PVC PPRODUCTION GREEN PROCESS

CONTENTS
1.
2.
3.
4.

Introduction
History
PVCs proprieties
PVC process
Row material
Chemical process
PVC production
5. Application
6. Green process
7. Eco-profiles and LCA
8. Benefits of useing PVC
9. References

1. INTRODUCTION
Poly Vinyl Chloride (abbreviated PVC), is the third-most widely produced polymer, after
polyethylene and polypropylene.
PVC comes in two basic forms: rigid (sometimes abbreviated as RPVC) and flexible. The
rigid form of PVC is used in construction for pipe, and in profile applications such as doors and
windows. It is also used for bottles and other non-food packaging, and cards (such as bank or
membership cards). It can be made softer and more flexible by the addition of plasticizers, the
most widely used being phthalates. In this form, it is also used in plumbing, electrical cable
insulation, imitation leather, signage, inflatable products and many applications where it replaces
rubber.

2. HISTORY
PVC was discovered accidentally on at least two occasions in the 19th century. The first, in
1838, was by the French physicist and chemist Henri Victor Regnault and the second in 1872 by
the German Eugen Baumann. On both occasions, the polymer appeared as a white solid inside
flasks of the newly discovered vinyl chloride gas that had been left exposed to sunlight. The
material was difficult to work with and no one mastered the challenge of commercial
applications.
In 1913, German inventor Friedrich Heinrich August Klatte took out a patent on PVC. His
method used polymerization of vinyl chloride with sunlight.

3. PVC's PROPRIETIES
PVC, PE, PP and PS are general purpose plastics. The features of the particular plastic are
determined by its chemical composition and type of molecular structure (molecular formation:
crystalline/amorphous structure)
Fire retarding properties
PVC has inherently superior fire retarding properties due to its chlorine content, even in
the absence of fire retardants. For example, the ignition temperature of PVC is as high as 455C,
and is a material with less risk for fire incidents since it is not ignited easily.

Furthermore, the heat released in burning is considerably lower with PVC, when
compared with those for PE and PP. PVC therefore contributes much less to spreading fire to
nearby materials even while burning.
Durability
Under normal conditions of use, the factor most strongly influencing the durability of a
material is resistance to oxidation by atmospheric oxygen. PVC, having the molecular structure
where the chlorine atom is bound to every other carbon chain, is highly resistant to oxidative
reactions, and maintains its performance for a long time. Other general purpose plastics with
structures made up only of carbon and hydrogen are more susceptible to deterioration by
oxidation in extended use conditions (such as, for example, through repeated recycling).
Oil/Chemical resistance
PVC is resistant to acid, alkali and almost all inorganic chemicals. Although PVC swells
or dissolves in aromatic hydrocarbons, ketones, and cyclic ethers, PVC is hard to dissolve in
other organic solvents. Taking advantage of this characteristic, PVC is used in exhaust gas
ducts, sheets used in construction, bottles, tubes and hoses.

Mechanical stability
PVC is a chemically stable material, which shows little change in molecular structure,
and also exhibits little change in its mechanical strength. However, long chain polymers are
viscoelastic materials and can be deformed by continuous application of exterior force, even if
the applied force is well below their yield point. This is called creep deformation. Although PVC
is a viscoelastic material, its creep deformation is very low compared with other plastics due to
limited molecular motion at ordinary temperature, in contrast to PE and PP, which have greater
molecular motion in their amorphous sections.
Processability and mouldability
The processability of a thermoplastic material depends largely on its melt viscosity. PVC
is not suitable for injection moulding of large sized products, since its melt viscosity is
comparatively high. On the other hand, the viscoelastic behaviour of molten PVC is less
dependent on temperature and is stable. Therefore PVC is suitable for complex shaped extrusion
profiling (e.g., housing materials), as well as calendaring of wide films and sheets (e.g.,
agricultural films and PVC leather).
Other properties that make PVC versatile
PVC has polar groups (chlorine), and is amorphous, therefore mixes well with various
other substances. The required physical properties of end products (e.g., flexibility, elasticity,
impact resistance, anti-fouling, prevention of microbial growth, anti-mist, fire retarding) can be
freely designed through formulation with plasticisers and various additives, modifiers, and
colouring agents. PVC is the only general purpose plastic that allows free, wide and seamless
adjustment of the required physical properties of products such as flexibility, elasticity, and
impact resistance, by adding plasticisers, additives and modifiers. Since the physical properties
of end products are adjustable through compounding with additives, only a few types of resin are
required to cover all applications (fibre, rigid and flexible plastic, rubber, paint, and adhesive).
This controllability is also extremely beneficial for recycling.

