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INEOS TECHNOLOGIES

EDC OXYCHLORINATION CATALYSTS

Vinyl India 2015

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Ineos Technologies website Follow us on:

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• INEOS: 3rd largest Vinyls producer.

• 70+ yrs experience in the Vinyls sector

• Worldwide scale PVC & EDC pilot plants.

• Multi-million tons operating Globally under INEOS Licenses.

• We provide lifetime services to our Customers.

INEOS Technologies Vinyls – Solutions to the Vinyls Industry.

We develop and license worldwide our EDC / VCM & PVC technologies.

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PVC Pilot Plant

EDC

Pilot Plant

INEOS Technologies Vinyls – Solutions to the Vinyls Industry.

• Develop innovative additives for PVC &

catalysts for Oxychlorination.

• Optimise clients operating / process conditions.

• Develop optimised PVC recipe.

• Dedicated Customer support.:

- Application trial.

- Additive / catalyst testing.

- Process development.

- Customer Specific studies / trainings.

Our target is to Add Value for our Customers.

Pore

Dis

trib

ution

Cu

mu

lati

ve P

ore

Vo

lum

e

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The Balanced EDC/VCM Production Process

2 C2H4Cl2 2 C2H3Cl + 2 HCl FIXED & FLUID

BED

C2H4 + 0.5 O2 + 2 HCl C2H4Cl2 + H2O

C2H4 + Cl2 C2H4Cl2

HTC & LTC

This document is the property of INEOS Technologies (Vinyls) Limited and the information it contains is

strictly confidential and may not be copied, used or disclosed without the express permission of Ineos

Technologies (Vinyls) Limited. 5

WHERE INEOS CATALYST IN THE WORLD (PAST and PRESENT)

Fixed Bed

Fluid Bed INEOS Fixed Bed INEOS Fluid Bed (before SOLVIN – INEOS JV)

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Our EDC/VCM R&D team is located near Venice, Italy:

• Research & development of new Oxychlorination Catalytic systems (fluid and fixed bed) and related pilot testing

• Catalyst Production Control and Catalyst Quality Control

• Technical support for Customers (world-wide) and INEOS production plants (UK, Germany, Norway, Sweden)

• Optimization of Technolgies and Processes for Oxychlorination

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Features

4m Oxychlorination reactor

(Nickel 200), condensation

system, on-line vent gas

analyser and vent gas treatment

Mass balance:

Vent gas, Acidity, EDC purity

Fluid Bed Oxy Pilot Plant

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Features

Two reactors

On line vent gas analysis, off line

analysis of EDC and water

Fully automised under DCS

control

Fixed Bed Oxy Pilot Plant

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R&D Catalysts: Oxychlorination Technologies

HCl Conversion

C2H4 Selectivity to EDC

Pressure Drop

Catalysts Life

HCl Conversion (C2H4 conversion – Air)

C2H4 Selectivity to EDC

Fluid Dynamic behavior - Sticking

Catalysts Losses

Steam

Boiling

Water

Ethylene

HCl, Oxygen

EDC &

By-Products

RO

Ethylene HCl

air/oxygen

TIC Catalyst

EDC + by-products

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INEOS OXYCHLORINATION FIXED BED CATALYSTS AND DILUENT

IVOC – P CATALYSTS:

P1D – P2 - P3 - P3P (NEW)

P1DT – P2T – P3T

IVOD-1 STANDARD DILUENT

IVOD-2F HIGH PERFORMANCE DILUENT

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A

S1

S2

S2

B C D E F

A B C D E F

S1

S30%

10%

20%

30%

40%

50%

60%

70%

% wt cat

sampling point

sampling line

rotation: 3 min

A B C D E F

S1

S30%

10%

20%

30%

40%

50%

60%

70%

80%

% wt cat

sampling point

sampling line

rotation: 6 min

A B C D E F

S1

S30%

10%

20%

30%

40%

50%

60%

70%

80%

% wt cat

sampling point

sampling line

rotation: 9 min

Fixed Bed oxychlorination catalysts Key Factors :

