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 H2 g(-1) 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).

Characteristics of biochars from crop residues: potential for carbon sequestration and soil amendment.

Biochar has potential to sequester carbon in soils and simultaneously improve soil quality and plant growth. More understanding of biochar variation is needed to optimise these potential benefits. Slow pyrolysis at 600 °C was undertaken to determine how yields and characteristics of biochars differ when produced from eight different agricultural residues. Biochar properties such as carbon content, surface area, pH, ultimate and proximate analysis, nutrient and metal content and the R50 recalcitrance index were determined. Significant variations seen in biochar characteristics were attributed to feedstock variation since pyrolysis conditions were constant. Biochar yields varied from 28% to 39%. Average carbon content was 51%. Ash content of both feedstocks and biochars were correlated with biochar carbon content. Macronutrients were concentrated during pyrolysis, but biochar macronutrient content was low in comparison to biochars produced from more nutrient rich feedstocks. Most biochars were slightly alkaline, ranging from pH 6.1 to pH 11.6. pH was correlated with biochar K content. Aromaticity was increased with pyrolysis, shown by a reduction in biochar H/C and O/C ratios relative to feedstock values. The R50 recalcitrance index showed biochars to be either class 2 or class 3. Biochar carbon sequestration potential was 21.3%-32.5%. The R50 recalcitrance index is influenced by the presence of alkali metals in the biochar which may lead to an under-estimation of biochar stability. The residues assessed here, at current global availability, could produce 373 Mt of biochar. This quantity of biochar has the potential to sequester 0.55 Pg CO2 yr(-1) in soils over long time periods.

Improving the Quality of Bio-oil Using the Interaction of Plastics and Biomass through Copyrolysis Coupled with Nonthermal Plasma Processing.

Bio-oil produced from the pyrolysis of biomass is chemically complex, viscous, highly acidic, and highly oxygenated. Copyrolysis of biomass and plastics can enhance oil quality by raising the H/C ratio, leading to improved biofuel properties. In this work, copyrolysis of polystyrene and biomass was passed to a second-stage dielectric barrier discharge nonthermal plasma reactor with the aim to further improve the product bio-oil. Pyrolysis of the polystyrene and biomass produces volatiles that pass to the second stage to undergo cracking and autohydrogenation reactions under nonthermal plasma conditions. There was a synergistic interaction between biomass and polystyrene in terms of overall oil and gas yield and composition even in the absence of the nonthermal plasma. However, the introduction of the nonthermal plasma produced a marked increase in monocyclic aromatic hydrocarbons (e.g., ethylbenzene), whereas polycyclic aromatic compounds decreased in concentration. Most notably, the influence of the plasma markedly reduced the quantity of oxygenated compounds in the product oil. It is suggested that the unique reactive environment produced by the plasma involving high-energy electrons, excited radicals, ions, and intermediates increases the interaction of the polystyrene and biomass pyrolysis volatiles. Increasing input plasma power from 50 to 70 W further enhanced the effects of the nonthermal plasma.

Supercritical Water Liquefaction of Mixed Waste Polystyrene, Polypropylene, and Polyethylene for Production of High Yield Oils.

Supercritical water liquefaction of different plastic wastes has been investigated under high-temperature and high-pressure conditions. The supercritical water liquefaction of commonly used plastic types, comprising polystyrene (PS), polypropylene (PP), and low-density polyethylene (LDPE) as well as their mixtures, is reported. The experiments were carried out at varying feedstock-to-water ratios with a residence time of 60 min under supercritical water reaction conditions. The process produced high oil yields of over 97 wt %, with the highest yields obtained at a plastic:water ratio of 1:3; at higher levels of input water, the yield of oil decreased slightly. The gas phase mainly consisted of light hydrocarbons such as methane, ethane, propane, and butane, with propane found to be the most abundant gas component. Aromatic hydrocarbons and alicyclic hydrocarbons were the major products in the product oil from the supercritical water liquefaction of polystyrene and polypropylene, whereas alkanes were predominant in the oil obtained from LDPE. Analysis of the oil obtained from binary (1:1) and ternary (1:1:1) plastic mixtures showed it exhibited aromatic hydrocarbons as the major constituent, indicating synergistic interaction. It was found that the incorporation of PP in the mixture facilitated the production of cyclic compounds and suppressed the production of alkanes. Supercritical water liquefaction offers an effective solution to plastic pollution, producing valuable products without the need for catalysts.

Hydrogen Production by Three-Stage (i) Pyrolysis, (ii) Catalytic Steam Reforming, and (iii) Water Gas Shift Processing of Waste Plastic.

The three-stage (i) pyrolysis, (ii) catalytic steam reforming, and (iii) water gas shift processing of waste plastic for the production of hydrogen have been investigated. The (i) pyrolysis and (ii) catalytic steam reforming process conditions were maintained throughout, and the experimental program investigated the influence of process conditions in the (iii) water gas shift reactor in terms of catalyst type (metal-alumina), catalyst temperature, steam/carbon ratio, and catalyst support material. The metal-alumina catalysts investigated in the (iii) water gas shift stage showed distinct maximization of hydrogen yield, which was dependent on the catalyst type at either higher temperature (550 °C) (Fe/Al2O3, Zn/Al2O3, Mn/Al2O3) or lower temperature (350 °C) (Cu/Al2O3, Co/Al2O3). The highest hydrogen yield was found with the Fe/Al2O3 catalyst; also, increased catalyst Fe metal loading resulted in improved catalytic performance, with hydrogen yield increasing from 107 mmol gplastic -1 at 5 wt % Fe loading to 122 mmol gplastic -1 at 40 wt % Fe/Al2O3 Fe loading. Increased addition of steam to the (iii) water gas shift reactor in the presence of the Fe/Al2O3 catalyst resulted in higher hydrogen yield; however, as further steam was added, the hydrogen yield decreased due to catalyst saturation. The Fe-based catalyst support materials investigated alumina (Al2O3), dolomite, MCM-41, silica (SiO2), and Y-zeolite; all showed similar hydrogen yields of ∼118 mmol gplastic -1, except for the Fe/MCM-41 catalyst, which produced only 88 mmol gplastic -1 of hydrogen yield.

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 (CNTs). 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 to 38.0 wt%. The increase in 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 (MWCNTs). The optimum process conditions for CNT 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/MWCNTs g-1 plastic was produced.