Evonik Catalysts for Vinyl Acetate Monomer Production

Dr. Cristiano Trionfetti

Global Petrochemicals Summit, November 15, 2016

1
Evonik at a glance

Evonik

Nutrition & Resource Performance

Care Efficiency Materials Corporate /
Services
Other
Sales*: €4.9 bn Sales*: €4.3 bn Sales*: €3.4 bn

Business Lines : Business Lines: Business Lines:

 Personal Care  Active Oxygens  Performance  Administrative  Corporate Center

 Household Care  Catalysts Intermediates Services  Strategic R&D
 Comfort & Insulation  Coating & Additives  Agrochemicals &  Technology &
Polymer Additives Infrastructure
 Interface &  Coating &
Performance Adhesive Resins  Functional
Solutions
 Baby Care  Crosslinkers
 Acrylic Monomers
 Health Care  High Performance
Polymers  Acrylic Polymers
 Animal Nutrition
 Oil Additives  CyPlus
Technologies
 Silanes
 Silica

Specialty chemicals segments

* Fiscal 2015

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 Overview

1 Evonik Catalysts – Markets and Products

2 Vinyl Acetate Monomer (VAM)

 Applications and markets

 Production technologies

3 Impact of Catalyst Design

4 Evonik solutions for VAM customers

3
 The Markets we serve

Market Life Sciences & Industrial & Polyolefins

Segment Fine Chemicals Petrochemicals

Market Agriculture Fatty Acids Polyethylene

Subsegment Care Specialties Functional Chemicals Polypropylene
Edible oils Intermediates
Feed & food Monomers
Pharma Solvents

Processes Slurry / Batch Continuous & Batch Continuous

Processes Processes Processes

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 Market segment
Industrial & Petrochemicals

Selected applications
 α-Methylstyrene
 1,4-Butanediol
 Caprolactam
 Vinyl Acetate Monomer
 Aniline
 Polishing C3-C4 streams
 Toluenediamine
 Vinyl Chloride Monomer

Brands
 Aerolyst®
 Noblyst®
 MC (Metal Catalysts)
 Octolyst®
 Specialyst®

5
 Product and project business

Product groups Project business

Toll Custom
Manufacturing Manufacturing

Continuous Olefin Metathesis Oils and Fats

Activated Metal Precious Metal
Process Polymerisation Catalysts Catalysts
Catalysts Catalysts
Catalysts Catalysts (homogeneous
(AMC) (PMC) (OFC)
(CPC) (OPC) cat.)
Custom Joint
Design Development

1:n relationship 1:1 relationship

default: non exclusive default: exclusive

Catalysts proprietary to Catalyst ownership depending

Evonik – BL Catalysts on business model

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 Globally present and expanding
Catalyst
production and
Catalyst
PMC plant and
refining services in
productions
refining services
and in
Hanau and Marl,
refining
Shanghai,services
China in
Germany
Catalyst Calvert City
productions
production andand
refining services in
Calvert City
City, USA

PMC plant and

refining services in
Catalyst Tsukuba, Japan
productions
production and
and
refining services in
Calvert
near Mumbai,
City India

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 Overview

1 Evonik Catalysts – Markets and Products

2 Vinyl Acetate Monomer (VAM)

 Applications and markets

 Production technologies

3 Impact of Catalyst Design

4 Evonik solutions for VAM customers

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 Vinyl acetate monomer derivatives

Photovoltaic components
Resins for the coatings industry

Waxes and resins

Hot metal adhesives Adhesive materials O2 barrier for food packaging

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 VAM producers

Vinyl Acetate
Monomer

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 VAM Market share by capacities

Showa Denka
4% Wacker
JV&P 4%
4% Other
5%
Kuraray
5% Celanese
33%
Nippon G.
5%
Dairen
17%
Sipchem
Sinopec
6%
DOW
9% Kuraray America
Dupont
8%

11 Source: IHS Chemical (2015)

 Market trend

Vinyl Acetate Monomer Market valued at USD 6.8 billion in 2013 and
Global Market
anticipated to reach USD 9.2 billion in 2020 (Source IHS)

Between 2014 and 2020 ca. 4.5% increase in Asia and up to 3% increase in
CAGR USA

Polyvinyl Acetate (PVA) and Polyvinyl Alcohol (PVOH); highest demand for
Coatings adhesives from end-user industries such as construction, automotive and
Industry furniture

Ethylene-vinyl Acetate (EVA); growing demand for rubber like materials for
Polymer &
encapsulation and solar cell components
Energy Industry

Packaging Ethylene-vinyl Alcohol (EVOH); growing demand for food packaging films
Industry

12 Source: CE&H Marketing Research Report (2014)

 Overview

1 Evonik Catalysts – Markets and Products

2 Vinyl Acetate Monomer (VAM)

 Applications and markets

 Production technologies

3 Impact of Catalyst Design

4 Evonik solutions for VAM customers

13
P
ag
 History of VAM production technologies

1930‘s 1970‘s 2000’s Today

Acetylene Based Process – Homogenous and Heterogeneous Phase

Ethylene based process – Bayer Technology

Ethylene based process – Millennium Technology

Ethylene based process – Vantage Technology

Ethylene based process– LEAP Technology

Fixed bed Fluidized bed

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Page 14
 Basic chemistry

Catalytic gas-phase reaction

O Catalyst O
+ + 0,5 O2 + H2O
OH 150−180°C O
8−9 bar

ΔRH = − 178 kJ mol-1

• Highly exothermic reaction

• Conversion level of ethylene lower than 10 %
• Major side reaction is the combustion of ethylene to carbon dioxide