INEOS catalysts CAN BE SUPPLIED ALREADY MIXED

MIXING HAS TO BE OPTIMIZE

TO MAXIMISE

HOMOGENEITY

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Fixed Bed oxychlorination catalysts Key Factors :

INEOS catalysts CAN BE SUPPLIED ALREADY MIXED

Simulation of a 1st reactor (O2 Technology)

TEMPERATURE PROFILE

210

220

230

240

250

260

270

280

0 0.5 1 1.5 2 2.5 3 3.5

z

°C

Normal Loadign Pattern - gas Temp 6% of catalysts in TOP zone - gas Temp

6% of catalysts in TOP zone - cat Temp Normal Loadign Pattern - cat Temp

NOT HOMOGENEOUS

MIXING

DIFFERENT CONDITIONS

IN DIFFERENT TUBES

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Fixed Bed oxychlorination catalysts Key Factors :

INEOS catalysts CAN BE SUPPLIED ALREADY MIXED

• Mixing is an important step to ensure homogeneity of activity and then good performance in terms of catalysts life and selectivity.

• INEOS has optimized the production of mixed materials (CATALYST– IVOD-1/IVOD-2F) than can be loaded as they are directly in the reactor

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Fixed Bed oxychlorination catalysts Key Factors :

PRESSURE DROP

Second Reactor Pressure Drop

60% 70% 80% 90% 100%

% capacity

Re

ac

tor'

s P

res

su

re

Dro

p

INEOS CATALYSTS 5x5 mm standard Catalyst

UP TO 20%

REDUCTION

LOW PRESSURE DROP HIGH CAPACITY

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The new high performance IVOD-2F diluent:

-Low dP for High Capacity Plant

-Higher reactor homogeneity for better performance at harded

conditions

First Reactor Pressure Drop

50% 70% 90% 110% 130% 150% Capacity

Re

ac

tor P

re

ss

ure

Dro

p

New IVOD-2F Diluent Standard IVOD-1 diluent

TUBE PACKING QUALITY

TU

BE

'S D

IST

RIB

UT

ION

STANDAR DILUENT NEW DILUENT

Fixed Bed oxychlorination catalysts Key Factors :

PRESSURE DROP

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Fixed Bed oxychlorination catalysts Key Factors :

CATALYST LIFE

Temperature profile and coke formation

150

170

190

210

230

250

270

290

0 50 100 150 200

z (reactor depth, 0=inlet)

°C

% o

f p

elle

t w

ith

Co

ke

New Generation - Temperature Profile OLD Generation - Temperature Profile

New Generation - coke formation OLD Generation - coke formation

LOW FOULING RATE

LOW COKE PRODUCTION

RATE

LONG CATALYST LIFE

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Fixed Bed oxychlorination catalysts Key Factors :

CATALYST LIFE

Reactor's Pressure Drop

Time on Stream

Pre

ssu

re D

rop

(cata

lyst

inte

gri

ty)

CASE B CASE A

THREE YEARS RUN WITHOUT CHANGE CATALYSTS LOW FOULING RATES

and

LONG STABLE ACTIVITY

Catalyst's Activity

Time on Stream

Ste

am

to

O2 r

ati

o

200

250

Re

ac

tor

Ou

tle

t

Te

mp

era

ture

Steam to O2 ratio Reactor out Temperature

THREE YEARS RUN WITHOUT CHANGE CATALYSTSHIGH CAPACITY FOR LONGER TIME

HIGHER FLEXIBILITY TO BUSINESS

REQUIRMENTS

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Fixed Bed oxychlorination catalysts Key Factors :

