Project description:Catalytic biomass pyrolysis is one of the most promising routes for obtaining bio-sustainable products that replace petroleum derivatives. This study evaluates the production of aromatic compounds (benzene, toluene, and xylene (BTX)) from the catalytic pyrolysis of lignocellulosic biomass (Pinus radiata (PR) and Eucalyptus globulus (EG)). Chilean natural zeolite (NZ) was used as a catalyst for pyrolysis reactions, which was modified by double ion exchange (H2NZ) and transition metals impregnation (Cu5H2NZ and Ni5H2NZ). The catalysts were characterized by nitrogen adsorption, X-ray diffraction (XRD), ammonium programmed desorption (TPD-NH3), and scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS). Analytical pyrolysis coupled with gas chromatography/mass spectrometry (Py-GC/MS) allowed us to study the influence of natural and modified zeolite catalysts on BTX production. XRD analysis confirmed the presence of metal oxides (CuO and NiO) in the zeolite framework, and SEM-EDS confirmed successful metal impregnation (6.20% for Cu5H2NZ and 6.97% for Ni5H2NZ). Py-GC/MS revealed a reduction in oxygenated compounds such as esters, ketones, and phenols, along with an increase in aromatic compounds in PR from 2.92% w/w (without catalyst) to 20.89% w/w with Ni5H2NZ at a biomass/catalyst ratio of 1/5, and in EG from 2.69% w/w (without catalyst) to 30.53% w/w with Ni5H2NZ at a biomass/catalyst ratio of 1/2.5. These increases can be attributed to acidic sites within the catalyst pores or on their surface, facilitating deoxygenation reactions such as dehydration, decarboxylation, decarbonylation, aldol condensation, and aromatization. Overall, this study demonstrated that the catalytic biomass pyrolysis process using Chilean natural zeolite modified with double ion exchange and impregnated with transition metals (Cu and Ni) could be highly advantageous for achieving significant conversion of oxygenated compounds into hydrocarbons and, consequently, improving the quality of the condensed pyrolysis vapors.
Project description:The influence of particle size (0.3 and 5.0 mm) and heating rate (5, 10, and 20 °C min-1) on the kinetic parameters of pyrolysis of waste tire was studied by thermogravimetric analysis and mathematical modeling. Kinetic parameters were determined using the Friedman model, the Coats-Redfern model, and the ASTM E1641 standard based on Arrhenius linearization. In the Friedman model, the activation energy was between 40 and 117 kJ mol-1 for a particle size of 0.3 mm and between 23 and 119 kJ mol-1 for a particle size of 5.0 mm. In the Coats-Redfern model, the activation energy is in a range of 46 to 87 kJ mol-1 for a particle size of 0.3 mm and in a range of 43 to 124 kJ mol-1 for a particle size of 5.0 mm. Finally, in the ASTM E1641 standard, the activation energy calculated was between 56 and 60 kJ mol-1 for both particle sizes. This study was performed to obtain kinetic parameters from different mathematical methods, examining how the particle size and heating rate influence them.
Project description:Waste tire pyrolysis has received increasing attention as a promising technology recently due to the shortage of fossil resources and the severity of environmental impact. In this study, the process of waste tire pyrolysis and upgrading to obtain high-value products was simulated by Aspen Plus. Also, based on life cycle assessment, the indexes of energy, environmental, economic, and comprehensive performance were proposed to evaluate different high-value pathways. Results demonstrate that the integrated system of waste tire pyrolysis, pyrolytic oil (TPO) refining, and pyrolytic carbon black (CBp) modification has higher energy efficiency than the independent system of TPO refining, with an improvement rate of 2.6%. Meanwhile, the resource-environmental performance of the integrated system is better. However, combined with the economic benefit, the independent system is more comprehensively beneficial, with the index of comprehensive performance (BEECR) of 0.94, which increases by 3.3% compared with the integrated system. Furthermore, the comparisons of different improved high-value paths based on the independent system as the benchmark indicate that the pathway of promoting sulfur conversion during pyrolysis to reduce the sulfur content in TPO can increase the BEECR from 0.94 to 1.064, with the growth of 13.2%. Also, the physical modification of CBp to reduce the production cost and environmental impact has better performance of BEECR, increasing by 20.2%. The final sensitivity analyses show that the combined improved high-value case established by the abovementioned two paths can achieve a favorable benefit in a wide range of crude oil and waste tire prices and the environmental tax.
