PHTHALIC ANHYDRIDE

[EIRI/EDPR/3844] J.C.: 1953

INTRODUCTION

Phthalic anhydride is an industrially important raw material for the production of

anthraquinone used in the manufacture of many vat dyes and in alizarin and
alizarin derivatives. It is used directly for the fluorescein, eosine, and rhodamine
dyes. Several esters are made from phthalic anhydride and are largely used in the
acquer industry as plasticizers. It is also used to manufacture alkyd resins, the
glyptal and rezyl resins, dioctyl phthalate and the poly-vinyl resins.

Phthalic anhydride, first discovered by Laurent in 1863, was originally prepared

by the oxidation of naphthalene with chromic acid. The early methods of
manufacture of phthalic anhydride involved liquid phase processes in which
expensive nitric and chromic acids were used as the oxidizing agents. The growing
demand for phthalic anhydride as an intermediate for dye manufacture in the
latter part of the nineteenth century made it imperative that cheaper means for its
production be obtained. Consequently, a method of oxidizing naphthalene by
sulfuric acid in the presence of mercury salts to form phthalic anhydride was
developed.

The discovery of the effectiveness of the oxides of the metals of the fifth and sixth
groups of the periodic table, especially of vanadium and molybdenum oxides, in
the vapor phase oxidation o£ naphthalene by air led to the present production. On
a large commercial scale, of phthalic anhydride in either fixed or fluidized bed
reactors.

The ever-increasing demand for phthalic anhydride has stimulated search for
alternative raw materials. Ortho-xylene, which is available in abundant quantities
from petroleum refineries, appears to be the most suitable. Phthalic anhydride
may be produced from o-xylene according to the following chemical equation.

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Phthalic anhydride is a white crystalline solid that is the commercial form of
phthalic acid. The largest markets for phthalic anhydride are phthalate
plasticizers, unsaturated polyester resins, and alkyd resins for surface coatings.
Commercial phthalic anhydride is 99.8–99.9% pure (99.5% is generally
guaranteed) and is available in two forms - flake and molten. Most worldwide
consumption of phthalic anhydride is molten.

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As a raw material for the production of phthalic anhydride, o -xylene has several
advantages. The theoretical amount of air required for oxidizing o-xylene is only
2/3 of that required for the oxidation of naphthalene; the heat given off during the
reaction is 121 Kcal less than that of naphthalene; the product is of higher purity;
theoretical yield per cent is higher than that of naphthalene. Furthermore, since
o-xylene is a liquid at ordinary temperature, its use permits a simpler feed system.

Phthalic anhydride forms long needles, m.p. 128oC, b.p. 285oC. It is used
extensively for the manufacture of anthraquinone, anthranilic acid, indigo,
butyl phthalate (nitrocellulose plasticiser) etc. with phosphorous penta chloride it
yields phthaloyl chloride, which exhibits ring-chain isomerism by reacting
chemically in both structures I and II. For instance phthalolyl chloride with
benzene and Aluminium chloride forms both anthraquinone and diphenyl
phthalide (Phthalophenone) (v), with hydrazine it reacts in form II to give a cyclic
hydrazole, where-as with zinc dust and acetic acid it reacts in form II to yield
phthalide (IV) , a carbo-cyclic lactone. Final proof of the existence of the two
tautomeric forms is afforded by their isolation. The symimetrical form (I) is
prepared by the action of Phosphorus pentachloride on phthalic anhydride and
on treatment with aluminium chloride is transformed into the unsymmetrical
form (II). This type of ring-chain isomerism is observed in the diacid halids of
those dicarboxylic acids whose carboxylic groups are in close proximity.

Phthalal al dehyde (III) and phthalide (IV) also finish examples of ring-chain
tautomerism.
CCl2
/COCl /\ /CHO
C6H4 / C6H4 / \O C6H4 /
\ \ / \
\COCl \/ \CHO
CO
(I) (II) (III)

C6H5
|
CH2 C-C6H5
/\ /\
C6H4 / \O C6H4 / \O
\ / \ /
\/ \/
CO CO
(IV) (V)

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Phthalic anhydride condenses with phenols to form triphenyl methane dyestuffs.
The reaction proceeds by the P-hydrogen atoms of two molecules of phenol uniting
with a carbongyl oxygen atom of anhydride to give water. The simplest of these
compounds is phenolphthalein which is prepared by heating phthalic anhydride
and phenol at 120o in the presence of sulphuric acid. It forms colourless
crystals and is a lactone which dissolves in alkali to give an intense red solution
from which the compound is precipitated in the colourless state by the
addition of acids.

