chloride (PVC)

This application claims priority to European application No. 121 8593.1 filed December 20, 2012, the whole content of this application being

incorporated herein by reference for all purposes.

The present invention relates to a process for the manufacture of ethylene dichloride (EDC), and to a process for the manufacture of vinyl chloride monomer (VCM) and of polyvinyl chloride (PVC).

For producing VCM, two methods are generally employed : the

hydrochlorination of acetylene and the dehydrochlorination of ethylene dichloride (1,2-dichloroethane) or EDC. The latter generally happens by thermal cracking and the EDC used therefore is generally obtained by direct chlorination and/or oxychlorination of ethylene.

As namely explained in "Chemical Process Design : Computer-Aided Case Studies", Alexandre C. Dimian and Costin Sorin Bildea, Copyright ° 2008 WILEY- VCH Verlag GmbH & Co. KGaA, Weinheim, ISBN :

978-3-527-31403-4, Chapter 7 entitled : "Vinyl Chloride Monomer Process", to date, most of the VCM technologies are based on "balanced" processes.

By this is meant that all intermediates and by-products are recycled in a way that ensures a tight closure of the material balance to only VCM as the final product, starting from ethylene, chlorine and oxygen. The main chemical steps involved are :

1. Direct chlorination of ethylene to 1,2 - ethylene dichloride (EDC) :

C2H4+C12→C2H4C12+218kJ/mol

2. Thermal cracking (pyro lysis) of EDC to VCM :

C2H4C12→C2H3 Cl+HCl-71 k J/mo 1

3. Recovery of HC1 and oxychlorination of ethylene to EDC :

C2H4+2HCl+0.5O2→C2H4C12+H2O+238kJ/mol

Hence, an ideal balanced process can be described by the overall equation : C2H4+0.5C12+0.25O2→C2H3Cl+0.5H2O+192.5kJ/mol.

This document gives, namely in sub-chapter 7.6, a flow chart (Figure 7.8) showing how the EDC (both "fresh" EDC coming from the (oxy)chlorination and recycled EDC, which has not been cracked and has been separated from the pyro lysis reaction products (VCM and the HQ)) is purified prior to being fed to the pyrolysis reactor. Such a purification is generally carried out in at least 3 steps : first, a purification in "light" impurities (having a boiling point below the one of EDC), generally using a distillation column ; then, a purification in "heavy" impurities (having a boiling point above the one of EDC), generally also using a distillation column (heavy ends column) and finally, on the bottom products of the latter, which still contains EDC in order to allow advanced removal of impurities, a concentration step, also using a distillation column (heavy ends concentration column).

This same document sets forth, namely in sub-chapter 7.7, several ways of saving energy in a "balanced" process as described above. However, none of them involves energy savings on the heavy ends column.

US 4,788,357 discloses a process involving an energy saving on this very column by adiabatically condensing the top product and by using the heat of condensation so obtained to heat up the reboiler at the bottom of the column.

US 7,182,840 also discloses a process involving an energy saving on this very column by heating up the boiler thereof, but it does so by recovering the reaction heat of the direct chlorination of ethylene into EDC.

The present invention aims at providing a new route for energy saving in an EDC manufacturing process. It is based on the idea of heating up the feed of the heavy ends column leading to a reduction of thermal duty of its reboiler, and doing so also by using heat available on the EDC manufacturing process itself.

To this end, the invention relates to a process for the manufacture of EDC or Ethylene Di-Chloride by chlorination and/or oxychlorination of ethylene, said process comprising the purification of an EDC stream according to the following steps:

- eventually removing the lower boiling impurities from the EDC stream so as to generate a stream of EDC substantially free from lower boiling impurities ;

- feeding this EDC stream to a heavy ends distillation column so as to get a top stream of substantially pure EDC and a bottom stream comprising higher boiling impurities and EDC,

wherein the EDC stream fed to the heavy ends distillation column is at least partly heated up by a heater using waste heat available in the EDC

manufacturing process itself or in a subsequent pyrolysis step of said EDC into vinyl chloride monomer or VCM.

In the above, the terais « substantially pure» or "substantially free from" mean in fact that there only remains a limited amount of impurities (typically : a few w% or less) in said streams.

The terms "EDC stream" intend to designate a stream of fluid, gaseous or liquid, but generally liquid, comprising preferably more than 90 % and more preferably more than 95 % and even more preferably more than 97 % of EDC, the remainder being lower or higher boiling impurities i.e. compounds having a boiling point lower or a higher than the one of EDC. Typical impurities are VCM, ethylchloride, 1 1EDC, chloroprene (a and β), carbon trichloride, carbon tetrachloride, trichlorethane, perchlorethylene, tetrachlorethane, dichlorobutane, dichlorobutene, tars.

