Historical details
Durene (1,2,4,5-tetramethylbenzene) derived chemicals
The ZSM5 catalysts of the Motunui Synfuels plant
produced a stream of "heavy gasoline" from which one could potentially obtain
approximately 35,000 t/a of durene, a hydrocarbon otherwise having to be produced by
chemical synthesis. In 1986, ICI Synchem Ltd, a joint venture company, won the rights
from the New Zealand Government (which owned the hydrocarbon stream) to purchase durene
to convert it to pyromellitic acid and to pyromellitic dianhydride, a raw material for a
number of temperature resistant polymers, including polyimides. Carina developed routes
for manufacturing a number of durene-based chemicals and investigated prospective uses
for them, including a number of pentacene-5,7,12,14-tetrones (mainly photochemical
properties), duroquinone , pyromellitic diimide, to be used as a ruminant methane
inhibitor or for polymer curing, 1,4-di(aminomethyl)-2,3,5,6-tetramethylbenzene, and a
number of polymer intermediates. The pentacene tetrones make dyes analogous to the
anthraquinone dyes as well as acid-base indicator dyes, but they can also be strong
photodegradative agents. 1 kg of pyromellitic diimide was made and was used to inhibit
methane formation in a number of sheep over a year. The objective here was to make food
supplements last longer during droughts, and food uptake efficiency was strongly
enhanced. Initial targets for the venture included low mobility plasticizers and
polyimides. The original promotion included a TV appearance with a demonstration of the
fire-resistance of "home-made" polyimide foam, and while the pictures of that are
unavailable, the effectiveness is shown on
http://www.youtube.com/watch?v=i4kCAP4sQU8.
Agar and Agarose production
In 1987, the joint venture company ICI Biocol Ltd
was formed to implement a technology I developed to make agar from mixed seaweed as
washed up on the Wairarapa coast, without sorting and drying it. The project terminated
when the two parties could not agree on the way to proceed, followed by difficulties
arising from the 1987 financial crash. A small production plant was constructed by the
company Vela Agarose Ltd, but this plant had to be dismantled when property development
was to lead to the demolition of the building in which it was contained.
Enhanced processing technologies for agar production
were developed, and are available for implementation. Standard extraction of agar from
Pterocladia lucida gives an agar in about 25% yield and with a gel strength of about 500
g/cm2 for a gel made from 1.5% agar concentration. The enhanced technology gives a yield
approaching 35% and approaching 1500 g/cm2 for a 1% gel. Similar relative improvements
are possible for a number of other agaroids, however there are some seaweeds for which
no such performance enhancement is possible. With suitable seaweed samples, it is
possible to make a moderate grade agarose directly without subsequent purification. It
is well-known that substitution of agarose gives agaroses that remelt at lower
temperatures, which is useful for certain applications in biotechnology. Usually, there
is an associated problem that gel strength also falls dramatically with lower
temperature. A process that significantly overcomes this difficulty is also available.
Chemicals and Fuels from Microalgae. A hydrothermal
process was developed for making fuels and chemicals from microalgae on behalf of
Aquaflow Bionomic Corporation, and several patents were applied for. The problems with
microalgae are that despite the fact they are amongst the fastest growing plants on
earth, they are difficult to harvest. Their tissue is soft and sticky and they are
small, which makes filtration difficult as they block filters. Their density is
essentially that of water, so they can remain suspended, hence centrifugation is
difficult. When they are "isolated" the "product" is often only a few per cent of
microalgae, the rest being water. Their components are mainly protein and lipid,
together with some outer structural membrane that contains the photosynthesis systems.
Extraction of the wet mass tends to make emulsions that are difficult to separate, while
there is considerable expense in drying the mass. Furthermore, the phospholipids and
lipoprotein represents lost resource. While microalgae are growing rapidly, the energy
is devoted to reproduction, and the composition is mainly protein, with about 5% free
lipids. This lipid content is actually over 20%, but most is locked into cell walls and
is not easily extracted.
Hydrothermal processing has the advantage that an
aqueous slurry is used and the whole organism becomes a resource. Products include
pyrazines, lactams, aromatic hydrocarbons, long chain alkanes and alkenes, a variety of
ketones and a range of other materials. An example of such products is given here.
Algal Polysaccharides Techniques were developed for
larger-scale substitution of algal polysaccharides, and a large number of methylated and
sulphated galactans were prepared. A number of these show biological activity, and
samples remain.