ACTIVITY AND SELECTIVITY

Effect of Cu - Additive ratio

on Activity

0.0

0.2

0.4

0.6

0.8

1.0

Additive / Cu mol/mol

Reaction R

ate

Effect of Cu exposed

on Activity

0.0

0.2

0.4

0.6

0.8

1.0

Copper Exposed (CO probe

molecule)R

ea

ctio

n R

ate

- QUALITY OF RAW MATERIAL: HIGH PURITY ALUMINAS

- CHEMICAL COMPOSITION: COPPER – ADDITIVE

- SURFACE AREA AND PORE VOLUME – DISTRIBUTION OF ACTIVE SITES

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Fixed Bed oxychlorination catalysts Key Factors :

ACTIVITY AND SELECTIVITY

INEOS CATALYSTS - PILOT PLANT RESULTS

0.0%

0.1%

0.2%

0.3%

0.4%

0.5%

0.6%

98.6 98.8 99.0 99.2 99.4 99.6 99.8 100.0

HCl Conversion

% E

thy

len

e t

o C

Ox

OLD GENERATION NEW GENERATION

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Fixed Bed oxychlorination catalysts Key Factors :

ACTIVITY AND SELECTIVITY

EXCELLENT RESULT CAN BE OBTAINED AT CAPACITY 10-20% ABOVE THE

DESIGN

INEOS Catalysts - Industrial Results

HCl conversion

Eth

yle

ne t

o C

Ox

OLD GENERATION NEW GENERATION

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INEOS Oxychlorination Fluid bed catalysts

Ineos Fluid bed catalyst portfolio

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INEOS Oxy Catalysts

Average Particle Size (microns) 55

Less than 20 microns (%) 2

Bulk Density (g/cc) 1.00-1.20

Very Low fines and moisture content

Main physical-mechanical features of our Catalysts

INEOS fluid bed catalysts can be also added to the already present charge of

catalyst. Mechanical properties and formulation allow mixing during top up

without adverse influence on the reactor functioning.

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Main Fluid Bed Catalyst Aspects

Catalyst agglomeration (sticking)

Active catalyst converts HCl and

prevents the loss in fluidization

Corrosion

Accumulation of Iron increases the

by products formation.

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Main Fluid Bed Catalyst Aspects

Erosion

Support hardness

Catalyst losses

The attrition test measures the tendency of a

catalyst to generate fines.

Top up of the catalyst

catalyst is periodically added to the reactor

depending on the catalyst losses.

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Fluid Bed Oxychlorination Catalysts: Activity

High reactant conversion:

Ethylene Conversion > 99.5%

HCl Conversion > 99.5%

50% increase in rate same performance

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High Selectivity

Reduced combustion rate

EDC Purity > 99% (V/V)

Fluid Bed Oxychlorination Catalysts: Selectivity

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High reaction stability/ No

sticking

Able to operate at different

reactant ratios without any

fluidization problem

Fluid Bed Oxychlorination Catalysts: Stability

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What impact could have Fluid Bed Catalysts?

Example & some assumptions:

300 ktpa VCM plant, 50 tons of catalyst hold-up, 15tons/year of catalyst losses

Operating rate 90%

Assume cost of ethylene 0.75 USD/kg

Assume EDC margins 100 USD/ton

Assume 100% Ineos FB Catalyst and an increase in Ethylene Yield by 5%

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What impact could have Fluid Bed Catalysts?

Results:

Increasing output by 10%: more than 2 M USD/yr

Oxygen+ethylene saving: more than 0.65 M USD/y

Caustic savings: more than 0.25 M USD/y

Increase of the operating rate estimated in 5 days of more production: 0.29 M USD/y

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On-site plant visit by INEOS catalyst expert to improve

plant optimisation and discussions

Training (fluid bed) of plant personnel during 3 to 5 days

in our R&D facilities and pilot plant in Italy.

Pilot plant tests at particular operating conditions

following customer requests

Studies concerning: Metal analysis (poisoning), Particle

size distribution, Catalyst hardness (attrition/erosion) and

mechanical strength, Stickiness, Catalyst activity-pilot

plant testing, Operating parameters optimization,

Our Technical Service Offer for FIXED AND FLUID BED CATALYSTS