Vinyl chloride and polyvinyl chloride
Going towards climate-friendliness by advanced technologies
The Vinnolit EDC/VCM/PVC process
a climate-friendly technology
Right from the outset, low primary energy consumption and heat recovery have always been a focus of the research and development activities relating to the Vinnolit EDC/VCM/PVC process, whether to the overall process or the individual process units.
Benefits of our CNC direct chlorination & oxychlorination technology
Our CNC direct chlorination technology enables operation at high temperatures coupled with superior product quality. Due to the high quality, the EDC produced does not need to be distilled before being fed to the EDC cracking unit, thereby saving energy. The high reaction temperature allows for several heat recovery options, e.g. for heating of distillation columns or for drying of PVC in a fluidized bed dryer.
The oxychlorination unit uses the reaction heat of the highly exothermic oxychlorination reaction to generate medium-pressure steam which covers a major part of the steam consumption of the entire EDC/VCM/PVC plant.
Energy recovery in EDC cracking and distillation units
The EDC cracking unit includes our unique EDC evaporator system which recovers the sensible heat of the reaction mixture leaving the cracking furnace by evaporating the feed EDC. Heating the cracking furnace partly or entirely with hydrogen (e.g. from a chlor-alkali electrolysis or green hydrogen plant) can lower the CO2 footprint of the EDC cracking unit further.
Special technical features in the EDC distillation unit result in a significant energy saving. Depending on the individual plant configuration, heat recovery can also be performed in the VCM distillation section. With our recycle EDC chlorination a dry lights distillation system is no longer necessary and this saves further energy.
Recirculation of process streams
The HCl recovery section generates steam, which also contributes to supplying the plant with steam from internal sources. Furthermore, gaseous HCl is fed back to the oxychlorination unit, which results in chlorine savings and thus energy savings.
The PVC technology boasts several environment-friendly features for example the utilization of heat from the centrifuges and the condensate and process water recycling with hot water charging back to the polymerization process.
Near-zero CO2 footprint
The entire EDC/VCM process can also be operated on ethylene feedstock from renewable sources.
Due to numerous possible combinations of heat recovery and energy-saving measures, the primary energy demand and thereby the CO2 footprint of the Vinnolit EDC/VCM/PVC process can be lowered to a near-zero value.
All of the above features are the result of over 25 years of continuous development work and have proven reliable in operation.
2
Table of contents
1. Company profile 3
2. The Vinnolit VCM process 4
2.1 General process description 5
2.2 Direct chlorination 6
2.3 Oxychlorination 8
2.4 EDC distillation 10
2.5 EDC cracking 11
2.6 VCM distillation 12
2.7 Measures to recover by-products and to protect the environment 13
2.7.1 HCl recycling with waste gas heat recovery 13
2.7.2 Waste water treatment 13
2.7.3 Liquid and waste gas collection systems 13
2.8 Cumulated capacity of reference plants 14
3. The Vinnolit S-PVC process 15
3.1 Description of the S-PVC process 16
3.2 Advantages of the S-PVC process 17
3.3 The new Vinnolit High-Performance Reactor for suspension PVC 18
3.4 The Vinnolit MST Cyclone Drier 19
3.5 Products and applications 20
4. References 21
The Chemical and Process Technologies business unit of
thyssenkrupp is a technology-driven engineering, procurement and
construction partner for the global chemical industry. It was founded
nearly 100 years ago under the name of Uhde. With its international
network of subsidiaries and branch offices, the company has to date
successfully completed over 2,500 projects throughout the world.
We develop innovative processes and products for a more sustainable
future and thus contribute to the long-term success of our customers in
almost all areas of the chemical industry. Our portfolio includes leading
technologies for the production of basic chemicals, fertilizers and
polymers as well as complete value-chains for green hydrogen and
sustainable chemicals.
tkIS and Vinnolit – Partners for vinyl chloride and polyvinyl chloride
Our licensor for the Ethylene Dichloride (EDC), Vinyl Chloride
Monomer (VCM) and for the Polyvinyl Chloride (PVC) process is
Vinnolit GmbH & Co. KG.
Vinnolit is one of Europe’s leading EDC, VCM and PVC producers
with a capacity of 780,000 t/year of PVC, 665,000 t/year of VCM
and upstream chlorine plants. They enhance and optimise their
process technology on a permanent basis. Vinnolit was founded
in 1993 as a 50/50 joint venture between Hoechst AG and
Wacker Chemie GmbH. The new company drew on the
experience of its two founders, both active in the vinyl sector for
almost 60 years. In 2014, Vinnolit became part of Westlake
Chemical Corporation, a leading international manufacturer and
supplier of petrochemicals, polymers and PVC construction
products headquartered in Houston.
Since 1964 the licensor has granted licences for a capacity of
more than 14 million tonnes of EDC, approx. 6.5 million tonnes
of VCM and about 2.9 million tonnes of S-PVC.
The cooperation between the licensor and tkIS has been successful
for some 50 years. tkIS is the sole basic engineering partner for
Vinnolit’s EDC, VCM and PVC processes.
