Volatile Pyrolysis Research Articles

Catalytic upgrading of lignite pyrolysis volatiles to light aromatics under methanol atmosphere over Zr and/or Fe modified hollow ZSM-5 zeolites

Fe and Zr modified hollow ZSM-5 zeolites were prepared and their applications in upgrading of lignite pyrolysis volatiles coupling with methanol to light aromatics were investigated. The results demonstrated that hollow zeolites with larger voids and shorter diffusion length favored the production of light aromatics. Adding Fe and Zr into ZSM-5 zeolites further enhanced BTX yields due to the synergism between metals and acid sites for promoting hydrodeoxygenation reactions. Meanwhile, Zr-Fe/HZ-5 catalyst with increasing Lewis acid sites facilitated methylation leading to high selectivity of xylene under methanol atmosphere. Moreover, diffusion behaviors of xylene were quantified. Higher self-diffusion coefficient of molecules in hollow zeolites led to the formation of less coke, while the incorporation of Fe and Zr promoted the formation of catalytic coke due to the increase of alkylation resulting in partial conversion of BTX into PAHs on external surfaces although the total coke yields were further decreased.

Base-acid tandem catalytic upgrading of coal pyrolysis volatiles: the effects of alkaline earth oxides and modified HZSM-5 zeolites

Catalytic upgrading of coal pyrolysis volatiles is a promising technology to bolster the production of value-added chemicals from coal. To optimize product distribution and mitigate catalyst deactivation, this work investigated tandem catalysts combining the upper alkaline earth oxides (CaO or MgO) with the lower modified HZSM-5 (mesopore creation and Ga loading). The pre-cracking of volatiles over CaO or MgO lowered the average molecule size of tar components. The diffusion properties and aromatization of these pre-cracking-derived intermediates were improved, facilitating the secondary upgrading over HZSM-5-based catalysts, promoting the formation of aromatics. The experimental results showed that tandem CaO-HZSM-5 catalysts presented better synergy to improve the tar components as compared to MgO-HZSM-5, considering the formation of aromatics in tar. In this context, the mesopore and metal Ga were introduced into HZSM-5 to further upgrade the tar quality. The mesoporous structure for HZSM-5-meso and Ga/HZSM-5-meso promoted the conversion of aliphatic hydrocarbons into aromatics. Simultaneous introduction of mesopores and Ga synergistically increased the aromatic content in tar to 41.6% and reduced the carbon deposition to 0.88wt.%. In summary, this work elucidated the mechanism of tandem CaO-modified HZSM-5 catalysis for the upgrading of volatiles from coal pyrolysis.

Formation and evolution of coke of pyrolytic volatiles of low-rank coal on the carbon-based catalysts

The catalytic upgrading of coal pyrolysis volatiles is an effective technique to achieve clean and efficient conversion of low-rank coal. However, a major problem in this process is catalyst deactivation caused by coke deposition. This study investigated the catalytic cracking effect of activated carbon and metal-modified activated carbon on coal pyrolysis volatiles. It also explained the physical and chemical properties of coke and its formation mechanism related to volatile cracking. The results indicate that phenolic oils, pitch, oxygen-containing compounds, and polycyclic aromatics are linearly related to the coke deposited on the surface of carbon-based catalysts. These compounds act as precursors and are easily transformed into coke via cracking, deoxidation, crosslinking, and polycondensation reactions when the cracking rate of volatiles does not match the hydrogen supply rate. The micro-morphology of coke is primarily composed of amorphous carbon, which is mainly found in pores ranging from 0.50 to 5.00 nm and on the outer surface of carbon-based catalysts. The chemical structure of coke primarily consists of large aromatic clusters containing at least six benzene rings and oxygen-containing cross-linking compounds with a high degree of graphitization and a low number of carbon structural defects. This results in an increase in radical concentration of carbon-based catalysts, as well as a decrease in combustion reactivity. The outcomes will aid in controlling coke deposition during catalytic cracking of pyrolytic volatiles of low-rank coal.

Catalytic conversion of biomass pyrolysis volatiles over composite catalysts of activated carbon and HY zeolite

Bio-oil has complex compositions and high oxygen content, which restricts its high-value utilization. Commercial activated carbon (AC) and HY zeolite were used as composite catalysts to study their effect on pyrolysis volatiles from rice straw and poplar sawdust by changing the mixing modes of two catalysts. The results showed that the loading modes of AC and HY zeolite obviously affected the products distribution and bio-oil components. The lowest yield of bio-oil was obtained when HY zeolite and AC were mechanically mixed at a mass ratio of 1:1 (YACM). But the loading mode of YACM was beneficial to the deoxidation and aromatic hydrocarbon generation. Under the mode of YACM, the aromatics content in rice straw and poplar sawdust bio-oil can be increased from 13.8% and 8.0% without catalyst to 56.4% and 53.1%, respectively. However, the layered loading with upper HY zeolite and lower AC (YTACL) was favorable for formation of phenolic compounds. The selectivity to monocyclic and bicyclic aromatic hydrocarbons followed the order of YTACL > ACTYL > YACM, and YACM > ACTYL > YTACL, respectively. Compared with HY zeolite, AC catalyst possessed smaller pore size and fewer acidity, and the active sites of AC were conducive to rearrangement of furan compounds to generate cyclopentanone, 2-cyclopentenone and methyl-cyclopentenone, and further rearrangement to form phenol. Therefore, the loading mode of YTACL exhibited a promotion effect on the formation of phenol, cresol, toluene, ethylbenzene and p-xylene. The strong acidic sites of HY zeolite were favorable for the aromatization, so the loading mode of ACTYL had good selectivity to the formation of naphthalene, methylnaphthalene, anthracene and pyrene. This work will provide a guide for products regulation from biomass pyrolysis and enrich aromatics and phenols in bio-oil.

