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innovation loves experience Phthalic Anhydride Catalysts
innovation loves experience
Phthalic Anhydride Catalysts
Introduction 3
Research & Development 8
Catalyst Portfolio 10
Phthalic Anhydride Catalysts for o-Xylene Oxidation
O4-68 Catalyst 12
O4-66 Catalyst 14
O4-88 Catalyst 16
Phthalic Anhydride Catalysts for Naphthalene/Mixed Feed Oxidation
O4-29 Catalyst 18
O4-29 HiFlex 18
CONTENT
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3
BASF – The Chemical Company
The world’s leading chemical company offers intelligent
solutions and high-quality products for almost all indus-
tries, uses new technologies to open up additional
market opportunities and combines economic success
with environmental protection and social responsibility.
●● BASF has produced Phthalic Anhydride for over
135 years
●● BASF has developed Phthalic Anhydride catalysts
for over 110 years
●● Total production of Phthalic Anhydride at Ludwigs-
hafen site since 1873 is more than 3.5 million tons
●● Production experience with post reactors since 1980
Important Facts About Phthalic Anhydride at BASF
INTRODUCTION
Founded in 1865 by Friedrich Engelhorn under the name
“Badische Anilin- und Sodafabrik”, today, BASF is the
World’s Leading Chemical Company – The Chemical
Company. Around 109,000 employees of the BASF
Group work to make customers from nearly all sectors
and almost every country in the world become more
successful.
BASF at a GlanceOur portfolio ranges from oil and gas to chemicals,
plastics and specialties such as crop protection products.
BASF has subsidiaries in more than eighty countries and
supplies products to a large number of business partners
in nearly every part of the world. We operate six Verbund
sites as well as approximately 390 additional production
sites worldwide.
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1968 Start-up of two commercial Phthalic Anhydride plants at BASF, Ludwigshafen,
BASF O4-20, o-Xylene load 42 g/Nm3
1980 First technical application at BASF, Ludwigshafen,
BASF O4-26, o-Xylene load 60 g/Nm3,
1993 First installation of BASF O4-28,
o-Xylene load 80 g/Nm3
2000 First Start-up of BASF O4-32
2002 Acquisition of Wacker’s Phthalic Anhydride catalysts and licensing business
2003 New Phthalic Anhydride catalysts for o-Xylene oxidation O4-40/42
First reference plant for O4-40
(o-Xylene up to 100 g/Nm3)
2004 New Phthalic Anhydride catalyst for naphthalene/mixed feed oxidation
O4-29 up to 80 g/Nm3
2005 New Phthalic Anhydride catalyst for o-Xylene oxidation O4-66
(o-Xylene up to 100 g/Nm3)
2009 First installation O4-68 (o-Xylene up to 80 g/Nm3)
2010 First installation O4-29 HiFlex
Maximum flexibility 0 – 65% o-Xylene
2011 First installation O4-88
Phthalic Anhydride yield up to 116.5 wt.-%
Phthalic Anhydride Catalyst History
4
Worldwide Use of Phthalic Anhydride
Plasticizers 52 %
Other Applications 14 %
Alkyde Resins 16 %
Unsaturated Polyesters 18 %
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Phthalic Anhydride ProcessPermanent improvement of process and catalyst
5
Pre-decomposer
SC
Offgas
Steam60 bar
Postreactor
2 columndistillation
Pure P Atank
Organization of the Phthalic Anhydride Catalyst Business
Iselin, New JerseyHeadquarters
Ludwigshafen Catalyst Global Business ManagementCatalyst ProductionCatalyst ResearchRegional MarketingTechnical Service
Hong KongRegional MarketingTechnical Service
Advantages of BASF as a Phthalic Anhydride Catalyst Supplier
From o-Xylene to Phthalic Anhydride
(Reaction mechanism)
6
BASF offers over 135 years experience in Phthalic
Anhydride (PA) production and 110 years in catalyst
research. This legacy forms a strong foundation for
continuous innovation and product improvement.
Products and services are continually reviewed for
alignment with our customers’ needs through regular
Global Phthalic Anhydride Customer Forum meetings.
Delivery of our product to the customer site is just
the beginning of our offering. BASF stands behind its
products and, through our global technical service
representatives, ensures that our products perform
and deliver value. We innovate to make our customers
successful.