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 Production process: flow chart

Steam Waste Carbon

gas dioxide
Fresh
Water ethylene

Water

Multi tubular Water

reactor

Acetic
Alkali metal acid
salt solution

Oxygen

Acetic
acid
To residue
work-up
Crude vinyl acetate for
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Ethylene distillation
 Multi tubular reactor and operations

Number of tubes: 2500 – 10000 Pressure: 5 – 12 bar

Tube diameter: 2.5 – 3.8 cm Temperature: 140 – 180 °C

Tube volume: 4.5 – 6 liter GHSV: 2000 – 4000 h-1

Heating medium: steam Ethylene conversion: 8 – 10 %

Material: stainless steel Oxygen conversion: 40 – 60 %

VAM selectivity: 90 – 95 %

Feeding of potassium acetate

Continuous feeding of potassium acetate improves space time yields and selectivity to VAM

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 Hurdles associated with ethylene process

SIGNIFICANT RECYCLE STREAMS due to low conversion of ethylene (≤ 10 %) and

acetic acid (< 35 %)

HIGHLY EXOTHERMIC REACTION needs accurate heat management and reactor

design

EXPLOSION LIMITS due to mixing of ethylene and oxygen [Oxygen] < 8,5 vol%

POTASSIUM ACETATE DOSING via gas phase to compensate potassium loss during
reaction

CATALYST DEACTIVATION and adaptation of reaction temperature along run time

(start of reaction: 145 °C, end of reaction: 180 °C)

DECREASE OF SELECTIVITY with increasing temperature and oxygen conversion

(formation of CO2)

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 Overview

1 Evonik Catalysts – Markets and Products

2 Vinyl Acetate Monomer (VAM)

 Applications and markets

 Production technologies

3 Impact of Catalyst Design

4 Evonik solutions for VAM customers

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 VAM Production:
Evonik proprietary catalysts

Bayer process

□ Natural Silica carrier

□ Palladium 0.5 – 1.3 wt%

□ Gold 0.2 – 0.6 wt%

□ Potassium acetate 4.0 – 7.0 wt%

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 Basic characteristics

• High uniformity of shape

• Spherical beads, diameter 5.0 mm

• Defined bulk density

• Highly homogeneous metals distribution

• Low attrition values

• High side crush strength

• Low chlorine content

Thin shell catalysts to suppress mass transfer limitation

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 Designing a highly productive catalyst

2500
metal loading Pd/Au
0.25 wt% / 0.25 wt%
0.50 wt% / 0.50 wt%
2000
0.75 wt% / 0.75 wt%
STY / g(VAM)/h*L(cat)

1.00 wt% / 1.00 wt%

1500

1000

500

0
0 500 1000 1500 2000 2500
d(shell) / µm

Catalysts performance strongly determines reactor volume

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 Designing a highly stable catalyst

STY / g(VAM)/h*L(cat)
175 500

Temperature (° C) (°C) 170 450

STY Target Range

165 400
Temperature

160

STY
350

Reactor temperature adaptation

155 300

to maintain target STY

150 250

145 0 50 100 150 200 250 300 350 400 450 500
200

Au Pd Au
Run time
Pd
PM / wt%

PM / wt%
Penetration profile
PM profile starting from corona to Penetration profile
PM profiles at end of the
interior of impregnation shell at start of reaction
the reaction

Fixing precious metals with low penetration into the core

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 Designing a highly selective catalyst
Au

Pd
Pd

Au

Pd

Au

SEM-EDX Top View

Au = green
Pd = red

Assembly of gold and palladium layers

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 Catalysts for specific reactor designs
Heat transfer capacity*

• High activity
high • Maintain high selectivity
at high degree of
oxygen conversion

• Boosting productivity
of existing reactors
limited based on innovative
catalysts operating at
low temperature
limited high
GHSV

*determined by reactor design and degree of capacity utilization

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 Overview

1 Evonik Catalysts – Markets and Products

2 Vinyl Acetate Monomer (VAM)

 Applications and markets

 Production technologies

3 Impact of Catalyst Design

4 Evonik solutions for VAM customers

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 Challenges for VAM manufacturers
Low cost Vinyl Acetate
production
- Feedstock What drives catalyst performance?
- Scale • STY (kgVAM/Lcat*h)
- Location • Selectivity
- Catalyst performance
• Life time
• Reliability
• Precious metal loading

Reliability Precious metal loading

• Assessing performance • 50 mt catalyst installed

• Reference • 300 ktVAM/y

• Guarantee • Life time 3 years

• IP protection • ca. $ 20 Mio net working capital

(500 kg Pd + 250 kg Au)
27 Example of production plant
 The ability of Evonik to provide
solutions for our customers

Understanding our customers needs Innovation

• Low cost VAM production • Ongoing customized catalyst
• Catalysts performance development
• Reliability • R&D centers in USA and Germany

Manufacturing excellence Supporting competencies

• Dedicated scale up teams • In-house advanced catalysts testing unit
• Extensive production capability • Accelerated catalyst qualification
• +20 years VAM catalyst production • Precious metals management and
• Production sites in USA and Germany refining services

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