Desulfurization and upgrade of pyrolytic oil and gas during waste tires pyrolysis: The role of metal oxides.

Pyrolysis can effectively convert waste tires into high-value products. However, the sulfur-containing compounds in pyrolysis oil and gas would significantly reduce the environmental and economic feasibility of this technology. Here, the desulfurization and upgrade of waste tire pyrolysis oil and gas were performed by adding different metal oxides (Fe2O3, CuO, and CaO). Results showed that Fe2O3 exhibited the highest removal efficiency of 87.7 % for the sulfur-containing gas at 600 °C with an outstanding removal efficiency of 99.5 % for H2S. CuO and CaO were slightly inferior to Fe2O3, with desulfurization efficiencies of 75.9 % and 45.2 % in the gas when added at 5 %. Fe2O3 also demonstrated a notable efficacy in eliminating benzothiophene, the most abundant sulfur compound in pyrolysis oil, with a removal efficiency of 78.1 %. Molecular dynamics simulations and experiments showed that the desulfurization mechanism of Fe2O3 involved the bonding of Fe-S, the breakage of C-S, dehydrogenation and oxygen migration process, which promoted the conversion of Fe2O3 to FeO, FeS and Fe2(SO4)3. Meanwhile, Fe2O3 enhanced the cyclization and dehydrogenation reaction, facilitating the upgrade of oil and gas (monocyclic aromatics to 57.4 % and H2 to 22.3 %). This study may be helpful for the clean and high-value conversion of waste tires.

Coupling dechlorination and catalytic pyrolysis to produce carbon nanotubes from mixed polyvinyl chloride and polyethylene.

The presence of chlorine in polyvinyl chloride (PVC) presents a major challenge for realizing the high-value utilization of real waste plastics. The objective of this research was to develop a chlorine-resistant process for the preparation of carbon nanotubes (CNTs) from mixed plastics containing PVC. This study investigates the influence of PVC content and various dechlorinating agents (CaO, Na2CO3, red mud (RM), ZSM-5, Fe-Al2O3, Fe(OH)3) on CNTs formation. The results showed that PVC content exceeding 5 % significantly inhibits CNTs formation. Employing dechlorinating agents in the pyrolysis process results in a substantial yield of CNTs from mixed plastics containing 10 % PVC. Among the dechlorinating agents, RM proves to be the most effective, leading to the highest carbon yield (at 30 wt%) and superior CNTs quality. Other dechlorinating agents, except for ZSM-5, yield comparable results, although there were some obvious variations of volatiles. Further investigation of the role of dechlorinating agents from the perspective of volatiles evolution was conducted via Py-GC/MS, and found that the dechlorination agent efficiently absorbs the HCl from mixed plastics pyrolysis, while also exhibiting catalytic and regulatory influence on volatile components. These findings offer valuable insights for the development of a chlorine-resistant process in the preparation of CNTs from mixed plastics that contain PVC.

Preparation of carbon nanotubes by catalytic pyrolysis of dechlorinated PVC.

Plastic waste is attracting growing interest for its utilization potential as a valuable resource. However, conventional thermochemical methods can hardly achieve high-value utilization of certain plastics, such as polyvinyl chloride (PVC) characterized with high chlorine content. Here, a low-temperature aerobic pretreatment method was introduced to realize high-efficiency dechlorination of PVC, and then the dechlorinated PVC was used to prepare carbon nanotubes (CNTs) by a catalytic pyrolysis. The results demonstrate that oxygen can significantly promote the HCl release in a pretty low-temperature range (260-340 °C). Chlorine was almost completely eliminated at 280 °C under 20 % oxygen concentration. Compared to untreated PVC, using the dechlorinated PVC as raw material, higher carbon deposition was obtained and over 60 % CNTs could be collected from the carbon deposition. This study provides a high-value utilization way for the production of CNTs from waste PVC.

Algae Pyrolysis in Molten NaOH-Na2CO3 for Hydrogen Production.

