New tailor-made biopolymers produced from lignocellulosic sugars waste for highly demanding fire-resistant applications

Final Report Summary - BRIGIT (New tailor-made biopolymers produced from lignocellulosic sugars waste for highly demanding fire-resistant applications)

Executive Summary:
BRIGIT consortium developed a cost-competitive and environmentally friendly process to produce biopolymers (PHB, PBS, its copolymers and blends) from waste-derived lignocellulosic sugar feedstock liquor from the wood sulfite pulping process. The fermentation process to produce PHB and succinic acid (SA) for the production of PBS was carried out in the spent sulfite liquor (SSL) through a without alteration of the quality of current lignosulfonates (LS) contained in liquor.
The main innovations in BRIGIT are the use of an existing sugar-rich waste stream from the production of cellulose and the process integration with the existing industrial operation. A selection of efficient microorganisms, and optimized fermentation and downstream technology allowed to reduce resources consumption, and operational costs. The obtained biopolymers, PHB and Bio-PBS showed properties comparable to commercial materials.
BRIGIT developed new flame retardants (FR) derived from modifications of the LS contained in the liquor, PHB, SSL and from crude biomass containing PHB.
By blending the biopolymers with flame retardants BRIGIT developed bio-based compounds for fire-resistant applications in the transport sector (trucks and buses). The compounds in combination with natural fibres and cork were used to produce 3D sandwich panels alternative to current panels made out with thermosetting resins reinforced with glass fibres. The panels were obtained by a continuous compression moulding (CCM) process in contrast to current available sandwich panels.
To fulfil the global objectives, BRIGIT developed cost competitive and environmental friendly bio-based composites for high-tech fire-resistance applications based on:
- The use industrial waste by-product as raw material (SSL) with no competition with food supply.
- Increase of the amount of suitable sugars resulting from the digestion of hardwood chips.
- Removal and handling of the inhibitors in the SSL to maximize biopolymer yield.
- PHB and SA process integration with the existing industrial operation (sulfite pulping).
- Development of environmental friendly and high performance separation technologies for PHB and SA purification.
- A PHB obtained using new fermentation culture conditions in a well-characterized sugar waste stream (SSL).
- Increase the SA yields, integrated fermentation and new separation technologies.
- Reduction of costs of current SA at purities higher than 90%. Process integration.
- Methodologies to obtain, Bio-PBS (Polybutylene-succinate) and some of its copolymers with improved performance to current market PBS.
- To enhance the low fire retardant properties of PHB based biopolymers by modifications of LS, and PHB with phosphate and nitrogen moieties.
- Biopolymer PHB/PBS blends and compounding with different halogen-free and new FR
- Development of multilayer structures to improve the final performance of sandwich panels.
- Continuous compression moulding in combination with natural fibres to produce 3D sandwich panels suitable to replace panels made of thermoset resins reinforced with glass fibres in applications for trucks and buses.
- Recyclability of biocompounds, up to a 30%.