3
1. Company profile
Knapsack (Cologne), which have a com-
bined capacity of 665,000 t/year, as well
as at many other plants worldwide.
The modern Vinnolit process for the pro-
duction of VCM has the following major
distinctive features:
High operational reliability:
Reliable reaction control
Time-proven materials and equipment
State-of-the-art process control system
2. The Vinnolit EDC/VCM process
Vinyl chloride (VCM), which is made from
ethylene and chlorine, is used as feedstock
in the production of the standard plastic
material PVC.
The market for PVC and hence VCM has
continued to grow, thus dispelling the fore-
casts made in the 80s, according to which
PVC would be substituted by other plastics.
The reasons for this were not only the mani-
fold applications and properties of PVC, but
also the progress made in limiting emissions
and by-products during production. PVC pro-
duction capacity attained growth rates of
approx. 6% per year, accounting for approx.
47 million tonnes worldwide in 2010. For the
next few years, growth rates in the order of
4% per year are again expected.
As a chemical engineering contractor, tkIS
added VCM to its range of processes some
40 years ago and has to date designed and
constructed plants with a total nominal ca-
pacity of approx. 6 million tonnes.
High economic efficiency:
Low energy consumption due to the
utilisation of reaction and waste gas
heat and integration with PVC or
caustic soda plants
High yields
Optimised reaction conditions and
reaction control
Utilisation of by-products containing
Cl2 along with the recycling of HCl gas
High on-stream factor
Low personnel requirement
Low maintenance costs
High flexible, wide range of load
Extremely low pollution levels:
≤ 0.01 ppm VCM (annual average)
in working areas
Extremely low VCM emissions
Small waste water quantities
with EDC/VCM contents ≤ 1 ppm
In-plant disposal of low-boiling and
high-boiling constituents in conjunction
with HCl gas recycling and steam
generation
Special facilities for preventing emissions
when the plant is shut down
Thermal waste gas treatment
Expected consumption figures for raw materials
and utilities per 1,000 kg VCM product
The VCM process applied by tkIS is licensed
by Vinnolit. The current high technological
standard was reached through intensive
development work on the part of Vinnolit in
collaboration with tkIS. The process has
been successfully applied at Vinnolit’s ex-
isting plants at Gendorf (Bavaria) and at
Ethylene (100 %) 459 kg
Chlorine (100 %) 575 kg
Oxygen (100 %) 139 kg
Steam 250 kg1
Fuel gas 2.7 GJ
1)Combined figure for VCM / PVC plant: 435 kg
4
Qatar Vinyl Company (QVC),
Mesaieed, Qatar
Capacities of the complex:
360,000 t/year of DC-EDC
175,000 t/year of Oxy-EDC
230,000 t/year of VCM
The process for the production of vinyl chlo-
ride monomer (VCM) from ethylene proceeds
in several process sections.
In the first process section, ethylene dichlo-
ride (EDC; 1,2 dichloroethane) is produced
by direct chlorination, in the second section
by oxychlorination. Both reactions are exo-
thermal.
1st section:
C2H4 + Cl2 C2H4Cl2 + 218 kJ/mole
2nd section:
C2H4 + 2HCl + 1/2O2
C2H4Cl2 + H2O + 238 kJ/mole
3rd section:
C2H4Cl2 C2H3Cl + HCl - 71 kJ/mole
VCM synthesis: 2 C2H4 + Cl2 + 1⁄2 O2 2 C2H3Cl + H2O Schematic diagram of a VCM plant
E t h y l en e
C 2 H 4
Chlorine
Cl2
O x y g e n
O 2
C2H4 C2H4Cl2
+ Cl2 Cat + 218 kJ/mole
Direct
chlorination
Oxychlorination
EDC
distillation
EDC
C2H4Cl2 ΔH C2H3Cl + HCl
– 71 kJ/mole
recycle EDC
chlorination
EDC
crack ing
HCl
VCM
distillation
HCl
liquid + gaseous
by-products
Vinyl chloride
VCM
by-product
recovery
2.1 General process description
Biggest VCM plant in China
SINOPEC Qilu Petrochemical Corp.
Linzi, Zibo, Shandong Prov., China
400,000 t/year of VCM (balanced)
The EDC produced by direct chlorination is
fed straight into the cracking section without
any further purification.
The heat of this exothermic reaction can be
used for PVC drying in the PVC plant or for
heating of columns in the EDC distillation
unit depending on the individual plant con-
figuration.
The EDC formed by oxychlorination passes
through a purification stage (EDC distillation).
In the third process section, the EDC is
cracked, and the VCM formed there, as well
as the hydrogen chloride and unconverted
EDC, are separated in a VCM distillation unit.
The VCM is temporarily stored in a tank,
while the HCl is returned to the oxychlorina-
tion unit and the unconverted EDC to the
cracking section.
Any process water obtained undergoes treat-
ment. Waste gases containing pollutants as
well as liquid by-products are fed to the HCl
recovery unit and converted to HCl, CO2 and
water.
The recovered HCl is reused in the oxychlo-
rination process, which leads to a complete
conversion of the input chlorine.
The diagram shows the individual sections
of the overall process which are described
on the following pages.
