Vinyl chloride and polyvinyl chloride - Lifting Synergies with Oxychlorination and Direct Chlorination - IHS Markit
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Vinyl chloride and polyvinyl chloride Lifting Synergies with Oxychlorination and Direct Chlorination
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
3
1. Company profile
The Chemical and Process Technologies business unit of Vinnolit is one of Europe’s leading EDC, VCM and PVC producers
thyssenkrupp is a technology-driven engineering, procurement and with a capacity of 780,000 t/year of PVC, 665,000 t/year of VCM
construction partner for the global chemical industry. It was founded and upstream chlorine plants. They enhance and optimise their
nearly 100 years ago under the name of Uhde. With its international process technology on a permanent basis. Vinnolit was founded
network of subsidiaries and branch offices, the company has to date in 1993 as a 50/50 joint venture between Hoechst AG and
successfully completed over 2,500 projects throughout the world. Wacker Chemie GmbH. The new company drew on the
experience of its two founders, both active in the vinyl sector for
We develop innovative processes and products for a more sustainable almost 60 years. In 2014, Vinnolit became part of Westlake
future and thus contribute to the long-term success of our customers in Chemical Corporation, a leading international manufacturer and
almost all areas of the chemical industry. Our portfolio includes leading supplier of petrochemicals, polymers and PVC construction
technologies for the production of basic chemicals, fertilizers and products headquartered in Houston.
polymers as well as complete value-chains for green hydrogen and
sustainable chemicals. Since 1964 the licensor has granted licences for a capacity of
more than 14 million tonnes of EDC, approx. 6.5 million tonnes
tkIS and Vinnolit – Partners for vinyl chloride and polyvinyl chloride of VCM and about 2.9 million tonnes of S-PVC.
Our licensor for the Ethylene Dichloride (EDC), Vinyl Chloride The cooperation between the licensor and tkIS has been successful
Monomer (VCM) and for the Polyvinyl Chloride (PVC) process is for some 50 years. tkIS is the sole basic engineering partner for
Vinnolit GmbH & Co. KG. Vinnolit’s EDC, VCM and PVC processes.
4
2. The Vinnolit VCM process
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
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
Qatar Vinyl Company (QVC), Vinyl chloride (VCM), which is made from Optimised reaction conditions and
Mesaieed, Qatar
ethylene and chlorine, is used as feedstock reaction control
Capacities of the complex:
in the production of the standard plastic Utilisation of by-products containing
360,000 t/year of DC-EDC material PVC. Cl2 along with the recycling of HCl gas
175,000 t/year of Oxy-EDC High on-stream factor
230,000 t/year of VCM The market for PVC and hence VCM has Low personnel requirement
continued to grow, thus dispelling the fore- Low maintenance costs
casts made in the 80s, according to which High flexible, wide range of load
PVC would be substituted by other plastics.
Extremely low pollution levels:
The reasons for this were not only the mani- ≤ 0.01 ppm VCM (annual average)
fold applications and properties of PVC, but in working areas
also the progress made in limiting emissions Extremely low VCM emissions
and by-products during production. PVC pro- Small waste water quantities
duction capacity attained growth rates of with EDC/VCM contents ≤ 1 ppm
approx. 6% per year, accounting for approx. In-plant disposal of low-boiling and
47 million tonnes worldwide in 2010. For the high-boiling constituents in conjunction
next few years, growth rates in the order of with HCl gas recycling and steam
4% per year are again expected. generation
Special facilities for preventing emissions
As a chemical engineering contractor, tkIS when the plant is shut down
added VCM to its range of processes some Thermal waste gas treatment
40 years ago and has to date designed and
constructed plants with a total nominal ca- Expected consumption figures for raw materials
pacity of approx. 6 million tonnes. and utilities per 1,000 kg VCM product
The VCM process applied by tkIS is licensed Ethylene (100 %) 459 kg
by Vinnolit. The current high technological Chlorine (100 %) 575 kg
standard was reached through intensive Oxygen (100 %) 139 kg
development work on the part of Vinnolit in Steam 250 kg1
collaboration with tkIS. The process has
Fuel gas 2.7 GJ
been successfully applied at Vinnolit’s ex-
isting plants at Gendorf (Bavaria) and at Combined figure for VCM / PVC plant: 435 kg
1)
5
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)
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
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.