Expert Technical Service
Our technical service staff has extensive professional
experience in Phthalic Anhydride catalysts, including
hands on operational expertise in the areas of super-
vision, start up assistance and catalyst optimization.
BASF has more than 70 years of experience in the loading
and start up supervision of Phthalic Anhydride catalysts.
●● o-Xylene and naphthalene/mixed feed oxidation
in fixed bed process
●● Xylene loadings up to 100 g/Nm³
●● Supply of complete catalyst filling and
measurement equipment on loan basis,
including 5-tube, 10-tube
and 20-tube catalyst filling machines
●● Optimization of catalyst operation condition
using portable COx analyzers
●● Verification of air flow measurements by
total combustion
Value Added Customer Service
From order placement through invoicing, BASF’s
Customer Service functions as the customer’s voice by:
●● Assigning a primary customer service representative
●● Providing a Customer Service Network with
3 central hubs
●● Addressing customer concerns in the language
of the customer
Main Byproducts in Reaction Gas
Typical concentrations in reactor outlet gas (ROG) at 100 g/Nm3
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RESEARCH & DEVELOPMENT
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With research and development we shape the future
and develop profitable growth. Therefore we spent
approximately € 1.49 billion in 2010 and increased our
R&D expenditures by 40 % compared with 2005.
Optimized processes and intelligent system solutions
along with new and innovative products make a key
contribution to the longterm success of our customers
and ourselves.
Worldwide, around 9,600 BASF employees work in
research and development. BASF’s Research Verbund
covers the central technology platforms, the research
and development units in our operating divisions world-
wide and at Group companies as well as affiliated
companies.
In addition, we are currently involved in more than
1,900 collaborative partnerships worldwide with leading
universities, research institutes, startup companies
and industrial partners, which deliver momentum to
our research activities around the world.
Research Organization at BASF
ResearchInstitutes
IndustryPartners
High-TechJoint Ventures
PlantBiotechnology
Research
BASFResearchVerbund
PolymerResearch
SpecialtyChemicalsResearch
Chemicals Research & Engineering
Universities
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Inorganic Solids
Zeolites
Catalysts for Oleochemicals
Amination Catalysts
Fuel Cell Catalysts
Catalysts for Petrochemicals
Hydrogenation Catalysts
Oxidation Catalysts
Acid/Base Catalysis
Catalyst Supports
49 Professionals 135 Technicians
International Cooperations with Universities
Catalyst Research Ludwigshafen
BASF Phthalic Anhydride Catalyst Research Experience in a Commercial Plant
O
O
O
+ Air
+ Byproducts
Universities
Catalyst Marketing
BASF
Phthalic Anhydride Plant
Catalyst Research
Online Monitoring of Test Results
Customers
Test Facilities
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PHTHALIC ANHyDRIDE CATALyST PORTFOLIO
Catalyst Portfolio for o-Xylene Oxidation
Phthalic Anhydride Catalyst O4 – 68 O4 – 66 O4 – 88
Load [g/Nm3] max. 80 80 – 100 80 – 100
Air max. [Nm3/h] 4.0 4.0 4.0
Layers 4 4 5
Filling Height [m] 2.2* – 3.4 3.0 – 3.7 3.0 – 3.7
Initial Salt Bath Temperature [°C] 345 – 350 345 – 350 345 – 350