HC CH CH
//\ C /\\ /\ //\ CO
HC // \/ \\CH 450o-520o, HC/ \C-COOH // \/ \
| | | ------------> | |-heat--> | | O
HC \\ /\ //CH Air Vana- HC\ /C-COOH \\ /\ CO/
\\/ C \// dium pentaoxide \/ \\/
HC HC CH

Naphthalene Phthalic Acid Phthalic Anhydride

Phthalicanhydride is an exceedingly important compound technically. It ia

used for the synthesis of many dyes of the odamine and fluorescein series, vat
dyes, phenolphthalein etc.

Indigo is prepared artificially from phthalic anhydride through thalimide and

anthranilic acid.
CO
//\ /\ //\ /CO\
// \/ \ NH3 // \/ \NH + H2O
| | O ------------> | | /
\\ /\ / \\ /\ /
\\/ \/ \\/ \CO
CO
Phthalic anhydride Phthalimide

On heating, or when submitted to the action of dehydrating agents phthalic

acids is very readily converted into phthalic anhydride. It crystallizes in daggling
white, long needles which melt at 128o.

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 CONTENTS

INTRODUCTION
PROPERTIES
USES AND APPLICATIONS
APPLICATIONS
PREPARATION OF PHTHALATE ESTERS
PREPARATION OF ALIPHATIC NITROALKENES
PRECURSOR TO DYESTUFFS
PHARMACEUTICALS
SAFETY
B.I.S. SPECIFICATION
MARKET POSITION
PRODUCTION CAPACITY UTILIZATION AND GROWTH
OF PHTHALIC ANHYDRIDE (PAN)
CONSUMPTION OF PHTHALIC ANHYDRIDE (PAN)
EXPORT OF PHTHALIC ANHYDRIDE (PAN)
CONSUMPTION OF PHTHALIC ANHYDRIDE (PAN)
NET IMPORT OF PHTHALIC ANHYDRIDE (PAN)
TOP FIVE DESTINATION OF PHTHALIC ANHYDRIDE (2016-17)
TOP FIVE SOURCES (COUNTRIES) OF IMPORT OF PHTHALIC
ANHYDRIDE (PAN) (2016-17)
IMPORT DATA OF PHTHALIC ANHYDRIDE
EXPORT DATA OF PHTHALIC ANHYDRIDE
GLOBAL MARKET POSITION OF PHTHALIC ANHYDRIDE
FURTHER KEY FINDINGS FROM THE STUDY SUGGEST:
NORTH AMERICA PHTHALIC ANHYDRIDE MARKET VOLUME
BY APPLICATION, 2012-2020, (KILO TONS)
APPLICATION INSIGHTS
REGIONAL INSIGHTS
PRESENT MANUFACTUREING OF PHTHALIC ANHYDRIDE
CHEMISTRY AND THERMODYNAMICS IN PHTHALIC
ANHYDRIDE MANUFACTURE
CATALYST PROPERTIES
THERMODYNAMICS
SAFETY
KINETICS
TECHNICAL DETAILS OF PHTHALIC ANHYDRIDE PRODUCTION
EMISSIONS AND CONTROLS
FLOW DIAGRAM FOR PHTHALIC ANHYDRIDE USING O-XYLENE
AS BASIC FEEDSTOCK.