The EDC produced by direct chlorination is
fed straight into the cracking section without In the third process section, the EDC is well as liquid by-products are fed to the HCl
any further purification. cracked, and the VCM formed there, as well recovery unit and converted to HCl, CO2 and
as the hydrogen chloride and unconverted water.
The heat of this exothermic reaction can be EDC, are separated in a VCM distillation unit.
used for PVC drying in the PVC plant or for The VCM is temporarily stored in a tank, The recovered HCl is reused in the oxychlo-
heating of columns in the EDC distillation while the HCl is returned to the oxychlorina- rination process, which leads to a complete
unit depending on the individual plant con- tion unit and the unconverted EDC to the conversion of the input chlorine.
figuration. cracking section.
The diagram shows the individual sections
The EDC formed by oxychlorination passes Any process water obtained undergoes treat- of the overall process which are described
through a purification stage (EDC distillation). ment. Waste gases containing pollutants as on the following pages.
VCM synthesis: 2 C2H4 + Cl2 + 1⁄2 O2 2 C2H3Cl + H2O Schematic diagram of a VCM plant
Chlorine Direct ED C VCM Vinyl chloride
ED C
Cl2 chlorination c r a c k i ng distillation VCM
C 2H 4 C2H4Cl2 C 2 H 4 Cl 2 ΔH C2H3Cl + HCl
+ Cl2 Cat + 218 kJ/mole – 71 kJ/mole
Ethylene EDC recycle EDC liquid + gaseous
C2H4 distillation chlorination by-products
H Cl
Oxygen by-product
Oxychlorination H Cl recovery
O2
C2H4 + 2 HCl + 1⁄2 O2 Cat C2H4Cl2 + H2O + 238 kJ/mole
6
2.2 Direct chlorination
In the direct chlorination process, EDC is Gaseous chlorine is added via an injector The process is particularly
produced by means of a highly exothermal nozzle to a relatively small circulating EDC environment-friendly, because:
reaction of ethylene and chlorine. side stream withdrawn in the downcomer The energy recovery options lead to a
section of the CNC reactor and cooled to significant reduction of CO2-emissions
The main feature of the Vinnolit direct allow the chlorine to be better pre- The formation of high-boiling
chlorination process is an innovative boiling dissolved. This cooling provides another constituents is significantly reduced
reactor with natural convection flow. opportunity to recover the heat of reaction. Extremely small quantities of low-boiling
Recently, as a result of a joint development constituents are formed (only a few ppm)
project of tkIS and Vinnolit, the compact The ethylene solution and the completely No scrubbing water is required and
natural circulation (CNC) reactor was devel- predissolved chlorine are mixed in the reac- No catalyst is discharged with the product.
oped and now is ready for introduction on tion zone of the riser and react to EDC in a
the market. In the CNC reactor, the natural fast liquid-phase reaction which significantly The catalyst has no corrosive properties be-
circulation is established in an internal loop lowers by-product formation. cause of its complex structure, and therefore
consisting of a riser section and a down- the process equipment can be made mainly
comer section, leading to a more contact Due to the reduced static pressure head of ordinary carbon steel. Existing plants can
and cost-saving reactor design. in the top section of the riser, the EDC be converted without any difficulty.