Biomass pyrolysis within the alkaline molten salt is attractive due to its ability to achieve high hydrogen yield under relatively mild conditions. However, poor contact between biomass, especially the biomass pellet, and hydroxide during the slow heating process, as well as low reaction temperatures, become key factors limiting the hydrogen production. To address these challenges, fast pyrolysis of the algae pellet in molten NaOH-Na2CO3 was conducted at 550, 650, and 750 °C. Algae were chosen as feedstock for their high photosynthetic efficiency and growth rate, and the concept of coupling molten salt with concentrated solar energy was proposed to address the issue of high energy consumption at high temperatures. At 750 °C, the pollutant gases containing Cl and S were completely removed, and the HCN removal rate reached 44.92%. During the continuous pyrolysis process, after a slight increase, the hydrogen yield remained stable at 71.48 mmol/g-algae and constituted 86.10% of the gas products, and a minimum theoretical hydrogen production efficiency of algae can reach 84.86%. Most importantly, the evolution of physicochemical properties of molten NaOH-Na2CO3 was revealed for the first time. Combined with the conversion characteristics of feedstock and gas products, this study provides practical guidance for large-scale application of molten salt including feedstock, operation parameters, and post-treatment process.

Hydrogen-rich syngas production from biomass gasification using biochar-based nanocatalysts.

Nanocatalysts are beneficial for tar elimination and syngas production during biomass gasification. In this study, novel biochar-based nanocatalysts loaded with Ni/Ca/Fe nanoparticles was prepared by one-step impregnation method for catalytic steam gasification of biomass. Results showed that the metal particles were evenly distributed with the particle size of less than 20 nm. With the introduction of nanoparticles, H2 yield and tar conversion were obviously increased. Ni and Fe particles help to maintain the stability of the carrier microporous structure. Fe loaded biochar showed the best catalytic gasification performance, with 87% tar conversion and 42.46 mmol/g H2 production. The catalytic effect of Fe was also higher than that of Ni and Ca if deducting the influence of carrier consumption. It demonstrated that Fe-loaded biochar was a promising catalyst candidate for hydrogen-rich syngas production from biomass gasification.

The reusing of waste bio-oil as additive on enhanced urea-based selective non-catalytic reduction denitrification.

Pyrolysis polygeneration has been proven to be effective in solid waste recycling, while cleaner production is hindered by nitrogen oxide emissions and waste oil utilization. In this study, waste bio-oil was proposed as additive for promoting urea-based selective non-catalytic reduction (SNCR) denitrification efficiency to establish bio-oil reusing process and the influence of waste bio-oil on promoting SNCR denitrification were investigated. Then the effects of temperature, bio-oil components and fly ash on SNCR denitrification characteristics were explored. The results illustrated that 5 wt% bio-oil additives would widen the optimum denitrification temperature window by 24.8 % (from 210.25 to 262.43 °C), reduce the reduction temperature by 62.11 °C (from 944.04 to 881.93 °C), and increase the denitrification efficiency by 21 %. Among the main components in waste bio-oil, acetic acid was more effective than phenol and furfural in promoting SNCR denitrification under 900 °C, a large amount of OH was produced to promote the reduction of NH3 and HNCO. In addition, the existence of fly ash could promote urea oxidation and reduce denitrification efficiency because of the catalytic effect of CaO and Fe2O3 on urea oxidation.

Production mechanism of high-quality carbon black from high-temperature pyrolysis of waste tire.

