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Versalis and the tyre market: a complete portfolio of technologies and products (ESBR, SSBR, HCBR) Gabriele Gatti- versalis Elastomer Process and Technology Manager

Bangkok, November 15th, 2013

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Focus on tyres

Elastomers are basic in most of tyre components. New Green Policies in Europe, NA, Japan, require extensive use of sSBR and BR Nd high cis in tread, and BR Nd high cis in sidewall to reduce CO2 emissions

Typical polymer content

Passenger Car tyre

NR: 1 kg

eSBR: 1,5 kg

sSBR: 1,2 kg

BR: 0,8 kg

Butyl rubber:0,5 kg

Heavy Truck tyre

NR: 15 kg

eSBR: 1.6 kg

sSBR: 1 kg

BR: 5.6 kg

Butyl rubber: 1 kg

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versalis with its proprietary technologies covers most of the synthetic elastomers requirement for the tyres’ manufacturing:

versalis has proven experience of large elastomers complexes in which all these technologies can be applied and mutually optimized

Available technologies for the tyre market:

Typical worldscale plant Size (at product mix)

1 Continuous (cold) emulsion SBR (eSBR) 65 – 130 kta

2 Batch solution SBR (sSBR/LCBR swing plant)

40 – 60 kta

3 Continuous solution SBR (sSBR/LCBR swing Plant)

40 – 60 kta

4 High Cis polybutadiene (NdBR) 45 – 80 kta

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Typical workflow

Kinetics

Structure & Formulation Chemistry

Scale-up Pilot plants

Process engineering Process development

Basic engineering Calculation design

Polymer processing End-uses properties

Industrialization

Chemical & physical characterization

Polymer physiscs

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versalis approach to the elastomers technologies for the tyre market

Technology Every product family requires a specific technology which has been

developed by versalis for years in its own Plants.

R&D Dept

New products are studied at our R&D Dept which is located at Ravenna, Italy, where pilot plants of many sizes allow us to produce from few grams of of rubber using bench-scale reactors up to 20 kg/h 24/7 to sample tons of elastomers to the tyre manufacturers

Process

Every step of production of each process has been deeply studied, applied and proven. This continuous development of technology is mirrored in the production Plants for the internal production, for JV or Licensing.

Application

The application of these technogies can be flexible in order to complain with the specific requirement of the Site or the Partner:

Stand-alone plants, single or multiple production lines, swing;

Integrated plants, with optimized lines configuration;

Multiple plants for different technologies, optimized and integrated in a larger Site.

Policy

Versalis policy is to provide the internal or external Client with a tailored design in order to shorten the normally long time required to make the integration and optimization of the lines before the EPC stage of the Project.

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versalis rubber complex – 3D general model – Project «α»

1 eSBR line

1 sSBR/LCBR swing line

1 HCBR line

1 SBC swing line

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versalis rubber complex – Plot Plan – Project «β»

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versalis sSBR Plant – Project «γ» – 3D general model

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versalis elastomers assets – tyre market

versalis assets – solution SBR (batch and continuous)

Continuous sSBR/LCBR swing versalis Grangemouth, U.K. Operation

Batch sSBR/LCBR swing versalis Grangemouth, U.K. Operation (under debottlenecking)

Batch sSBR versalis Ravenna, Italy Construction

Batch sSBR/LCBR/TPR swing Licensed to Petrochina Dushanzi, PRC

Operation

Continuous sSBR/LCBR/TPR swing

Licensed to Petrochina Dushanzi, PRC

Operation

Batch sSBR/LCBR/TPR swing Licensed, Mid East Construction

Continuous sSBR/LCBR swing Licensed, South East Asia Construction

Continuous sSBR/LCBR swing JV, Far East Engineering

Batch sSBR/LCBR swing JV, Far East Engineering

Continuous sSBR/LCBR swing Licensed, Mediterrean area Engineering

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Versalis assets – emulsion SBR and HCBR

versalis assets – emulsion SBR

eSRB versalis Hythe, U.K. Operation

eSBR versalis Ravenna, Italy Operation

eSBR Licensed, Mid East Construction

eSBR Licensed, South East Asia Construction

eSBR Licensed, India Start-up

versalis assets – HCBR (Nd BR)