C2H4 + 2 HCl + 1⁄2 O2 Cat C2H4Cl2 + H2O + 238 kJ/mole
5
6
2.2 Direct chlorination
In the direct chlorination process, EDC is
produced by means of a highly exothermal
reaction of ethylene and chlorine.
The main feature of the Vinnolit direct
chlorination process is an innovative boiling
reactor with natural convection flow.
Recently, as a result of a joint development
project of tkIS and Vinnolit, the compact
natural circulation (CNC) reactor was devel-
oped and now is ready for introduction on
the market. In the CNC reactor, the natural
circulation is established in an internal loop
consisting of a riser section and a down-
comer section, leading to a more contact
and cost-saving reactor design.
The Vinnolit Direct Chlorination process
operates at boiling conditions with a tem-
perature of 120°C. The heat of reaction is
removed by boiling off EDC from the boiling
reactor. A big portion of this heat can be
recovered by several heat recovery options,
e.g. heating of distillation columns in the
EDC distillation unit or heating of a fluidised
bed PVC drier in the PVC plant yielding a
reduction of steam consumption of up to
700 kg / tonne of EDC.
The reaction is carried out in the riser sec-
tion of the CNC reactor. In contrast to other
processes, gaseous ethylene is first com-
pletely pre-dissolved in the lower part of the
riser section of the CNC reactor.
Gaseous chlorine is added via an injector
nozzle to a relatively small circulating EDC
side stream withdrawn in the downcomer
section of the CNC reactor and cooled to
allow the chlorine to be better pre-
dissolved. This cooling provides another
opportunity to recover the heat of reaction.
The ethylene solution and the completely
predissolved chlorine are mixed in the reac-
tion zone of the riser and react to EDC in a
fast liquid-phase reaction which significantly
lowers by-product formation.
Due to the reduced static pressure head
in the top section of the riser, the EDC
starts boiling. The product amount and
some excess EDC are withdrawn from the
upper part of the CNC reactor and passed
on to the product vessel and a stripping
column to achieve 'Sales EDC' quality, if
required. The excess EDC is recycled to
the main reactor loop.
In contrast to competitive direct chlorination
processes, the Vinnolit Direct Chlorination
process does not use FeCl3, but a complex
compound as catalyst. The catalyst sup-
presses the formation of by-products and
ensures higher selectivity to EDC.
Thus the Vinnolit Direct Chlorination process
combines the energy efficiency of a high-
temperature chlorination (HTC) process with
the EDC purity of a low-temperature chlorin-
ation (LTC) process. The catalyst is fed to the
reactor loop before start-up and does not
have to be topped up in normal operation.
The process is particularly
environment-friendly, because:
The energy recovery options lead to a
significant reduction of CO2-emissions
The formation of high-boiling
constituents is significantly reduced
Extremely small quantities of low-boiling
constituents are formed (only a few ppm)
No scrubbing water is required and
No catalyst is discharged with the product.
The catalyst has no corrosive properties be-
cause of its complex structure, and therefore
the process equipment can be made mainly
of ordinary carbon steel. Existing plants can
be converted without any difficulty.
The advantages of the process can be
summarised as follows:
Nearly no consumption of catalyst
High raw material yields
High EDC purity: 99.9 %
Utilisation of reaction heat, e.g. for
heating of distillation columns or drying
of PVC, leading to a reduction in steam
consumption of up to 700 kg / tonne of
EDC.
Low investment costs
Complete reaction in only one reactor
Proven materials and reliable and simple
equipment
High active and selective catalyst
Utilising the reaction heat saves energy and
reduces emissions of CO2 by an amount
equivalent to the energy savings. Thus, car-
bon certificate trading has a positive effect
on production costs.
7
Refrigerant Direct chlorination process
using a boiling reactor Waste gas to
incineration
Heat
recovery
C W
Chlorine
Stripping
column Ethylene
P r o d uc t v es s e l
Sales - EDC Heat N2
recovery
CNC Reactor Furnace feed EDC
2.3 Oxychlorination
In the oxychlorination process, EDC is formed
by a highly exothermal catalytic reaction of
ethylene with hydrogen chloride and oxygen.
The reaction takes place in a fluidised-bed
reactor, and the reaction heat is used for
steam generation. In the downstream quench
column, a major portion of the reaction water
is removed by condensation. To remove
small quantities of chlorinated hydrocarbons
from the reaction water, it is transferred to
the effluent treatment facilities.
By cooling the reaction gases further by
means of cooling water (CW) and refrigerant
(R), the raw EDC is removed by condensation
and fed to the EDC distillation unit, where it is
purified to obtain “feed EDC quality”.
The Vinnolit oxychlorination process can use
oxygen from air separation units as well as
oxygen from pressure swing adsorption
units (PSA oxygen). In the reactor the cata-
lyst is fluidised with circulation gas. Just
enough oxygen is added to the reactor to
keep the concentration of the circulation gas
outside the flammable range (oxygen lean
operation). The very small off-gas stream of
inerts and carbon oxides which is formed in
the process is fed to the HCl recycle unit
without further treatment. The reaction
mixture, consisting of C2H4, HCl and O2, is
catalytically converted in the fluidised-bed
reactor to EDC in a highly exothermal reaction
at a temperature of > 200°C. The heat is
dissipated via internal cooling coils and
recovered to generate steam. Independent of
load the generated steam has a constant
pressure level.