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FLOW DIAGRAM FOR PHTHALIC ANHYDRIDE USING NAPHTHALENE
AS BASIC FEEDSTOCK.
COMMERCIAL PRODUCTION OF PHTHALIC ANHYDRIDE
APPROXIMATE OPERATING CONDITIONS IN THE PRODUCTION
OF PHTHALIC ANHYDRIDE FROM ORTHO-XYLENE AND NAPHTHALENE
MANUFACTURING PROCESS OF PHTHALIC ANHYDRIDE
PROCESS IN DETAILS
CHEMICAL REACTION
DETAILS OF MANUFACTURING PROCESS FROM NAPHTHALENE
REACTION
MATERIAL REQUIREMENT
BASIS : 1 TON PHTHALIC ANHYDRIDE
PROCESS
PRODUCTION OF PHTHALIC ANHYDRIDE FROM O-XYLENE
PROCESS DETAILS
FEED STREAMS
EQUIPMENT
PHTHALIC ANHYDRIDE FROM O-XYLENE
REACTION
PROCESS
PROCESS FLOW SHEET
PRODUCT AND BY PRODUCT SPECIFICATION
TYPICAL QUALITIES OF PHTHALIC ANHYDRIDE
BY PRODUCTS
NAPHTHOQUINONE
WATER & EMISSION
PROCESS FLOWSHEET FOR PHTHALIC ANHYDRIDE
METHOD OF TESTING FOR PHTHALIC ANHYDRIDE
A-1 QUALITY OF REAGENTS
A-2 DETERMINATION OF CRYSTALLIZING POINT
A-3 MEASUREMENT OF COLOUR OF THE MOLTEN MATERIAL
A-3.1 APPARATUS
A-3.2.1 COBALTOUS CHLORIDE, HEXAHDYDRATE
A-3.2.4 POTASSIUM CHLOROPLATINATE
A-3.4 PROCEDURE
A-4. DETERMINATION OF FREE ACIDITY
A-4.1 REAGENTS
A-4.1.1 PHTHALIC ACID
A-4.3 CALCULATION
A.5 DETERMINATION OF TOTAL AVAILABLE ACIDITY
A-5.1 REAGENTS
A-5.3 CALCULATION
A-6 DETERMINATION OF MALEIC ANHYDRIDE AND OTHER OXIDIZABLE
IMPURITIES

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A-7 DETERMINATION OF ASH
A-8 DETERMINATION OF IRON CONTENT
A-9 TEST FOR NAPHTHAQUINONE
A-10 TEST FOR NAPHTHALENE
PLANT LAYOUT
PRINCIPLES OF PLANT LAYOUT
PLANT LOCATION FACTORS
EXPLANATION OF TERMS USED IN THE PROJECT REPORT
PROJECT IMPLEMENTATION SCHEDULES
INTRODUCTION
PROJECT HANDLING
PROJECT SCHEDULING
PROJECT CONSTRUCTION SCHEDULE
TIME SCHEDULE
SUPPLIERS OF RAW MATERIALS
SULPHURIC ACID
HDPE WOVEN BAGS
SUPPLIERS OF PLANT AND MACHINERY
REACTORS
HEAT EXCHANGER
BOILER
AIR COMPRESSORS
DISTILLATION COLUMN
LABORATORY EQUIPMENTS/LABORATORY TESTING EQUIPMENTS

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APPENDIX – A:

01. PLANT ECONOMICS

02. LAND & BUILDING
03. PLANT AND MACHINERY
04. OTHER FIXED ASSESTS
05. FIXED CAPITAL
06. RAW MATERIAL
07. SALARY AND WAGES
08. UTILITIES AND OVERHEADS
09. TOTAL WORKING CAPITAL
10. TOTAL CAPITAL INVESTMENT
11. COST OF PRODUCTION
12. TURN OVER/ANNUM
13. BREAK EVEN POINT
14. RESOURCES FOR FINANCE
15. INSTALMENT PAYABLE IN 5 YEARS
16. DEPRECIATION CHART FOR 5 YEARS
17. PROFIT ANALYSIS FOR 5 YEARS
18. PROJECTED BALANCE SHEET FOR (5 YEARS)

COST ESTIMATION

Plant Capacity 15 Ton/Day

Land & Building (2 Acres) Rs. 4.67 Cr
Plant & Machinery Rs. 7.10 Cr
Working Capital for 2 Months Rs. 4.18 Cr
Total Capital Investment Rs. 16.58 Cr
Rate of Return 20%
Break Even Point 61%

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