HCBR versalis Ravenna, Italy Operation

HCBR Licensed, Far East Construction

HCBR JV, Far East Engineering

HCBR Licensed, South East Asia Construction

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Solution SBR (sSBR)

Polymerization basics

Solution polymerized styrene-butadiene rubber is obtained by anionic copolymerization of styrene and butadiene initiated by lithium alkyls in aliphatic or cycloaliphatic solvent; due to the large difference of reactivity ratios for the two monomers, addition of a living chain-end modifier changing the above-mentioned reactivities is required to obtain a well randomized copolymer.

A proper choice of modifier allows to carry out the polymerization reaction without any termination of active chain-ends; which in turn leads to high yields through the coupling or branching reactions taking place at monomers depletion.

The rubber macrostructure can be efficiently managed/driven by a proper selection of polymerization type (batch, continuous), reaction conditions and suitable coupling or branching agents, greatly enhancing the final properties of vulcanized rubber.

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The competitiveness of our proprietary sSBR/LCBR swing technology is based on the following main key-points

1 Relevant savings in term of steam consumption due to aliphatic or cycloaliphatic nature of solvent, which in turn also leads to improvements in environmental impact.

2 Relevant reduction in investment cost due to carrying out the reaction adiabatically or in temperature rise control, which also allows easier reaction control as well as saving in energy consumption.

3 Large production flexibility due to availability of both batch and continuous polymerization technologies, whose selection is driven by the final application of the product.

4 High and medium vinyl grades as well as Dry and Oil Extended polymers are allowed.

5 Special purification section brings raw material impurities to negligible level, avoiding detrimental effects on both the process and structural parameters of the product.

6 Capacity up to 60 kt/y per reaction unit is afforded, with a single finishing line capacity up to 30 kt/y for batch grades and 40 kt/y for continuous grades.

7 Perfect randomization of styrene in polymer chain is allowed by the proper use of substances which modify the leaving chain ends.

8 Production of different grades of sSBR ranging from low styrene-low vinyl to high styrene-high vinyl grades is allowed, based on both batch or continuous processes.

9 Production of polymers with different macrostructure: linear radial or branched.

Highlights

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versalis sSBR swing technology – sSBR Plant block diagram

Polymerization Flash and blending

Stripping

Finishing

Solvent purification

Monomer(s) purification

Chemicals preparation

Chemicals & additives

Monomers

Finished product (25-35 kg bales)

Fresh solvent

Wet solvent

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versalis sSBR/LCBR swing technology – Batch Plant

Batch reactors, boiling type:

The reactor is first supplied with solvent, than monomer(s) are added and the initiator starts the polymerization. Polymerization heat is used to reach the required temperature, that is controlled by means of a vapour condenser. This Reactor is able to produce also LCBR grades. For both families (sSBR/LCBR) dry or oil-extended grades can be produced.

Solvent, monomers, chemicals

Polymer solution (cement)

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versalis sSBR/LCBR swing technology – Continuous Plant

Solvent, monomers, chemicals

SSBR Polymer solution (cement)

Note (*) – Reactors’ alignment changes in case of LCBR production, but no other equipment is required

Continuous reactors:

SSBR: The reactor train requires a first boiling reactor (peak reactor) followed by 3/4 adiabatic reactors to complete the polymerization

LCBR: 1 adiabatic reactor and 1 flash tank (*)

chemicals

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versalis sSBR swing technology – main info

Batch process Continuous process

Reactor type: Batch stirred reactor, boiling type

Continuous stirred tank reactor, first one (peak reactor) boiling type

Reactors Number: 2-4 reactors / polymerization line

1 peak + 3-4 afterpeak reactors/ pol. line

Polymerization Pressure: < 10 bar(g) < 10 bar(g)

Polymerization Temperature:

< 120 °C < 120 °C

Solids concentration: < 25% < 25%

Monomers conversion: complete complete

Solvent: Cyclohexane, cyclopentane, n-Hexane

LCBR production capability

Yes Yes

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versalis sSBR swing technology

Raw materials: solvent choice

According to specific products’ needs and Site climate conditions, several solvents can be used. The following table shows the possible options:

Cyclohexane: Lower volatility, less solvent consumption, better for warm/hot climates;

n-Hexane: Preferred for warm/cold climates for random copolymers, lower energy consumption;

Cyclopentane: Best choice for warm/cold climates, the lowest energy consumption.