The excellent distribution in the fluidised-bed
makes it possible to maintain a constant tem-
perature, to ensure low by-product formation
and to achieve optimum process control.
The reaction gas passes a filter unit in which
the catalyst fines are separated from the
gas. Depending on customer's require-
ments, also a waste water treatment section
comprising a precipitation and sludge filtra-
tion step can be implemented. To remove
the reaction water, the hot reaction gases
are quenched and the EDC is condensed
with the aid of chilled water in a multi-stage
condensation unit. The crude EDC is purified
in an EDC distillation unit to obtain “feed
EDC quality”.
The reaction water obtained is passed to
the waste water treatment facilities to re-
move the small quantities of chlorinated
hydrocarbons it contains.
8
Hydrogenation reactor
Hydrogen chloride
Oxygen
Ethylene
HCl from TDI / MDI possible
Hydrogen
Oxychlorination reactor
Circulating-gas compressor
Boiler feedwater
Steam
Catalyst f i l tration
Quench column
C W
water treatment
Effluent to waste
Waste gas to
incineration
Crude EDC
Refrigerant
9
Oxychlorination reactor Erection of oxychlorination reactor BorsodChem Rt., Hungary
The modern oxychlorination process of Vinnolit has
the following distinctive features:
Fluidised-bed reactor with good reaction heat distribution:
no hot spots, no catalyst stickiness
Proven materials and reliable and simple equipment
Reactor and cooling coils made of carbon steel
Crude EDC purity: 99.6 %
High conversion of C2H4 to EDC: 99.0 %
Low catalyst consumption
Removal of catalyst fines either by simple waste water
treatment or by catalyst filtration
High flexibility of the plant, wide range of load
Production of 10 bar steam for distillation units possible
High safety standard, O2 content < 1 %
2.4 EDC distillation
To produce pure feed EDC, both the EDC
obtained in the oxychlorination process and
the EDC not converted in the cracking
process (recycle EDC) are treated in the EDC
distillation unit in order to remove water as
well as low-boiling and high-boiling com-
ponents.
The wet raw EDC from the oxychlorination
unit is fed to the heads column in order to
remove the water and low-boiling substanc-
es by distillation. The water phase of the
head product containing small quantities of
chlorinated hydrocarbons and sodium
chloride is transferred to the waste water
treatment unit. The organic phase and the
off-gas are fed to the incineration unit.
The dry bottom product from the heads
column together with the unconverted EDC
from the cracking process are separated
from the high-boiling compounds in the
high-boil and vacuum columns. These high-
boiling compounds are withdrawn from the
bottom of the vacuum column and sent to
the incineration unit.
By default, the high-boil column is oper-
ated at elevated pressure and the
overhead vapours of this column are used
to heat the heads column and the vacuum
column. Depending on customer's
requirements also other heat recovery
options can be realized.
10
EDC evaporator and cracking furnace
from VCM distillation
Crude EDC
from oxychlorination
Recycle EDC
Head s co l um n
C W
S t e a m
C o n d .
High-boils column
C W
Vacuum co lum n
Low-boiling components to incineration
Effluent to waste water treatment
Waste gas to incineration
CW ______________ R
from cracking
High-boiling components to incineration
Cracking EDC
2.5 EDC cracking
The cracking of 1,2 dichloroethane takes
place in a cracking furnace heated by fuel.
VCM and HCl are formed at temperatures
of 480°C, the reaction being endothermic
and incomplete.
In addition to VCM and HCl, by-products of
various chemical structures and co*ke are
formed.
The external EDC pre-evaporation facility
reduces the formation of co*ke in the crack-
ing furnace considerably. The operating
periods between two deco*king intervals are
very long (up to 2 years).
The advantages of Vinnolit’s modern EDC
cracking process can be summarised as
follows:
High reliability due to low co*ke formation
High savings in primary and secondary
energy, due to:
- External EDC pre-evaporation using
cracking gas heat
- Utilisation of flue gas and cracking
gas heat to preheat combustion air, to
generate steam or to preheat EDC
Low maintenance costs
Proven materials and reliable equipment
3D model of one of the world's largest PVC complexes
build in Middle East
On the left: The EDC cracking furnaces
Capacities of the complex:
570,000 t/year of chlorine
329,000 t/year of sales EDC
343,000 t/year of VCM
340,000 t/year of PVC
11
Cracking EDC
Cond. Steam
Combustion air
Fuel
CW HCl
to VCM distillation
to VCM distillation
Cracking product
Recyle EDC
to EDC distillation
Fuel
2.6 VCM distillation
The product from the cracking unit consists
of VCM, HCl, unconverted EDC and by-prod-
ucts of various chemical structures.
Hydrogen chloride is recovered in the HCl
column and fed to the oxychlorination unit.
Vinyl chloride is obtained at the top of the
VCM column.
