Type: M.sC/ Textile Engineering
Thesis advisor: Prof. Dr. Hale KARAKAŞ
Co-Advisor: Prof. Dr.Steven De MEESTER
Student's name/surname: Esen ÇAKIR
Summary
According to the European Union Community Research and Development Information Service (CORDIS) report, the European Union's carpet consumption reaches nearly 1,8 million tonnes (Mt) annually, with approximately 1,6 Mt generated as waste each year. Post-consumer carpet waste occupies a significant space in landfills by volume and poses serious environmental threats due to the chemicals they contain.
The collection process for carpet recycling has a different dynamic from other textile materials. This process usually occurs when a new carpet is installed or collected from a designated location by a specific recycler. Globally, in major carpet import centers such as America, Europe, and the United Kingdom, waste carpet collection organizations have been established through government-supported initiatives. However, in the US in 2019, only 8% of carpet waste could be collected, and only 5% of this could be recycled. In the EU, only about 3% of carpets are recycled, while 60% end up in landfills and 37-40% are incinerated. One of the reasons causing these low recycling rates is the heterogeneity of carpets containing various types of polymers, additives, adhesives, fillers, and dyes.
For example, tufted carpets consisting of 42% of the world carpet trade share, are produced from different types of polymers such as synthetic fibers, especially polyamide (PA), polypropylene (PP), and polyester (PES). Polystyrene butadiene rubber (SBR) latex and Poly(vinyl acetate:ethylene) (EVA) latex are the mostly used adhesives, usually together with calcium carbonate (CaCO₃) as a filler material.
Considering this broad variety in carpet composition, a tailored recycling route needs to be followed for each specific carpet sample. At the outset of this research, a detailed examination of 12 different carpet samples with the front faces made of wool, viscose, polyamide, and polypropylene, and backings composed of polypropylene and polyester was conducted to understand their composition and features. These carpet samples have action, felt, and fusion types of backings, and they are bonded with Carboxylated styrene butadiene rubber (XSBR), Polyvinyl butyral (PVB), SBR, EVA adhesive materials and contain calcium carbonate filler material. According to international trade statistics, carpets with PA6 face yarn are the most traded. Therefore, among the samples examined, experimental studies focused on recycling Sample PAPP_SBR which consists of 40% PA6 face yarn, 14% PP backings, 42% CaCO₃ filling, and 4%SBR adhesive. There are several studies about the chemical recycling of PA6 in the literature, and depolymerization is generally accepted by the industry. However, depolymerization processes and following monomer purification and repolymerization steps are complex and energy consuming. In this study, solvent-based selective dissolution techniques were utilized to separate polymers of a tufted carpet. Life Cycle Assessment (LCA) was made to check the environmental feasibility of the selective dissolution process.
Mechanical separation methods were examined in the first place to determine the most effective and environmentally friendly approach. This involved shredding and pulverizing carpet samples to minimize filler content without chemical involvement, followed by their introduction into a flotation unit. Utilizing this process, polypropylene (PP) with a lower density of 0,93 g/cm³ was initially separated, followed by polyamide6 (PA6) with a density of 1,13 g/cm³, using water-based bubbles, achieving significant separation from filling material without chemicals. However, due to their fibrous structures, PA6 and PP became entangled, requiring a subsequent chemical process for complete separation.
Before conducting the selective dissolution method, the maximum solubility limits of the polymers in suitable solvents were first studied. Calcium carbonate (CaCO₃) which is a common filler material in most tufted carpets, dissolves yielding calcium acetate, along with the release of carbon dioxide when it undergoes a reaction with acetic acid. Experimental studies conducted with pure acetic acid and acetic acid/water mixture revealed that water presence is needed to dissolve calcium carbonate. PA6 can dissolve in both pure acid and acetic acid/water mixture, while polypropylene can be dissolved in xylene. Experimental studies were evaluated by using solid/liquid (S/L) ratios of 0,02, 0,04, and 0,10 kg/L. On a laboratory scale, maximum solubility limits were identified for PA6 with 0,10 kg/L in acetic acid at 80 °C, for PP with 0,10 kg/L in Xylene at 130 °C and CaCO₃ with 0,04 kg/L in 75% acetic acid at 80 °C.
In this study, the selective dissolution method by using acetic acid, which is a milder acid, at a reduced temperature of 80°C employed to dissolve PA6. This approach effectively enabled the dissolution and isolation of PA6 from other polymers such as polypropylene and SBR in the carpet through a subsequent hot filtration process which helps maintain the solvent's temperature during filtration to avoid any precipitation.
