Team:UCL/Science/Bioprocessing

In the textile industry today, the global production of dyestuff amounts to over millions of tonnes per year. Azodyes represent two thirds of this value, a majority of which find their way to wastewater effluent streams. Characterized by the presence of one or more azo group (more on chemistry), this type of organic colorant is also found in cosmetics, pharmaceuticals and food industries. While the desirable properties of azodyes i.e. chemical stability, high molar extinction coefficient and fastness make them a dye-class of choice, their widespread use in countries such as India and China make them a dye to die for—literally. This is because, in parallel to being aesthetically intrusive to ecosystems, azodye breakdown products have been found to be mutagenic and carcinogenic. With such a high worldwide consumption, the benefits in developing and integrating a sustainable strategy for dealing with such effluent streams is clear. It is worth to note that the ‘azodye problem’ is exacerbated by the high costs, both financial (economic) and environmental, of current physio-chemical and biological methods of treatment (more on current treatment). This year, we are looking into the processing options that are relevant to tackling the problem of azodye discharges. In order to assess the feasibility and determine key engineering parameters for each option, the most important dyestuff sector will be used as a case study: textiles and dyeing industry.

Current issues with azodyes and their treatment technologies

With azodyes The contamination of natural habitats surrounding textile factories by coloured (azodye-rich) effluents is a real problem (more). This is because the enzymatic breakdown products of azodyes i.e. aromatic amines, are carcinogenic when ingested. These can not only build up within local ecosystems but can also be a hazard to humans through bio-accumulation in the food chain. With a large section of dyehouse effluents consisting of dyes that have half-lives spanning over decades, the latter remain in the environment for long periods of time.

With current technologies in the textile industry, exorbitant volumes of water are used for processing (around 90%), the rest being used for heat exchange purposes. Unfortunately most of the water used for processing is discharged as waste, resulting in highly diluted azodye effluent streams. Secondly, the recalcitrant nature of azodyes hikes the inherent costs of large-scale physical separation systems. As a result, industrial processes used to deal with such soluble hazardous wastes would not be a feasible option to deal with azodye effluents.

By using whole cell biocatalysis as the workhorse for detoxification, this process will yield lucrative byproducts such as quinones, that can then be separated from the process stream and sold off.

Rational for immobilization

The following outlines the general consensus on the benefits of using the immobilized biocatalyst format, with respect to free-floating systems.
Catalyst Retention – A huge decrease in the losses of valuable catalyst into product streams. These losses are exponential in ‘free biocatalysts’ systems, and economically unfeasible when using costly enzymes.
Minimized Contamination of product streams, eliminating the requirement for subsequent protein deactivation and further downstream processing. This is especially important for containment of our recombinant organisms.
Flow-rates are not limited by a threshold critical value for “biomass washout”, and only impact substrate-catalyst contact time. Catalyst concentrations can remain steady through independence of the dilution rate (see figure 1.3). High volumetric flow-rates can enhance mass transfer and speed up the removal of inhibitors (e.g. Azo-dye metabolites) from the system.

Industrial Consultation

A major part of our project involved engaging with key industrial experts to better understand their wants and needs. We identified the pigment manufacturing and waste water disposal sectors as the two major players who would benefit from our work. By meeting with these leading corporations we have been able to tune our research towards the assenbly of a process that would be most attractive for industry to utilise.

Meeting with ETAD - Ecological and Toxicological Association of Dye and Pigment Manufacturers

ETAD - an association based in Basel represents over 35 different pigment and dyeing corporations internationally, coordinating a group initiative to limit adverse effects on health and the environment by their industry.Present at the meeting were Walter Hoffman – Director of ETAD, Dr Stefan Ehrenberg - Pigment Manufacturing R&D at Bezema, Georg Roentgen – Director of R&D Colours and Textile Effects at Huntsman.

The main reasons for this meeting were:

To encourage industry to consider synthetic biology as a realistic, viable option when looking to reduce the toxicity of their process.

