Abstract

Process Economics Program Report 34B

PHTHALIC ANHYDRIDE
(October 1998)
Worldwide consumption of phthalic anhydride (PA) reached 6.6 billion lb/yr in 1996, and is
projected to reach 7.9 billion lb/yr by 2001. About 90% of consumption is concentrated in 3 major
uses: (1) PA esters are widely used as plasticizers for polyvinyl chloride resins; (2) unsaturated
(thermosetting) polyesters find major uses to fabricate fiberglass-reinforced parts such as boats
and bath tubs; and (3) glycerol-phthalate alkyd resins are a widely used base for paints.
Since our first PA reports, PEP Report 34 (March 1968) and PEP Report 34A (June 1974),
respectively, several aspects of PA production have changed: o-Xylene is now the major
feedstock, whereas naphthalenes use as a feedstock has diminished to about 16% of the total.
Catalyst improvements allow smaller reactors. Improvements in equipment and safety release
device designs provide for safe operation within the explosive limits of the higher o-xylene
loadings desired. And environmental concerns now require the addition of an exhaust gas
incinerator.
Currently, almost all PA is manufactured by the single fixed bed oxidation reactor process
with conventional switch condensers that collect PA as a solid, and fully developed technology is
available for licensing from several sources.
We show that economic improvements over the fixed bed process are possible with (1) a
dual fixed bed reactor design with o-xylene injection in between, and (2) a design in which PA is
recovered as a liquid by using a eutectic of PA and maleic anhydride (MA) as the
cooling/scrubbing fluid. In addition, we examine the technology for producing PA in a fluidized
bed reactor (currently, not a practical option), and discuss the improvements needed in catalyst
attrition resistance and life required for the process to compete with fixed bed technology.
The liquid recovery system requires less capital, has a lower product value, and produces
more steam that is available for export than does the single fixed bed; the dual bed system
offers an additional improvement in economies. Moreover, the effects of liquid recovery and dual
bed systems appear to be additive if the systems are implemented in the same plant.
No commercial liquid recovery systems have been announced, but the dual reactor system
has been, in part, commercialized by BASF and plans to commercialize a similar system have
recently been announced by Nest. We show that fluidized bed technology offers promise, and
we quantify the additional catalyst improvements required to realize this potential.

PEP96 34B ERM

CONTENTS
GLOSSARY..................................................................................................................................... xi
1

INTRODUCTION ....................................................................................................................1-1

SUMMARY..............................................................................................................................2-1
GENERAL ASPECTS .............................................................................................................2-1
PA Market and Capacity ........................................................................................................2-1
Capacity Utilization.................................................................................................................2-1
Major Uses for PA ..................................................................................................................2-5
TECHNICAL ASPECTS..........................................................................................................2-5
PA from o-Xylene with a Single Fixed Bed Reactor ...............................................................2-6
Oxidation .............................................................................................................................2-6
PA Recovery........................................................................................................................2-6
Catalytic Combustion of the Waste Gas Stream .................................................................2-6
Decomposer ........................................................................................................................2-6
Distillation ............................................................................................................................2-6
PA in Dual Fixed Beds with o-Xylene Injection Between Each Bed .......................................2-6
Oxidation .............................................................................................................................2-6
PA Recovery .......................................................................................................................2-7
Additional Processing ..........................................................................................................2-7
Single Fixed Bed Reactor with Molten MA for PA Recovery ..................................................2-7
PA Recovery........................................................................................................................2-7
Additional Processing ..........................................................................................................2-7
PA from o-Xylene in a Fluidized Bed Reactor ........................................................................2-8
Oxidation .............................................................................................................................2-8
ECONOMIC ASPECTS ..........................................................................................................2-8

PA INDUSTRY STATUS ........................................................................................................3-1

OVERVIEW.............................................................................................................................3-1
PRICE HISTORY....................................................................................................................3-2
PRODUCTION CAPACITIES .................................................................................................3-3
CONSUMPTION...................................................................................................................3-16
United States ........................................................................................................................3-16
Western Europe....................................................................................................................3-16
Japan ....................................................................................................................................3-17
Mexico ..................................................................................................................................3-18
Other Regions.......................................................................................................................3-18

CONTENTS (Continued)
4

TECHNICAL REVIEW (Concluded)

Decomposer .........................................................................................................................4-16
MA Recovery ........................................................................................................................4-16
Final PA State .......................................................................................................................4-17