Any traces of HCl are removed from the VCM
in the HCl stripper. The overhead product of
the HCl stripper is recycled to the HCl column
via a H2O removal unit which removes
moisture from the distillation process and
protects against moisture build-up.
The bottom product of the VCM column,
i.e. un-converted EDC, is returned to the
EDC distillation process after the low-
boiling compounds have been converted
by chlorination to high-boiling compounds.
Thus the difficult and energy-consuming
separation of recycle EDC from other low-
boiling components is avoided.
The Vinnolit EDC distillation unit can do
without a low-boil column for recycle
EDC with all its related problems.
Advantages of the VCM column:
HCl content in VCM < 1 ppm without
using caustic
Long on-stream time of VCM distillation
unit, because of no co*ke carry over from
hot quench system
Vapor feed of HCl stripper overhead
product to the HCl column, no
condensation system necessary
Lower power consumption for HCl
condensation compared to low
pressure HCl column
Advantages of the recycle EDC chlorination:
No separation of low-boiling compounds
necessary
Low investment cost in comparison to
a low-boil column
Easy operation
No steam consumption
Low maintenance cost
12
S t e a m
C o n d .
Cl2
from Cracking
quench
Cracking
unit product
HCl to oxychlorination
HCl column
Refrigerant
S t e a m
C o n d . Heat
recovery
VCM column
C W
EDC chlorination unit
S t e a m
C o n d .
H2O removal
HCl stripper
C W
to EDC distillation
Product
VCM
Recycle EDC
2.7 Measures to recover by-products and to protect the environment
2.7.1 HCl recycling with waste gas
heat recovery
In the production of VCM, not only 1,2
dichloro-ethane is produced as a desirable
intermediate product, but also further by-
products, consisting of a mixture of high-
boiling and low-boiling compounds, are
obtained in liquid or gaseous form.
In a new modified Vinnolit process, these
by-products are completely converted in an
oxidation process to form CO2, water and
hydrogen chloride. This process operates
with an excess of air at approx. 1,150°C.
The heat of the hot combustion gases is ex-
ploited to generate steam, and the hydrogen
chloride is recovered as a valuable feedstock
which is returned in gaseous form to the
oxychlorination process.
Alternatively, aqueous HCl of 25 to 30% can
be produced.
The treated waste gas complies with all
applicable German statutory regulations in
force since 3.5.2000, including those con-
cerning the concentration of dioxins and
furanes (< 0.1 ng TE/m3).
The advantages of the HCl recycling
process are:
Recovery of hydrogen chloride from the
by-products
Optimum utilisation of the input chlorine
to produce VCM
Utilisation of the energy content of the
by-products in the form of steam
Use of proven technology and materials
Environment-friendly process
2.7.2 Waste water treatment
The process effluent from the VCM plant
and any splash water are sent to a waste
water treatment unit. Chlorinated hydrocar-
bons are removed by distillation, hydrogen
chloride by neutralisation with caustic soda
solution. A copper content of less than 1
ppm is ensured either by dry catalyst
filtration in the oxychlorination or by treat-
ment of the waste water using flocculation,
sedimentation and filtration.
The treated effluent, which meets the statu-
tory purity requirements, is subsequently
fed to a biological treatment unit.
The sludge obtained as a waste product is
dumped or incinerated.
2.7.3 Liquid and waste gas collection
systems
Liquid EDC and VCM from drains, cleaning
of filters, reboilers etc. are collected in
closed systems and returned to the process
loop to protect the environment.
Sources of continuous waste gas streams
are connected to waste gas headers and
the gas is sent to the HCl recovery unit.
13
HCl recovery unit
14
The view of Europe's biggest and
most modern VCM plant at Vinnolit
in Knapsack near Cologne.
Capacity: 190,000 t/year of EDC
370,000 t/year of VCM
1 5
3. The Vinnolit S-PVC process
The suspension polymerisation process for
manufacturing polyvinyl chloride is the most
important way to produce a variety of
general-purpose and highly sophisticated
grades of PVC. This process was invented in
1935 and first patented by Wacker Chemie
GmbH, one of the former parent companies
of Vinnolit. Continuous developments had
been made in recipes, product quality and
technology. Due to this long experience and
continuous improvements, Vinnolit can offer
a modern and highly economic process for
the production of S-PVC worldwide. A
Vinnolit team of specialists is available to
tailor plant design according to licensee’s
requirements.
Vinnolit technology is characterised by:
Vinnolit‘s proprietary technology for all units
Clean and closed reactor technology
High productivity
Low raw materials consumption
Low waste water amount
(waste water recovery)
Low energy consumption
Low investment cost
Low maintenance cost
High safety level
Leading in environmental
protection – DIN ISO 14001 certified
High product quality – DIN ISO 9001
certified
3D model of one of the world's
largest PVC complexes build in
Middle East
Capacities of the complex:
570,000 t/year of chlorine
329,000 t/year of sales EDC
343,000 t/year of VCM
340,000 t/year of PVC
176
3.1 Description of the S-PVC process
Vinyl chloride and hot water are fed to the
Vinnolit High-Performance Reactor by
means of a special charging program.
