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Sustainable Surfactants: Renewable Feedstocks for the 21st Century - The needs of the surfactants industry |
The Needs of the Surfactants Industry
Dr. G. Bognolo, ICI Surfactants, Everberg, Belgium
Introduction
Around the turn of the 17th century the philosopher Gianbattista
Vico developed the idea of the cyclical nature of history. according to Vico history repeats itself, a process that, although
involving increasingly complex events and ever changing features, is in fact driver by the same underlying principles and
eventually produces the same results. It is really like issuing the same book all over again by just modernising it and printing it
with more sophisticated technologies, such that the basic content stays unchanged but the presentation is renewed
continuously
Thin idea has undoubtedly some merit: mutatis mutandis it can interpret remarkably well past historic events and with a bit of visionary input it could be perhaps an useful tool to develop hypotheses for future developments. In any case I could not avoid thinking of it when, in an admittedly much more limited context, I began to compile these notes. As we shall see, this century has witnessed a dramatic swing from natural renewable to man-made, only to show a steady trend back to natural again.
Historic evolution
For centuries before coal and hydrocarbons became part of
everyday use, renewable resources were the only source of energy for mankind: wood for fire, water and wind to power mills
and factories, animals for transportation. They were also the only source for textiles and provided much of our building
material. For centuries after soap was accidentally discovered in Egypt or Mesopotamia about 5000 years ago it remained the
main tool for personal cleansing. wood ashes or extracts from saponaria roots provided fabric detergency, other preparations
rich in surface active substances like lecithin, glycerides, proteins served specific purposes in a variety of uses from food to
ink production and fabrics dyeing. And then in the second decade of this century, man-made surfactants began to take over
from natural material. Why ?
In my view, in order that a market develops or that a trend changes or emerges, four conditions must be present:
Whichever of these factors comes first or last is irrelevant, as long as at some point in time they are all there and meet. When the switch natural to man- made first began, the following conditions were at play:
They also provided the consumer with a disposable income to pay for these benefits.
These factors created the premise for the consumption of man-made surface active agents to grow from virtually zero at the time of world war one, to something in the region of 8 to 10 millions of metric tons by the middle of the nineties.
The criteria I have used to differentiate a natural from a man-made surfactant is that:
The major surfactants families, classified in the above context, may be summarised as follows:
Natural/renewable: alkyl polyglucosides, biosurfactants, fatty amides, fatty amines, glucamides, glycerol and polyglycerol esters, lecithins, lignin sulphonates, phosphoric esters of naturally derived fatty acids, protein derivatives, saponins, soaps, sorbitol and sorbitan esters, sucroglycerides, sucrose esters, sulphates from naturally derived fatty alcohols.
Man-made: alkanolamides, alkyl and alkyl aryl ether carboxylates, alkyl aryl sulphates, alkyl aryl sulphonates, alkyl aryl ether sulphates, alkyl capped ethoxylates, alkyl ethyl sulphates, alkyl isothionates, alkyl phenol ethoxylates, alkyl phenol/formaldehyde condensates and derivatives, alkyl sulphates from synthetic fatty acids, alkyl sulphonates, amino oxides, betaines and amidobetaines, ester quats, ethylene oxide/propylene oxide copolymers, fatty acid ester ethoxylates and polysorbates, fatty acid ethoxylates, fatty alcohols alkoxylates, fatty amines alkoxylates, fatty amides alkoxylates, fluorinated surfactants, imidiazoline derivatives, lower amines and polyamines alkoxylates, napthalene sulphonates and related compounds, olefin sulphonates, petroleum sulphonates, phenol alkoxylates, phosphate esters of synthetic fatty alcohols, polyacrylate disperssants, polyamines and derivaties, polyethylene and polypropylene glycols, polyhedric alcohols alkoxylates, polymeric surfactants, quaternary ammonium compounds, sarcosinates, silicone surfactants, sulfosuccinates and sulfonsuccinamates, taurates, etc, etc.
The global surfactant market, which is today probably of the order of 10 millions of metric tons, is largely dominated by petrochemical derived products, notably akylbenzene sulphonates, alkylphenol ethoxylates, synthetic fatty alcohols and their derivatives. These products are believed to account for 70-75% of the surfactant consumption in the industrialised countries.
Future developments
Perhaps an useful way to look at what the future might hold
is to test what the underlying drivers for development will be. Are they likely to be reconducted to the four key ones above
capable of catalysing major changes ? In this process a few observations appear relevant.