Lower and higher boiling impurities, generally called light ends and heavy ends, are preferably both separated in order to obtain a purified EDC that can be used to feed the furnaces of the cracking section of a VCM plant or that can be sold on the market. Hence, in a preferred embodiment of the invention, light ends are separated in a first step, preferably in a distillation column. This column can also be used simultaneously as dewatering column. Depending on the plant, this column can be dedicated to one source of EDC (in this case several light ends columns are generally installed) or common for different EDC sources.

The distillation column(s) used in the process of the invention is a fractionating column, device widely used in the chemical process industries where a multi-component mixture must be separated in groups of compounds within a relatively small range of boiling points, also called fractions. The "lightest" products with the lowest boiling points exit from the top of the column and the "heaviest" products with the highest boiling points exit from the bottom.

Inside the column, the down flowing reflux liquid provides cooling and condensation of up flowing vapours thereby increasing the efficacy of the distillation column. The more reflux and/or more trays provided, the better is the separation of lower boiling materials from higher boiling materials.

Bubble-cap "trays" or or sieve "trays" or valve "trays" are one of the types of physical devices which can be used to provide good contact between the up flowing vapour and the down flowing liquid inside an industrial fractionating column.

However, in the frame of the invention, it might be advantageous to use a packing material instead of trays, because it allows a lower pressure drop across the column. This packing material can either be random dumped packing such as Pall, CMR or Raschig rings (1-3" wide) or structured sheet metal.

According to the invention, the EDC stream fed to the heavy ends distillation column is at least partly heated up by using waste heat available in the EDC manufacturing process or in a subsequent pyro lysis step to VCM.

Preferably, the complete feed is heated up.

According to the invention, a shell and tube type or a falling film type heat exchanger can be used to heat up the EDC stream fed to the heavy ends column.

Tube and shell heat exchangers can be provided in either a vertical position with the heating fluid in the shell side or in the horizontal position with the heating fluid in the tubes.

Preferably, the heater is a falling film heat exchanger. Falling film exchanger are generally heat exchangers with vertical tubes, where a fluid is heated and partially evaporated while flowing as a thin film downward on the heated tube-walls. Falling film heat exchangers are preferred because they allow a low difference between the temperature of the heating medium on shell side and the temperature of the fluid heated and evaporating inside the tubes.

In a first preferred embodiment of the invention, the waste heat used in the heater is generated by compressing part of the top stream of substantially pure EDC from the heavy ends column itself using a Vapour Recompression (VR) device. If vapour compression is performed by a mechanically-driven compressor or blower, this evaporation process is usually referred to as MVR (Mechanical Vapour Recompression). In case of compression performed by high pressure motive vapour ejectors, the process is usually called TVR

(Thermal Vapour Recompression) or thermo compression or Vapour

Compression. The latter (TVR) allows saving less thermal energy but it does not require any additional mechanical power consumption.

In a second preferred embodiment of the invention, the waste heat used in the heater is a hot EDC stream coming from a direct chlorination unit of ethylene to EDC. As explained above, such a direct chlorination is generally used in a VCM production.

By "unit" is intended to designate all devices/apparatus used in the production facility, like reactor(s), drum(s), pipe(s), pump(s)... In practice, it is convenient to get the hot stream directly from the direct chlorination reactor.

Depending on the direct chlorination type, the hot stream can be vapour

EDC coming from the top of a direct chlorination reactor (in this case, it is a boiling reactor) that is condensed in the heat exchanger, or hot liquid EDC circulating in a loop from the direct chlorination reactor to the heat exchanger and back to the direct chlorination reactor.

In a first sub-embodiment, the heater is directly heated by the hot stream coming from the direct chlorination unit of ethylene in EDC.

In a second sub-embodiment, a VR device is inserted between the direct chlorination unit and the heater, to increase the temperature level of the waste heat recovered from the direct chlorination unit. This VR device may either be a MVR or a TVR.

In a third preferred embodiment of the invention, the waste heat used in the heater is a hot stream leaving the quenching device from an oxychlorination unit of ethylene to EDC. As explained above, such an oxychlorination step is generally used in a "balanced" VCM production. This step converts in a reactor, the HC1 coming from the VCM production in EDC by addition of ethylene and oxygen (pure or from air). The reactor is generally followed by a quenching step where unconverted C1H (HC1 in gaseous form) is absorbed.

In a fourth preferred embodiment of the invention, the waste heat used in the heater is a hot stream leaving the bottom of the VCM purification column of a VCM production unit starting from EDC obtained from ethylene, before said stream is sent to the light end removal step.

The invention also relates to a process for the manufacture of vinyl chloride monomer (VCM) by pyro lysis of a purified EDC obtained by a process as described above.