Project Context and Objectives:
BRIGIT project aims to develop a cost-competitive and environmentally friendly process to produce biopolymers (PHB, PBS, its copolymers and blends) from waste-derived lignocellulosic sugar feedstock liquor from the wood sulfite pulping process. The fermentation process to produce PHB and succinic acid (SA) for the production of PBS will be carried out in the spent sulfite liquor (SSL) through a without alteration of the quality of current lignosulfonates (LS) contained in liquor.
The digestion of wood by sulfite pulping process lead to high quality cellulose fibres and black liquor containing lignin, sugars from the hydrolysis of hemicelluloses and the other wood components. In this process, lignin is converted to lignosulphonate (LS) salts and hemicellulose is hydrolysed to sugars usually by reaction with calcium or magnesium sulphite. Lignosulfonates from sulﬁte process are still the main source of lignin for industrial additives; dispersing, binding, complexing and emulsion-stabilizing agents. BRIGIT will propose new high added value applications for them as the base production of flame retardant additives.
Nowadays, sugars produced during sulfite pulping process (near 0.5 Million tons/ year) are mainly destroyed using different chemical products as they have a negative effect over lignosulfonates quality.
As summary, BRIGIT aims to transform an existing sugar-rich waste in a high added value biopolymer to be used in the manufacture of panels for passenger transportation industry. The multidisciplinary consortium set up in order to carry out the R&D working areas and technologies addressed in BRIGIT has representatives from the entire value chain from feedstock, biosynthesis of the polymer or polymer precursor, through to the optimization of product recovery, purification and further conversion towards the final product (3D sandwich panel validation on prototype trucks and buses). Proposed applications represent a significant step respect to the current applications of biopolymers, based only in low-cost low-demanding applications.
In comparison with previous projects to obtain biopolymers from different sources, the main innovation in BRIGIT is the use of an existing sugar-rich waste stream and the process optimization and integration with the existing pulping industrial operation that will permit an overall reduction in resource consumption and reduction of operational costs. To minimize the potential problems with inhibitors, different routes will be studied such especial separations devices and new microorganisms strains under inhibitors conditions.
Bio-composites manufactured from natural materials, such as fibres and bio-based polymers have become an alternative to conventional thermoplastic materials in several low added-value commercial applications in sectors such as packaging and agriculture. These limitations can be overcomed by developing improved bio-based polymers and by engineering new composite materials from renewable resources combining proposed biopolymers with flame retardant additives (including new developments in intrinsically fire-resistant copolymers) and natural fabrics.
Polyhydroxybutyrate (PHB) is one of the most promising alternative bio-polymers due to its highly crystalline structure, which contributes to improve thermal and chemical resistance, having fast biodegradability in different environments and a positive environmental impact during production, despite of limited mechanical properties (fairly stiff and brittle), narrow processing windows and high production costs
To solve these limitations, PHBs are normally blended with thermoplastic aliphatic biodegradable polyesters, normally synthesized from petrol-based monomers. One of them is the polybutylene succinate (PBS), which is expected to have the highest rate of market penetration due to its favourable properties. PBS, which is produced by polymerization of succinic acid and 1,4-butanediol is biodegradable and has low young modulus, thermal and chemical resistance and an excellent processability.
For these reasons, BRIGIT aims to develop cost competitive and environmental friendly bio-based composites for high-tech fire-resistance applications based on:
- Increase of the amount of suitable sugars resulting from the digestion of hardwood chips (Eucalyptus globulus and Eucalyptus nitens) in at least 35% in the sulphite pulping process.
- Removal and handling of the inhibitors in lignocellulosic waste materials to maximize biopolymer yield. Our objective is to remove more than 75% of acetic acid, furfural and hydroxymethylfurfural.
- PHB and succinic acid (SA) process integration with the existing industrial operation (sulfite pulping) to achieve an overall reduction in resource consumption and emissions.
- Assessment of the use of bio-based and biodegradable solvents and high performance separation technologies for PHB and SA purification.
- A PHB obtained using new fermentation culture conditions in a well-characterized sugar waste stream.
- Increase the SA yields from current 22-24 g/L to more than 40 g/L. Integrated fermentation and new separation technologies are the suitable way proposed to achieve this yield.
- Reduce the cost of current SA from 1.2 €/kg to less than 1 €/kg at purities higher than 90%. Process integration, and direct SA ester production from fermentation broth may lead to such low production cost.
- Methodologies to obtain, via enzymatic route, new PBS (Polybutylene-succinate) and some of its copolymers with improved performance to current market PBS.