Project description:Functional surfaces and polymers with branched structures have a major impact on physicochemical properties and performance of membrane materials. With the aim of greener approach for enhancement of permeation, fouling resistance and detrimental heavy metal ion rejection capacity of polyetherimide membrane, novel grafting of poly (4-styrenesulfonate) brushes on low cost, natural bentonite was carried out via distillation-precipitation polymerisation method and employed as a performance modifier. It has been demonstrated that, modified bentonite clay exhibited significant improvement in the hydrophilicity, porosity, and water uptake capacity with 3 wt. % of additive dosage. SEM and AFM analysis showed the increase in macrovoides and surface roughness with increased additive concentration. Moreover, the inclusion of modified bentonite displayed an increase in permeation rate and high anti-irreversible fouling properties with reversible fouling ratio of 75.6%. The humic acid rejection study revealed that, PEM-3 membrane having rejection efficiency up to 87.6% and foulants can be easily removed by simple hydraulic cleaning. Further, nanocomposite membranes can be significantly employed for the removal of hazardous heavy metal ions with a rejection rate of 80% and its tentative mechanism was discussed. Conspicuously, bentonite clay-bearing poly (4-styrenesulfonate) brushes are having a synergistic effect on physicochemical properties of nanocomposite membrane to enhance the performance in real field applications.
Project description:A deposit of raw kaolin, located in West Andalusia (Spain), was studied in this work using a representative sample. The methods of characterization were X-ray diffraction (XRD), X-ray fluorescence (XRF), particle size analysis by sieving and sedimentation, and thermal analysis. The ceramic properties were determined. A sample of commercial kaolin from Burela (Lugo, Spain), with applications in the ceramic industry, was used in some determinations for comparison purposes. The kaolin deposit has been produced by alteration of feldspar-rich rocks. This raw kaolin was applied as an additive in local manufactures of ceramics and refractories. However, there is not previous studies concerning its characteristics and firing properties. Thus, the meaning of this investigation was to conduct a scientific study on this subject and to evaluate the possibilities of application. The raw kaolin was washed for the beneficiation of the rock using water to increase the kaolinite content of the resultant material. The results indicated that the kaolinite content of the raw material was 20 wt % as determined by XRD, showing ~23 wt % of particles lower than 63 µm. The kaolinite content of the fraction lower than 63 µm was 50 wt %. Thus, an improvement of the kaolinite content of this raw kaolin was produced by wet separation. However, the kaolin was considered as a waste kaolin, with microcline, muscovite and quartz identified by XRD. Thermal analyses by Thermo-Dilatometry (TD), Differential Thermal Analysis (DTA) and Thermo-Gravimetry (TG) allowed observe kaolinite thermal decomposition, quartz phase transition and sintering effects. Pressed samples of this raw kaolin, the fraction lower than 63 µm obtained by water washing and the raw kaolin ground using a hammer mill were fired at several temperatures in the range 1000-1500 °C for 2 h. The ceramic properties of all these samples were determined and compared. The results showed the progressive linear firing shrinkage by sintering in these samples, with a maximum value of ~9% in the fraction lower than 63 µm. In general, water absorption capacity of the fired samples showed a decrease from ~18-20% at 1050 °C up to almost zero after firing at 1300 °C, followed by an increase of the experimental values. The open porosity was almost zero after firing at 1350 °C for 2 h and the bulk density reached a maximum value of 2.40 g/cm3 as observed in the ground raw kaolin sample. The XRD examination of fired samples indicated that they are composed by mullite, from kaolinite thermal decomposition, and quartz, present in the raw sample, as main crystalline phases besides a vitreous phase. Fully-densified or vitrified materials were obtained by firing at 1300-1350 °C for 2 h. In a second step of this research, it was examined the promising application of the previous study to increase the amount of mullite by incorporation of alumina (α-alumina) to this kaolin sample. Firing of mixtures, prepared using this kaolin and α-alumina under wet processing conditions, produced the increase of mullite in relative proportion by reaction sintering at temperatures higher than 1500 °C for 2 h. Consequently, a mullite refractory can be prepared using this kaolin. This processing of high-alumina refractories is favoured by a previous size separation, which increases the kaolinite content, or better a grinding treatment of the raw kaolin.