Once the polymerisation has been completed
the content of the reactor is discharged into a
blowdown vessel and from here continuously
fed to the Intensive Degassing System.
The nonconverted monomer is stripped out,
condensed and fed back into the process.
After degassing and recovery of the latent
heat, the water is separated by centrifuge and
the wet PVC leaving the centrifuge is fed into
the drying section. A big part of the water
from the centrifuge is recovered in a waste
water recovery unit (for pipe grade) and sent
back to the high performance reactors.
The wet PVC is dried by means of heated
air in a fluidized bed drier or the Vinnolit
MST Cyclone drier
After drying, the PVC powder is conveyed
pneumatically to the silo and bagging unit.
Consumption figures for raw materials and
energy
Low consumption of monomers, demin.
water, chemicals and auxiliary materials,
low energy consumption due to heat re-
covery, results in low production cost.
Especially, the utilization of hot water gener-
ated in the VCM plant for heating of the PVC
drier yields very low energy consumption in
the PVC plant.
Consumption per 1,000kg of PVC powder
at the production plant including VCM
recovery:
Vinyl chloride 1,001 kg
Demineralised water 1.4 m3)
Chemicals 2.5 kg
Steam 700 kg4)
3) Without waste water recovery 2.3 m3
4) Combined figure for VCM and PVC plant: 435 kg
This data is based on average values.
The consumption values depend on K
values, on recipes and location.
VCM
Activator
Demin. water
Dispersing agent
C W
Recovered VCM
High-performance-
reactor
Polymerisation
C W
Blowdown
vessel
Slurry
Pre-degassing
vessel
Degassing
Waste water
recovery
Steam
Degassing
column
H o t w a t e r
Centrifuge
Fluidized bed drier
to waste water treatment unit
Drying
Hot water
PVC powder to silo
off-air
A i r
Clean reactor technology
Scale-free operation is achieved through the
use of reliable lining inhibitors, optimum
operating conditions during polymerisation
and a reactor designed to suit the require-
ments specified.
This means:
High-Performance Reactor
Clean and closed reactor technology
Heat dissipation remains constant
It is therefore not necessary to frequently
open the reactor for cleaning purposes.
Process control system
The whole plant is controlled with the aid
of a digital process control system.
This results in:
Precise metering of the individual
components during reactor charging
High constancy of the present process
parameters
Excellent reproducibility of the process giv-
ing extremely consistent product quality
High level of plant safety and reliability
Low personnel requirement
Intensive Degassing System
Our own work on the development of an
intensive column degassing technology has
resulted in perfect, continuously operating
processes with the following conditions:
Extremely low residual VCM content in
the PVC slurry and in the PVC products
Gentle degassing conditions
Grade change without opening the
column
Extremely low VCM emissions
Drying
In a fluidized bed drier, the PVC is dried to
the required moisture content. This op-
eration can be performed highly economic
because of the possible heat integration
with the VCM plant.
PVC High-Performance Reactor (inside view)
In addition, the polymerisation system is
completely safeguarded and can stop the
reaction under extreme conditions e.g.
simultaneous failure of coolant and
power supply.
Emissions
According to Vinnolit’s commitment with
regard to environmental protection, the
offered S-PVC process sets a new standard.
Clean and closed reactor technology, pro-
cess automation and effective degassing of
product means that VCM emissions are
kept at an extremely low level and under
normal operating conditions are far lower
than the figures required at present:
Less than 1 mg/m3 in drier off-air
Less than 1 mg/m3 in waste water
Less than 2 vol. ppm (shift average
value in the air at the workplace).
Effective measures keep PVC emissions in
the drier off-air to less than 10 mg/m3.
1 7
3.2 Advantages of the S-PVC process
Polymerisation Reactors
The safety concept
The whole safety concept, including its
computer process control system, permits
a particularly high level of operational
safety.
The requirements of a modern high-perfor-
mance polymerisation reactor with a high
productivity:
Short non-reaction time
to be reached by:
- Closed and clean reactor technology
- Efficient anti-fouling technology
- No reactor opening
- No high-pressure cleaning
- No heating up of the batch
- Optimised charging procedure, i.e.
simultaneous hot water/VCM charging
- Automatic catalyst charging
Minimal reaction time to be reached by:
- Fast reaction-heat dissipation
- Large reactor technology
- Volumes up to 160 m3
- Adapted recipes
To achieve a minimal reaction time, the
reaction heat has to be dissipated out of
the reactor quickly.
by increasing the heat transfer area by
arrangement of half pipe coils inside
by increasing the differential
temperature between inside reactor and
jacket, e.g. using chilled water
by improving the heat-transition coef-
ficient, e.g. using a thinner wall between
inside reactor and cooling water
by adding an external condenser
Step by step Vinnolit has realised all
requirements for a high-performance poly-
merisation reactor. The inner cooler reactor
was developed as a last link in the optimi-
sation. This completely new reactor design
has been created and improved by Vinnolit
engineers. The inner cooler reactor has
demonstrated its outstanding suitability for
the production of suspension PVC on an
industrial scale for many years and is
therefore a proven design.