starts boiling. The product amount and
The Vinnolit Direct Chlorination process some excess EDC are withdrawn from the The advantages of the process can be
operates at boiling conditions with a tem- upper part of the CNC reactor and passed summarised as follows:
perature of 120°C. The heat of reaction is on to the product vessel and a stripping Nearly no consumption of catalyst
removed by boiling off EDC from the boiling column to achieve 'Sales EDC' quality, if High raw material yields
reactor. A big portion of this heat can be required. The excess EDC is recycled to High EDC purity: 99.9 %
recovered by several heat recovery options, the main reactor loop. Utilisation of reaction heat, e.g. for
e.g. heating of distillation columns in the heating of distillation columns or drying
EDC distillation unit or heating of a fluidised In contrast to competitive direct chlorination of PVC, leading to a reduction in steam
bed PVC drier in the PVC plant yielding a processes, the Vinnolit Direct Chlorination consumption of up to 700 kg / tonne of
reduction of steam consumption of up to process does not use FeCl3, but a complex EDC.
700 kg / tonne of EDC. compound as catalyst. The catalyst sup- Low investment costs
presses the formation of by-products and Complete reaction in only one reactor
The reaction is carried out in the riser sec- ensures higher selectivity to EDC. Proven materials and reliable and simple
tion of the CNC reactor. In contrast to other equipment
processes, gaseous ethylene is first com- Thus the Vinnolit Direct Chlorination process High active and selective catalyst
pletely pre-dissolved in the lower part of the combines the energy efficiency of a high-
riser section of the CNC reactor. temperature chlorination (HTC) process with Utilising the reaction heat saves energy and
the EDC purity of a low-temperature chlorin- reduces emissions of CO2 by an amount
ation (LTC) process. The catalyst is fed to the equivalent to the energy savings. Thus, car-
reactor loop before start-up and does not bon certificate trading has a positive effect
have to be topped up in normal operation. on production costs.
7
Refrigerant
Direct chlorination process
using a boiling reactor
Waste gas to
incineration
CW
H ea t
r ec o v er y
Chlorine
Product Stripping
vessel column
Ethylene
Sales - EDC
Heat N2
recovery
CNC Reactor Furnace feed EDC
8
2.3 Oxychlorination
In the oxychlorination process, EDC is formed mixture, consisting of C2H4, HCl and O2, is
by a highly exothermal catalytic reaction of catalytically converted in the fluidised-bed
ethylene with hydrogen chloride and oxygen. reactor to EDC in a highly exothermal reaction
at a temperature of > 200°C. The heat is
The reaction takes place in a fluidised-bed dissipated via internal cooling coils and
reactor, and the reaction heat is used for recovered to generate steam. Independent of
steam generation. In the downstream quench load the generated steam has a constant
column, a major portion of the reaction water pressure level.
is removed by condensation. To remove
small quantities of chlorinated hydrocarbons The excellent distribution in the fluidised-bed
from the reaction water, it is transferred to makes it possible to maintain a constant tem-
the effluent treatment facilities. perature, to ensure low by-product formation
and to achieve optimum process control.
By cooling the reaction gases further by
means of cooling water (CW) and refrigerant The reaction gas passes a filter unit in which
(R), the raw EDC is removed by condensation the catalyst fines are separated from the
and fed to the EDC distillation unit, where it is gas. Depending on customer's require-
purified to obtain “feed EDC quality”. ments, also a waste water treatment section
comprising a precipitation and sludge filtra-
The Vinnolit oxychlorination process can use tion step can be implemented. To remove
oxygen from air separation units as well as the reaction water, the hot reaction gases
oxygen from pressure swing adsorption are quenched and the EDC is condensed
units (PSA oxygen). In the reactor the cata- with the aid of chilled water in a multi-stage
lyst is fluidised with circulation gas. Just condensation unit. The crude EDC is purified
enough oxygen is added to the reactor to in an EDC distillation unit to obtain “feed
keep the concentration of the circulation gas EDC quality”.
outside the flammable range (oxygen lean
operation). The very small off-gas stream of The reaction water obtained is passed to
inerts and carbon oxides which is formed in the waste water treatment facilities to re-
the process is fed to the HCl recycle unit move the small quantities of chlorinated
without further treatment. The reaction hydrocarbons it contains.