- To improve the cost competitiveness of PHB and PBS biopolymer by optimization of the fermentation process (increasing yield) and the use of waste sugar of sulphite pulping process as fermentation main raw material.
- To use industrial waste by-products as raw materials, no competition with food supply chain exists. Currently, the sugars of spent pulping process are destroyed to avoid interaction with other high value liquor components.
- To enhance the low fire retardant properties of PHB based biopolymers.
- Enzymatic modifications of lignosulfonates (LS) to increase their molecular weight between 5-20 times than the initial one, and thus to improve the processability and fireproof capacity of develop biopolymers.
- Production on new FR additives based on chemical modifications of lignosulfonates (LS) and PHB with phosphate and nitrogen moieties.
- Biopolymer PHB/PBS blends and compounding with different halogen-free fireproof additives, lignosulfonate based fillers and intrinsically FR-polymers to fulfil the fire resistance requirements of the selected case-studies (inner panels of buses, trams, industrial vehicles or trucks )
- Development of multilayer structures to improve the final performance of sandwich panels and reduced the amount of additives, mainly flame retardant.
- Continuous compression moulding in combination with natural fireproof fabrics to produce 3D sandwich panels as a real alternative to current thermoset-glass fibre reinforced panels at low weight (less than 2.30 kg/m2 in comparison with 2.65 kg/m2 of current ones).
- Biopolymer sandwich panels that have to meet tough design requirements of the collective passenger/goods transport industry.
- The cost of final panel at industrial level will be lower than 22€/m2, 15% cheaper than current thermoset based panels.
- Fully recyclable biocompounds, up to a 30% of recycled materials will be added to the virgin material without significant loss of mechanical properties (less than 10%).
Partners involved in the project:
1- AIMPLAS - role in the project: PHB/PBS blends optimization. Fire resistant compounds based on lignosulfonate fillers, intumescent additives and intrinsically FR PHB copolymers. Co-extrusion and thermoforming tests at pilot plant level. Support co-extrusion case studies. Recyclability analysis, biodegradation tests. Regulatory analysis report.
2- ULUND - role in the project: Establishment/upgrading of genome-scale models to assist for optimized medium (liquor) supplementation targeting optimum productivities. Protocol for the adaptation of microorganisms to substrates containing (potential) inhibitors. Production of succinic acid using the xylose-metabolising yeast
3 - UNICAN - role in the project: Study at lab scale the spent pulping liquor process to increase the amount of hydrolysable sugars and reduce the amount of inhibitors. New source of sugars based on waste sugarcane bagasse.
4 - BIOTREND - role in the project: BIOTREND actively participate in the fermentation process optimization of the PHB and in the process integration activities of the project. BIOTREND perform the technical and economic viability assessment of the process options.
5 - SILICOLIFE - role in the project: Computational solutions, including text-mining algorithms, to search genomic and bibliographic databases as support to finding candidate microorgansims that are able to produce one of the target biopolymers using xylose as main raw material, preferably isolated from complex residues (more likely to have inhibitors).
6- AUA - role in the project: AUA optimise succinic acid production (WP2) regarding fermentation conditions and separation of lignosulfonates and succinic acid. AUA is involved in technology scale-up. Environmental (LCA) studies.
7- AVECOM - role in the project: Technical and economical feasibility evaluation of all tested options and/or combinations and/or integrations of the steps of liquor pre-processing (or not), fermentation, separation, purification.
8- BANGOR - role in the project: Production and purification of different monomers for PBS-co polymers. Enzymatic production of PBS co-polymers.
9- NEXTEK - role in the project: NEXTEK participate in the fermentation process optimization and scale-up of Succinic Acid and PBS production and in the process integration activities of the project.
10 - DLABS - role in the project: DLAB, using different chemical routes, prepare different PHB copolymers containing chemical modified lignosulfonates and intumescent flame retardant components.
11 - GSOUR: role in the project: Optimize the current spent pulping liquor process to increase the amount of hydrolysable sugars and reduce the amount of inhibitors. New source of sugars based on waste sugarcane bagasse.
12 - ADDCOMP - role in the project: Scale-up of the new PHB/PBS composites including, compounding process modification, blend compatibilization and provide compounds for multilayer studies and case-studies production and validation.
13 - PROFORM - role in the project: Study multilayer structures (Co-Extrusion & thermoforming) using combinations of different PHB/PBS compounds containing flame retardant. Case studies definition design, thermoforming tool production and co-extrusion and thermoforming processing optimization.
14 - XPERION - role in the project: Production of flat sandwich panels using their patented Continuous Compression Moulding (CCM) process.
15 - SOLARIS - role in the project: Definition and design of at least two case studies using develop sandwich panels for the coach industry. Full case-studies validation
16 - CRF - role in the project: Definition and design of at least two case studies using develop sandwich panels. Full case-studies validation.