In view of Vinnolit’s inner cooler reactor,
the choice was made for a combination of:
Increased heat transfer area due to the
half-pipe coil on the inner reactor wall
Improved heat-transition coefficient due
to the reduced thickness of the half-pipe
coil
Increased heat transfer due to
higher turbulences at the wall.
This design combines high heat transfer
rate with safe operation in a closed mode.
Of course the other internal components of
the inner cooler reactor like the agitator,
baffles and nozzles are optimised as well to
apply the reactor technology in the same
way as in Vinnolit’s conventional reactors.
The essential advantages of the Vinnolit
High-Performance Reactor are:
High output of up to 600 mt/m3/year
- Very short non-reaction time
- Very short reaction time
High quality of product grades
- Use of the Vinnolit recipes
- Wide range of licensed grades
- Heat dissipation only in the liquid phase
as in a conventional reactor
Large reactor Volumes of up to 160 m3
ensuring
- Low investment costs
- Low maintenance costs
Large heat transfer area and high heat-
transition coefficient, providing a cooling
capacity twice that of a conventional reac-
tor; therefore no additional cooling area
(such as a reflux condenser) is required
Very simple and safe operation
- Closed and clean reactor technology:
using the Vinnolit anti-fouling tech-
nology dispenses with high-pressure
cleaning or reactor opening
- Automatic catalyst charging
- Simultaneous charging of hot
water and VCM
- No heating up by means of a heating
jacket
Low operating costs because of
- Adapted recipes
- Use of cooling water instead of chilled
water
1 8
3.3 The Vinnolit High-Performance Reactor for suspension PVC
Heat transfer graph (typical) Heat transfer graph (typical)
of conventional reactor cooling of Vinnolit’s High-Performance Reactor
A Cooling channel
C PVC-suspension
B Cladded steel wall
D Half-pipe wall
E Cooling coil
A B C D E
Suspension
Ultrafiltration unit for waste water in an S-PVC plant
Description
Suspension PVC is produced in an aqueous
process. Approx. 2.3 m3 of precious water
are used in a conventional process per ton
of PVC. Up to now this water could only be
used for flushing purposes, but the demand
for flush water in the downstream units is
small compared with the water demand for
polymerisation. So the water is usually after
treatment in a biological waste water
treatment discharged to a recipient.
Re-use of the waste water in the poly-
merisation was so far inhibited by quality
problems caused by the residual PVC solid
content. But today the required purity can
be achieved by a tailor-made special filtra-
tion process.
Ultrafiltration
Ultrafiltration is employed to remove any
solids from the decantation waste water.
Ceramic membranes compatible with the
other ingredients in the waste water are
used in that process. The PVC contami-
nated waste water from the decantation
centrifuge is treated in the special filtration
unit. The treated water is free of PVC solids
and is recycled into the polymerization pro-
cess in order to reduce the consumption of
fresh de-mineralized water and at the same
time the amount of waste water. The flux
through the membranes can be preserved
on an acceptable level by regular cleaning
operations for at least 1 year.
Features
Reduction of fresh water consumption
to approx. 1.4 m3/t PVC (pipe grade)
Reduction of waste water
Proven in production scale for pipe grade
Re-use of waste water in the
suspension PVC process
VC
1 9
3.4 Waste Water Recycling
VC Recycling
Poly-
merisation
Thermal
Drying PVC
Centrifuge
Drying PVC
PVC solid
H20 vapor
PVC
separation
H20 Reuse
Additives
H20
2 0
3.5 Products and applications
K value Viscosity
number
ISO 1628/2 ISO 1628/2
Bulk
density
g/l
DIN 53468
Screen analysis
< 63 µm > 250µm
DIN 53734
> 315 µm
Plasticiser
absorption
DIN 53417
57 80 600 2 % < 1 % < 0.1 % low
60 89 570 2 % < 1 % < 0.1 % medium
65 105 580 1 % < 5 % < 0.1 % medium
67 112 570 1 % < 5 % < 0.1 % medium
68 116 570 1 % < 5 % < 0.1 % medium
65 124 510 5 % < 1 %
high
70 124 480 5 % < 1 %
high
75 145 470 5 % < 1 % < 0.1 % high For further product information please
refer to Vinnolit’s website:
www.vinnolit.com
Application
Test method
Injection-moulded articles, rigid film, hollow articles
Rigid film, injection-moulded articles, plates, bristles
Rigid and semi-rigid sections
Rigid pipes and sections
Rigid pipes and sections
Plasticised film, sections and flexible tubing
Plasticised film, sections, injection-moulded articles, cable
Platicised film and profiles, medical articles
S-PVC, in particular, can be
produced in both a crystal clear, hard
and a very soft flexible finished form,
with good electrical properties. Only
the major applications of the different
basic types are listed as follows:
Coarse-grained, porous, free-
flowing S-types with a high bulk
density for rigid and semi-rigid
extrusion (pipes, sections, plates),
bubble extrusion (hollow items) and
injection moulding, low-fish-eye S-
types for the calendering of rigid and
semi-rigid film, the production of
PVC bristles and deep-drawable
rigid film.