Refrigerant
Waste gas to
incineration
Steam
CW
HCl from TDI / MDI possible
Hydrogenation Catalyst
reactor filtration
Boiler
feedwater
Hydrogen
Oxychlorination
Hydrogen chloride Quench
reactor
column
Crude EDC
Oxygen
Circulating-gas
Ethylene compressor
Effluent to waste
water treatment
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 %
10
2.4 EDC distillation
To produce pure feed EDC, both the EDC The dry bottom product from the heads
obtained in the oxychlorination process and column together with the unconverted EDC
the EDC not converted in the cracking from the cracking process are separated
process (recycle EDC) are treated in the EDC from the high-boiling compounds in the
distillation unit in order to remove water as high-boil and vacuum columns. These high-
well as low-boiling and high-boiling com- boiling compounds are withdrawn from the
ponents. bottom of the vacuum column and sent to
the incineration unit.
The wet raw EDC from the oxychlorination
unit is fed to the heads column in order to By default, the high-boil column is oper-
remove the water and low-boiling substanc- ated at elevated pressure and the
es by distillation. The water phase of the overhead vapours of this column are used
head product containing small quantities of to heat the heads column and the vacuum
chlorinated hydrocarbons and sodium column. Depending on customer's
chloride is transferred to the waste water requirements also other heat recovery
treatment unit. The organic phase and the options can be realized.
off-gas are fed to the incineration unit.
EDC evaporator and cracking furnace
Waste gas to incineration
Recycle EDC
CW
from VCM distillation
CW CW ______________ R
Heads
column
High-boils Vacuum
column column
Crude EDC
from
oxychlorination
from cracking
Steam High-boiling
Cond. components
to incineration
Cracking EDC
Low-boiling components to incineration
Effluent to waste water treatment11
2.5 EDC cracking
The cracking of 1,2 dichloroethane takes The advantages of Vinnolit’s modern EDC
place in a cracking furnace heated by fuel. cracking process can be summarised as
VCM and HCl are formed at temperatures follows:
of 480°C, the reaction being endothermic
and incomplete. High reliability due to low coke formation
High savings in primary and secondary
In addition to VCM and HCl, by-products of energy, due to:
various chemical structures and coke are - External EDC pre-evaporation using
formed. cracking gas heat
- Utilisation of flue gas and cracking
The external EDC pre-evaporation facility
gas heat to preheat combustion air, to
reduces the formation of coke in the crack-
generate steam or to preheat EDC
ing furnace considerably. The operating
periods between two decoking intervals are Low maintenance costs
very long (up to 2 years). 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
Cracking EDC
CW HCl
Combustion air
Cond. Steam
to VCM distillation
Cracking product
to VCM distillation
Fuel Fuel
Recyle EDC
to EDC distillation12
2.6 VCM distillation
The product from the cracking unit consists The Vinnolit EDC distillation unit can do
of VCM, HCl, unconverted EDC and by-prod- without a low-boil column for recycle
ucts of various chemical structures. EDC with all its related problems.
Hydrogen chloride is recovered in the HCl Advantages of the VCM column:
column and fed to the oxychlorination unit. HCl content in VCM < 1 ppm without
Vinyl chloride is obtained at the top of the using caustic
VCM column. Long on-stream time of VCM distillation
unit, because of no coke carry over from
Any traces of HCl are removed from the VCM hot quench system
in the HCl stripper. The overhead product of Vapor feed of HCl stripper overhead
the HCl stripper is recycled to the HCl column product to the HCl column, no
via a H2O removal unit which removes condensation system necessary
moisture from the distillation process and Lower power consumption for HCl
protects against moisture build-up. condensation compared to low
pressure HCl column
The bottom product of the VCM column,
i.e. un-converted EDC, is returned to the Advantages of the recycle EDC chlorination:
EDC distillation process after the low- No separation of low-boiling compounds
boiling compounds have been converted necessary
by chlorination to high-boiling compounds. Low investment cost in comparison to
Thus the difficult and energy-consuming a low-boil column
separation of recycle EDC from other low- Easy operation
boiling components is avoided. No steam consumption
Low maintenance cost
HCl to oxychlorination
H2O removal
CW
Refrigerant
from Cracking HCl column VCM column HCl stripper
quench
Cracking
unit product
Steam Steam Steam CW
Cond. Cond. Cond.
