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Wut. Sci. Tcch. Vol. 26, No. 1-2. pp. 309-317, 1992 0273-1 22302 $15.00
I
Printed in Great Britain. All rights reserved. Copynght 0 1992 IAWPRC
ABSTRACT
Stilbene optical brighteners are produced at CIBA-GEIGY in the McIntosh,
Alabama.plant. In producing 4 , 4 t d i a m i n o s t i l b e n e - 2 , 2 ' d i s u l f o n i c acid, a major
intermediate in the production of these brighteners, a large volume of
discharges was generated. These discharges were reduced significantly by a
number of process improvements consisting of a yield improvement, reducing
the volume of an inert non-recoverable solvent and by replacing a Bechamps
iron reduction with a catalytic hydrogenation.
KEYWORDS
Stilbene Optical Brighteners; Brightener Intermediates production; Waste
Reduction; Process improvements
BACKGROUND
Stilbene optical brighteners are produced at CIBA-GEIGY in the McIntosh,
Alabama plant. These brighteners are formed by reacting cyanuric chloride
with 4 , 4 r d i a m i n o s t i l b e n e - 2 , 2 ' d i s u l f o n i c acid (DAS) and other amines. DAS is
produced at the McIntosh plant starting with p-nitrotoluene (PNT),
sulfonating it to form p-nitrotoluene sulfonic acid (PNTSA), oxidizing the
PNTSA to 4 , 4 r d i n i t r o s t i l b e n e - 2 , 2 ' d i s u l f o n i c acid (DNS) and finally reducing
the DNS to DAS.
Optical brighteners are important products of CIBA-GEIGY 's Chemicals
Division. The old processes used in the synthesis of brightener
intermediates formed large quantities of waste by-products. The quantity of
these wastes had been a source of concern to the company and, since the early
1 9 7 0 t s , attempts had been made to develop processes with lower waste
production.
Numerous concepts for waste reduction were generated and evaluated. However,
because of process safety, operator hygiene or economic considerations, many
of these concepts were rejected. Development efforts started bearing fruit
in the 1980's and in 1988 the first unit, a sulfonation with a major
reduction in sulfuric acid waste, was started up. Since then a new
hydrogenation unit has been started up which eliminated the formation of
waste Bechamps iron, and a new oxidation unit is currently (November, 1991)
being started up and is expected to have a five-fold reduction in organic
waste discharges compared to the old one.
309
310 S.E.SADEK et al.
This paper presents the results of these process improvements.
A
CHEMISTRY 1
t
The basic raw material for the brightener intermediates is p-nitro-toluene
(PNT). The sulfonation of PNT to the sulfonic acid, P N T S A , its subsequent
oxidation and reduction to the diaminostilbene disulfonic acid DAS are
described in the following reactions.
Sulfonation
p-nilrololucne p-nilraloluene
sulfonic acid
Oxidat ion
p-nilrolalucne 4.4'dinilrorliIbcne-
s u l l a n i c acid
2.2'disulfonic acid
Hvdroaenation
4.4'dinilrasliIbene- 4,l'diominosliIbene-
2 . 2 ' d i s u l f o n i c a c i d 2.2'disulfanic acid
Brightener intermediates production 31 1
OLD PROCESS
A block diagram of the old intermediates synthesis steps is shown in Figure
1. These steps were in use before 1988, and are described in more detail
below.
-toluene
DAS
CAUSTIC
ACETIC ACID
SALT
IRON
V \1
I
v
IRON SLUDGE AOUEOUS WASTE
PNTSA Step
Prior to 1988, the sulfonation of PNT to PNTSA was carried out with 20-308
oleum in a continuous three-stage stirred reactor system. The sulfonated
product was then precipitated out of solution by adding water to reach a
sulfuric acid concentration of about 6 0 % , at which point the solubility of
PNTSA was greatly reduced. The mixture was Cooled and the crystals were
filtered out and recovered as a wet cake. The PNTSA wet cake was then
redissolved in water to form a 3 0 8 PNTSA solution which was stored € o r use in
the next reaction step. The dilution and filtration led to the formation of
a large volume of sulfuric acid. This dilute acid could not be re-used in the
plant and had to be disposed of. Before 1988, this acid was disposed of b y
neutralizing it in the plant wastewater treatment system. The amounts of acid
and organics to be disposed of (as TOC) are shown in Table 1.