High-temperature pyrolysis of waste tires is a promising method to produce high-quality carbon black. In this study, carbon black formation characteristics were investigated during tire pyrolysis at 1000-1300 °C with residence times of < 1 s, 1-2 s, and 2-4 s. It is shown that with temperature increasing from 1000 °C to 1300 °C carbon black yield was increased from 10% to 27% with residence times of 2-4 s. Carbon black exhibited a core-shell nanostructure over 1100 °C and the graphitization degree was promoted with the temperature and residence time. While the mean particle diameter decreased with the temperature to 69 nm at 1300 °C and further increased by residence time. The molecular-level evolution from tire to initial carbon black was further revealed by reactive force field molecular dynamics simulations. Light oil, gas, and radicals were transformed to initial cyclic molecules and long carbon chains via carbon-addition-hydrogen-migration, H-abstraction-C2H2-addition, and radical-chain reactions, subsequently forming PAHs. The coupling of PAHs aliphatic side chains formed large graphene layers that gradually bent to fullerene-like cores and generated incipient carbon black. The process mechanism from volatiles evolution to carbon black was proposed, which may be helpful for obtaining high-quality carbon black from high-temperature pyrolysis of waste tires.

Effect of support type and crystal form of support in the catalytic gasification of old corrugated containers using Fe-based catalysts.

Catalytic gasification of old corrugated containers with Fe-based catalysts is a promising way to produce renewable H2 along with the utilization of solid waste. In this study, the effect of support type and crystal form of support in Fe-based catalysts on the catalytic gasification of old corrugated containers was systematically investigated. The results show that, the introduction of Fe/γ-Al2O3, Fe/TiO2, Fe/SiO2, and Fe/ZSM5-30 promote H2 production. Among them, Fe/TiO2 has the highest catalytic activity on H2 yield (25.10 mmol/g) related to the formation of Fe2TiO5 solid-melt material. Fe/γ-Al2O3 shows the best H2 selectivity (46.34 %) and good H2 yield (24.19 mmol/g) due to good dispersity of Fe. Further, the order of catalytic effect on H2 selectivity is Fe/amorphous Al2O3 (51.46 %) > Fe/α-Al2O3 (46.98 %) > Fe/γ-Al2O3 (46.34 %). With the increase in cycle index, Fe/amorphous Al2O3 shows the best catalytic effect on H2 yield (25.56 mmol/g) after 11 indexes due to the formation of Al2FeO4. Fe/γ-Al2O3 shows the best stability on H2 selectivity (∼43 %) after 11 indexes.

Simultaneous removal of cadmium, lead, chromate by biochar modified with layered double hydroxide with sulfide intercalation.

In this study, a novel KOH-activated biochar modified with Mg2Al-LDH with S2- intercalation (KBC-LDH-S) was proposed for simultaneous adsorption of anions and cations. The adsorption capacity, thermodynamic and kinetic studies, effects of initial temperature and solution pH were investigated. Furthermore, the adsorption characteristics in both single and ternary Pb-Cd-Cr systems were investigated. Comparing with bare biochar, the adsorption capacity of KBC-LDH-S was increased by 387.8 % for Cd2+ (190.4 mg/g), 358.1 % for Pb2+ (392.2 mg/g), 1106.0 % for total Cr (170.7 mg/g) and 4602 % for Cr6+ (833.8 mg/g). The S2- intercalation effectively increased the adsorption capacity of CrO42- by 3370 % and promoted simultaneous adsorption. The interlayer anion exchange and redox reaction occurred between CrO42- and S2- to generate Cr3+, and then promoted the adsorption of CrO42-. Besides, the adsorption amount and total removal efficiency first increased and then decreased with the increasing concentration in the Pb-Cd-Cr ternary system.

Pyrolysis of boron-crosslinked lignin: Influence on lignin softening and product properties.

In this study, ammonium borate was used as an additive to inhibit lignin softening during the pyrolysis process, and the influence on the pyrolysis process and product characteristics were investigated with potential mechanism being explored in depth. Results showed that with boron addition, glassy transition temperature and thermal stability of lignin increased, and the yield of gas and liquid decreased, while the content of CO, CO2 and H2 increased. Simultaneously, liquid oil showed higher content of simple phenols, especially the diphenols which the maximum reached 80% with 3%BN at 650 ℃, while the yield of heavy components (300 âˆ¼ 400 Da) decreased. With regard to B-doped char, oxygenic groups and specific surface area (509 m2/g of 5%BN at 650 ℃) increased greatly. Increasing temperature promoted the transformation of B doping form from BC2O to BCO2.

