Pyrolysis-catalytic reforming/gasification of waste tires for production of carbon nanotubes and hydrogen

The production of high-value carbon nanotubes and hydrogen from the two-stage pyrolysis catalytic-steam reforming/gasification of waste tires have been investigated. The catalysts used were Co/Al₂ O₃ , Cu/Al₂ O₃ , Fe/Al₂ O₃ and Ni/Al₂ O₃ . The pyrolysis temperature and catalyst temperature were 600 °C and 800 °C, respectively. The fresh catalysts were analysed by temperature programmed reduction and X-ray diffraction. The product gases, including hydrogen were analysed by gas chromatography and the carbon nanotubes characterized by scanning and transmission electron microscopy and Raman spectrometry. The results showed that the Ni/Al₂ O₃ catalyst produced high quality multiwalled carbon nanotubes along with the highest H₂ yield of 18.14 mmol g⁻¹ tire, compared with the other catalysts, while the Co/Al₂ O₃ and Cu/Al₂ O₃ catalysts produced lower hydrogen yield, which is suggested to be associated with the formation of amorphous type carbons on the surface of the Co/Al₂ O₃ and Cu/Al₂ O₃ catalyst

Pyrolysis-catalysis of waste plastic using a nickel-stainless steel mesh catalyst for high value carbon products.

A stainless steel mesh loaded with nickel catalyst was produced and used for the pyrolysis-catalysis of waste high density polyethylene with the aim of producing high value carbon products, including carbon nanotubes. The catalysis temperature and plastic to catalyst ratio were investigated to determine the influence on the formation of different types of carbon deposited on the nickel-stainless steel mesh catalyst. Increasing temperature from 700 to 900 °C resulted in an increase in the carbon deposited on the nickel loaded stainless steel mesh catalyst from 32.5 wt.% to 38.0 wt.%. The increase of sample to catalyst ratio reduced the amount of carbon deposited on the mesh catalyst in terms of g carbon g(-1) plastic. The carbons were found to be largely composed of filamentous carbons, with negligible disordered (amorphous) carbons. Transmission electron microscopy analysis of the filamentous carbons revealed them to be composed of a large proportion (estimated at ∼40%) multi-walled carbon nanotubes. The optimum process conditions for carbon nanotube production, in terms of yield and graphitic nature, determined by Raman spectroscopy, was catalysis temperature of 800 °C and plastic to catalyst ratio of 1:2 where a mass of 334 mg of filamentous/multi-walled carbon nanotubes g(-1) plastic was produced

Waste-derived activated carbons for control of nitrogen oxides

Activated carbons were produced from waste and investigated for their efficiency for the removal of mono-nitrogen oxides (NOx) in simulated flue gases at a low temperature. The wastes used were waste biomass (date seeds), processed municipal solid waste in the form of refuse-derived fuel and waste tyres. The morphology, porous texture and surface chemistry of the prepared activated carbons were evaluated by scanning electron microscopy, energy-dispersive X-ray spectrometry, nitrogen adsorption and Boehm titration, and were compared with several commercial activated carbons. The carbons were then investigated in terms of their use in adsorbing NOx at a low temperature. The waste-derived activated carbons had NOx adsorption efficiencies at 50°C which were between 50 and 70% of those achieved for the commercial activated carbons. Increasing the adsorption temperature from 25 to 100°C significantly reduced nitrogen oxide (NO) adsorption. It was also shown that the NO adsorption efficiency depends on the porous structure, particularly the presence of micropores in the activated carbon, but to a lesser extent on the surface area of the carbons and acid–base surface groups on the carbon surface