The first observation is that despite widespread consumption and multiplicity of products and applications from products of petrochemical origin, oleochemicals always had a role to play in the surfactant industry, either as the starting materials for the production of fatty acids, alcohols and amines, or as building blocks for the synthesis of amides and esters. Transformed in soaps, they were widely used as laundry detergents until washing machines become a common feature in the households of the industrialised countries and as the personal cleaning agent per excellence until the advent of formulated hair and body shampoos. Soaps are still the all purpose surfactant in developing countries, although increasingly threatened by various sulphonates, ethoxylates and formulated detergents.
The following table gives the approximate consumption of fatty acids (1997 in 1000 tonnes) in industralised countries (N America, W Europe, Japan) for surfactancy related uses.
| Soaps | 250 |
| Personal care products | 45 |
| Cutting oils | 50 |
| Ore floatation, oilfield, paper de-inking, etc | 30 |
| Emulsion polymerisation | 90 |
| Plastic/textile lubricants | 35 |
These numbers suggest that about 5% of the demand for surface active agents is still fulfilled by fatty acids or their salts. The percentage is significantly higher if Eastern Europe, the FSU and countries in Asia, South America and Africa (for which I do not have reliable statistics) are included. The next table gives the fatty acid consumption in the same countries by main application categories, expressed in the same units.
| Direct consumption (as above) | 500 | |
| Derivatives | ||
| Fatty esters | 360 | |
| Diesters/synlubes | 130 | |
| Metal salts | 240 | |
| Ester quats | 90 | |
| Intermediates for production of | ||
| Fatty alcohols | 65 | |
| Amines/polyamines | 80 | |
| Amino oxides | 35 | |
| Amphoterics | 45 | |
| Quaternaries | 125 | |
| Amides | 70 | |
| Alkanolamides | 70 | |
| Amindo amines | 45 | |
| Polyamides | 90 | |
| Specialty surfactants | 75 | |
| Other applications | 80 | |
The second observation is that in the years to come there will be a continuous improvement in the socio-economic conditions, which will be particularly pronounced in developing countries. The macro-effects include:
The third observation is that, perhaps as corollary of rising concern for environment and of the incentives put forwards by authorities, recycling is growing in importance in the industrialised countries. It has already been for some time a source of revenues in developing countries. Recycling is likely to affect consumption of established, low-price surfactants (e.g. fatty acids, linear alkylbenzene sulphonate, fatty alcohols sulphates and ethoxylates, ethylene oxide propylene/oxide copolymers in paper de-inking) because of the low added value of the application and the reliance for the time being in established, low technology industrial processes.
These macro-environmental and economic factors will have a different weighting in different regions. However the study of their possible impact for the surface active agent markets would require a quite complex analysis, involving a large volume of information difficult to develop or not available at all. Market changes will affect the demand of surface active agents through a sort of domino effects by which a surfactant more capable of responding to prevailing needs will displace its closest functional precursor, which in turn will replace its ancestor(s) in a stage process that can be schematised as follows (for the major surfactant classes).
Surfactants substitution pathways
Driver: washing formulations and habits, mildness, performance, environment and human safety
| PHO | GLU | |||
| Ý | Ý | |||
| LAB Þ | PS, OS Þ | AS, AEX SP Þ | AEO ÞAMP | |
| ß | ß | ß | ||
| SUL | APS | APS | ||
|
Driver: environmental and human safety | ||||
| APE Þ AEO, APS | ||||
|
Driver: environmental | ||||
| QUA Þ EQU | ||||
AEO = alcohol ethoxylates, AEX SP = alkylether sulphate, APE = alkyl phenol ethoxylate, APS = alkyl polyglucoside, AS = alkyl sulphate, EQU = Ester quat, GLU = Glucamide, LAB = linear alkyl benezene sulphonate, OS = olefin sulphonate, PHO = phosphate ester, PS = paraffin sulphonate, QUA = Quaternary ammonium compounds, SUL = sulphosuccinate.
The technologies to manufacture all types of surfactants at the industrial scale are available and are being continuously upgraded. On the other hand the progresses in the technologies for the manufacture of finished goods (e.g. high speed fibres spinning just to quote one) demand specialised products in the industrialised countries. Likewise, these factors are accelerating the transition from soaps to synthetic surfactants in the developing countries.