PA-Yield (Reactor Gas) [wt.-%]
114 – 115 114 – 115 115.5 – 116.5
Phthalide (Reactor Gas) [wt.-%]
0.02 – 0.07 0.02 – 0.1 0.02 – 0.1
Aromatics (In Off Gas) [mg/m3]
20 – 40 20 – 40 20 – 40
Start-Up Time To 80 g/Nm3 To
100 g/Nm3 [Days]
18
–
18
45
24
52
Restart Time To 80 g/Nm3 To
100 g/Nm3 [Days]
1
–
1
1 – 2
1
1 – 2
* in combination with post reactor
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Catalyst Portfolio for Naphthalene/Mixed Feed Oxidation
Phthalic Anhydride Catalyst O4–29 O4–29 HiFlex
Feed (Ratio)Naphthalene: 100 – 50 %
o-Xylene: 0 – 50 %
Naphthalene: 100 – 35 %
o-Xylene: 0 – 65 %
Load [g/Nm3]Naphthalene: 80
Mixed Feed: 80
Naphthalene: 80
Mixed Feed: 85
Phthalic Anhydride Yield (Reactor Gas) [wt.-%]
Naphthalene: 104 – 105
o-X/Naphthalene (50:50): 109 – 110
Naphthalene: 105 – 106
o-X/Naphthalene (50:50): 110 – 111
Byproducts Reactor Gas Naphthoquinone [wt.-%]
Phthalide [wt.-%]
0.05 – 1.0
0 – 0.1
0.05 – 1.0
0 – 0.1
Layers 3 4
Filling Height [m] 2.9 – 3.4 2.9 – 3.4 m
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PHTHALIC ANHyDRIDE CATALySTS FOR O-XyLENE OXIDATION
Expected Quality of Pure PA
Purity: > 99.90 wt.-%
Solidification Point: > 131.0 °C
Colour (Hazen): 5 – 10 APHA
Heat Stability: 15 – 30 APHA (90 min., 250 °C)
Application: Gasphase Oxidation of o-Xylene to PA
Description: 4-Layer Catalyst (CL1, CL2, CL3, CL4)
o-Xylene Load: max. 80 g/Nm3
Air flow rate: max. 4.0 Nm3/h
Composition: V2O5, TiO2 and Promotors
on Ceramic Rings
Shape: Rings, 7 x 7 x 4 mm
Filling Density: approx. 0.93 kg/l
Filling Height: 2.2* – 3.4 m
Thermal Stability: up to 500 °C
Salt Bath Temp.: 345 – 350 °C
Phthalic
Anhydride Yield: 114 – 115 %
PD Content: 0.02 % in CPA
SO2: no need
* in combination with post reactor
Expected Reactor Gas Composition
(after break in period)
Phthalic Anhydride 94.50 – 95.60 wt.-%
Maleic Anhydride 3.30 – 4.00 wt.-%
Citraconic Anhydride 0.35 – 0.50 wt.-%
Benzoic Acid 0.40 – 0.80 wt.-%
Phthalide 0.02 – 0.07 wt.-%
o-Toluic Aldehyde 0.005 – 0.02 wt.-%
o-Xylene 0.005 – 0.05 wt.-%
(at 80 g/Nm3 OX Loading and 4.0 Nm3 Air per Tube and Hour)
O4-68 Catalyst (o-Xylene Load 80g/Nm3) The Latest Generation of 4-Layer Catalysts
CL1 CL2 CL3 CL4
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Reference List
Company Country Company Country
OCI Korea Kamtex Russia
Kawasaki Kasei Chemical Japan Lanxess Germany
Mysor Petrochemicals India BASF Corporation USA
Nimir Pakistan Koppers USA
Lijin Petrochemicals China Kemiplas Slovenia
Vartego Argentina Mexichem Mexico
Orgachim Bulgaria BASF SE Germany
CEPSA Spain Isegen South Africa
●● Improved 4-layer catalyst generation
●● Designed for harsh operation conditions
(numerous shut downs)
●● Improved stability of 1st catalyst layer
●● Higher proportion of selective layers per tube
●● Hot Spot (HS) remains longer in selective layers
●● Higher Phthalic Anhydride yield in 2nd operation year
●● Top performance for low loading
O4-68 Catalyst Advantages
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●●●
CL1 CL2 CL3 CL4
Expected Quality of Pure PA
Purity: > 99.90 wt.-%
Solidification Point: > 131.0 °C
Colour (Hazen): 5 – 10 APHA
Heat Stability: 15 – 30 APHA (90 min., 250 °C)
PHTHALIC ANHyDRIDE CATALySTS FOR O-XyLENE OXIDATION
Application: Gasphase Oxidation of o-Xylene to PA
Description: 4-Layer Catalyst (CL1, CL2, CL3, CL4)
o-Xylene Load: max. 100 g/Nm3