4. PVC PROCESS
PVC manufacturing process

From a chemical viewpoint, PVC is a thermoplastic polymer based on chlorinated hydrocarbons. This figure provides an overview of the production processes leading from raw materials to finished products.
PVC is produced from two primary raw materials, ethylene and chlorine. These react to form
ethylene dichloride (EDC) which, upon cracking, yields vinyl chloride monomer (VCM). Free
radical polymerisation is used to produce the PVC polymer itself.
The two most important polymerisation techniques are suspension polymerisation and emulsion polymerisation, leading to the production of S-PVC and E-PVC, respectively. These two
types of PVC polymer have different properties and are used for distinct applications. The SPVC process yields granules of polymer of 100 to 200 microns in diameter, which are used in
processes such as injection moulding, extrusion and PVC film manufacture. Here, S-PVC is
analysed in more detail, as it is more commonly used. The differ-ence between S- and E-PVC
is rather small, as the type of polymerisation has a low impact on the overall performance of
the PVC over its life cycle.

Row Material
Row material for PVC industry are: Chlorine and Ethylene
Production of ethylene and chlorine
Definition: The raw materials for PVC are petroleum (which contributes to 43% of the polymer
weight) and rock salt (57%). Petroleum is refined to naphtha, which is then cracked to form
ethylene. Chlorine is obtained from rock salt through an electrolytic process.
Manufacture: Ethylene is produced, together with a variety of co-products, by the steam
cracking of naphtha or natural gas liquids. The natural gas liquids contain ethane, butane and
propane and when they are pyrolysed the products are ethylene and propylene. Ethylene
production via steam cracking is a basic chemical process. The ethylene used as an intermediate in PVC production is the minor portion of the chemicals produced during this process.
Products from the steam cracker are used as intermediates for a variety of other products.
Thirty percent of the chlorine produced in Germany is used for Vinylchloride (VCM) and EDC
(dichloroethane) production. Chlorine is produced by the electrolysis of a salt solution or
brine. During electrolysis chlorine is produced at the anode while sodium or caustic soda and
hydrogen are produced at the cathode. The products of the electrode processes must be kept
separately; otherwise they will react to form unwanted by-products. Either chemical or physical separation is employed. Today, there are three different commercial electrolysis processes available: the amalgam process, the diaphragm process and the membrane process.

The amalgam process requires a higher consumption of electrical power than the diaphragm
or membrane processes but produces a purer and more concentrated caustic soda solution.
Substantial quantities of steam are required to concentrate the caustic soda solutions, produced by the diaphragm and membrane cells, to the concentration levels that are produced
by the amalgam process. The Best Available Technology (BAT) for chlorine manufacture is
recognised to be the membrane process, which consumes less electricity compared to the
amalgam and diaphragm processes.
Environmental impact: Emissions from ethylene production are released to air and water.
They consist primarily of ethylene and propylene emissions to air, and methanol and propane/butane emissions to water. Other emissions, such as Total Organic Compound (TOC),
Sodium Hypochlorite (NaOCl), etc. are also present.