In the dissolution of PA6, two distinct processes were employed. In Process-1, a 75% acetic acid solution was used, which enabled the dissolution of both PA6 and the residual CaCO₃ in the sample. After the selective dissolution of PA6 in acetic acid through hot filtration, PP and SBR remained on the filter paper. Subsequently, a suitable ethanol/water mixture was prepared to separate PP and SBR from each other based on their density differences. However, the dissolution of CaCO₃ necessitates the use of virgin raw material as a replacement.
In Process-2, 100% acetic acid was utilized to prevent the dissolution of CaCO₃, leaving it in the residue. The experimental studies have demonstrated that pure CaCO₃ does not dissolve in pure acetic acid; rather, water needs to be present in the solvent for dissolution to occur. PA6, which dissolved in the acid, was isolated through hot filtration. The remaining CaCO₃, SBR, and PP on the filter paper were separated from each other based on their density differences using an appropriate ethanol/water mixture. It was visually observed that the presence of CaCO₃ in the solution resulted in more CaCO₃ residual material on PP.
Process-3 was developed to address the CaCO₃ residue issue observed on PP in Process-2. Similar to Process-2, only PA6 was dissolved by using 100% acetic acid, while the remaining PP was selectively dissolved using 130°C Xylene. As a result, only CaCO₃ and SBR remained as residues. However, this approach necessitated a second dissolution process, leading to additional energy consumption.
The recovered components from these three processes were analyzed using Fourier Transform Infrared Spectroscopy (FTIR) to ensure they retained their desired properties and composition. The results showed that the spectra of recovered PA6 and PP polymers matched those in library databases and the original carpet yarns. Additionally, 5 g of recovered PA6 powder and PP samples obtained from Process-1 were sent to Centexbel (Belgium) for thermal stability analysis. According to Differential Scanning Calorimetry (DSC), the melting temperature (Tm) of PA6 was observed at 216-220°C, with no peaks at lower temperatures, indicating an effective dissolution process with no residue of other carpet components such as PP, SBR, CaCO₃. The crystallization temperature (Tc) of the recovered PA6 at 189°C remained within the average range, suggesting the preservation of the material's thermal properties. Thermogravimetric Analysis (TGA) results demonstrate compatibility with reference values, and no thermal degradation has been observed in the recovered PA6 and PP. These results demonstrate the successful maintenance of essential thermal characteristics during the recycling process.
This thesis aims to determine the most effective and environmentally friendly approach for the recycling of tufted carpets. For this purpose, a Life Cycle Assessment (LCA) analysis was conducted using open source openLCA software for each applied process. This analysis calculated and evaluated the environmental impacts of all possible recycling methods. Considering the developments in industrial applications, LCA calculations were performed for 3 possible S/L ratios 0,02, 0,04, and 0,10 kg/L. In the reference scenario of the PAPP_SBR carpet sample, the carbon footprint for 1 kg of this carpet sample was calculated to be 5,40 kg CO₂-equivalent. Of this emission, 85% is attributed to the virgin production and incineration of PA6, with 93% of this portion directly resulting from the virgin production of PA6.
In Process 1, a 30% reduction in global warming potential was observed at an S/L ratio of 0,02 kg/L. This reduction increased to 67% at an S/L ratio of 0,10 kg/L when compared to the reference scenario. Similarly, in Process 2, a 42% reduction in global warming potential was noted at an S/L ratio of 0,02 kg/L, which escalated to 74% at an S/L ratio of 0,10 kg/L compared to the reference scenario. For Process 3, the reduction in global warming potential was 38% at an S/L ratio of 0,02 kg/L, reaching up to 73% at an S/L ratio of 0,10 kg/L relative to the reference scenario. These results underscore a significant decrease in carbon footprint correlating with higher S/L ratios. Particularly, the shift from an S/L ratio of 0,02 to 0,10 kg/L leads to a maximum reduction of 55% in the carbon footprint across the processes. This finding emphasizes the critical influence of the S/L ratio over the type of process, highlighting its importance in evaluating and optimizing recycling strategies for more effective environmental impact mitigation.
In conclusion, at the end-of-life scenario of Sample PAPP_SBR, by recycling it through selective dissolution method at a 0,10 kg/L S/L ratio, we can achieve a 74% reduction in global warming potential without any degradation of thermal characteristics compared to production with virgin raw materials and subsequent incineration. These results underscore the significant potential of the selective dissolution process in facilitating the efficient recycling of tufted carpet components.