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INEOS TECHNOLOGIES
EDC OXYCHLORINATION CATALYSTS
Vinyl India 2015
Scan to visit
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
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ution
Cu
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lati
ve P
ore
Vo
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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