Environmental Impact and sources:

Ethylene supply (for S-PVC)

100%

Naphtha
NL: Nat. Gas
NO: Nat. Gas
Methanol
NaOH

80%
60%
40%

Steam Cracker (process)

Electricity
Thermal energy (process)
Steam (process)

20%
0%
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DCB
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Et
[kg

HTP

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[kg
AP

POCP
GW

Environmental Impact of Ethylene Production

During chlorine production, emissions of chlorine and hydrogen are possible from all three
processes (amalgam, diaphragm and membrane). Mercury can be emitted from the amalgam
process only. Asbestos fibres within the diaphragm process are a potential workplace hazard
but the existence of the fibres as such presents no environmental problem, since the fibres
are chemically inert and no release during regular use appears. The diaphragm keeps the
products of electrolysis separate while allowing the passage of electric current. A matter of
concern is the handling and disposal of the diaphragm. Mercury disposal on-site can affect
the water, air and soil in the plant neighbourhood, posing a hazard to plant operators and to
the people and animal life living near the plant. Chlorine as a toxic gas has a potential
environmental impact, if released to the environment.

Environmental Impact and sources:

Chlorine supply (for S-PVC)

100%

NaCl salt

80%

Soda

60%

Sulphuric acid
HCl

40%

Steam (process)
20%

Elektrolysis

0%

Electricity (process)
]

ergy
E

-Eq

rimary

ETP
EP

[kg
P

HTP
P

th

[kg
TP

CB

[kg

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q

-Eq
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Phosphat

[kg

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[kg

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q

[kg

Environmental Impact of Chlorine Production

These figures show the environmental profile of these materials in impact catego-ries. In the
case of ethylene, naphtha occupies a major part in all impact categories, espe-cially
Photochemical Ozone Creation Potential (POCP). This is mainly due to the processing of
crude oil, which causes VOC emissions.
The high consumption of electricity is the main characteristic of the electrolysis process for
the production of chlorine (see Figure 4-4), causing CO2 and SO2 emissions, which result in
a high Global Warming Potential (GWP) and Acidification Potential (AP). In comparison to
the other process steps, the electricity production of the electrolysis process also results in a
high Human Toxicity Potential (HTP). The German Environmental Protection Agency
considers the mercury emission from the production of chlorine with the amalgam process
and the elec-tricity consumption (its production and supply for the electrolysis) as the main
environmental factor of concern for the chlorine production process. New installations of
electrolysis processes have be operated with the membrane process.
A step-by-step shift to the membrane process for chlorine electrolysis is in progress. This is
seen as a major step to further reduce environmental impacts of chlorine production.
Risk characterisation: In the case of PVC, the production of chlorine plays a very important
role and it is a continuing topic of discussion in the assessment of risk. Information regarding
exposure: limits and areas of exposure, risks to the environment and health should be mentioned. Moreover, the production of the petrochemical part of PVC, as for all plastics,
includes various risks: sea pollution from drilling to shipping, and risks associated with

explosive gases such as ethylene.Risk characterisation is not a primary task within LCA, as
LCA deals with potential impacts of regular operation. Today, initial approaches are in
development that address the integration of risk aspects into LCA. Nevertheless, existing
methods, such as Risk Assessment, are more suitable to answer specific questions related
to the risks of chlorine.

Chemical Process
The chemical process for making PVC involves taking the simplest unit, called the
monomer, and linking these monomer molecules together in the polymerization process. Long
molecular chains are formed called polymers (which are also called macromolecules).
This is the case for PVC, which is made from vinyl chloride monomer known usually by
its initials VCM through polymerization. Some monomers exist in the form of reactive gaseous
chemical substances, and some of these may cause health hazards when in direct contact with
humans. In these cases they are manufactured and processed under strict control for health,
safety and environmental protection. On the other hand, polymers such as PVC, which are
manufactured from monomers through polymerization, are solid and chemically stable
substances, therefore do not affect human health. VCM, which is the raw material for PVC, is a
gas at ambient temperature but is usually stored in liquid form under pressure. Ethylene and
chlorine are raw materials for PVC. Upstream industries are those that provide these materials
and include producers of basic petrochemicals (sometimes known as feedstocks), which supply
ethylene, and the chlor-alkali (caustic soda) industry, which supplies chlorine.
At a first stage in the PVC production process ethylene and chlorine are combined to
produce an intermediate product called 1.ethylene dichloride; this is then transformed into vinyl
chloride, the basic building block of polyvinyl chloride or PVC. The process of `polymerization'
links together the vinyl chloride molecules to form chains of PVC. The PVC produced in this
way is in the form of a white powder. This is not used alone, but blended with other ingredients
to give formulations for a wide range of products.
PVC is a thermoplastic made of 57% chlorine (derived from industrial grade salt) and
43% carbon (derived predominantly from oil / gas via ethylene). It is less dependent than
other polymers on crude oil or natural gas, which are nonrenewable, and hence can be
regarded as a natural resource saving plastic, in contrast to plastics such as PE, PP, PET and
PS, which are totally dependent on oil or gas.

