Thermal Chemical Conversion of High-Density Polyethylene for the Production of Valuable Carbon Nanotubes Using Ni/AAO Membrane Catalyst

© 2017 American Chemical Society. Thermal chemical conversion of waste plastics for syngas production is a promising alternative method for the management of waste plastics. However, one of the challenges of facilitating the deployment of this technology is the low economic benefit of waste-plastic recycling. By producing a high-value carbon nanotubes (CNTs) byproduct, an interesting alternative solution is provided. To further enhance the quality of CNTs produced from catalytic thermal chemical conversion of waste plastics, a template-based catalyst (Ni/anodic aluminum oxide, AAO) is proposed in this work. In addition, reaction temperature, Ni content and water injection were studied for their influences on the formation of CNTs on Ni/AAO using a two-stage fixed bed reactor. Various analytical methods, e.g., scanning electronic microscopy (SEM) and X-ray diffraction (XRD), were used to evaluate the performance of catalyst in relation to the production of CNTs. The results show that a higher loading of Ni on AAO resulted in the formation of metal particles with various sizes, thus leading to the production of nonuniform CNTs. In addition, an optimal catalytic temperature of 700 °C is suggested for the production of CNTs. Because the catalyst might not be activated at 600 °C, which produced a low yield of CNTs. However, a reaction temperature of 800 °C resulted in a low yield of CNTs. Carbon deposition decreased with an increase of steam injection, but the quality of CNTs formation in relation to the uniform of CNTs seemed to be improved in the presence of steam

Development of Ca/KIT-6 adsorbents for high temperature CO2 capture

The incorporation of CaO into an inert porous solid support has been identified as an effective approach to improve the stability of adsorbents for CO2 capture. In this work, we focus on enhancing the capacity of carbon capture and cyclic stability of CaO by impregnating CaO particles into a three-dimensional mesoporous silica (KIT-6) support. At a low CaO loading, the three-dimensional mesoporous support was filled with CaO nano-particles. The further increase of CaO loading resulted in the aggregation of CaO particles on the external surface of the support material, as identified by electron microscopy analysis. These CaO/KIT-6 adsorbents show excellent high-temperature CO2 carbonation/calcination stability over multiple cycles of CaO carbonation and calcination. The enhancement of the performance of carbon capture is attributed to the interaction between CaO and the silica skeleton of KIT-6 through the formation of interfacial CaSiO3 and Ca2SiO4 which enhanced the resistance of CaO sintering

Producing carbon nanotubes from thermochemical conversion of waste plastics using Ni/ceramic based catalyst

As the amount of waste plastic increases, thermo-chemical conversion of plastics provides an economic flexible and environmental friendly method to manage recycled plastics, and generate valuable materials, such as carbon nanotubes (CNTs). The choice of catalysts and reaction parameters are critical to improving the quantity and quality of CNTs production. In this study, a ceramic membrane catalyst (Ni/Al2O3) was studied to control the CNTs growth, with reaction parameters, including catalytic temperature and Ni content investigated. A fixed two-stage reactor was used for thermal pyrolysis of plastic waste, with the resulting CNTs characterized by various techniques including scanning electronic microscopy (SEM), transmitted electronic microscopy (TEM), temperature programmed oxidation (TPO), and X-ray diffraction (XRD). It is observed that different loadings of Ni resulted in the formation of metal particles with various sizes, which in turn governs CNTs production with varying degrees of quantity and quality, with an optimal catalytic temperature at 700 °C

Tailored mesoporous silica supports for Ni catalysed hydrogen production from ethanol steam reforming

Mesoporous silica supported Ni nanoparticles have been investigated for hydrogen production from ethanol steam reforming. Ethanol reforming is structure-sensitive over Ni, and also dependent on support mesostructure; three-dimensional KIT-6 possessing interconnected mesopores offers superior metal dispersion, steam reforming activity, and on-stream stability against deactivation compared with a two-dimensional SBA-15 support

Development of Ni- and Fe- based catalysts with different metal particle sizes for the production of carbon nanotubes and hydrogen from thermo-chemical conversion of waste plastics

Co-production of valuable hydrogen and carbon nanotubes (CNTs) has obtained growing interest for the management of waste plastics through thermo-chemical conversion technology. Catalyst development is one of the key factors for this process to improve hydrogen production and the quality of CNTs. In this work, Ni/SiO2 and Fe/SiO2 catalysts with different metal particle sizes were investigated in relation to their performance on the production of hydrogen and CNTs from catalytic gasification of waste polypropylene, using a two-stage fixed-bed reaction system. The influences of the type of metals and the crystal size of metal particles on product yields and the production of CNTs in terms of morphology have been studied using a range of techniques; gas chromatography (GC); X-ray diffraction (XRD); temperature programme oxidation (TPO); scanning electron microscopy (SEM); transmission electron microscopy (TEM) etc. The results show that the Fe-based catalysts, in particular with large particle size (∼80 nm), produced the highest yield of hydrogen (∼25.60 mmol H2 g−1 plastic) and the highest yield of carbons (29 wt.%), as well as the largest fraction of graphite carbons (as obtained from TPO analysis of the reacted catalyst). Both Fe- and Ni-based catalysts with larger metal particles produced higher yield of hydrogen compared with the catalysts with smaller metal particles, respectively. Furthermore, the CNTs formed using the Ni/SiO2-S catalyst (with the smallest metal particles around 8 nm) produced large amount of amorphous carbons, which are undesirable for the process of CNTs production