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

Steam reforming of phenol as biomass tar model compound over Ni/Al₂O₃ catalyst

Catalytic steam reforming of phenol over Ni/Al₂O₃ catalyst with 10 wt% of Ni loading was carried out in a fixed bed reactor. The effect of temperature (650–800 °C), reaction time (20–80 min) and catalyst amount (0–2 g corresponding to 0–4.5 gcat h gphenol−1) on carbon conversion, H2 potential and catalyst deactivation was studied. High efficiency of Ni/Al₂O₃ catalyst in steam reforming of phenol is observed at 750 °C for a reaction time of 60 min when 1.5 g of catalyst (3.4 gcat h gphenol−1) is used, with carbon conversion and H2 potential being 81 and 59%, respectively. An increase in temperature enhances phenol reforming reaction as well as coke gasification, minimizing its deposition over the catalyst. However, at high temperatures (800 °C) an increase in Ni crystal size is observed indicating catalyst irreversible deactivation by sintering. As catalyst time on stream is increased the coke amount deposited over the catalyst increases, but no differences in Ni crystal size are observed. An increase in catalyst amount from 0 to 1.5 g increases H2 potential, but no further improvement is observed above 1.5 g. It is not observed significant catalyst deactivation by coke deposition, with the coke amount deposited over the catalyst being lower than 5% in all the runs

Steam reforming of different biomass tar model compounds over Ni/Al2O3 catalysts

This work focuses on the removal of the tar derived from biomass gasification by catalytic steam reforming on Ni/Al2O3 catalysts. Different tar model compounds (phenol, toluene, methyl naphthalene, indene, anisole and furfural) were individually steam reformed (after dissolving each one in methanol), as well as a mixture of all of them, at 700 °C under a steam/carbon (S/C) ratio of 3 and 60 min on stream. The highest conversions and H2 potential were attained for anisole and furfural, while methyl naphthalene presented the lowest reactivity. Nevertheless, the higher reactivity of oxygenates compared to aromatic hydrocarbons promoted carbon deposition on the catalyst (in the 1.5–2.8 wt.% range). When the concentration of methanol is decreased in the feedstock and that of toluene or anisole is increased, the selectivity to CO is favoured in the gaseous products, thus increasing coke deposition on the catalyst and decreasing catalyst activity for the steam reforming reaction. Moreover, an increase in Ni loading in the catalyst from 5 to 20% enhances carbon conversion and H2 formation in the steam reforming of a mixture of all the model compounds studied, but these values decrease for a Ni content of 40%. Coke formation also increased by increasing Ni loading, attaining its maximum value for 40% Ni (6.5 wt.%)

Catalytic Pyrolysis of Waste Plastics using Staged Catalysis for Production of Gasoline Range Hydrocarbon Oils

The two-stage pyrolysis-catalysis of high density polyethylene has been investigated with pyrolysis of the plastic in the first stage followed by catalysis of the evolved hydrocarbon pyrolysis gases in the second stage using solid acid catalysts to produce gasoline range hydrocarbon oil (C8-C12). The catalytic process involved staged catalysis, where a mesoporous catalyst was layered on top of a microporous catalyst with the aim of maximising the conversion of the waste plastic to gasoline range hydrocarbons. The catalysts used were mesoporous MCM-41 followed by microporous ZSM-5, and different MCM-41:zeolite ZSM-5 catalyst ratios were investigated. The MCM-41 and zeolite ZSM-5 were also used alone for comparison. The results showed that using the staged catalysis a high yield of oil product (83.15 wt.%) was obtained from high density polyethylene at a MCM-41:ZSM-5 ratio of 1:1 in the staged pyrolysis-catalysis process. The main gases produced were C2 (mainly ethene), C3 (mainly propene), and C4 (mainly butene and butadiene) gases. In addition, the oil product was highly aromatic (95.85 wt.% of oil) consisting of 97.72 wt.% of gasoline range hydrocarbons. In addition, pyrolysis-staged catalysis using a 1:1 ratio of MCM-41: zeolite ZSM-5 was investigated for the pyrolysis–catalysis of several real-world waste plastic samples from various industrial sectors. The real world samples were, agricultural waste plastics, building reconstruction plastics, mineral water container plastics and household food packaging waste plastics. The results showed that effective conversion of the real-world waste plastics could be achieved with significant concentrations of gasoline range hydrocarbons obtained

Processing real-world waste plastics by pyrolysis-reforming for hydrogen and high-value carbon nanotubes