The conditions under which the pyro lysis may be carried out are known to persons skilled in the art. This pyro lysis is advantageously obtained by a reaction in the gaseous phase in a tubular oven. The usual pyro lysis

temperatures are between 400 and 600°C with a preference for the range between 480°C and 540°C. The residence time is advantageously between 1 and 60 s with a preference for the range from 5 to 25 s. The rate of conversion of the EDC is advantageously limited to 45 to 75 % in order to limit the formation of by-products and the fouling of the tubes of the oven.

The present invention also relates to a process for the manufacture of PVC. To this effect, the invention relates to a process for the manufacture of PVC by polymerization of the VCM obtained by a process as described above.

The process for the manufacture of PVC may be a mass, solution or aqueous dispersion polymerization process ; preferably, it is an aqueous dispersion polymerization process.

The expression "aqueous dispersion polymerization" is understood to mean free radical polymerization in aqueous suspension as well as free radical polymerization in aqueous emulsion and polymerization in aqueous microsuspension.

The expression "free radical polymerization in aqueous suspension" is understood to mean any free radical polymerization process performed in aqueous medium in the presence of dispersing agents and oil-soluble free radical initiators.

The expression "free radical polymerization in aqueous emulsion" is understood to mean any free radical polymerization process performed in aqueous medium in the presence of emulsifying agents and water-soluble free radical initiators.

The expression "aqueous microsuspension polymerization", also called polymerization in homogenized aqueous dispersion, is understood to mean any free radical polymerization process in which oil-soluble initiators are used and an emulsion of droplets of monomers is prepared by virtue of a powerful mechanical stirring and the presence of emulsifying agents.

The present invention is illustrated in a non limitative way by figures 1 to 7 attached, which show some preferred embodiments thereof by

comparison with prior art. In these figures, identical reference numbers designate identical or similar items.

Figures 1 and 2 show typical arrangements for EDC purification columns and figures 3 to 9 show seven different embodiments of

arrangements according to the invention. More precisely :

- Figure 1 shows the disposal of typical EDC purification columns

- Figure 2 details a heavy ends column and the devices typically associated therewith

- Figure 3 shows an embodiment of the invention in which the waste heat is coming from a MVR device compressing part of the top stream of

substantially pure EDC from the heavy ends column

- Figure 4 shows an embodiment of the invention in which the waste heat is coming from a TVR device compressing part of the top stream of

substantially pure EDC from the heavy ends column

- Figure 5 shows an embodiment of the invention in which the waste heat is directly and completely coming from a direct chlorination unit of ethylene to EDC

- Figure 6 shows an embodiment of the invention in which the waste heat is coming from the top of a direct chlorination unit of ethylene to EDC that has additionally been compressed using a MVR

- Figure 7 shows an embodiment of the invention in which the waste heat is coming from the top of a direct chlorination unit of ethylene to EDC that has additionally been compressed using a TVR

- Figure 8 shows an embodiment of the invention in which the waste heat is coming from the quenching device of an oxychlorination unit of ethylene to EDC

- Figure 9 shows an embodiment of the invention in which the waste heat is coming from the bottom of the VCM purification column.

In these figures, similar devices have similar or identical reference numbers.

As can be seen from figure 1, in a typical EDC purification process, a feed of impure EDC (4) is separated in a first distillation column (1) (or light ends column) in light ends at the top (5) and in a stream (6) of EDC containing heavy impurities at the bottom. This stream is fed to a second distillation column (2) (or heavy ends column), where it is separated again in a top stream of substantially pure EDC (7) and a bottom stream of EDC enriched in heavy ends (8). This bottom stream is sent to a concentration column (3) where it is separated in a stream of substantially pure EDC (9) which is sent back to column (2), and to heavy ends (10) which can for instance be further treated or eliminated (for instance by incineration).

In this typical arrangement, all 3 purification column are classical distillation columns with reboiler, condenser...

Figure 2 details the heavy ends column (2) and associated devices, wherein the top stream of substantially pure EDC (7) leaving said column (2) is first condensed in a condenser (13) and then, sent to a reflux drum (14) from which vent gases (16) are separated, eventually using a vacuum system (15), from a liquid stream of purified EDC (71 ) which is partly recycled as reflux to column (2) using a pump (121). The other part of purified EDC is send to a downstream application (70), like a pyrolysis step to VCM. A reboiler (1 1) is used to heat the bottom of column (2) and the bottom stream of EDC enriched in heavy ends (8) is removed from the column (2) using a pump (12).

In a first embodiment of the invention, illustrated in Figure 3, one part (7') of stream (7) is treated as explained above (condensed in a condenser (13) and sent to a reflux drum (14)), while the rest (7") of said stream (7) is sent to a MVR (17) which generates heat used in a heat exchanger (18) heating up the feed (6) of the column (2).

Figure 4 shows a second embodiment of the invention, identical to the one of Figure 3 except for the MVR (17) which is replaced by a TVR (19) also receiving vapour from an evaporator (20) fed with an EDC stream (71 ') leaving the reflux drum (14) and conveyed to said evaporator (20) through a pump (122).

