Process description of process flow diagram (PFD)

Raw Material Storage Chlorine, oxygen and ethylene are fed as gases into the respective reactors. These feed gases are stored in spherical tanks under pressure. Chlorine is stored in T01, Ethylene in T02 and Oxygen in T03. It is from these storage tanks that t he feed gases are pumped to the oxychlorination and direct chlorination reactor vessels.

Direct Chlorination Reactor Section The direct chlorination reaction takes place in a liquid phase reactor (R01). Chlorine and ethylene are mixed with liquid EDC at 1200C and 15psig pressure1. This reaction is an exothermic reaction and the heat of reaction is -180KJ/mol. The heat of reaction is removed by circulating cooling water around an external heat exchanger (HE-01). In some commercial processes liquid EDC is used as a cooling medium instead of cooling water. The reaction is catalysed by ferric chloride. The reaction is normally run with excess ethylene to make sure most of the chlorine reacts to form EDC and to maintain the vent gases fuel rich for incineration1. Conversion of Chlorine is usually 100%, and EDC selectivity is always above 99% 1. After the reactor (R01) the product stream goes through a condenser (HE-04). There it is cooled down most of the EDC is cooled down to its liquid state. The Condenser uses cooling water to cool down the product stream. After the Condenser the stream goes into the Knock out Drum (S01), where the liquid EDC is separated from the unreacted excess ethylene and other gaseous by-products. The gas stream goes to the incineration unit (E01) where it is burnt to generate steam for the use in the distillation columns. The liquid stream containing mainly of EDC is pumped (P03) to the EDC storage tank (T04).

Oxychlorination Reactor Section

In the oxychlorination reactor (R02), Ethylene, Hydrogen Chloride and Oxygen are reacted together at 2900C and 90psig pressure. The reactor is a fixed bed type reactor utilising cupric chloride as catalyst with potassium chloride additive. The reaction is exothermic and the heat of reaction is removed by an internal heat exchanger (HE-02). Cooling water is used as cooling medium and it is converted to high pressure steam. The product stream passes through a condenser (HE-03) where it is cooled and all of the EDC and water is converted from gas to Liquid. The condenser uses cooling water which is converted to steam for use in distillation columns. From the condenser the product stream is pumped (by P01) to a knock out drum (S02) where the liquid EDC and water are separated from the unreacted HCl and other gaseous by-products. The gaseous stream goes on to a scrubbing Vessel (V01) where unreacted HCl and chlorine are absorbed out of the flue gases before they are sent to an incineration Unit. The liquid stream containing water and EDC is sent to a dehydrator column (C01). In this column water is separated from EDC, the waste water stream goes on to a waste treatment unit which is not shown in the process flow diagram. The EDC joins the EDC recycle stream from the VCM purification section to get combined with the EDC from the direct chlorination section in the EDC storage tank (T04).

EDC Purification Section The EDC still contains chlorinated by-products at this stage therefore it has to go through a purification process. Impurities in EDC inhibit the pyrolysis reaction and cause fouling therefore the EDC must be above 99% purity before it can be cracked1. From the EDC storage tank (T04), EDC is pumped (by P04) to the Light Ends column (C02). At the column, all lower boiling point impurities are separated as an overhead product. The bottom Product from the column (C02) is pumped (by P05) into a second distillation column referred to as the Heavy Ends Column (C03). At the Heavy ends Column, high boiling point impurities are separated from the EDC. Highly chlorinated hydrocarbons, tars and water make up most of these impurities that are removed as a bottom product of the column (C03). The top product of this column is EDC of over 99% purity.

The pure EDC is pumped (by P06) to the cracking furnace also referred to in the PFD as the Pyrolysis reactor (PYRO-REAC).

EDC Pyrolysis/Cracking The pyrolysis reactor is a gas-fired furnace and the flue gases released from the combustion of the fuel gas (normally natural gas) are released directly into the atmosphere. In the pyrolysis reactor (PYRO-REAC), EDC is broken down into VCM and HCl. The reaction takes place at temperatures around 5000C and 200psig1 pressure. In the reaction only about 50-60% of the EDC fed to the pyrolysis reactor is reacted. Therefore the product stream from the pyrolysis reactor contains almost equimolar proportion of EDC, VCM and HCl1. The product stream is passed through a quenching heat exchanger (HE05), where it is cooled to about 25-500C1. The Heat exchanger utilises cooling water to cool down the product stream and the cooling water is converted to high pressure steam for use in distillation columns. After the stream is condensed, it goes on to the VCM purification section.

VCM Purification Section The product stream from the quench unit above enters the HCl recovery Column (C04), where all the Hydrogen chloride is recovered and recycled back to the oxychlorination reactor. The HCl is recovered as a top product because it is a gas at the stream temperature (20-500C). The pressure at the top of the HCl column (C04) is 135psig and a top temperature of -310C1. The bottom product of C04 contains unreacted liquid EDC and liquid VCM. The bottom product of the HCl recovery column (C04) is pumped (by P08) to another distillation column, referred to as the VCM recovery Column (CO5). At the VCM recovery column (C05), all the unreacted EDC is separated and recycled (pumped by P07) to the EDC purification section, where it combined with crude EDC from the Oxychlorination and direct chlorination sections. The column (C05) has a top pressure of around 65psig1. The EDC is the bottom product and the VCM is the top product. The VCM product has a purity of above 99%.

The VCM is condensed at the top of the column and sent to the VCM storage tanks (T05 and T06). It is from these storage tanks that the VCM is pumped to tankers and transported to the customer.

NB: All distillation columns specified in this process are tray columns.

References:
1- Anonymous. (1992). Vinyl Chloride monomer (VCM Plant). Available

online from: http://chemelab.ucsd.edu/CAPE/simsci_vcm.pdf, (last accessed: 4/12/11)