Coarse-grained, highly porous,
free-flowing plasticiser S-types for
dry blend production, free-flowing
plasticised PVC mix for low-fish-
eye extrudates and film, for cable
sheaths and hoses.
Probably no other plastic can match the wide variety of possible uses offered by PVC.
2 1
4. References
Completion Customer Plant Site Product Plant Capacity mtpy
Selected references of EDC and VCM plants
2021 EPC Alexandria, Egypt VCM 125,000
2021 PT. Sulfindo Adiusaha Banten, Indonesia EDC, Oxychlorination VCM
200,000 250,000
2018 PT Asahimas Chemical Cilegon, Indonesia EDC, Oxychlorination 243,000
2018 BorsodChem Borsod, Hungary EDC, Oxychlorination 292,000
2015 Sayanskchimplast Sayansk, Russia VCM 350,000
2014 Qatar Vinyl Co. (QVC) Mesaieed, Qatar EDC (Expansion) 470,000
2014 Mexichem SA de CV Coatzacoalcos, EDC, Direct Chlorination 460,000
Mexico EDC, Oxychlorination 480,000
VCM, EDC Cracking 600,000
2013 Petroquímica de Maracaibo, Venezuela EDC (Expansion) 155,000
Venezuela VCM (Expansion)
2010 S.N.E.P. Morocco EDC Direct chlorination, 115,000
EDC, Oxychlorination 112,000
2010 Sayanskchimplast Russia VCM, EDC Cracking 200,000
2009 Undisclosed Middle East EDC, Direct chlorination 551,000
EDC, Oxychlorination 332,000
(Sales EDC) 329,000
VCM, EDC Cracking 343,000
2008 Formosa Plastics Corp. USA EDC Cracking 240,000
2007 Sahara Petrochemical Co. KSA EDC Direct chlorination 300,000
(Basic engineering
implementation pending)
2009 Vinnolit GmbH & Co. Middle East EDC Direct chlorination 660,000
EDC, Oxychlorination 1,300,000
Sales EDC 100,000
VCM 1,020,000
2008 Tokuyama Corp. Japan EDC, Direct chlorination 200,000
(Basic engineering for feasibility study)
2007 Liwa Petrochemical Sohar, Oman EDC, Direct chlorination 307,000
Company LLC
2006 Limburgse Vinyl Tessenderlo, Belgium EDC, Direct chlorination 250,000
Maatschappij (LVM)
2005 Sasol Polymers Sasolburg, South Africa EDC, Direct chlorination 168,000
EDC, Oxychlorination 160,000
VCM, EDC Cracking 205,000
(Expansion)
2005 VESTOLIT GmbH Marl Germany VCM, EDC Cracking 190,000
(Revamp)
2004 Sinopec International / Zibo, Shandong, China EDC, Direct chlorination 330,000
Qilu Petrochemical Co. EDC, Oxychlorination 315,000
VCM, EDC Cracking 400,000
2004 BorsodChem Rt. Kazincbarcika, Hungary EDC, Oxychlorination 225,000
(Expansion)
2004 Shanghai Chlor Shanghai, China VCM, EDC Cracking 130,000
Alkali Chemical Co. (Expansion)
2003 Petkim Petrokimya Aliaga/Izmir, Turkey EDC, Direct chlorination 136,000
Holding VCM, EDC Cracking 152,000
2002 Vinnolit GmbH & Co. KG Knapsack, Germany EDC, Oxychlorination 170,000
VCM, EDC Cracking 330,000
Completion Customer Plant Site Product Plant Capacity mtpy
Selected references of PVC plants
2013 Petroquímica de
Venezuela
Maracaibo, Venezuela S-PVC (Expansion) 48,000
2010 Lukoil Neftochim JSC Kalush, Ukraine S-PVC, Polymerisation
S-PVC, Degasing
S-PVC, Cyclone drier
300,000
2009 S.N.E.P. Morocco S-PVC, Cyclone drier 85,000
2009 Ercros Spain S-PVC, Polymerisation 120,000
2008 Spolana A.S. Czech Republic S-PVC, Cyclone drier 2 x 100,000
2007 Braskem Brasil S-PVC, Polymerisation 130,000
2007 Undisclosed USA S-PVC, Polymerisation 250,000
2006 Undisclosed Middle East S-PVC
PVC-E 300,000
40,000
2002 Zaklady Azotowe w
Tarnowie-Moscicach
Tarnow, Poland S-PVC 100,000
2001 Royal Polymer Ltd. Sarnia, Canada S-PVC, Cyclone drier 80,000
1997 S.N.E.P. Morocco S-PVC, Cyclone drier 52,000
1996 Hydro Polymers Ltd. Newton Aycliffe, UK S-PVC, Cyclone drier 92,000
1996 Georgia Gulf Corp.
(former Vista Chemical
Corporation)
Aberdeen, MS, USA S-PVC, Cyclone drier 110,000
2 2
Chemical and Process Technologies
thyssenkrupp Industrial Solutions AG
Friedrich-Uhde-Strasse 15
44141 Dortmund, Germany
P: +49 231 547-0
F: +49 231 547-3032
www.thyssenkrupp-industrial-solutions.com