Air flow rate: max. 4.0 Nm3/h
Composition: V2O5, TiO2 and Promotors
on Ceramic Rings
Shape: Rings, 7 x 7 x 4 mm
Filling Density: approx. 0.93 kg/l
Filling Height: 3.0 – 3.4 m
Thermal Stability: up to 500 °C
Salt Bath Temp.: 345 – 350 °C
Phthalic
Anhydride Yield: 114 – 115 %
PD Content: 0.02 % in CPA
SO2: no need
Expected Reactor Gas Composition
(after break in period)
Phthalic Anhydride 94.50 – 95.60 wt.-%
Maleic Anhydride 3.30 – 4.00 wt.-%
Citraconic Anhydride 0.35 – 0.50 wt.-%
Benzoic Acid 0.40 – 0.80 wt.-%
Phthalide 0.02 – 0.1 wt.-%
o-Toluic Aldehyde 0.005 – 0.02 wt.-%
o-Xylene 0.005 – 0.05 wt.-%
(at 100 g/Nm3 OX Loading and 4.0 Nm3 Air per Tube and Hour)
O4-66 Catalyst (o-Xylene Load up to 100g/Nm³) The most successful Phthalic Anhydride Catalyst
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Reference List
Company Country Company Country Company Country
Henan Qing’an China UPC Zhuhai China Lanxess Germany
Shandong Hongxin China UPC Zhongshan China Perstop Sweden
Jiangyin Zhongrun China UPC Taizhou China ZAK Poland
Qilu Plasticizer China Movalledan Iran Lida Belarus
Zhenhai Taida China IG Petrochemical India CarboQuimica Colombia
UPC Taiwan Zhejiang Qing’an China BASF-Petronas Malaysia
Thirumalai IndiaHarbin China Blue
Star ChemicalChina
Continental
PetrochemicalThailand
Asian Paints India Shijiazhuang Bailong China Petkim Turkey
Aekyung KoreaPetro China Jingzhou
Petrochemicals China NanYa Taiwan
Hanwa Korea Wuxi Coking China BASF SE Germany
Mistubishi Gas
ChemicalJapan
Taixing Union Zond
Chemicals China Oltchim Romania
Shanghai Coking China Petrom Brasil Panimex Chile
PetroChina Jinzhou
Petrochemical China Gadiv Israel
Dongguan
Shenghe China
UPC Zhenjiang ChinaChangzhou
New SolarChina Zhejiang GST China
●● Improved 4-layer catalyst generation
●● Designed for harsh operation conditions
(numerous shut downs, high loading operation)
●● Improved stability of 1st catalyst layer
●● Higher proportion of selective layers per tube
●● Hot Spot (HS) remains longer in selective layers
●● Higher Phthalic Anhydride yield in 2nd operation year
O4-66 Catalyst Advantages
”Our production philosophy is to always use
the best catalyst in the market. Consequently
we are operating O4-66 catalysts in all
BASF phthalic anhydride production facilities
worldwide.“
Dr. Rainer Rahm, Process Manager
BASF SE, Petrochemicals Division
●●
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PHTHALIC ANHyDRIDE CATALySTS FOR O-XyLENE OXIDATION
Application: Gasphase Oxidation of o-Xylene to PA
Description: 5-Layer Catalyst
(CL0, CL1, CL2, CL3, CL4)
o-Xylene Load: max. 100 g/Nm3
Air flow rate: max. 4.0 Nm3/h
Composition: New designed active mass
Shape: Rings, 7 x 7 x 4 mm
Filling Density: approx. 0.93 kg/l
Filling Height: 3.0 – 3.7 m
Thermal Stability: up to 500 °C
Salt Bath Temp.: 345 – 350 °C
Phthalic
Anhydride Yield: 115.5 – 116.5 %
PD Content: 0.02 % in CPA
SO2: no need
Expected Reactor Gas Composition
(after break in period)
Phthalic Anhydride 95.00 – 96.90 wt.-%
Maleic Anhydride 2.20 – 3.50 wt.-%
Citraconic Anhydride 0.35 – 0.50 wt.-%
Benzoic Acid 0.50 – 0.80 wt.-%
Phthalide 0.02 – 0.10 wt.-%
o-Toluic Aldehyde 0.005 – 0.02 wt.-%
o-Xylene 0.005 – 0.05 wt.-%
(at 100 g/Nm3 OX Loading and 4.0 Nm3 Air per Tube and Hour)
O4-88 Catalyst (o-Xylene Load up to 100g/Nm3) The New Generation of 5-Layer Catalysts
●●
CL0 CL1 CL2 CL3 CL4