Project Results:
The work in the project has been structured as shown in Figure 1.
Figure 1. Graphical presentation of the project activities showing their interdependencies.
The main scientific and technological results achieved in each technical work package (WP1 to WP9) and WP10 Project management are detailed in the following tables:
Please check the report attached with the tables

Potential Impact:
BRIGIT project afforded the development of a high added-value new tailor-made PHB and PBS biocomposite from waste, which will have a great impact on the wide introduction of biopolymers into traditional markets. In addition, the identified markets for high performance applications were automotive and passenger and goods transport sectors. The processes and technologies for those composites obtaining are sustainable production processes.
Biocomposites are a very versatile and widely used class of engineering materials with many applications in the automotive, construction, or aerospace sectors, among others.
The development of new tailor-made PHB/PBS-based composites for high tech flame retardant applications using natural fabrics as reinforcement elements provide high-added value engineered materials with high biomass content and also represents a real interest for industries with high volumes of lignocellulosic residues.
Also, obtaining PHB and PBS from fermentation of renewable sources form industrial by products/waste has a very positive effect both on the cost and on the environmental impact of the developed materials. BRIGIT project was success in the increase in the PHB and PBS production yields.
Sustainable production processes were also developed along the project implementation, considering the process integration in current industrial facilities.
The possibility of formulating new PHB/PBS with other materials and their potential improvements of PHB properties widens the range of its usability and applications.
Also, in this sense, processability of PHB and PBS at industrial level of the material has been significantly improved.
The potential of bioplastics to substitute plastics derived from fossil sources is well known due to the continuous improvement in their properties, increasing production capacity and sustainability.
According to a recent market study on Bio-based Polymers carried out by Nova-Institut, the worldwide production capacity of bio-based polymers (biodegradable and non-biodegradable polymers) is expected to increase from 5.7 million tonnes registered in 2014 to nearly 17 million tonnes in 2020 (see Figure 11)
Figure 11. Evolution of production capacity of bio-based polymers according to Nova-Institut survey.
Polyhydroxyalkanoates (PHA) are 100% biobased and biodegradable polymers that are produced in fermentation processes carried out microorganisms . The market was very small (34,000Ton/y in 2014) but is expected to grow tremendously as producers and several new players are optimistic and see potential in PHA. Therefore, production capacity is expected to have grown tenfold by 2020.
Polybutylene succinate (PBS) is biodegradable and currently fossil-based but could in theory be 100% bio-based. PBS is produced from 1,4-butanediol and succinic acid . Bio-PBS is currently available by using bio-based succinic acid as building block (by Mitsubishi Chemical). PBS is currently produced exclusively in Asia (125,000Ton/y), and it is expected to have grown fourfold by 2020.
PBS will allow tuning the properties of PHB in terms of flexibility, impact resistance and processability. These blends combined with different Flame retardants additives and natural fabrics becoming a suitable candidate to replace panels made by thermoset resins (phenolic and polyester) reinforced and glass fibre mostly used in sectors such as passenger and goods transport vehicles, which are the target sectors in BRIGIT.
Finally, PHB fermentation process is more eco-friendly than PLA chemical synthesis .
Lignin based fillers as an alternative proposed in BRIGIT ensures new applications for lignosulfonates as alternative to petrol based additives. The filler are traditionally use to modify the polymeric matrix properties, mainly stiffness and thermal resistance, in the case of
BRIGIT project the properties are moving forward also in terms of fire-resistant and improvement of processability in the developed PHB and PBS grades.
BRIGIT will support new market opportunities for biocomposites from several renewable carbon raw materials helping to create new high qualified jobs especially in biotechnological processes like fermentation, down-streaming enzyme applications and also in the plastic industry in fields such as reactive extrusion, high performance compounding, eco-design and especially in biopolymers processing.
The new biotechnologically-based sustainable routes developed in BRIGIT will foster the composite production activities while minimising environmental impact through hazardous materials, waste and emissions reduction.