There is little doubt that in the industrialised countries the combination of the above forces will favour an increasing utilisation of renewable raw materials for two reasons:
It has been reported that in western Europe, the consumption of surfactants based on carbohydrates and renewable fatty acids or alcohols has seen a six-fold expansion in the space of five years to exceed 60 ktons in 1997. A sustained growth is expected in the years to come, albeit at a somewhat reduced rate. Glycerol, glucose, glucamine and sucrose will continue to be the naturally derived hydrophiles of choice. For the hydrophobic moiety:
The scenario in the developing countries will be dominated by the progressive substitution of soaps by man-made surfactants. This effect is difficult to quantify given the scarcity and margins of errors in the available data. It is however likely that soaps will continue to play a significant role in the detergency habits of those countries.
Historically, the consumption of surface active agents has outgrown demographic and economic developments as measured by indicators like GDP. The forecast over the decade 1995 to 2005 is for global volume growth of about 3.5 % per year. There are however significant regional differences; the largest increases (4-7 %) are expected in Asia Pacific, FSU, China, followed in order by Latin America (2.5 %), Japan (1.5 %), North America (1.0 %) and Western Europe (0 3 %). Such growth in demand is not expected to put a strain on the supply capabilities of either the petrochemical or the oleochemical industry to maintain an adequate supply of feedstocks.
Only 5% of the fossil fuels production was consumed in 1996 as primary feedstock for petrochemicals. Less than 0.1% was used for surfactant manufacture. In the industrialised countries, a moderate increase in overall demand and any likely switch from petrochemicals to oleochemicals feedstock over the decade 1995-2005 is not going to affect the demand of oleochemicals by more than 0.1% of the global available supply. In the developing countries, the increasing demand of soaps following the demographic and economic expansion will be mitigated to some extent by the displacement of soaps by synthetic detergents likely to use to a large extent petrochemical raw materials. Even if we assume the extreme situation of the entire surfactants growth being fulfilled by oleochemlcal resources, this will represent approximately 10% of the projected increase in production of oleochemicals to the year 2005.
80% of the world-wide production of fats and oils is used in the human food sector if this proportion is maintained also over the next decade, the projected availability of oils and fats will ensure a growth of the per- capita consumption 13.4 kg/year in 1997 to 15.2 kg/year by the year 2007 (as a reference tbe per-capita growth over the previous 25 years period was from 9.9 kg/year to 13.4 kg/year) and still leave enough spare to satisfy even suden surge in the consumption for non-edible purposes.
The fact that there are no obvious shortages at the macroscopic level do not exclude however that local disruptions could happen as the result of weather, political unrest, economic crisis, or that the balance in individual countries could be shifted as the consequence of specific agricultural or energy policies. Certain fatty acid acids, notably the C8 to C14 chain lengths, the 12 hydroxy oleic and the isostearic acids are particularly exposed. Sudden changes in availability call have dramatic effect on prices, especially when chemical or functional substitutes from petrochemical sources are not available.
There is an increasing interest from the academic world for the synthesis of biosurfactants (including in this definition surface active agents produced by living organisms or natural processes, e.g. through enzymatic routes). Some limited commercial applications or pilot experimentation are in their infancy, with focus on oil extraction, storage and transportation. There are considerable technological, economic and emotional barriers to overcome before biosurfactants becomes a broadly accepted reality (and at the present time there are still questions on whether they will ever reach this stage). However there are major potential advantages to be gained, ranging from technical effects such as:
I would suggest that this opportunity is not overlooked. Also it should be kept in mind that there is an open question on the long term opportunities offered by recycling. At present recycling is a relatively low volume sector, limited to the delivery of cleaning at the lowest possible cost But surfactants provide many other useful effects and fulfil several purposes, including emulsification, dispersion, foaming, wetting, cleaning/removal, demulsification, coagulation/coalescence, de-foaming/anti-foaming, de-wetting, deposition /coating. Is there something worth following-up in these areas ?
The detergent, personal care and consumer product sectors utilise nearly 60% of all surfactants and, apart from a few major industrial uses, these areas will afford the main potential for the development of new, high tonnage surfactants. However, it must be understood that many products in these sectors are regarded as "commodity surfactants" and sell (on a 100% active basis) between £600 and £1,000 per metric tonne. Likewise the consumer has become more sophisticated since the late 1980s and is not willing to sacrifice performance and/or pay a high premium for so-called "green" products. "Speciality" surfactants, mainly used in industrial and agrochemical applications still only command prices up to a maximum of £3,000 per tonne. Hence, there are both cost and performance constraints when considering the development of new surfactants derived from natural resources. Nevertheless, the surfactant industry has already proved its commitment to naturally derived raw materials and is enthusiastically progressing development of newer products.
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Contact
© Copyright 2006 Policy Statements
Updated
by CPL Press:
03/07/2007
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