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Wut. Sci. Tcch. Vol. 26, No. 1-2. pp. 309-317, 1992 0273-1 22302 $15.00
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Printed in Great Britain. All rights reserved. Copynght 0 1992 IAWPRC

* WASTE REDUCTION BY PROCESS

IMPROVEMENT IN THE BRIGHTENER
I INTERMEDIATES PRODUCTION
\k.'
'i
S. E. Sadek, J. G. Lee, R. B. Lund and W. W. McConnell
CIBA-GEIGY Corporation, McIntosh. AL 36553. USA

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

i Fig. 1. Old process for intermediates synthesis.

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

The discharges from the brightener intermediates synthesis at McIntosh were

deemed unacceptable in the long term by CIBA-GEIGY. AS a result, the Company
embarked on a program to reduce the waste generated in these processes. A
major effort was undertaken and a number of development projects were
initiated to investigate alternatives for reducing process discharges. The
development work was completed successfully and its benefits are now being
reaped in the plant. Figure 2 shows a block diagram of the new process now
at McIntosh.

16% OLEUM CAUSTIC

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

Fig. 2. New process for intermediates synthesis.

 S.E. SADEK et al.
PNTSA SteQ
It is the free SO, in oleum that sulfonates the p-nitrotoluene molecule. The Uni
H,SO,merely serves as a solvent for the reaction, and after the process is re:
completed this solvent is diluted and discharged as a waste from the process. wi:
twc
Recovery of the sulfuric acid from the spent acid was first considered but dii
was rejected as too costly on a permanent basis. Long-term solutions re8
considered were the use of higher oleum concentrations which would reduce the ani
amount of spent acid generated. The reduction of acid also reduces the l o s s blf
of soluble PNTSA in the filtrate. Ultimately, using SO, would eliminate re
totally the formation of waste sulfuric acid. The use of SO, was, however, th
abandoned because of inherent safety problems. Various oleum concentrations ba
were investigated and a process using 6 5 4 6 % oleum was selected as optimum.
ox
The new process now consists of sulfonating p-nitrotoluene in a continuous ox
reactor with 65-66% oleum. This combines a reduction of waste sulfuric acid th
with good process safety characteristics. After sulfonation, the reaction mi
mass is diluted. PNTSA is neutralized with caustic to form the sodium salt ar
of PNTSA (NaPNTSA) and sodium sulfate. The diluted reaction mass is cooled,
and NaPNTSA is crystallized and filtered out of the solution. The wet cake
is then stored for the next step.
The filtrate from the NaPNTSA filtration contains the excess sulfuric acid
(as sodium sulfate) and organics lost in this step. The discharge
characteristics are summarized in Table 2 .

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,

Reduction by the Bechamps reaction resulted in a large volume of waste iron

which had to be disposcd of. A catalytic hydrogenation was developed
successfully for converting DNS to DAS. Conditions were found in which the
conversion and selectivity of the catalytic hyd.rogenation were equal to those
of the Bechamps reduction.
DNS slurry is now charged into the hydrogenation vessel with the catalyst,
and hydrogen is introduced. When the reaction is complete the reaction mass
is filtered and the catalyst recovered. The catalyst is partially recycled
to the next hatch and the DAS is recovered as the final product in the
Intermediates synthesis. Spent catalyst is returned to the manufacturer for
recovery.
In contrast to the Bechamps reduction, no waste stream is generated by the
hydrogenation.

JIiST ?6:1.'?-V
 316 S . E.SADEK et al.
ANALYSIS

In the Brightener Intermediates synthesis, process improvements have resulted

in large reductions of major waste streams (Table 3).

60% Sulfuric acid 175 kg 0 k9

Hydraulic Load 1190 l i t r e s 285 litres

I TOC
NaCl
26.6 Kg
192.5 Kg
4.3 kg

Solvents -- 0.15 kg

The principles of waste reduction by process improvement applied may be

summarized as follows.

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).

Reducinq the Use of Non-Recoverable Filtrate

A ) Leading to a Reduction in Solvent Loss -
By increasing the oleum concentration and thus reducing the amount of carrier
H,SO., in the sulfonat5on process, the acid waste was decreased from 175 kg of
60% sulfuric acid (equivalent to 104 kg of 100% sulfuric acid) to 37.9 kg of
Na2S0, (equivalent to 26 kg of 100% sulfuric acid).
B) Leading to a Reduction of Solubility Losses -
Loss in the aqueous filtrate is also reduced because of the lower volume of
waste aqueous filtrate disposed of in the PNTSA Step (3.5 kg TOC in the old
process compared to 0.8 kg/100 kg of DAS produced in the new process).

Use of Recoverable and Recvclable Catalvst in 8tClean8t

Reactions
Using recoverable and recyclable catalyst instead of the Bechamps iron
eliminated the need to dispose of large volumes of waste sludge, replacing it
with smaller volumes of recyclable catalyst.
 Brightener intermediates production
CONCLUSION
Discharges from the brightener intermediates process at the CIBA-GEIGY plant
in McIntosh, Alabama were reduced significantly by an extensive effort to
improve the process. These improvements consisted of a yield improvement
(PNTSA oxidation in a solvent instead of using bleach), the reduction in
volume of an inert non-recoverable solvent (H,SO, in sulfonation), and the
replacement of a Bechamps reduction by catalytic hydrogenation.
As a result of these improvements, the generation and disposal of 175 kg of
60% sulfuric acid/100 kg DAS was eliminated, over-all organic wastes were
reduced from 26.6 kg TOC to 4 . 3 kg TOC, and inorganic salts discharged (NaC1
and Na,SO,) were reduced from a total of 330 kg to 70 kg/100 kg DNS.

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).

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cg of

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: old

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ig it