Heat Product
r ec ov er y
VCM
EDC chlorination unit
Recycle EDC
to EDC distillation
Cl 213
2.7 Measures to recover by-products
and to protect the environment
The treated waste gas complies with all
HCl recovery unit
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.
2.7.1 HCl recycling with waste gas oxidation process to form CO2, water and
heat recovery hydrogen chloride. This process operates 2.7.3 Liquid and waste gas collection
with an excess of air at approx. 1,150°C. systems
In the production of VCM, not only 1,2
dichloro-ethane is produced as a desirable The heat of the hot combustion gases is ex- Liquid EDC and VCM from drains, cleaning
intermediate product, but also further by- ploited to generate steam, and the hydrogen of filters, reboilers etc. are collected in
products, consisting of a mixture of high- chloride is recovered as a valuable feedstock closed systems and returned to the process
boiling and low-boiling compounds, are which is returned in gaseous form to the loop to protect the environment.
obtained in liquid or gaseous form. oxychlorination process.
Sources of continuous waste gas streams
In a new modified Vinnolit process, these Alternatively, aqueous HCl of 25 to 30% can are connected to waste gas headers and
by-products are completely converted in an be produced. the gas is sent to the 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 VCM15
3. The Vinnolit S-PVC process
3D model of one of the world's The suspension polymerisation process for Vinnolit technology is characterised by:
largest PVC complexes build in manufacturing polyvinyl chloride is the most
Middle East
important way to produce a variety of Vinnolit‘s proprietary technology for all units
Capacities of the complex: general-purpose and highly sophisticated Clean and closed reactor technology
570,000 t/year of chlorine grades of PVC. This process was invented in High productivity
329,000 t/year of sales EDC 1935 and first patented by Wacker Chemie Low raw materials consumption
343,000 t/year of VCM GmbH, one of the former parent companies
340,000 t/year of PVC Low waste water amount
of Vinnolit. Continuous developments had (waste water recovery)
been made in recipes, product quality and Low energy consumption
technology. Due to this long experience and
Low investment cost
continuous improvements, Vinnolit can offer
Low maintenance cost
a modern and highly economic process for
High safety level
the production of S-PVC worldwide. A
Vinnolit team of specialists is available to Leading in environmental
tailor plant design according to licensee’s protection – DIN ISO 14001 certified
requirements. High product quality – DIN ISO 9001
certified176
3.1 Description of the S-PVC process
Vinyl chloride and hot water are fed to the The wet PVC is dried by means of heated Consumption per 1,000kg of PVC powder
Vinnolit High-Performance Reactor by air in a fluidized bed drier or the Vinnolit at the production plant including VCM
means of a special charging program. MST Cyclone drier recovery:
Vinyl chloride 1,001 kg
Once the polymerisation has been completed After drying, the PVC powder is conveyed
Demineralised water 1.4 m3)
the content of the reactor is discharged into a pneumatically to the silo and bagging unit.
blowdown vessel and from here continuously Chemicals 2.5 kg
fed to the Intensive Degassing System. Consumption figures for raw materials and Steam 700 kg4)
energy 3) Without waste water recovery 2.3 m3
The nonconverted monomer is stripped out, 4) Combined figure for VCM and PVC plant: 435
condensed and fed back into the process. Low consumption of monomers, demin. kg
water, chemicals and auxiliary materials,
This data is based on average values.