The compounds will be processed in the form of co-extrusion multilayer structures in order to obtain multifunctional material properties to improve the final performance of the panels in target sectors.
The economic assessment developed along the project implementation provides an estimate of costs and the processes to produce PHB, SA, PBS and the final product of FR panels
Table 2 provides a summary from the cost model and an estimated final cost for panels.
Table 2: Cost estimation summary for intermediate materials and final panel product.
The cost model has assumed that the detoxification, PHB and SA synthesis would be co-located with a pulp mill, which would have substantial ecological and economic benefits by eliminating the need for steam generation, wastewater treatment and SSL transport, which all assist to reduce operating costs. The process capacities are at a scale of 10,000 tonne per year for fermentation and polymerisation as the smallest commercial scale that should be considered, to reduce operating costs compared to operations with lower capacity processes.
The cost estimate for PHB €4.58/kg is higher than the project target; however, due to the relatively high commercial value of PHB, estimated at €6.50kg the PHB fermentation process could be commercially viable. The estimated cost for SA is also above the target at €3.13/kg and the economic viability for SA fermentation is more challenging because of the lower commercial value of SA, estimated at €2.30/kg. The estimated cost for PBS €6.07/kg (made from the SA at cost) meets the project target and presents an economically viable process.
The manufacture of flame retardant compounds from the LS at a cost of 1.26 €/kg, appears to present an opportunity for commercialisation, with an existing demand for high performance flame retardant compounds, and this development is being pursued.
After additional processing to blend in SSL-derived FR compounds, with other additives and lamination using biodegradable fibre and core materials, a 7-layer structure panel is able to be produced at an estimated cost of €26.14/m2. This is slightly above the project cost target of €22.00/m2 but may be reduced with additional reformulation. Currently only higher weight 11-layer or 13-layer laminate structures, which are higher cost, are able to meet the physical properties and performance specifications set for truck and bus panels. The 3D panel BRIGIT proposal is fast, continuous, high output and low energy consuming in comparison with the current market thermoset panels solutions, there are 15% cheaper than current thermoset based panels.
It was estimated that 15 million square meters panels consume 34,500 tonne of materials, which would require 15,500 tonne of polymer (12,400 tonne of PHB and 3,100 tonne of PBS at a ratio of 80:20) and 19,000 tonne of additives, natural fibre and core foams.
Based on a market penetration of 10% over 5 years, an overall stakeholder profitability was estimated at €48,7 million, based on a turnover of €227.4 million over the 5 years (table 3).
Table 3. BRIGIT economic impact for biopolymers partners.
Table 4. BRIGIT economic impact for main partners.
Table 4 shows similar market penetration and calculations for the other main project players: sugars and lignosulfonate based polymers and additives producers, compounders, sheet processors, panel’s manufacturer and end-users.
A compounding process cost between 0.4-0.5 €/kg and a extrusion sheet production cost between 0.6-0.7 €/kg has been used. In the case of panels, a production cost of 26.14 €/m2 (including profit) is estimated. This means that the project will yield an estimated benefit of 48 M€ after 5 years project end.
BRIGIT will also impact in other sectors, such as passenger and good transport, aeronautics, shipping and rail-road. The paper industry and the agricultural sectors will be affected since BRIGIT will contribute to use renewable resources from those industries reducing the dependence on fossil resources and replacing other materials, which caused human injuries and energy intensive productions.
The advances in bioplastics, in particular the PHB and PBS new technology developed in BRIGIT will provide to the participating companies in particular, and the EU plastic industry in general, the opportunity to offer high added value and innovative products to strengthen their competitiveness. These advantages and the new markets that will be opened will stimulate sales and consequently support and increase employment.

List of Websites:
http://www.brigit-project.eu/
AIMPLAS
C/ Gustave Eiffel, 4
València Parc Tecnològic
46980 Paterna (Valencia)
ESPAÑA/SPAIN
Tel: +34 961 366 040 Ext. 150
Fax: +34 961 366 041
E-mail: proyectos@aimplas.es
Website: www.aimplas.es

Final Report Summary - BRIGIT (New tailor-made biopolymers produced from lignocellulosic sugars waste for highly demanding fire-resistant applications)

Verwandte Dokumente

Diese Seite teilen

Herunterladen