PHTHALIC ANHYDRIDE FROM O-XYLENE IN A FIXED BED REACTOR ..........................5-1

PROCESS DESCRIPTION.....................................................................................................5-1
Section 100Oxidation ..........................................................................................................5-1
PA Recovery ......................................................................................................................5-2
Catalytic Combustion of the Waste Gas Stream ................................................................5-2
Section 200Purification........................................................................................................5-2
Decomposer .......................................................................................................................5-2
Distillation ...........................................................................................................................5-2
PROCESS DISCUSSION .....................................................................................................5-10
Oxidation...............................................................................................................................5-10
Reactor Start-up ...................................................................................................................5-11
Catalytic Incineration of the Exhaust Gas Stream ................................................................5-11
PA Condensation ..................................................................................................................5-11
Decomposer .........................................................................................................................5-12
Distillation..............................................................................................................................5-12
Waste Treatment ..................................................................................................................5-12
Materials of Construction ......................................................................................................5-13
COST ESTIMATES ..............................................................................................................5-13
Capital Costs ........................................................................................................................5-13
Capital Changes from Earlier Studies ..............................................................................5-13
Comparative Capital Costs...............................................................................................5-14
Production Costs ..................................................................................................................5-14

PHTHALIC ANHYDRIDE FROM O-XYLENE IN DUAL FIXED BED REACTORS.................6-1

INTRODUCTION ....................................................................................................................6-1
REVIEW OF PROCESSES ....................................................................................................6-1
Dual Reactor Background.......................................................................................................6-1
Oxidation of o-Xylene to PA....................................................................................................6-2
PROCESS DESCRIPTION.....................................................................................................6-2

iii

CONTENTS (Continued)
6

PHTHALIC ANHYDRIDE FROM O-XYLENE IN

DUAL FIXED BED REACTORS (Concluded)
Section 100Oxidation ..........................................................................................................6-3
PA Recovery ......................................................................................................................6-3
Catalytic Combustion of the Waste Gas Stream ................................................................6-3
Section 200Purification........................................................................................................6-4
Decomposer .......................................................................................................................6-4
Distillation ...........................................................................................................................6-4
PROCESS DISCUSSION .....................................................................................................6-12
Oxidation...............................................................................................................................6-12
Reactor Start-up ...................................................................................................................6-12
COST ESTIMATES ..............................................................................................................6-13
Capital Costs ........................................................................................................................6-13
Capital Cost Changes from Earlier Studies ......................................................................6-14
Capital Cost Changes from the Single Fixed Bed Reactor Design ..................................6-14
Production Costs ..................................................................................................................6-14

PHTHALIC ANHYDRIDE RECOVERY

WITH MOLTEN MALEIC ANHYDRIDE SCRUBBING............................................................7-1
INTRODUCTION ....................................................................................................................7-1
PROCESS REVIEW ...............................................................................................................7-1
Background.............................................................................................................................7-1
PA Recovery by Scrubbing with High Boiling Point Organic Solvents....................................7-1
Evaporative Cooling, Collecting, and Melting in a Filtering Chamber .....................................7-1
Molten MA Scrubbing..............................................................................................................7-2
MA Recovery ..........................................................................................................................7-2
PROCESS DESCRIPTION.....................................................................................................7-2
Section 100Oxidation ..........................................................................................................7-3
PA Recovery ......................................................................................................................7-3
Catalytic Combustion of the Waste Gas Stream ................................................................7-3
Section 200Purification.......................................................................................................7-4
Decomposer .......................................................................................................................7-4
Distillation ...........................................................................................................................7-4
PROCESS DISCUSSION .....................................................................................................7-12
Major Changes with Molten MA Scrubbing...........................................................................7-12

iv

CONTENTS (Concluded)
7

PHTHALIC ANHYDRIDE RECOVERY

WITH MOLTEN MALEIC ANHYDRIDE SCRUBBING (Concluded)
PA Condensation ..................................................................................................................7-12
Precooling Exhaust Gases ...............................................................................................7-12
Initial Partial PA Recovery ................................................................................................7-12
PA Recovery with Molten MA Scrubbing..........................................................................7-12
Distillation..............................................................................................................................7-13
COST ESTIMATES ..............................................................................................................7-13
Capital Costs ........................................................................................................................7-14
Production Costs ..................................................................................................................7-14

PHTHALIC ANHYDRIDE FROM O-XYLENE IN A FLUIDIZED BED REACTOR ..................8-1

INTRODUCTION ....................................................................................................................8-1
PROCESS REVIEW ...............................................................................................................8-1
PROCESS DESCRIPTION.....................................................................................................8-1
Section 100Oxidation ..........................................................................................................8-2
PA Recovery ......................................................................................................................8-2
Catalytic Combustion of the Waste Gas Stream ................................................................8-2
Section 200Purification........................................................................................................8-2
Decomposer .......................................................................................................................8-2
Distillation ...........................................................................................................................8-2
PROCESS DISCUSSION .....................................................................................................8-11
Oxidation ..............................................................................................................................8-11
Other Process Sections .......................................................................................................8-11
COST ESTIMATES ..............................................................................................................8-11
Capital Costs ........................................................................................................................8-11
Production Costs ..................................................................................................................8-11
RESEARCH SUGGESTIONS ..............................................................................................8-14

APPENDIX A: PATENT SUMMARY TABLE ..............................................................................A-1

APPENDIX B: PRODUCTION COSTS FOR CATALYSTS WITH IMPROVED WHSV .............B-1
APPENDIX C: DESIGN AND COST BASES ............................................................................. C-1
APPENDIX D: CITED REFERENCES ....................................................................................... D-1
APPENDIX E: PATENT REFERENCES BY COMPANY............................................................E-1
APPENDIX F:

PROCESS FLOW DIAGRAMS ...........................................................................F-1

ILLUSTRATIONS
2.1

PA from o-Xylene via Fluidized Bed Oxidation

Product Value as a Function of Catalyst Life and WHSV.................................................. 2-11

3.1

U.S. Price of PA and o-Xylene ............................................................................................3-2

5.1

PA from o-Xylene by Air Oxidation in Fixed Bed Reactors..................................................F-3

6.1

PA from o-Xylene by Fixed Bed Reactors, Dual Beds with o-Xylene Injection ...................F-5

71

PA from o-Xylene by Air Oxidation in Fixed Bed Reactors (Molten MA Scrubbing)............F-7

8.1

PA from o-Xylene by Fluidized Bed Oxidation.....................................................................F-9

8.2

PA from o-Xylene by Fluidized Bed Oxidation

Product Value as a Function of Catalyst Life and WHSV..................................................8-13

vi

TABLES
2.1

PA Consumption..................................................................................................................2-2

2.2

Global PA Capacity, 1996 ...................................................................................................2-3

2.3

Price History of PA in Major World Markets .......................................................................2-4

2.4

PA Capacity versus Consumption for 1996.........................................................................2-4

2.5

Major PA Uses.....................................................................................................................2-5

2.6

PA Production Costs from o-Xylene by Air Oxidation........................................................2-10

3.1

U.S. Producers of PA ..........................................................................................................3-5

3.2

PA Producers in Western Europe........................................................................................3-6

3.3

PA Producers in Eastern Europe.........................................................................................3-8

3.4

PA Producers in Japan......................................................................................................3-10

3.5

Other PA Producers ..........................................................................................................3-11

3.6

U.S. PA Consumption........................................................................................................3-19

3.7

Western European PA Consumption.................................................................................3-19

3.8

Japanese PA Consumption ...............................................................................................3-20

3.9

Mexican PA Consumption .................................................................................................3-20

3.10 PA Consumption in Other Regions....................................................................................3-21

5.1

PA from o-Xylene in a Fixed Bed Reactor

Design Bases ......................................................................................................................5-3

5.2

PA from o-Xylene in a Fixed Bed Reactor

Stream Flows.......................................................................................................................5-5

5.3

PA from o-Xylene in a Fixed Bed Reactor

Major Equipment .................................................................................................................5-7

5.4

PA from o-Xylene in a Fixed Bed Reactor

Utilities Summary.................................................................................................................5-9

5.5

PA from o-Xylene in a Fixed Bed Reactor

Total Capital Investment....................................................................................................5-16

5.6

PA from o-Xylene in a Fixed Bed Reactor

Production Costs ...............................................................................................................5-17

6.1

PA from o-Xylene in Dual Fixed Bed Reactors

Design Bases ......................................................................................................................6-5

6.2

PA from o-Xylene in Dual Fixed Bed Reactors

Stream Flows.......................................................................................................................6-7

6.3

PA from o-Xylene in Dual Fixed Bed Reactors

Major Equipment .................................................................................................................6-9

6.4

PA from o-Xylene in Dual Fixed Bed Reactors

Utilities Summary...............................................................................................................6-11

vii

TABLES (Concluded)
6.5

PA from o-Xylene in Dual Fixed Bed Reactors

Total Capital Investment....................................................................................................6-16

6.6

PA from o-Xylene in Dual Fixed Bed Reactors

Production Costs ...............................................................................................................6-17

7.1

PA Recovery with Molten MA Scrubbing

Design Bases ......................................................................................................................7-5

7.2

PA Recovery with Molten MA Scrubbing

Stream Flows.......................................................................................................................7-7

7.3

PA Recovery with Molten MA Scrubbing

Major Equipment .................................................................................................................7-9

7.4

PA Recovery with Molten MA Scrubbing

Utilities Summary...............................................................................................................7-11

7.5

PA Recovery with Molten MA Scrubbing

Total Capital Investment....................................................................................................7-15

7.6

PA Recovery with Molten MA Scrubbing

Production Costs ...............................................................................................................7-16

8.1

PA from o-Xylene in a Fluidized Bed Reactor

Design Bases ......................................................................................................................8-4

8.2

PA from o-Xylene in a Fluidized Bed Reactor

Stream Flows.......................................................................................................................8-6

8.3

PA from o-Xylene in a Fluidized Bed Reactor

Major Equipment .................................................................................................................8-8

8.4

PA from o-Xylene in a Fluidized Bed Reactor

Utilities Summary...............................................................................................................8-10

8.5

PA from o-Xylene in a Fluidized Bed Reactor

Total Capital Investment....................................................................................................8-15

8.6

PA from o-Xylene in a Fluidized Bed Reactor

Production Costs ...............................................................................................................8-16

viii