After degassing and recovery of the latent low energy consumption due to heat re- The consumption values depend on K
heat, the water is separated by centrifuge and covery, results in low production cost. values, on recipes and location.
the wet PVC leaving the centrifuge is fed into
the drying section. A big part of the water Especially, the utilization of hot water gener-
from the centrifuge is recovered in a waste ated in the VCM plant for heating of the PVC
water recovery unit (for pipe grade) and sent drier yields very low energy consumption in
back to the high performance reactors. the PVC plant.
CW off-air
Recovered VCM
VCM
Activator
Demin. water
Centrifuge
Dispersing agent
Fluidized bed drier
Hot
water
CW Stea m
Hot water
Slu rry
PVC powder to silo
Air
Waste water
recovery
to waste water treatment unit
High-performance- Blowdown Pre-degassing Degassing
reactor vessel vessel column
Polymerisation Degassing Drying17
3.2 Advantages of
the S-PVC process
Clean reactor technology Excellent reproducibility of the process giv-
ing extremely consistent product quality
Scale-free operation is achieved through the High level of plant safety and reliability
use of reliable lining inhibitors, optimum Low personnel requirement
operating conditions during polymerisation
and a reactor designed to suit the require-
Intensive Degassing System
ments specified.
Our own work on the development of an
This means:
intensive column degassing technology has
High-Performance Reactor resulted in perfect, continuously operating
Clean and closed reactor technology processes with the following conditions:
Heat dissipation remains constant Extremely low residual VCM content in
the PVC slurry and in the PVC products
It is therefore not necessary to frequently
open the reactor for cleaning purposes. Gentle degassing conditions
Grade change without opening the
Process control system column
Extremely low VCM emissions Polymerisation Reactors
The whole plant is controlled with the aid
of a digital process control system. Drying The safety concept
This results in: In a fluidized bed drier, the PVC is dried to The whole safety concept, including its
Precise metering of the individual the required moisture content. This op- computer process control system, permits
components during reactor charging eration can be performed highly economic a particularly high level of operational
High constancy of the present process because of the possible heat integration safety.
parameters with the VCM plant.
In addition, the polymerisation system is
completely safeguarded and can stop the
PVC High-Performance Reactor (inside view) 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/m3.18
3.3 The Vinnolit High-Performance
Reactor for suspension PVC
Step by step Vinnolit has realised all High output of up to 600 mt/m3/year
requirements for a high-performance poly- - Very short non-reaction time
merisation reactor. The inner cooler reactor - Very short reaction time
was developed as a last link in the optimi- High quality of product grades
sation. This completely new reactor design
- Use of the Vinnolit recipes
has been created and improved by Vinnolit
- Wide range of licensed grades
engineers. The inner cooler reactor has
- Heat dissipation only in the liquid phase
demonstrated its outstanding suitability for
as in a conventional reactor
the production of suspension PVC on an
industrial scale for many years and is Large reactor Volumes of up to 160 m3
therefore a proven design. ensuring
- Low investment costs
In view of Vinnolit’s inner cooler reactor, - Low maintenance costs
the choice was made for a combination of: Large heat transfer area and high heat-
Increased heat transfer area due to the transition coefficient, providing a cooling
half-pipe coil on the inner reactor wall capacity twice that of a conventional reac-
tor; therefore no additional cooling area
Improved heat-transition coefficient due
(such as a reflux condenser) is required
to the reduced thickness of the half-pipe
coil Very simple and safe operation
Increased heat transfer due to - Closed and clean reactor technology:
The requirements of a modern high-perfor- higher turbulences at the wall. using the Vinnolit anti-fouling tech-
mance polymerisation reactor with a high nology dispenses with high-pressure
productivity: cleaning or reactor opening
This design combines high heat transfer