Project description:Bentonite clay is an integral component of the engineered barrier system of deep geological repositories (DGRs) that are planned for the long-term storage of high-level radioactive waste. Although nucleic acid extraction and analysis can provide powerful qualitative and quantitative data reflecting the presence, abundance, and functional potential of microorganisms within DGR materials, extraction of microbial DNA from bentonite clay is challenging due to the low biomass and adsorption of nucleic acids to the charged clay matrix. In this study, we used quantitative PCR, gel fingerprinting, and high-throughput sequencing of 16S rRNA gene amplicons to assess DNA extraction efficiency from natural MX-80 bentonite and the same material "spiked" with Escherichia coli genomic DNA. Extraction protocols were tested without additives and with casein and phosphate as blocking agents. Although we demonstrate improved DNA recovery by blocking agents at relatively high DNA spiking concentrations, at relatively low spiking concentrations, we detected a high proportion of contaminant nucleic acids from blocking agents that masked sample-specific microbial profile data. Because bacterial genomic DNA associated with casein preparations was insufficiently removed by UV treatment, casein is not recommended as an additive for DNA extractions from low-biomass samples. Instead, we recommend a kit-based extraction protocol for bentonite clay without additional blocking agents, as tested here and validated with multiple MX-80 bentonite samples, ensuring relatively high DNA recoveries with minimal contamination.IMPORTANCE Extraction of microbial DNA from MX-80 bentonite is challenging due to low biomass and adsorption of nucleic acid molecules to the charged clay matrix. Blocking agents improve DNA recovery, but their impact on microbial community profiles from low-biomass samples has not been characterized well. In this study, we evaluated the effect of casein and phosphate as blocking agents for quantitative recovery of nucleic acids from MX-80 bentonite. Our data justify a simplified framework for analyzing microbial community DNA associated with swelling MX-80 bentonite samples within the context of a deep geological repository for used nuclear fuel. This study is among the first to demonstrate successful extraction of DNA from Wyoming MX-80 bentonite.
Project description:Adhesion tests were performed on concentrated suspensions of Kaolin clay. At low concentrations samples formed conical deposits on both the top and bottom plates with the central region narrowing to a filament before undergoing breakup. In contrast high concentration samples deformed as a cylinder before apparently fracturing into two pieces. As the concentration of the samples was increased the samples underwent quite different forms of slip which it is shown can be deduced from their respective force distance curves. The type of slip behaviour for a given concentration of clay could be modified with changes to surface roughness, the initial compressive load prior to an experiment and with the separation velocity of the plates. The different slip characteristics appear to arise from the concentration dependent way in which particles interact with the rough surface topography.
Project description:Pyrolysis of used tires is a promising method for recovering valuable chemicals. However, the conventional high-temperature pyrolysis of natural rubber (polyisoprene)-based tires suffers from a low-selective isoprene recovery, heavy carbon black (CB) damage, and coke formation on the CB. In this paper, we report on characteristics of the low-temperature pyrolysis of CB-containing polyisoprene-based tire rubber that is vulcanized with sulfur. The low-temperature pyrolysis of the tire rubber cleaves the main chain and cross-linking bonds, which allows for the recovery of low-molecular-weight tire rubbers, tire rubber dissolution into the solvent, and CB isolation from the rubber matrix. The maximum liquid rubber recovery rate was 76.7% after 1 h of heating at 282 °C. In addition, the molecular weight of the thermally treated rubber substantially decreased from M w 340,000 to approximately 20,000 after 1 h of heating at 282 °C. Furthermore, the maximum isoprene skeleton retention rate of the recovered rubber was 83% at 267 °C after 1 h of heating. The remaining rubber matrix on the recovered CB surface was nearly eliminated at temperatures above 320 °C. In conclusion, we believe that the low-temperature pyrolysis of tire rubber is a promising pretreatment method for recovering CB without thermal damage and reducing the molecular weight of tire rubber, which will improve the recovery of isoprene.