Discuss the major concerns and problem areas the dyeing and pigments industry are currently facing.

Dye Houses vs Dye Synthesis Waste

The meeting with ETAD raised a number of points for our project. Mr Roentgen questioned how the survival of our bacterial cell would be effected in dyehouse waste as opposed to dye synthesis plant waste. The waste from a dyehouse is a complex mix of azo dyes at approximately 1%-5% concentration in a high salt concentration with the presence of metals copper and chromium. This a harsh environment compared with the waste of a dye synthesis plant, generally containing one or two azo dyes in a simple mixture at 10% concentration.

This is new information for our project and has greatly influenced us to direct our research towards optimising remediation of dye synthesis waste water. Another advantage of remediation of dye synthesis plant waste water is that the low variety of azo dyes in each batch mixture will make filtration of valuable products a much easier and viable process, enhancing the economic feasibility of our device.

Sulphonated Azo Dyes

The current trend in the textile industry is to reduce the volume of water consumed, leading to a greater use of more soluble dyes. For a dye to be more soluble it must be more polar, as such, many of these soluble dyes have sulfonated groups. The sulphur atom has a electron withdrawing effect making reduction of the azo bond difficult, the industry are finding chemical processes to degrade these dyes to be ineffective.

We feel we can offer an alternative since ..lignin peroxidase…. change this is known to be effective working on azo bonds with sulphur group.

Conclusions

Overall the meeting was a great success in guiding our project towards an industrial relevant direction. Running through our presentation highlighted a number of changes needed before the jamboree, specifically putting more emphasis on the novelty and innovation of our project. Ensuring our project delivers a solution that is conscious of the needs of the industry is extremely important to us, meetings such as these are invaluable to the progression of our work.

Assessment of commercial feasibility is widely based on evaluating the target market’s “readiness” to receive and integrate an innovative product or process. This primarily involves defining and characterising the target market and quantifying economic potential in terms of projected demand. Furthermore technical feasibility based on forecasted costs and resource requirements must be considered whilst remaining aware of potential risks and obstacles.

The potential market segmentation for this novel process is based on relative contribution to global dyeing effluent pollution. The textile industry represents a vast proportion of this contribution over other potential market segments (cosmetic, pharmaceutical, food industries) and has therefore appropriately become the thematic focus of this project. Considering the world market for textile dyeing operations, a majority of dye effluent waste can be attributed to Asia, followed by North America and Western Europe. However receptiveness to environmental initiatives and the magnitude of investment in projects of the sort are heavily skewed away from developing regions of Asia. Hence a stronger approach to achieving a realistic impact would start in the UK where socio-economic conditions are more suitable. This should be taken into consideration in further technical development and strategic commercialisation steps.
The following clarifies the net and indirect value of our bioprocessing solution to key stakeholders, and elucidates incentive for its integration into current waste management systems.

Improving Reputations
In society, a growing culture for Eco-friendliness with an increasing political voice can be observed. Accordingly, mounting pressure to reduce harmful emissions is probing investment in effluent remediating infrastructure, not excluding that of the textile industry. Furthermore consumer demands are evolving (particularly in developed regions) to favour environmentally neutral products, with initiatives such as “Sustainable fashion” edging further into the public eye and threatening the reputation of irresponsible market players.

Evolving Legislation
There exists an array of national and international regulations addressing ‘controlled used and allowed emissions from textile factories’ such as the EU Eco-label criteria and REACH (Registration, Evaluation, Authorization and Restriction of Chemical substances) (regulation (EC) No 1907/2006) (3). As global pollution levels rise, so does concern from the international community. Consequently governments can be expected to enact new laws, adjust legislation, and increase stringencies on emission permits. A cost-effective process that facilitates textile companies to meet these progressive requirements would be an ideal solution if integrated at the end of each factory, to stop short poisonous releases.

