OXYCHLORINATION

HOW TO HANDLE OXY-REACTOR HCL IMPREGNATION

Author: Horacio Torres, MSc Gas, Refinery, and Petrochemical Engineering,

Ethylene oxychlorination is the key process technology in Vinyl Chloride production (VCM´s
monomer of PVC) to close the chlorine loop by consuming the HCL released from the cracking
step. Due to the high demand for PVC, oxychlorination is one of the most important processes in
the PVC industry.

The reaction is carried out in a fluidized bed reactor with an internal coil to remove the heat of
the reaction by generating medium-pressure steam. Hydrogen chloride (HCl) is first
hydrogenated in a fixed-bed reactor to remove acetylene formed during EDC cracking, which
cannot be removed by distillation in the HCl column (MVC PurificationUnit). Hydrogen is fed
to the hydrogenation reactor and reacts with the acetylene on the surface of the palladium
catalyst. The degree of reaction is observed by the temperature increase between the inlet and
outlet streams.

The ethylene and HCl are heated up to 180 °C and fed into the oxychlorinator reactor. The
oxygen (or air, according to the licensee) is fed in a different line; it enters a distributor located
below the catalytic bed and allows the mixing of components.

Fig 1 Oxychlorination Vinnolit Process

1
𝐶𝐻2 = 𝐶𝐻2 + 𝑂2 + 𝐻𝐶𝑙 → 𝐶𝑙𝐶𝐻2 − 𝐶𝑙𝐶𝐻2 + 𝐻2 𝑂
2
𝐸𝑡ℎ𝑦𝑙𝑒𝑛𝑒 + 𝑂𝑥𝑖𝑔𝑒𝑛 + 𝐻𝐶𝑙 → 𝐸𝐷𝐶 + 𝑊𝑎𝑡𝑒𝑟

According to the licensee and catalyst manufacturer, the catalyst for the process is CuCl2/Al2O3 with 8–
12% CuCl2, doped with Mg, K, and Ni..

In the oxychlorination reaction; ethylene, HCl and oxygen (or air) react over a CuCl2/Al2O3
catalyst with 8–12% CuCl2 at process conditions of 220–230 °C, 1–2,5 bar g. EDC and water are
the final products, with small amounts of impurities such as ethyl chloride (C2H5Cl), 1,1,2-
trichloroethane (C2H3Cl3), chloral (C2Cl3HO), carbon tetrachloride (CCl4), chloroform
(CHCl3), CO, and CO2. The reaction is strongly exothermic, and good temperature control is
essential both to ensure high selectivity and to avoid catalyst deactivation.
One of the main troubles in the oxychlorination process is the loss of catalyst and deactivation of
the reaction due to the HCL over-dosification, called HCL impregnation. The equilibrated
catalyst (Ecat) should be impregnated with HCL if the processes failure occurs or if the
equipment exhibits abnormalities, the main causes are:

1. HCL valves remain open during the shoot-down procedure.

An impregnation of the catalyst with HCL will cause that the catalyst's behavior change from a
fluidizable powder to a sticky or viscous solid that is very difficult to fluidize. The HCL
penetrates into the pores of the catalyst and forms physical bonds with its active sites that
transform it into a sticky substance. Of course, Process Engineers has decided that it shall be
consider in an un-normal process operation or emergency reactor shoot down.

I must mention that in stable operations, the DSC shift operator SHALL avoid an HCL catalyst
impregnation because he receive signals from the process that warns him to avoid it; training of
the DCS control room operators is key factor. Due to the poor stoichiometric ratio, he will see
an increase in the density of the fluidized catalyst, a low level of catalyst (they are measured on
line because it is a fluidized bed), and excesses of HCL will be detected in the quench tower
bottom, as well as excess ethylene and oxygen at the same time due to loss of reaction in the
process analyzers. In parallel, he will notice dragging of the catalyst in the quench above the
maximum value of 1 ml/lt of sampling.

However, the DCS has the facilities to run the reactors using advanced process control (APC) to
handle the process conditions arising from the uncontrolled reactions (5). E. Altamiranda and H.
Torres develop a supervisory control scheme based on hybrid systems and fuzzy event detection.
The proposed supervisory control scheme was successfully implemented for an oxichlorination
reactor in a vinyl monomer plant.

How to Reduce the Catalyst Impregnation

The VCM Process Engineer must take immediate action and follow carefully defined steps to
eliminate the HCL from the catalyst pore. The actions are:

1. Shoot down the reactor.

2. Recirculate it with air for at least 48 hours and raise the temperature by means of HP steam in
the cooling coil.

3. Check the variation in acidity in the quench until it drops to PH 5, the oxy plant will have
important catalyst losses observed in the quench bottom sampling due to its impregnation.

Some plants have taken the risk of feeding ethylene to the reactor (not recomended) while
ensuring that the process conditions will be outside the explosive range. These procedures and
the risk involved depend on the technology and design of the reactor. Plants designed by
Mitsubishi and UHDE allow it. Other technologies, such as Geon, are not possible. I always
refused to proceed with this procedure because the failure probability calculations were as high
as 10-4 for any scenario considered.

Safe plant designs imply that the HCL and ethylene valves must have block and bleed valves,
that is, two fail-close valves with fast closure of less than 3 seconds when the interlock or safety
loop signal is presented. Actually, there are three motorized valves actuated by an electrical
signal: two in the main line and one in the center of these as a vent.

Reference
1. Critical Review of Catalysis for Ethylene Oxychlorination

Hongfei Ma, Yalan Wang, Yanying Qi, Kumar R. Rout, and De Chen

2. https://www.vinnolit.com/en/licensing/edc-oxychlorination-process/
3. Catalytic Oxychlorination Process Optimization for the Conversion of Ethylene to
Ethylene Dichloride

Rehab M. El-Maghraby, Alaa El-Din A. Youssef, and Abeer M. Shoaib

4. Kinetic Modeling Study of the Ethylene Oxychlorination to 1,2-Dichloroethane in

Andrea Montebelli, Enrico Tronconi, Carlo Orsenigo, and Nicola Ballarini. Politecnico di
Milano, Dipartimento di Energia, Via La Masa 34, 20156 Milano, Italy. Clariant Prodotti
Italia, Via G. Fauser 36/B, 28100 Novara, Italy

5. Supervisory control design based on hybrid systems and fuzzy events detection.
Application to an oxichlorination reactor.

Edmary Altamiranda, Horacio Torres, Eliezer Colina, Edgar Chacón