PVC production

The process that take place are

1 Row material depozitation

9 Polyerasition

2 Chlorination

10 Stripping

3 Oxichlorination and Cracking

11 Centrifuging

4 Quenching

12 Drying

5 Cooling

13 Sieving

6 Purifiction

14 VSN storage

7 VCM purified

15 PVC recovery

8 Control room

16 Packing

First, the raw material VCM is pressurized and liquefied, and then fed into the polymerization
reactor, which contains water and suspending agents in advance. Through high-

speed agitation within the reactor, small droplets of VCM are obtained. Next, the initiator for
polymerizations is fed into the reactor, and PVC is produced by reaction under a few bar at 40 60C.
PVC obtained through suspension polymerization is suspended in water as particles of
50~200 m diameter (in slurry form). Thereafter the slurry discharged from the polymerization
reactor is stripped of residual monomer, dehydrated, dried and the particle size controlled by
screening to yield PVC in the form of a white powder. The un-reacted VCM is entirely recovered
through the stripping process, and after purification, recycled as raw material for reuse in this
process. PVC resin produced via this suspension process is referred to within the industry using
the abbreviation S-PVC.
Emulsion polymerization and bulk polymerization are alternative, much less extensively
employed, technologies to manufacture PVC. Emulsion polymerization produces finer resin
grades having much smaller particles, which are required by certain applications. This type of
resin is sometimes called paste PVC and referred to within the industry using the abbreviation
P-PVC to distinguish it from S-PVC.

5. APPLICATION
PVC is one of the most used plastic materials in the world. At global level, demand for
PVC exceeds 35 million tonnes per annum and it is in constant growth (+5% on global
average), with higher growth rates in the developing countries.
In Europe (EU-32), the production of PVC products including exports totals about 8
million tonnes per year. European PVC resin consumption totals some 6.5 million tonnes
per year, or 15% of all plastics use in Europe, with an average growth of 2-3% per year.

6. GREEN PROCESS
The concept of sustainability is often stated in a number of ways but four core principles
appear throughout: Protect the environment, promote human health, conserve resources, and
assure social and economic well-being to the global population. PVC resin has intrinsic
properties that allow finished products to meet all four of these objectives. PVC resin and
products compare favorably to other materials in life cycle assessments when reviewing key
impacts of resource and energy conservation, and greenhouse gas emissions.
The 12 Principles of Green Chemistry

Those principles designated with an * illustrate at least seven areas with which PVC resin
production conforms.
Principle No.2, Atom Economy, refers to the conversion of raw materials into finished
products. Overall conversion efficiency for ethylene dichloride to vinyl chloride to PVC is
estimated to be 94% , which puts it among the highest for polymer resins. Key to achieving this
is steam stripping of PVC resin that removes unreacted monomer and recycles it back to the front
of the polymerization process which drives the polymerization (step 5) to nearly complete
utilization of monomer feedstock.
As shown in Figure 1, PVC has one of the lowest embodied energy profiles for a polymer
because of its composition with chlorine, use of catalysts in feedstock preparation, and
exothermic monomer polymerization reaction, which all combine to adhere to Principle No.6
Design for Energy Efficiency. A further look at embodied energy is warranted since it should
be basic to any material sustainability evaluation due to the amount of GHG emitted to produce
the material. In the case of PVC, replacement of ethylene with chlorine in the polymer matrix
creates an interesting tradeoff between the electrical energy intensive derivative chlorine (total
energy for process and transportation = 17.67 MJ/Kg including salt mining) versus the fuel and
electrical energy intensive derivative ethylene (total energy for process and transportation =
17.73 MJ/Kg), with the net result of PVC having a low total embodied energy. It should be
pointed out that comparisons of polymers or other materials on a unit basis would only be an

indication of certain intrinsic attributes, and may not be representative of actual impacts of any
material when a complete cradle to grave life cycle assessment (LCA) is performed.