In-situ polymerized composite polymer electrolyte with cesium-ion additive enables dual-interfacial compatibility in all-solid-state lithium-metal batteries.

Solid composite polymer electrolytes (CPEs) that combine the advantages of inorganic and organic electrolytes are regarded as the most appealing candidates for all-solid-state lithium-metal batteries (ASSLMBs). Nonetheless, the interfacial incompatibility issues resulting from poor cathode/electrolyte contact and uncontrolled dendrite growth on Li anode are fundamentally challenging for the development of ASSLMBs. Herein, we design a solid CPE with dual-interface compatibility based on in-situ thermal polymerization of a precursor solution containing polymer monomer, cesium-ion (Cs+), and inorganic Li+ conductor. The resultant Cs+ containing CPE creates intimate interface contact with the cathode while achieving high interfacial stability with the Li-metal anode. Accordingly, this solid electrolyte can perform reversible Li plating/stripping over 750 h at 0.3 mA cm-2 and a critical current density (CCD) of 0.8 mA cm-2, in sharp contrast with its Cs+-free counterpart (failure after 11 h and a CCD of 0.5 mA cm-2). Furthermore, the full ASSLMBs (Li|LiFePO4) enable decent capacity retention of 90% over 100 cycles at 0.5C and high Coulombic efficiency of nearly 100%. Therefore, constructing solid-state electrolytes with dual-interfacial compatibility may be an effective avenue to achieve high-performance ASSLMBs.

Biomass hydrothermal conversion under CO2 atmosphere: A way to improve the regulation of hydrothermal products.

In this study, batched hydrothermal experiments on corn stalk were conducted at 240-330 °C under CO2 or inert (N2) atmosphere. The distribution and characteristics of gaseous, solid, and liquid products were analyzed in detail to comprehensively investigate the effects of CO2 on the hydrothermal conversion of biomass, especially on the cellulose and lignin in biomass. The results demonstrate that compared with N2, CO2 slightly increased the liquid and gas yields and significantly improved the control effect of temperature on bio-oil components. Under CO2 atmosphere, bio-oil achieved effective enrichment of ketones and phenols at 240 °C and 300 °C, respectively, and their highest relative contents reached 44.8% and 62.0%, respectively. In addition, the hydrochar obtained under CO2 atmosphere showed higher crystallinity, which is conducive to its subsequent utilization. This study explored the feasibility of introducing CO2 into the biomass hydrothermal process to realize the high-value utilization of biomass waste and the reuse of CO2.

Coeffect of pyrolysis temperature and potassium phosphate impregnation on characteristics, stability, and adsorption mechanism of phosphorus-enriched biochar.

Potassium phosphate (K3PO4)-impregnated bamboo was pyrolyzed at temperatures ranging from 350 to 950 °C to explore the coeffect of pyrolysis temperature and K3PO4 impregnation on biochar's characteristics and adsorption behavior. The degree of aromatization and graphitization in phosphorus-enriched biochars (PRBCs) rose as temperature increased, whereas H/C and O/C ratios, pH value, and O-containing group content decreased. The pre-aging impact of K3PO4 impregnation results in increased stability and adsorption performance of PRBCs. Adsorption mechanism of PRBCs to heavy metal varies from pyrolysis temperature. Micropores dominate medium-temperature PRBCs (prepared at 550 âˆ¼ 750 °C), possessing the highest P-containing group content (116 % that of PRBC-350) and maximal adsorption capacity (greater than289 mg/g). The medium-temperature PRBCs adsorb Cd (II) via the role of O-containing groups, PO43-, and P2O74-, mainly by reactions of organic complexation, precipitation and inorganic complexation, respectively. 550 °C is the optimal pyrolysis temperature for both energy saving and heavy metal adsorption.

High-value products from ex-situ catalytic pyrolysis of polypropylene waste using iron-based catalysts: the influence of support materials.