A third embodiment of the invention is shown in Figure 5, which has a layout quite similar to the one of Figure 4 but where a hot stream coming from a direct chlorination reactor (200) is used in the heat exchanger (18) heating up the feed (6) of column (2).

Figures 6 and 7 show two embodiments of the invention quite similar to the one of Figure 5 but where a VR is inserted between the direct chlorination reactor (200) and the heat exchanger (18).

This VR is either a MVR (17) as shown in Figure 6, or a TVR (19) as shown in Figure 7. In the latter case, the TVR also receives high pressure vapour coming from an evaporator (20) which evaporates part of the stream condensed in exchanger (18), collected in drum (21) and pumped through pump (122), the other part of said stream being returned to the direct chlorination reactor (200).

Figure 8 shows an embodiment of the invention in which the waste heat used to heat up the feed (6) of column (2) is a hot stream leaving the quenching device (300) of an oxychlorination unit of ethylene to EDC.

Figure 9 shows an embodiment of the invention in which the waste heat used to heat up the feed (6) of column (2) is a hot stream leaving the bottom of the VCM purification column (400) before it is sent to the light end removal step (500) of a VCM production process as described above.

Table 1 hereafter shows the results of simulation/calculations made using the 7.2 release of the AspenONE ^® software.

These results are based on the layouts of Figures 2-2 to 7-2 (which are slight modified versions of corresponding Figures 2 to 7 described above) and of Figures 8 and 9 attached, using the working conditions set forth in Tables 2 to 9 (Table 2 giving the working conditions of Figure 2-2 etc... until Table 9, which gives those of Figure 9).

The layout of the Figures used for the calculations incorporates the flows from Tables 2 to 9, which are all put into squares (to avoid confusion with device features).

The energy savings indicated in Table 1 (as negative figures, the positive ones concerning new energy consumptions) for the layouts of Figures 3 -2 to 9 are all calculated versus the energy consumption of the layout of Figure 2-2.

The embodiments of Figures 3 and 6 (and Figures 3-2 and 6-2) require additional electricity consumption, while the embodiments of Figures 4 and 7 (and 4-2 and 7-2) require additional medium pressure steam consumption in the evaporator (20). However, they all lead to net energy savings.

The embodiments of figures 3 and 4 allow recovery of waste heat available on top of the heavy end column. These embodiments avoid any connexion to other parts of EDC or VCM production. They also allow a reduction of cooling capacity on top of the heavy end column. The sub-embodiment with the MVR allows the highest heat recovery but requires new electricity consumption.

The embodiments of figures 5, 6 and 7 allow recovery of waste heat available in the production of EDC by direct chlorination. Depending on the level of temperature of the gaseous EDC flow available in the chlorination section, waste heat can be used directly or a VR device is required. Installation of a VR device is more expensive. The MVR solution requires additional electricity. These embodiments lead to a reduction of cooling capacity in chlorination section, while cooling capacity on top of heavy end column increases slightly.

The embodiment of figure 8 allows recovering waste heat available in oxychlorination and leads to a reduction of cooling capacity in the

oxychlorination section, while cooling capacity on top of the heavy end column increases slightly.

The embodiment of figure 9 allows recovering waste heat available in the hot EDC stream leaving the bottom of the VCM column.

Should the disclosure of any patents, patent applications, and publications which are incorporated herein by reference conflict with the description of the present application to the extent that it may render a term unclear, the present description shall take precedence.

MPS= Medium Pressure Steam CD= condenser

Stream 16 6 7 70 71

Description From 14 From 2 From SPLIT From 14

To 18 To 13 To 121

State - L V L L

Mass frac / Mole frac kg/kg kg/kg kg/kg kg/kg kg/kg

Component Formula B.P.( 'C) M

1 .2-DICHLOROETHANE C2H4CL2 83.51 98.96 N.A. 0.9907 0.9930 0.9930 0.9930 1 ,1 ,2-TRtCHLOROETHANE C2H3CL3 1 13.71 133.40 N.A. 0.0015 200 PPM 200 PPM 200 PPM

BYPRODUCTS C4H6CL2-E2 N.A. 0.0078 0,0068 0.0068 0.0068

Total 1.0000 1.0000 1 .0000 1.0000 1 .0000

Mass flow t h 0 68.8500 101.6265 68.6630 101 .6265 Temperature °C N.A. 97.5 86.8 35.1 35.0 Abs. pressure bar abs 1.00 1 .50 1 .1 0 2 10 1 .00

Vapor fraction (mass fraction) N.A. 0.000 1.000 0.000 0.000

Enthalpy flow kW N.A. -29771 .0 -35253.8 -31320.4 -46360.3

Enthalpy flow kW -48781.0 -51707.5