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versalis sSBR swing technology

Formulation

Raw Materials: Chemicals/Additives:

Butadiene Monomer Initiator

Styrene Monomer Coupling agents, shortstop

Extender oil (DAE, RAE, TDAE, MES) Activator

Solvent Antioxidants

Stripping additives

Finishing additives

Monomer column additive

All the chemicals and additives are easily available on the worldwide market

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Emulsion SBR (eSBR)

Polymerization basics

Emulsion polymerized styrene-butadiene rubber for the tyre market is obtained by free radical emulsion (cold) polymerization. The emulsion system is composed by an aqueous phase in which monomer droplets , initiator, chain transfer agent and surfactant molecules are present.

Polymerization takes place when a radical migrates into a micelle and reacts with monomer. The chain continues to propagate with the available monomer until another radical enters the same micelle. The final product is a dispersion of polymer particles in water (latex) stabilized by an adsorbed layer of soap

A shortstopping chemical is added to stop the reaction before crosslinking occurs.

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The competitiveness of our proprietary eSBR technology is based on the following main key-points

1 High polymerization conversion reduces monomers and utilities consumptions leading to both high productivity and process capability. Lower dimensions of recovery section leads to lower capital investment.

2 Rejected monomer quantity is reduced thanks to a specific section design, integrated with upstream plants, allowing reduction of slop quantity. versalis is able to design this recovery section based on both client needs as well as site conditions.

3 The wide range of products grades coupled with a real process know-how enables meeting the specific needs of the customer. High capacity and flexibility allow production, in the same continuous reactors train, of base Latexes blendable with batch or semibatch latexes to produce a HSR/HSL grades and SBR latexes.

4 All the enviromental issues coming from gaseous effluents, liquid effluents, water consumption and solids effluents have been deeply considered in the design base of each process stage, according to the best available technologies as well as to the IISRP suggestions to the E.U. Authorities.

5 Water recycle: the watery phase recovered after the latex stripping are recycled to reaction, no water streams from reaction or monomer recovery to CWWT.

6 VOC captation: vapour streams from reaction and recovery areas are connected to abatement/flare system also for maintenance operations (low emission factors).

7 High valuable technical assistance is given to the customer by versalis R&D structure

Highlights

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versalis eSBR technology – eSBR Plant block diagram

Finishing

Extender oil storage

Refrigerating unit

Chemicals & additives

Finished product (25-35 kg bales)

Fresh monomers, demi water

Unreacted monomers

Solvent for chemical cleaning and waste

water stripping

Extender oil

Polymerization

Monomers and demi water

storage

Chemicals preparation

Monomers recovery

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versalis eSBR technology

Stirred reactors:

Reactors are full of polymerizing latex. Reaction is isothermal; chilling is provided by boiling ammonia (ammonia is the cheapest coolant). Reactors are chemically cleaned (no need of mechanical cleaning procedures)

Latex in

Liquid NH3

Gaseous NH3

Latex to other reactors

Mid size reactor (15-22 m3 each) to better fit the Smith-Ewart curve, to control the polymerization temperature

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versalis eSBR technology – main info

eSBR process

Reactor type: train of continuous stirred tank reactors in series

Reactors Number: Typically 12-14, 15 to 22 m3 each

Polymerization Pressure: < 10 bar(g)

Polymerization Temperature: 5 - 10 °C

Solids concentration: < 25%

Solids at end of reaction: 20 – 30%

Monomers conversion: 62 – 75%

Emulsifying agent: fatty and/or rosin acid soap

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versalis eSBR technology

Formulation

Raw Materials: Chemicals/Additives:

Butadiene Monomer Redox system (oxydant, reductant) and chelating agent

Styrene Monomer Shortstop

Extender oil (DAE, RAE, TDAE, MES, Naphtenic)

Rosin & fatty acids

Ammonia (refrigeration) Soda, Potash, Solfuric acid

Solvent for chemical cleaning

Single antioxydant, no-staining and no-nitrosamine precursor

Stripping additives

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High-Cis Polybutadiene (NdBR)

Polymerization basics

High Cis Polybutadiene (HCBR) is a solution polymer (solvent: tipically n-hexane) obtained by using a Ziegler–Natta catalyst prepared by the reaction between an organic salt of Neodymium, an Aluminum Alkyl and an organic chlorinated compound. This catalyst is able to coordinate the reaction of butadiene monomer in Cis form producing a high cis polymer (> 97%).

Catalyst is preparation is based on two subsequent reactions:

Neodymium salt (Pre-catalyst) is prepared mixing Nd with organic and inorganic acids;

Catalyst is obtained by a second reaction which involves Pre-catalyst, an organometallic alkyl compound (aluminium based) and an organic chloride.

The preparation reactions are exothermic.

CIS 1,4 H H CIS UNIT H H \ / \ / C == C C == C / \ / \

-- CH2 CH2 -- CH2 CH2 -- CH2 CH2 --

\ / C == C / \ H H

TRANS 1,4 TRANS UNIT

H CH2 -- CH2 H H CH2 --

\ / \ \ \ / C == C C == C C == C / \ \ \ / \

-- CH2 H H CH2 -- CH2 H

VINYL 1,2

CH2 CH2 CH2

\\ \\ \\ CH H CH H CH H \ / \ / \ / C C C

\ / \ / \ / \ C C C

H2 H2 H2

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The competitiveness of our proprietary HCBR technology is based on the following main key-points

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Very high Cis content, low vinyl and high chain linerity which enhances the products’ mechanical properties:

high 1,4 cis content: Better tack and green strength

low vinyl content: Better crack growth and fatigue resistance

high chain linearity: Better wear resistance

Lower Hysteresis (lower RR)

Higher elasticity

2 Relevant savings in term of steam consumption due to aliphatic nature of solvent (typically industrial n-hexane), which in turn also leads to improvements in environmental health

3 Very good control of impurities level through a special design in purification section that leads to market required product quality

4 Special design of continuous and adiabatic section in order to minimize reactors fouling, to lower investment costs and to save energy

5 Recovery and recycle of non-reacted monomers which enhance the raw material consumption figures.

6 Normal antioxidants easily protect HCBR from oxidation during processing and storage because Nd does not catalyze the action of oxygen on HCBR, which is possible with the other metals (Ni, Co)

Highlights

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versalis HCBR technology – HCBR Plant block diagram

Polymerization Flash and Blending

Stripping

Solvent purification

Chemicals & additives

Finished product (25-35 kg bales)

Fresh solvent

Chemicals preparation

Finishing

Recycle solvent + unreact. monomers purification

Wet solvent

Precatalyst and Catalist

preparation

Monomer purification

1,3 butadiene

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versalis HCBR technology

Train of two continuous stirred reactors

Polymerization reaction is performed through two completely filled continuous reactors in series.

Solvent, monomer and catalyst are fed to first reactor where the monomer is partially converted. Then the cement is moved into the second reactor where the reaction is completed (98-99%). Solvent,

monomer and catalyst

Polymer solution

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versalis HCBR technology – main info

HCBR process

Reactor type: train of 2 continuous stirred tank reactors in series + 1 spare, adiabatic

Temperature control: Monomer dilution Solvent feed temperature

Reactors Size: 50 m3 each

Polymerisation Pressure: < 10 bar(g)

Polymerisation Temperature: < 120 °C

Solids concentration: 12,5 – 14,5%

Monomers conversion: Min. 98%

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versalis HCBR technology

Formulation

Raw Materials: Chemicals/Additives:

Butadiene Monomer Components of the catalytic system

Solvent Antioxidants

Stripping additives

Finishing additives

Monomer column additive

All the chemicals and additives are easily available on the worldwide market

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Thank you!