Short non-reaction time rate with safe operation in a closed mode. - Automatic catalyst charging
to be reached by: Of course the other internal components of - Simultaneous charging of hot
the inner cooler reactor like the agitator, water and VCM
- Closed and clean reactor technology
baffles and nozzles are optimised as well to - No heating up by means of a heating
- Efficient anti-fouling technology
apply the reactor technology in the same jacket
- No reactor opening
- No high-pressure cleaning way as in Vinnolit’s conventional reactors. Low operating costs because of
- No heating up of the batch - Adapted recipes
- Optimised charging procedure, i.e. The essential advantages of the Vinnolit - Use of cooling water instead of chilled
simultaneous hot water/VCM charging High-Performance Reactor are: water
- Automatic catalyst charging
Minimal reaction time to be reached by: Heat transfer graph (typical) Heat transfer graph (typical)
of conventional reactor cooling of Vinnolit’s High-Performance Reactor
- Fast reaction-heat dissipation
- Large reactor technology
- Volumes up to 160 m3
- Adapted recipes
To achieve a minimal reaction time, the
A Cooling channel
reaction heat has to be dissipated out of
the reactor quickly. B Cladded steel wall
by increasing the heat transfer area by C PVC-suspension
arrangement of half pipe coils inside D Half-pipe wall
by increasing the differential E Cooling coil
temperature between inside reactor and Suspension
jacket, e.g. using chilled water
by improving the heat-transition coef-
ficient, e.g. using a thinner wall between
A B C D E
inside reactor and cooling water
by adding an external condenser19
3.4 Waste Water Recycling
Ultrafiltration unit for waste water in an S-PVC plant content. But today the required purity can and is recycled into the polymerization pro-
be achieved by a tailor-made special filtra- cess in order to reduce the consumption of
tion process. fresh de-mineralized water and at the same
Description
time the amount of waste water. The flux
Ultrafiltration through the membranes can be preserved
Suspension PVC is produced in an aqueous
on an acceptable level by regular cleaning
process. Approx. 2.3 m3 of precious water
Ultrafiltration is employed to remove any operations for at least 1 year.
are used in a conventional process per ton
solids from the decantation waste water.
of PVC. Up to now this water could only be
Ceramic membranes compatible with the Features
used for flushing purposes, but the demand
other ingredients in the waste water are
for flush water in the downstream units is
used in that process. The PVC contami- Reduction of fresh water consumption
small compared with the water demand for
nated waste water from the decantation to approx. 1.4 m3/t PVC (pipe grade)
polymerisation. So the water is usually after
centrifuge is treated in the special filtration Reduction of waste water
treatment in a biological waste water
unit. The treated water is free of PVC solids Proven in production scale for pipe grade
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
Re-use of waste water in the Thermal PVC solid
suspension PVC process Drying PVC H20 vapor
VC
VC Recycling
Poly- Centrifuge PVC
Additives
merisation Drying PVC separation
H20
H20
Reuse20
3.5 Products and applications
Application K value Viscosity Bulk Screen analysis Plasticiser
number density absorption
Test method g/l < 63 µm > 250µm > 315 µm
ISO 1628/2 ISO 1628/2 DIN 53468 DIN 53734 DIN 53417
Injection-moulded articles, 57 80 600 2 %21
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 EDC, Oxychlorination 200,000
PT. Sulfindo Adiusaha Banten, Indonesia
VCM 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 330,00022
Completion Customer Plant Site Product Plant Capacity mtpy
Selected references of PVC plants
2013 Petroquímica de Maracaibo, Venezuela S-PVC (Expansion) 48,000
Venezuela
2010 Lukoil Neftochim JSC Kalush, Ukraine S-PVC, Polymerisation 300,000
S-PVC, Degasing
S-PVC, Cyclone drier
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 300,000
PVC-E 40,000
2002 Zaklady Azotowe w Tarnow, Poland S-PVC 100,000
Tarnowie-Moscicach
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. Aberdeen, MS, USA S-PVC, Cyclone drier 110,000
(former Vista Chemical
Corporation)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
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