all light, heavy chlorinated and no-
chlorinated components formed in the cracking furnace are treated in the
chlorination sections where chloroprene, benzene and high unsaturated
components are removed in reactors with chloride addition and catalyst.

It must be mention that unsaturated components have vapor pressure

close to the EDC, therefore they are difficult to remove by distillation. To
complement the analysis, as more unsaturated are formed in the cracking
furnace, it becomes more difficult to remove and they end up returning to
the furnace feed EDC.

The complex cracking of EDC is considered to proceed via free-radical

reactions. Rigorous reaction mechanisms have been studied by various
researchers (5,6) some of them use a reaction kinetic model with more
than 200 elementary reactions and more than 40 molecular species and
radicals involved in the EDC pyrolysis reaction. This means that the
licensors must design the unsaturated chlorinations units, distillation
columns and stream mixing, which allow these compounds to be
separated in the EDC distillation train and exit the process in the heavy
streams.

Likewise, field operating personnel and control rooms operators must be

trained in the importance of keep the quality of the EDC, the continuous
online monitoring of impurities in the laboratory of the plant and how to
deal effectively when variations in the process that may affect the quality
of EDC produced.

Unsaturated compounds can also come from the direct chlorination unit,
when excesses of free chlorine or HC produce unsaturated components;
however, these events do not last over time because the operating
procedures establish a shutdown of this unit when uncontrolled events of
excess Cl2 or HCL are detected.

A particular case is the acetylene impurities in the feed EDC, the actual
furnace design and coils configuration have reduced the skin temperature
in the coils. If a plant has events of acetylene, furnace operation must be
check and control.

3. Saturated chlorinated impurities

Saturated organochlorine compounds are generally removed in the EDC
purification unit, by the EDC column and sent to the vacuum column.
However, when de-stabilization events occur in the EDC column,
eventually saturated impurities of 2 -3 chlorine molecules will reach the
cracking furnace which by thermal cracking of them will produce HCL, its
reacts with the EDC reducing the selectivity to MVC but with small
increased in the kinetics of coke formation. If two separate events of high
acetylene (or other unsaturated) and saturated compounds are combined,
then heavier fractions will begin to form which due the high temperature,
will drive carbon of the type described by Mochida (7).
Bibliography

1- Operation Manual MVC II facility. PEQUIVEN. 2000.

Ing. Gerardo Castillo. VCM Process Engineer Specialist

2- Modeling of a 1,2-Dichloroethane Cracker. Ingrid Nyeng.

Norwegian University of Science and Technology. 2015

3- Internal Memo Process Senior Ing Humberto Martinez. PEQUIVEN. 1988.

4- Proceso Produccion de VCM. Texto Diplomado Procesos Petroquimicos

Horacio Torres. 2022.

5- Coke Deposition Influence Based on a Run Length Simulation of a 1,2

Dichloroethane Cracker.
C. Li, G. Hu, W. Zhong, W. Du, and F. Qian Ind. Eng. Chem. Research 2013.

6. Advanced modelling of vinyl chloride monomer production via thermal

cracking of ethylene dichloride
Renato do Carmo Claro Yih Wong. IFT Técnico Lisboa 2014

7. Coke Produced in the Commercial Pyrolysis of Ethylene Dichloride into

Vinyl-Chloride
Mochida I, Tsunawaki T, Sotowa C, Korai Y, Higuchi K
Industrial & Engineering Chemistry Research, Vol.35, No.10, 3803-3807, 199