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Phthalic Anhydride Catalysts

CONTENT

Introduction

Research & Development

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

INTRODUCTION
BASF The Chemical Company
The worlds leading chemical company offers intelligent
solutions and high-quality products for almost all industries, uses new technologies to open up additional
marketopportunities and combines economic success
with environmentalprotection and social responsibility.

BASF at a Glance
Founded in 1865 by Friedrich Engelhorn under the name
Badische Anilin- und Sodafabrik, today, BASF is the
Worlds 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.

Our 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.

Important Facts About Phthalic Anhydride at BASF

BASF has produced Phthalic Anhydride for over


135years

BASF has developed Phthalic Anhydride catalysts


forover 110 years

Total production of Phthalic Anhydride at Ludwigs


hafensite since 1873is more than 3.5 million tons

Production experience with post reactors since 1980

Phthalic Anhydride Catalyst History


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 Wackers 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.-%

Worldwide Use of Phthalic Anhydride

Plasticizers

52%

Other Applications

14%

Alkyde Resins

16%

Unsaturated Polyesters

18 %

Phthalic Anhydride Process


Permanent improvement of process and catalyst

Offgas
Steam
60 bar

Pure P A
tank
Post
reactor

SC

Predecomposer
2 column
distillation

Organization of the Phthalic Anhydride Catalyst Business

Ludwigshafen
Iselin, New Jersey
Headquarters

Catalyst Global Business Management


Catalyst Production
Catalyst Research
Regional Marketing
Technical Service

Hong Kong

Regional Marketing
Technical Service

From o-Xylene to Phthalic Anhydride


(Reaction mechanism)

Advantages of BASF as a Phthalic Anhydride Catalyst Supplier


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 supervision, 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.

 -Xylene and naphthalene/mixed feed oxidation


o
in fixed bed process

Xylene loadings up to 100 g/Nm

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, BASFs
Customer Service functions as the customers voice by:

Assigning a primary customer service representative

Providing a Customer Service Network with


3 central hubs

 ddressing customer concerns in the language


A
of the customer

Main Byproducts in Reaction Gas

Typical concentrations in
reactor outlet gas (ROG) at
100 g/Nm3

RESEARCH & DEVELOPMENT


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
contributionto the longterm success of our customers
and ourselves.

Worldwide, around 9,600 BASF employees work in


research and development. BASFs Research Verbund
covers the central technology platforms, the research
anddevelopment units in our operating divisions worldwide 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
andindustrial partners, which deliver momentum to
ourresearch activities around the world.

Research Organization at BASF

Research
Institutes

Universities
Chemicals
Research &
Engineering
Specialty
Chemicals
Research

BASF
Research
Verbund

Polymer
Research

Plant
Biotechnology
Research
High-Tech
Joint Ventures

Industry
Partners

BASF Phthalic Anhydride Catalyst Research


Experience in a Commercial Plant

+ Air
Catalyst Research
BASF

Test Facilities

Universities

Online Monitoring of
Test Results
Phthalic
Anhydride Plant

O
O

+ Byproducts
Catalyst Marketing

Customers

Catalyst Research Ludwigshafen


Inorganic Solids

Fuel Cell Catalysts

Zeolites

Catalysts for Petrochemicals

Catalysts for Oleochemicals

Amination Catalysts

49 Professionals
135 Technicians

Hydrogenation Catalysts
Oxidation Catalysts
Acid/Base Catalysis
Catalyst Supports

International Cooperations with


Universities

Phthalic Anhydride CATALYST PORTFOLIO


Catalyst Portfolio for o-Xylene Oxidation
Phthalic Anhydride Catalyst

O468

O466

O488

Load [g/Nm3]

max. 80

80 100

80 100

4.0

4.0

4.0

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

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
12

1
12

Air max. [Nm3/h]


Layers

Aromatics
(In Off Gas) [mg/m3]

* in combination with post reactor

10

Catalyst Portfolio for Naphthalene/Mixed Feed Oxidation


Phthalic Anhydride Catalyst

O429

O429 HiFlex

Feed (Ratio)

Naphthalene:
o-Xylene:

100 50% Naphthalene:


0 50 % o-Xylene:

Load [g/Nm3]

Naphthalene: 80
Mixed Feed:
80

Naphthalene:
Mixed Feed:

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.-%]

Layers

Filling Height [m]

0.05 1.0
0 0.1
3
2.9 3.4

100 35%
0 65%
80
85

0.05 1.0
0 0.1
4
2.9 3.4 m

11

Phthalic Anhydride CATALYSTS FOR


o-XYLENE OXIDATION
O4-68 Catalyst (o-Xylene Load 80g/Nm3)
The Latest Generation of 4-Layer Catalysts
Expected Reactor Gas Composition
Application:

Gasphase Oxidation of o-Xylene to PA

(after break in period)

Description:

4-Layer Catalyst (CL1, CL2, CL3, CL4)