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Expected Quality of Pure Phthalic Anhydride
Purity: > 99.90 wt.-%
Solidification Point: > 131.0 °C
Colour (Hazen): 5 – 10 APHA
Heat Stability: 15 – 30 APHA (90 min., 250 °C)
Reference List
Company Country Company Country
UPC Zhenjiang China Deza Czech Republic
●● 1 – 1.5 % higher yield vs. O4-66
●● 3 selective layers (CL0, CL1, CL2)
●● 5 years development time to ensure highest quality
●● Easy start-up behaviour
●● Hot Spot (HS) position directly in CL0
●● Patented new active mass (CL0)
O4-88 Catalyst Advantages
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PHTHALIC ANHyDRIDE CATALySTS FOR NAPHTHALENE/MIXED FEED OXIDATION
Application: Gasphase Oxidation of Naphthalene /
Mixed Feed to PA
Description: 4-Layer Catalyst (CL1, CL2, CL3, CL4)
Feed Ratio
O4-29:
Naphthalene: 100 – 50 %
o-Xylene: 0 – 50 %
Feed Ratio
O4-29 HiFlex:
Naphthalene: 100 – 35 %
o-Xylene: 0 – 65 %
Load O4-29: max. 80 g/Nm³
Load
O4-29 HiFlex:max. 85 g/Nm³
Air flow rate: max. 4.0 Nm3/h
Composition: V2O5, TiO2 and Promotors
on Ceramic Rings
Shape: Rings, 8 x 6 x 5 mm
Filling Density: approx. 0.88 kg/l
Filling Height: 2.9 – 3.4 m
Thermal Stability: up to 500 °C
Salt Bath Temp.: 355 – 365 °C
Phthalic
Anhydride Yield
O4-29:
109 – 110 %
Phthalic
Anhydride Yield
O4-29 HiFlex:
110 – 111 %
in Mixed Feed Operations (50:50)
NQ Content: 0.01 – 0.1 % in CPA
O4-29/O4-29 HiFlex Mixed Feed Catalyst
Phthalic Anhydride Catalyst
O4–29 / O4-29 HiFlex
Phthalic Anhydride: 94.50 – 97.50 wt.-%
Maleic Anhydride 2.00 – 3.50 wt.-%
Benzoic Acid 0.40 – 0.50 wt.-%
Naphthoquinone: 0.05 – 1.00 wt.-%
Expected Reactor Gas Composition (after break in period)
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CL1 CL2 CL3 CL4
●●w
O4-29/O4-29 HiFlex
Phthalic Anhydride Catalyst
O4-29 / O4-29 HiFlex
Purity: > 99.90 wt.-%
Solidification Point: > 131.0 °C
Colour (Hazen): 5 – 10 APHA
Heat Stability: 15 – 30 APHA (90 min., 250 °C)
Reference List
Phthalic Anhydride Plant DEZA, Czech Republic; Reference Plant BASF
Expected Quality of Pure Phthalic Anhydride
O4-29/O4-29 HiFlex Catalyst Advantages
Company Country
Shijiazhuang Bailong China
DEZA Czech Republic
DCC Pohang Korea
ISEGEN South Africa
KOPPERS USA
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Americas BASF Corporation 25 Middlesex/Essex Turnpike Iselin, NJ 08830, USA Tel: +1-732-205-5000 Fax: +1-732-205-5687 Email: [email protected]
Asia Pacific BASF East Asia Regional HQ Ltd. 45th Floor, Jardine House No. 1 Connaught Place Central, Hong Kong Tel: +852-2731-0191 Fax: +852-2731-5634 Email: [email protected]
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About Us
BASF’s Catalysts division is the world’s leading supplier of environmental and process catalysts. The group offers exceptional expertise in the develop-ment of technologies that protect the air we breathe, produce the fuels that power our world and ensure efficient production of a wide variety of chemi-cals, plastics and other products, including advanced battery materials. By leveraging our industry-leading R&D platforms, passion for innovation and deep knowledge of precious and base metals, BASF’s Catalysts division develops unique, proprietary solutions that drive customer success.
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www.catalysts.basf.com/chemicals
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