Catalytic pyrolysis is considered a promising strategy for the utilisation of plastic waste from the economic and environmental perspectives. As such, the supporting materials play a critical role in the properties of the catalyst. This study clarified this influence on the dispersion of the iron (Fe) within an experimental context. Four different types of typical supports with different physical structures were introduced and explored in a two-stage fixed-bed reactor; these included metallic oxides (Al2O3, TiO2), a non-metallic oxide (SiO2), and molecular sieves (ZSM-5). The results show that the liquid products were converted into carbon deposits and lighter gaseous products, such as hydrogen. The Al2O3-supported catalyst with a relatively moderate specific surface areas and average pore diameter exhibited improved metal distribution with higher catalytic activity. In comparison, the relatively low specific surface areas of TiO2 and small average pore diameters of ZSM-5 had a negative impact on metal distribution and the subsequent catalytic reformation process; this was because of the inadequate reaction during the catalytic process. The Fe/Al2O3 catalyst produced a higher yield of carbon deposits (30.2 wt%), including over 65% high-value carbon nanotubes (CNTs) and hydrogen content (58.7 vol%). Additionally, more dispersive and uniform CNTs were obtained from the Fe/SiO2 catalyst. The Fe/TiO2 catalyst promoted the formation of carbon fibre twisted like fried dough twist. Notably, there was interesting correspondence between the size of the reduced Fe nanoparticles and the product distribution. Within certain limits, the smaller Fe particle size facilitates the catalytic activity. The smaller and better dispersed Fe particles over the support materials were observed to be essential for hydrocarbon cracking and the subsequent formation of carbon deposits. The findings from this study may provide specific guidance for the preparation of different forms of carbon materials.

Effects of phosphorous precursors and speciation on reducing bioavailability of heavy metal in paddy soil by engineered biochars.

Ammonium phosphate (AP), phosphoric acid (PC), and potassium phosphate (TKP) were used for the modification of biochar for enhanced heavy metal passivation in soil. The effect of various phosphorus (P) precursors on adsorption-related properties, P speciation distribution pattern, and the passivation mechanism was investigated by BET, FTIR, XRD, XPS, and 31P NMR analysis. The mobility and bio-availability of cadmium (Cd) were studied by extraction experiments, and the P release kinetics was also determined. Results showed that the immobilization efficiency of Cd (II) by biochars followed the order: TKP-BC > PC-BC > AP-BC > BC, and TKP-BC reduced available Cd content by 81% treated with 2% addition. The P speciation shows a significant effect on the P-enriched biochars' passivation performance, especially orthophosphate, which is essential for the immobilization of Cd2+ by forming phosphate precipitation. Pyrophosphate and orthophosphate monoester in AP-BC and PC-BC can promote Cd2+ passivation via the formation of P-Cd complexes or organometallic chelates. It is also shown that PC-BC has the lowest P release rate while TKP-BC has the highest percentage of P (15.50%) remaining in the biochar. The results may contribute to the development of modified biochar for soil remediation based on P-related technologies.

Machine learning prediction of pyrolytic gas yield and compositions with feature reduction methods: Effects of pyrolysis conditions and biomass characteristics.

This study aimed to utilize machine learning algorithems combined with feature reduction for predicting pyrolytic gas yield and compositions based on pyrolysis conditions and biomass characteristics. To this end, random forest (RF) and support vector machine (SVM) was introduced and compared. The results suggested that six features were adequate to accurately forecast (R2 > 0.85, RMSE < 5.7%) the yield while the compositions only required three. Moreover, the profound information behind the models was extracted. The relative contribution of pyrolysis conditions was higher than that of biomass characteristics for yield (55%), CO2 (73%), and H2 (81%), which was inverse for CO (12%) and CH4 (38%). Furthermore, partial dependence analysis quantified the effects of both reduced features and their interactions exerted on pyrolysis process. This study provided references for pyrolytic gas production and upgrading in a more convenient manner with fewer features and extended the knowledge into the biomass pyrolysis process.