Phthalic Anhydride

94.50 95.60 wt.-%

o-Xylene Load:

max. 80 g/Nm3

Maleic Anhydride

3.30 4.00 wt.-%

Air flow rate:

max. 4.0 Nm3/h

Citraconic Anhydride

0.35 0.50 wt.-%

Benzoic Acid

0.40 0.80 wt.-%

Composition:

V2O5, TiO2 and Promotors


on Ceramic Rings

Phthalide

0.02 0.07 wt.-%

Shape:

Rings, 7 x 7 x 4 mm

o-Toluic Aldehyde

0.005 0.02 wt.-%

Filling Density:

approx. 0.93 kg/l

o-Xylene

0.005 0.05 wt.-%

Filling Height:

2.2* 3.4 m

(at 80 g/Nm3 OX Loading and 4.0 Nm3 Air per Tube and Hour)

Thermal Stability: up to 500C


Salt Bath Temp.:

345 350C

Expected Quality of Pure PA

Phthalic
Anhydride Yield:

114 115%

Purity:

> 99.90 wt.-%

PD Content:

0.02 % in CPA

Solidification Point:

> 131.0C

SO2:

no need

Colour (Hazen):

5 10 APHA

Heat Stability:

15 30 APHA (90 min., 250C)

* in combination with post reactor

CL1 CL2 CL3 CL4

12

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

O4-68 Catalyst Advantages

Improved 4-layer catalyst generation

Hot Spot (HS) remains longer in selective layers

Designed for harsh operation conditions


(numerous shut downs)

Higher Phthalic Anhydride yield in 2nd operation year

Top performance for low loading

Improved stability of 1st catalyst layer

Higher proportion of selective layers per tube

13

Phthalic Anhydride CATALYSTS FOR


o-XYLENE OXIDATION
O4-66 Catalyst (o-Xylene Load up to 100g/Nm)
The most successful Phthalic Anhydride Catalyst
Expected Reactor Gas Composition
Application:

Gasphase Oxidation of o-Xylene to PA

(after break in period)

Description:

4-Layer Catalyst (CL1, CL2, CL3, CL4)

Phthalic Anhydride

94.50 95.60 wt.-%

o-Xylene Load:

max. 100 g/Nm3

Maleic Anhydride

3.30 4.00 wt.-%

Air flow rate:

max. 4.0 Nm3/h

Citraconic Anhydride

0.35 0.50 wt.-%

Benzoic Acid

0.40 0.80 wt.-%

Composition:

V2O5, TiO2 and Promotors


on Ceramic Rings

Phthalide

0.02 0.1 wt.-%

Shape:

Rings, 7 x 7 x 4 mm

o-Toluic Aldehyde

0.005 0.02 wt.-%

Filling Density:

approx. 0.93 kg/l

o-Xylene

0.005 0.05 wt.-%

Filling Height:

3.0 3.4 m

(at 100 g/Nm3 OX Loading and 4.0 Nm3 Air per Tube and Hour)

Thermal Stability: up to 500C


Salt Bath Temp.:

345 350C

Expected Quality of Pure PA

Phthalic
Anhydride Yield:

114 115%

Purity:

> 99.90 wt.-%

PD Content:

0.02% in CPA

Solidification Point:

> 131.0C

SO2:

no need

Colour (Hazen):

5 10 APHA

Heat Stability:

15 30 APHA (90 min., 250C)

CL1 CL2 CL3 CL4

14

Reference List
Company

Country

Company

Country

Company

Country

Henan Qingan

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 Qingan

China

BASF-Petronas

Malaysia

Thirumalai

India

Harbin China Blue


Star Chemical

China

Continental
Petrochemical

Thailand

Asian Paints

India

Shijiazhuang Bailong

China

Petkim

Turkey

Aekyung

Korea

Petro China Jingzhou


Petrochemicals

China

NanYa

Taiwan

Hanwa

Korea

Wuxi Coking

China

BASF SE

Germany

Mistubishi Gas
Chemical

Japan

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

China

Changzhou
New Solar

China

Zhejiang GST

China

O4-66 Catalyst Advantages

Improved 4-layer catalyst generation

Higher proportion of selective layers per tube

Designed for harsh operation conditions


(numerous shut downs, high loading operation)

Hot Spot (HS) remains longer in selective layers

Higher Phthalic Anhydride yield in 2nd operation year

Improved stability of 1st catalyst layer

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
15

Phthalic Anhydride CATALYSTS FOR


o-XYLENE OXIDATION
O4-88 Catalyst (o-Xylene Load up to 100g/Nm3)
The New Generation of 5-Layer Catalysts
Expected Reactor Gas Composition
Application:

Gasphase Oxidation of o-Xylene to PA

(after break in period)

Description:

5-Layer Catalyst
(CL0, CL1, CL2, CL3, CL4)

Phthalic Anhydride

95.00 96.90 wt.-%

Maleic Anhydride

2.20 3.50 wt.-%

o-Xylene Load:

max. 100 g/Nm3


Citraconic Anhydride

0.35 0.50 wt.-%

Benzoic Acid

0.50 0.80 wt.-%

Air flow rate:

max. 4.0 Nm /h

Composition:

New designed active mass

Phthalide

0.02 0.10 wt.-%

Shape:

Rings, 7 x 7 x 4 mm

o-Toluic Aldehyde

0.005 0.02 wt.-%

Filling Density:

approx. 0.93 kg/l

o-Xylene

0.005 0.05 wt.-%

Filling Height:

3.0 3.7 m

(at 100 g/Nm3 OX Loading and 4.0 Nm3 Air per Tube and Hour)

Thermal Stability: up to 500C

16

Salt Bath Temp.:

345 350C

Phthalic
Anhydride Yield:

115.5 116.5 %

PD Content:

0.02% in CPA

SO2:

no need

Expected Quality of Pure Phthalic Anhydride


Purity:

> 99.90 wt.-%

Solidification Point:

> 131.0C

Colour (Hazen):

5 10 APHA

Heat Stability:

15 30 APHA (90 min., 250C)

Reference List
Company

Country

Company

Country

UPC Zhenjiang

China

Deza

Czech Republic

O4-88 Catalyst Advantages

11.5 % higher yield vs. O4-66

Easy start-up behaviour

3 selective layers (CL0, CL1, CL2)

Hot Spot (HS) position directly in CL0

5 years development time to ensure highest quality

Patented new active mass (CL0)

CL0

CL1

CL2

CL3

CL4

17

Phthalic Anhydride Catalysts for


Naphthalene/Mixed Feed Oxidation
O4-29/O4-29 HiFlex
Mixed Feed Catalyst

Application:

Gasphase Oxidation of Naphthalene/


Mixed Feed to PA

Composition:

V2O5, TiO2 and Promotors


on Ceramic Rings

Description:

4-Layer Catalyst (CL1, CL2, CL3, CL4)

Shape:

Rings, 8 x 6 x 5 mm

Feed Ratio
O4-29:

Naphthalene: 100 50%


o-Xylene:
0 50%

Filling Density:

approx. 0.88 kg/l

Feed Ratio
O4-29 HiFlex:

Naphthalene: 100 35%


o-Xylene:
0 65%

Filling Height:

2.9 3.4 m

Load O4-29:

max. 80 g/Nm

Salt Bath Temp.:

355 365C

Load
O4-29 HiFlex:

max. 85 g/Nm

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

Air flow rate:

max. 4.0 Nm /h

Expected Reactor Gas Composition

Thermal Stability: up to 500C

(after break in period)

Phthalic Anhydride
Catalyst

O429/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.-%

CL1 CL2 CL3 CL4

18

O4-29/O4-29 HiFlex
Expected Quality of Pure Phthalic Anhydride
Phthalic Anhydride
Catalyst

O4-29/O4-29 HiFlex

Purity:

> 99.90 wt.-%

Solidification Point:

> 131.0C

Colour (Hazen):

5 10 APHA

Heat Stability:

15 30 APHA (90 min., 250C)

Reference List
Company

Country

Shijiazhuang Bailong

China

DEZA

Czech Republic

DCC Pohang

Korea

ISEGEN

South Africa

KOPPERS

USA

O4-29/O4-29 HiFlex Catalyst Advantages

Phthalic Anhydride Plant DEZA, Czech Republic; Reference Plant BASF

19

About Us
BASFs Catalysts division is the worlds
leading supplier of environmental and
process catalysts. The group offers
exceptional expertise in the development of technologies that protect the
air we breathe, produce the fuels that
power our world and ensure efficient
production of a wide variety of chemicals, plastics and other products,
including advanced battery materials.
By leveraging our industry-leading
R&Dplatforms, passion for innovation
and deep knowledge of precious and
base metals, BASFs Catalysts division
develops unique, proprietary solutions
that drive customer success.

BASF The Chemical Company

Americas
BASF Corporation
25 Middlesex/Essex Turnpike
Iselin, NJ 08830, USA
Tel: +1-732-205-5000
Fax: +1-732-205-5687
Email: catalysts-americas@basf.com
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: catalysts-asia@basf.com
Europe, Middle East, Africa
Customer Service
BASF Nederland B.V.
Tel: +31-30-6669555
Fax: +31-30-6669340
Email: catalysts-europe@basf.com

Although all statements and information in this publication are belived to be accurate and reliable, they
are presented gratis and for guidance only, and risks
and liability for results obtained by use of the products or application of the suggestions described are
assumed by the user. NO WARRANTIES OF ANY
KIND, EITHER EXPRESS OR IMPLIED, INCLUDING
WARRANTIES OF MERCHANTABILITY OR FITNESS
FOR A PARTICULAR PURPOSE, ARE MADE REGARDING PRODUCTS DESCRIBEDOR DESIGNS,
DATA OR INFORMATION SET FORTH. Statements
or suggestions concerning possible use of the products are made without representation or warranty
that any such use is free of patent infringement and
are not recommendations to infringe any patent. The
user should not assume that toxicity data and safety
measuresare indicated or that other measures may
not be required.

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