Coal and plastic waste co-pyrolysis by thermal analysis–mass spectrometry

Simultaneous thermogravimetry–mass spectrometry studies of a pyrolytic decomposition of mixtures of different plastic wastes/coking coal were carried out. The investigation was performed at temperatures up to 1000 °C in a helium atmosphere under dynamic conditions at a heating rate of 25 °C/min. Five thermoplastics, commonly found in municipal wastes: low density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene (PP), polystyrene (PS), polyethylene terephthalate (PET) and a plastic mixture rich in polyolefins were selected. Thermogravimetric parameters, together with different characteristic ion fragments from selected libraries of evolving products during the co-pyrolysis process were monitored, such as hydrogen, CO2 and aliphatic and aromatic hydrocarbons. Based on the results obtained, a synergistic effect between coal and individual residues has been found. The maximum interaction occurs at temperatures close to the maximum release of volatile matter of the plastic waste. There is a delay in the decomposition of the plastics that together with the changes in the composition of the volatile matter evolved, promote interactions between the components and have negative effects on coal fluidity. The polyolefinic wastes (HDPE, LDPE and PP) degrade at temperatures close to that of maximum coal degradation, modifying the thermal behaviour of the coal to a lesser degree. However, PS and PET, that release their volatile matter mostly in the early stage of the coal decomposition, show a more pronounced influence on the thermal behaviour. Moreover, the kinetic data demonstrates that the addition of polyolefins increases the energy required to initiate pyrolysis compared to PS and PET. All of these results agree with the fact that polyolefins reduce coal fluidity in a more moderate way than PET and PS

Investigation of Ni/SiO2 catalysts prepared at different conditions for hydrogen production from ethanol steam reforming

Ni/SiO2 catalysts prepared by a sol–gel method have been investigated for hydrogen production via steam reforming of ethanol using a continuous flow, fixed bed reactor system. Chemical equilibrium calculations were also performed to determine the effects of temperature and molar steam to carbon ratio on hydrogen production. The acidity of the preparation solution (modified by nitric acid and ammonia) and calcination atmosphere (air and N2) were investigated in the preparation of the catalysts. BET surface area and porosity, temperature-programmed oxidation (TPO), X-ray diffraction (XRD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM) were used to characterise the prepared catalysts. The BET surface area was reduced when the solution acidity was lowered during the sol–gel preparation process. A pH value less than 2.0 was necessary to achieve high metal dispersion in the catalyst. Smaller NiO particles were obtained when the catalyst was calcined in N2. Material balances on ethanol steam reforming at 600 °C using the prepared Ni/SiO2 catalysts were determined, and higher hydrogen production with lower coke deposition on the reacted catalysts were also obtained from the catalysts calcined in N2 atmosphere

Hydrogen production from biomass and plastic mixtures by pyrolysis-gasification

The addition of plastics to the steam pyrolysis/gasification of wood sawdust with and without a Ni/AlO catalyst was investigated in order to increase the production of hydrogen in the gaseous stream. To study the influence of the biomass/plastic ratio in the initial feedstock, 5, 10 and 20 wt.% of polypropylene was introduced with the wood in the pyrolysis reactor. To investigate the effect of plastic type, a blend of 80 wt.% of biomass and 20 wt.% of either polypropylene, high density polyethylene, polystyrene or a mixture of real world plastics was fed into the reactor. The results showed that a higher gas yield (56.9 wt.%) and a higher hydrogen concentration and production (36.1 vol.% and 10.98 mmol H g sample, respectively) were obtained in the gaseous fraction when 20 wt.% of polypropylene was mixed with the biomass. This significant improvement in gas and hydrogen yield was attributed to synergetic effects between intermediate species generated via co-pyrolysis. The Ni/Al O catalyst dramatically improved the gas yield as well as the hydrogen concentration and production due to the enhancement of water gas shift and steam reforming reactions. Very low amounts of coke (less than 1 wt.% in all cases) were formed on the catalyst during reaction, with the deposited carbonaceous material being of the filamentous type. The Ni/AlO catalyst was shown to be effective for hydrogen production in the co-pyrolysis/gasification process of wood sawdust and plastics

Influence of process conditions on the formation of 2-4 ring polycyclic aromatic hydrocarbons from the pyrolysis of polyvinyl chloride

Municipal solid waste (MSW) contains significant amounts of polyvinyl chloride (PVC). The reactivity of PVC may form polycyclic aromatic hydrocarbons (PAHs) during the pyrolysis of MSW, which can become a key challenge during the development of pyrolysis technologies. However, there is very limited work in relation to the influence of pyrolysis process conditions in terms of temperature and heating rate on PAHs formation during pyrolysis of PVC. In this work, the formation of 2-4-ring PAHs from the pyrolysis of PVC at temperatures of 500, 600, 700, 800, or 900°C and at fast and slow heating rates was investigated under a N2 atmosphere in a fixed bed reactor. With the increase of temperature from 500 to 900°C, HCl yield decreased from 54.7 to 30.2 wt.%, while the yields of gases and PAHs in the tar increased. Slow pyrolysis generated higher HCl yield, and lower gas and tar yield than fast pyrolysis; the PAH yield obtained from the slow pyrolysis was much lower compared to fast pyrolysis. The results suggest that for fast pyrolysis, the dehydrochlorination of the PVC might be incomplete, resulting in the formation of chlorinated aromatic compounds