Thc
dec
emf
ma:
in]
dev
ret
at
Brightener intermediates production 313
NEW PROCESS
to DNS
rolled
ed and
ltered AIR WATER
harged
9
. The
1, not .I
waste
I
AOUEOUS WASTE
shown
FRESH CATALYS~
-\I/
? HVOROGEN
uction
e iron
3e was
or use
This
e also
I1
TABLE 2 Amroximate Discharses From New ii
Brishteners Intermediates Production TI
fl
Basis: 100 kg of DAS produced h
&&Q Discharue Discharue Rate T:
PNTSA 60% WASTE SULFURIC ACID:
Hydraulic load 75 liters
TOC 0 . 8 kg -D
NaZS04 37.9 kg
DNS AQUEOUS FILTRATE:
Hydraulic load 210 liters
TOC 3.5 kg
Solvent 0.15 kg
N+O~ 32.0 kg
DAS
I
t
J
Brightener intermediates production 315
DNS Step
Lecule. The Unavoidable side-reactions in the aqueous bleach oxidation of PNTSA t o DNS
process is result in yield losses of 25-30%. A search for oxidation conditions which
he process. will improve the yield was first conducted. The oxidation is essentially a
two-step reaction: PNTSA is first oxidized to the intermediate
zider
I SOlL
reduce the
k: dinitrodibenzyl (DNDB) which is then further oxidized to DNS. Side-
reactions, forming undesirable side-products by the oxidation of PNTSA, DNDB
and D N S , are continuously occurring. A study of these reactions in the
es the loss bleach oxidation process showed that conditions favoring any one of the major
I eliminate reaction steps resulted in an increase in side-products from the others; in
3, however , this process, no condition could be found to increase the yield above 75%,
zentrations based on PNTSA.
IS optimum.
Oxidation in various solvents was then investigated. Using air as the
continuous oxidant, a number of solvents and solvent mixtures were discovered in which
lfuric acid the reaction mass can be carried out (e.g. a dimethylsulfoxide and toluene
le reaction mixture, dimethyl formamide, among others) and in which the chemical yield is
sodium salt around 95%.
is cooled,
he wet cake A solvent was selected having good recovery characteristics and a solvent
process was developed. This process is now (November, 1991) being started
up. A s in all solvent processes, minimization of solvent loss was an
Lfuric acid important environmental consideration. By meticulous recovery and recycle,
discharge solvent losses are being kept to a minimum; losses are expected to be less
than 0 . 2 k g f 1 0 0 kg of product DAS when the unit is in full operation. This
is better than 99.98% recovery of the volume of solvent recycled through the
system.
In the current process, the wet cake of the sodium salt of PNTSA is dissolved
in the solvent and oxidized by blowing air until the reaction is complete,
The solvent is then distilled off from an aqueous DNS slurry and recovered
for recycling. The DNS is filtered and reslurried in water for
hydrogenation, the next step.
The discharges from this process are summarized in Table 2.
DAS Ster,
JIiST ?6:1.'?-V
316 S . E.SADEK et al.
ANALYSIS
I TOC
NaCl
26.6 Kg
192.5 Kg
4.3 kg
Solvents -- 0.15 kg
Yield Imvrovement
By improving the yield of the DNS reaction from about 70% to 94%, the organic
waste from the process was reduced significantly. The loss, measured as TOC,
is reduced about fivefold (from 18 to 3.5 kg TOC per 100 kg of DAS produced).
ACKNOWLEDGEMENT
The authors express their sincerest gratitude to their colleagues in Basle,
Switzerland; specifically to Dr. W. Regenass for his support and to Dr. J.
Beyrich and his group for their development work on the DNS process.
ranic
TOC ,
:ed).
:rier
cg of
ne of
: old
iron
ig it