Green
Chemistry—
evolution or
revolution?
Stuart Cook of Hickson
and Welch describes how
an elderly multistage
production process has
been made more green by
an innovative evolutionary
strategy applied to
existing technology
The manufacture of optical brighteners used in today’s washing powders, is a good
example of green chemistry evolution.
T
here is a perception of a need for cost. Such additional costs can, of course, ● The high output of dilute nitrophenol
revolutionary change in technology be either from additive ‘end-of-pipe’ pro- sodium salt washings is toxic to
to introduce commercial ‘green’ cessing equipment and costs, or from biotreatment systems.
chemistry. Industrial experience is, how- major reinvestment in entirely new ● There is high energy consumption
ever, that whilst a revolution is sometimes ‘green’ technology. in sulfuric acid production and high-
necessary to find ‘green’ as opposed to Each step shown in the scheme is temperature vacuum distillation.
‘end of pipe’ solutions, often there is described below in numbered sequence,
much that can be achieved by an and the ‘green’ revolutionary and The ‘Green’ chemistry solution
innovative evolutionary strategy evolutionary options described. The vision over many years has been the
applied to existing technology. direct nitration of toluene with nitric acid
A good illustration of this mixed Step 1 using catalysts such as modified clays,
approach is illustrated by a review of the Toluene is conventionally mononitrated which are known to be capable of
last decade of progress in the manufacture with mixed sulfuric/nitric acids, adjusted producing high proportions of the higher
of stilbene-based fluorescent brightening to 80% sulfuric acid strength with water. value p-nitrotoluene isomer (conventional
agents. These are produced on a The spent mixed acid was separated and mixed acid gives 65% of the saleable but
ca. 100,000 tpa scale world-wide, with discharged to waste, and the mixed mono- lower value o-nitrotoluene isomer).
Ciba-Geigy (EU and USA), Sigma (Italy) nitrotoluene isomers washed with sodium The problem is that the water of
and Hickson & Welch Ltd. (UK) as some hydroxide solution to remove ca. 0.5% reaction released from direct nitric acid
of the major producers. Waste and phenolic and oxidation products. The nitration tends to degrade the catalyst.
emission problems figured in many of alkaline washings are discharged to Hickson piloted such technology
the processing stages since production waste. The washed mononitrotoluenes using reduced pressure distillation to strip
began in the 1950s. As one of the few are fractionally vacuum-distilled at high reaction water from the heterogeneous
fully integrated producers, working until temperature to isolate pure p-nitrotoluene. catalyst continuously.
recently from basic toluene to finished Unwanted by-products from the still Rapid evolutionary progress on
fluorescent brightener, over a 7-stage base are incinerated. the conventional technology made the
sequence (see scheme opposite), Hickson planned reinvestment and switch
& Welch’s processing perspective Problems uneconomic, however.
contains some interesting lessons, ● There is heavy output of ‘spent’
showing evolution to be as important and contaminated 70% sulfuric acid wastes The evolutionary approach
effective as revolution in side-stepping to low grade acid users such as the The disappearance of the demand for
‘green’ challenges at minimum additional coking and steel industries. ‘used’ sulfuric acid in the coke and steel
Step 2
p-Nitrotoluene is sulfonated by adding
25% oleum to the liquid mononitro-
toluene, then adding the mixture to water
to give the optimum 50% sulfuric acid
strength for filtration of the solid
sulfonated product which precipitates.