Economic Benefits
The significant economic activity of textiles and clothing in the global market makes it incredibly relevant for industrialists to consider process alterations aimed at optimizing resource allocation and reducing environmental burden. Consequently, in the long term, financial returns in the form of savings on costs of goods can be expected to outweigh initial capital and installation costs. It is important to bear in mind however from an investors perspective, accurate foresight into technical project feasibility requires accurate quantification of resource requirements (time, skills, money) and an awareness of possible risks and pitfalls.

Why invest

In the implementation of any new product or process there exists an interplay between several elements that have the ability to effect the adoption of that product: jpeg.
1.Environmental: ensuring appropriate waste disposal in terms of toxicity levels and concentrations for example. Our process solution will bring forward sustainable textile processing
2.Economic: This aspect can be broken down into the financial returns of the product and the costs of goods saved through its use.
3.Legislative: Regulatory bodies and governments set emission margins and environmental burden limits for factories
4. Societal: through our public engagement campaigns (link), communicating a message to the wider society can bring about change.

The significant economic activity of textiles and clothing in the global market makes it incredibly relevant for industrialists to consider process alterations aimed at optimizing resource allocation and reducing environmental burden.

“According to the EIPRO study, clothing alone is responsible for 2 to 10% of the EU’s life-cycle environmental impacts. This results in textiles coming fourth in the ranking of product category which cause the greatest environmental impact”(1)’

The carcinogenic properties of Azodye precursors and degradation products (such as aromatic amines)(3) are exacerbated by the low susceptibility for azodye bio-degradation under aerobic conditions (4,5). This environmental burden has been going up ranks with industrial fresh water pollution due to textile treatment and dyeing reach 20% in 2010 (2).

Furthermore, growing concerns regarding water consumption in textile processes due to astronomical usage of ‘potable industrial water’ (6). According to the 2010 global market report on sustainable textiles, the world used three trillion gallons of fresh water to produce 60 billion kgs of fabric. With over 80000 tonnes of reactive dyes produced and consumed each year, the heavily polluted dye baths issuing off the dyeing processes need to be treated before any reuse can be conceived (2). According to various reviews (2, , ,), conventional membrane processes and coagulation are among the suggested methods to achieve this. Implementing a water recycle strategy for a textile plant would require in-plant treatment processes (6). There exists an array of national and international regulations addressing ‘controlled used and allowed emissions from textile factories’ such as the EU Eco-label criteria and REACH (Registration, Evaluation, Authorization and Restriction of Chemical substances) (regulation (EC) No 1907/2006) (7). A cost-effective process that facilitates textile companies to meet these requirements would be an ideal solution if integrated at the end of each factory, to stop short poisonous releases. Thus, by improving their performance and earning one of these eco-criteria could result in improved branding, bringing forward a strong connection with aware consumers by informing them of such sustainability initiatives.

Optimizing process performance at a microfluidic level is often necessary for the economically feasible development of a process due to the small volumes of liquid associated with it. Subsequently, creating a microfluidic prototype device of the large-scale module is extremely relevant in quantifying process variables such as the flow rate to determine residence time of the azodye suspension within the module. This allows for preliminary mass transfer calculations and azodye degradation rates.

After experimentation with dyed water at controlled flow rates, slight dead zones were observed within the device. A second prototype was developed:

This versatile and simple process offers a wide range of future developments into various chemical producing sectors. It would be possible to use this technology in parallel with different industries as a form of platform technology using different synthetic biology anchors, in order to detoxify various effluent polluting chemicals.

An example of one of our microfluidic devices designed on AutoCAD can be downloaded here. This device utilises the basic concept of mixing the cells and dyes, producing a single output stream; much alike to the bioprocessing concept. During the course of designing the microfluidic device, several key considerations must be taken into account: ability to withstand high pressure without leakage; materials of construction to be inert and transparent; size constraints of inlet and outlet piping; ability to accurately 3D-print the device.