Figure 1: Resin GHG Emissions vs. Embodied Energy, Data Reference: ACC Cradle to Gate LCI Report

Principles No. 3 and 12, Less Hazardous Chemical Syntheses and Inherently Safer Chemistry
for Accident Prevention intend to reduce environmental and workplace hazards through
chemical selection. But all organic raw materials, whether in a solid or liquid form, can present
combustible dust or flammable liquid hazards which require responsible care during handling
and processing, and whether derived from biomaterials or fossil fuels, cause issues when
released into the environment. Alternatively, process safety practices and workplace monitoring
are ways to accomplish the same end result. The PVC industry has a history of implementing
safeguards and a proven record of achieving both of these aforementioned green chemistry
principles through sophisticated process monitoring and controls. Year over year reductions in
criteria emissions for vinyl chloride and dioxin are shown in Figures 2 and 3 respectively.
PVC plants are equipped with an elaborate array of continuous air samplers that alert employees
quickly in the event of any monomer leak. These monitors and the continual emphasis by the
industry for safety has resulted in an illness and injury rate that is one-third that of the overall
chemical industry, and one-sixth that of overall manufacturing, as recorded in Figure 4.

Figure 2: PVC Industry Cradle to Resin Vinyl Chloride Emissio

Figure 3: PVC Industry Cradle to Resin Dioxin

Emission

Principle No. 8 Reduce Derivatives can be shown to be met by the examining the block flow
diagram in Figure 5 which depicts the relatively simple route to manufacture PVC resin in just 5
steps.
Several steps incorporate catalysts which drive reactions more effectively as required by
Principle No. 9 Catalysis.
Each step is computer controlled and continuous process parameter monitors assure optimal
operations, which meets the requirement of Principle No.11 Real-time Analysis of Pollution
Prevention.

Figure 4: Illness and Injury Rate, PVC Resin

Figure 5: Cradle-to-Resin Flow Diagram of PVC Production

7. ECO-PROFILES AND LCA

Life Cycle Assessment (LCA): Method to evaluate the magnitude of resources
consumption and impacts on the environment for a material or product throughout its whole
life cycle (production, use, waste disposal and recycling) .Rather than focusing on the
environmental load alone, it evaluates from a comprehensive viewpoint. It has been highlighted
as one of the guidelines for material comparison and green procurement.
By using LCAs correctly it can be ensured that:

Product systems are not erroneously favored or condemned on the basis of

individual results.

Developments do not inadvertently shift or even increase environmental impact but

in fact reduce it.

The resources available are directed in such as way that they achieve the
greatest environment benefit for the entire system.

PVC product systems have been investigated using LCA methodology in almost all
significant application areas in terms of production quantity.
Eco-profiles
Eco-profiles form part of Life-Cycle Assessment (LCA). Whereas LCAs are cradle-to-grave
analyses of the environmental impact of a product, eco-profiles stop at the factory gate
("Cradle-to-gate"). The Eco-profiles of PVC were fully updated in 2006. They can be
downloaded here.

The key impacts calculated in these eco-profiles are aggregated according to a standard
methodology and published in Environmental Declarations.

8. BENEFITS OF USEING PVC

9.

REFERENCES

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Multicriteria optimization of production conditions for a new phthalate-free PVC plasticizer
Journal of Industrial and Engineering Chemistry, 2014,
G.G. Liang, W. D. Cook, H. J. Sautereau, A. Tcharkhtchi, Diallyl orthophthalate as a
reactive plasticizer for improving PVC processibility,Part II: Rheology during cure, Polymer
2009, 26352642
M. Balkaya , I. D. Moore, A. S.lamer. Study of non-uniform bedding support under
continuous PVC water,distribution pipes, Tunnelling and Underground Space
Technology,2013.
S. Z.Gaoa, J. S. Wangb, X. W. Gaoc, Modeling and advanced control method of PVC
polymerization Process Journal of Process Control 23 (2013) 664 681