Producing both hydrogen and high-value carbon nanotubes (CNTs) derived from waste plastics is reported here using a pyrolysis-reforming technology comprising a two-stage reaction system, in the presence of steam and a Ni-Mn-Al catalyst. The waste plastics consisted of plastics from a motor oil container (MOC), commercial waste high density polyethylene (HDPE) and regranulated HDPE waste containing polyvinyl chloride (PVC). The results show that hydrogen can be produced from the pyrolysis-reforming process, but also carbon nanotubes are formed on the catalyst. However, the content of 0.3 wt.% polyvinyl chloride in the waste HDPE (HDPE/PVC) has been shown to poison the catalyst and significantly reduce the quantity and purity of CNTs. The presence of sulfur has shown less influence on the production of CNTs in terms of quantity and CNT morphologies. Around 94.4 mmol H g plastic was obtained for the pyrolysis-reforming of HDPE waste in the presence of the Ni-Mn-Al catalyst and steam at a reforming temperature of 800 C. The addition of steam in the process results in an increase of hydrogen production and reduction of carbon yield; in addition, the defects of CNTs, for example, edge dislocations were found to be increased with the introduction of steam (from Raman analysis)

Pyrolysis-catalytic hydrogenation of cellulose-hemicellulose-lignin and biomass agricultural wastes for synthetic natural gas production

The production of methane from the biopolymers; cellulose, hemicellulose and lignin, and also four different agricultural waste biomass samples was investigated using a two-stage pyrolysis-catalytic hydrogenation reactor. The biomass agricultural waste samples were rice straw, willow, sugar cane bagasse and ugu plant. Pyrolysis of the biomass samples was carried out in a 1st stage reactor while the catalytic hydrogenation was carried out the 2nd stage reactor using a 10 wt.% Ni/Al2O3 catalyst maintained at 500 °C with heating rate of 20 °C min−1 and a H2 space velocity of 3600 ml h−1 g−1catalyst. The thermal degradation characteristics of the biomass components, mixtures of the components and the biomass waste samples was also conducted using thermogravimetric analysis (TGA). TGA of the mixtures of the biomass components showed interaction, illustrated by a shift in the thermal degradation temperatures for hemicellulose and lignin. The results from the pyrolysis-catalytic hydrogenation revealed that the methane yield increased in the presence of the catalyst; the methane yield obtained from the hemicellulose (7.9 mmoles g−1biomass) and cellulose (7.65 mmoles g−1biomass) was significantly higher than that produced from lignin, (3.7 mmoles g−1biomass). The pyrolysis-catalytic hydrogenation of the mixtures of the biopolymers showed clear interaction, producing higher total gas yield and methane yield compared to calculated values. Pyrolysis-catalytic hydrogenation of the agricultural biomass wastes suggests that the product methane yield was influenced by the percentage of hemicellulose and cellulose content in the biomass

Hydrogen production from catalytic reforming of the aqueous fraction of pyrolysis bio-oil with modified Ni-Al catalysts

Hydrogen production from renewable resources has received extensive attention recently for a sustainable and renewable future. In this study, hydrogen was produced from catalytic steam reforming of the aqueous fraction of crude bio-oil, which was obtained from pyrolysis of biomass. Five Ni-Al catalysts modified with Ca, Ce, Mg, Mn and Zn were investigated using a fixed-bed reactor. Optimized process conditions were obtained with a steam reforming temperature of 800 °C and a steam to carbon ratio of 3.54. The life time of the catalysts in terms of stability of hydrogen production and prohibition of coke formation on the surface of the catalyst were carried out with continuous feeding of raw materials for 4 h. The results showed that the Ni-Mg-Al catalyst exhibited the highest stability of hydrogen production (56.46%) among the studied catalysts. In addition, the life-time test of catalytic experiments showed that all the catalysts suffered deactivation at the beginning of the experiment (reduction of hydrogen production), except for the Ni-Mg-Al catalyst; it is suggested that the observation of abundant amorphous carbon formed on the surface of reacted catalysts (temperature programmed oxidation results) may be responsible for the initial reduction of hydrogen production. In addition, the Ni-Ca-Al catalyst showed the lowest hydrogen production (46.58%) at both the early and stabilized stage of catalytic steam reforming of bio-oil