Temperature-dependent magnesium citrate modified formation of MgO nanoparticles biochar composites with efficient phosphate removal.

Nano-MgO biochar composites (nMBCs) have been considered as potential adsorbents for phosphate removal from aqueous solution. It is an effective strategy to improve P removal efficiency that adjustment of the size, distribution and crystallinity of MgO particles embedded into the carbon matrix. Herein, we prepared a highly efficient phosphate adsorbent by co-pyrolysis of lotus seedpod and magnesium citrate and studied its adsorption mechanisms. Results showed that the uniformly dispersed MgO nanoparticle was formed on the surface of nMBCs with the temperature increasing, with the particles size ranging from 3 to 10 nm. Furthermore, high temperature promoted the formation of a large amount of reactive lattice oxygen, which was demonstrated to be the main active adsorption site, thus the phosphate immobilization capacity of nMBCs was greatly improved with the pyrolysis temperature increasing from 450 °C to 750 °C. Besides, some stable CO bonds were formed due to the catalysis of Mg2+, which could bond to HPO42-/H2PO4- by hydrogen bond, enhancing the adsorption performance. The isotherm adsorption experiment showed that MBC-750 achieved an excellent phosphorus adsorption amount of 452.752 mg-P/g. The effectiveness of nMBCs is enhanced and a method for producing an effective nanocomposite adsorbent material for removing phosphate from wastewater is provided.

Characteristics and Evolution of Nitrogen in the Heavy Components of Algae Pyrolysis Bio-Oil.

Algae pyrolytic bio-oil contains a large quantity of N-containing components (NCCs), which can be processed as valuable chemicals, while the harmful gases can also be released during bio-oil upgrading. However, the characteristics of NCCs in the bio-oil, especially the composition of heavy NCCs (molecular weight ≥200 Da), have not been fully studied due to the limitation of advanced analytical methods. In this study, three kinds of algae rich in lipids, proteins, and carbohydrates were rapidly pyrolyzed (10-25 °C/s) at different temperatures (300-700 °C). The bio-oil was analyzed using a Fourier transform ion cyclotron resonance mass spectrometer equipped with electrospray ionization, and the characteristics and evolution of nitrogen in heavy components were first obtained. The results indicated that the molecular weight of most heavy NCCs was distributed in the 200-400 Da range. N1-3 compounds account for over 60% in lipid and protein-rich samples, while N0 and N4 components are prominent in carbohydrate-rich samples. As temperature increases, most NCCs become more aromatic and contain less O due to the strong Maillard and deoxygenation reactions. Moreover, the heavier NCCs were promoted to form lighter compounds with more nitrogen atoms through decomposition (mainly denitrogenation and deoxygenation). Finally, some strategies to deal with the NCCs for high-quality bio-oil production were proposed.

Nano nickel embedded in N-doped CNTs-supported porous biochar for adsorption-reduction of hexavalent chromium.

Nitrogen-doped carbon coated transition metal hybrids for the removal of hazardous hexavalent chromium (Cr(VI)) has attracted increasing attention in wastewater treatment recently. In this study, three-dimensional nano-nickel particles embedded in N-doped carbon nanotubes supported on porous biochar (Ni@N-K-C) were synthesized by a two-stage strategy of KOH activation followed by annealing. The effect of KOH activation treatment on the doping process and Cr(VI) removal properties were investigated. The results indicate that KOH activation can improve the pore parameters and promote subsequent doping of Ni and N and the growth of carbon nanotubes (CNTs). After KOH pretreatment, the specific surface area of Ni@N-K-C increased significantly to 604.62 m2/g. The improved pore structure accelerates the mass diffusion of Cr(VI) ions and provides an available surface for the adsorption and reduction of Cr(VI). Therefore, the Ni@N-K-C obtained at 900 °C showed a high removal capacity for Cr(VI) (824.4 mg/g) and a stronger ability to reduce to Cr(III).