Impact of several sludge dewatering conditioners on municipal sludge pyrolysis properties, kinetics, by-products, and environmental risk assessment

The pyrolysis characteristics of four different types of conditioned sludge were ascertained, and PAM, CaO, K2FeO4, and K2FeO4-CaO-PAM (KCP) conditioners were employed as sludge dewatering conditioners. The sludge pyrolysis reaction's activation energy (E) dropped with the addition of four conditioners. CaO, PAM, KCP, and K2FeO4 were the sequences of E needed for the pyrolysis of four different types of conditioned sludge. The addition of K2FeO4, CaO, and KCP resulted in an increase in the yields of H2 and CO. Except for the K2FeO4 conditioning sludge carbon, the pyrolytic carbon of the other three groups of samples showed an increase in S contents, while the pyrolytic carbon of the four groups of samples treated with conditioners clearly showed lower C and N contents compared to the raw sludge carbon. Protein-N made up the majority of N in sludge pyrolytic carbon. After adding conditioner, the level of organic sulfur decreased. Organic sulfur could then be broken down by K2FeO4 and CaO. The four conditioners efficiently mitigated the ecological and environmental risks posed by heavy metals. Alkynes were the most abundant result in pyrolytic volatiles of sludge pyrolysis; the other products included acids, alcohols, lipids, furans, ketones, phenols, hydrocarbons, N-components, and so on. All samples' acids, alcohols, and ketones from pyrolysis were decreased once the conditioner was added. The acid reduction rate reached 66.7 %, and the alkynes clearly increased during the KCP conditioned sludge's pyrolysis. The sulfur level of the bio-oil was decreased by all four conditioners. Everything mentioned above indicated that the KCP aided in the subsequent pyrolysis of the sludge, leading to the production of an advantageous pyrolysis bio-oil.

Lignin pyrolysis assisted by molten salt medium: Evolution behavior of volatiles and biochar structure

This study focuses on the use of a molten salt reaction medium (NaCl-KCl-LiCl) in the lignin pyrolysis process to modify the pyrolysis volatiles and biochar structure. The effect of pyrolysis reaction temperature (300°C, 400°C, 500°C, and 600°C) and lignin/molten salt mass ratios (3:1, 1:1, 1:3 and 1:5) on the evolution behavior of volatiles and biochar structure was explored. The pyrolysis products were determined using GS-MS, CO2 adsorption-desorption analyses, SEM, elemental analysis, proximate analysis, Raman, XRD, and TG/DTG analysis. Results indicated that the introduction of molten salt can enhance the lignin depolymerization, leading to the production of phenolic precursors. Moreover, the metal cation (Na+, K+ and Li+) of molten salt can in-situ induce the modification of biochar structure with high porosity. The lower sulfur content in biochar was attributed to the immobilize function of molten salt. The evolution behaviour of volatiles and biochar structure during molten salt-assisted lignin pyrolysis was proposed. This study can serve as a benchmark for the high-value recycling of industrial lignin waste.

Rapid pyrolysis of cellulose: Revealing the role of volatile matter and char structure evolution

The complexity of the cellulose structure hinders its energy conversion and utilization. Pyrolysis is not only an independent thermochemical conversion technology but also a necessary stage in the gasification process. The real-time capture of volatile components in cellulose pyrolysis is difficult, and the evolution of char structures is lacking, which is extremely challenging. In this work, elemental analysis, industrial analysis, thermogravimetric analysis, infrared spectroscopy (FTIR), Raman spectroscopy (Raman), and X-ray diffraction spectroscopy (XRD) were used to characterize the raw materials and products. Combined with rapid pyrolysis experiments, the pathways of cellulose pyrolysis volatiles and char structure evolution were explored. Dehydrated sugars are the initial products formed below 350 ℃, which quickly dehydrate to form furan compounds at 400 ℃ and then break CC bonds at 600 ℃ to generate fatty aldehydes, ketones, and carboxylic acids. Biochar generated at low temperatures (<300°C) has strong lipid solubility. An increase in pyrolysis temperature leads to a continuous decrease in the content of H and O in biochar, which destroys its functional groups and physical structure, and ultimately tends to form graphite-type char with aromatic structures. Based on the correlation between the volatile matter release characteristics and the evolution of the semichar structure, a cellulose pyrolysis pathway was established, providing theoretical support for the high-value utilization of cellulose.

Ex-situ catalytic fast pyrolysis of waste polycarbonate for aromatic hydrocarbons: Utilizing HZSM-5/modified HZSM-5

Catalytic pyrolysis has been proven as a highly efficient process for transforming waste polycarbonate (PC) into valuable aromatic hydrocarbons, especially benzene, toluene, ethylbenzene, and xylene (BTEX). In the present work, the ex-situ catalytic fast pyrolysis of PC on metal- or alkali-modified HZSM-5 was investigated using the double micro-fixed bed system. Experimental results indicate that the rapid pyrolysis of PC may follow a homolytic chain scission mechanism, resulting in pyrolysis products dominated by phenols. Metal- or alkali-modified HZSM-5 significantly enhances the cleavage of C-OH bonds in phenols, improving the yield of aromatics. The yield of aromatics in the liquid product is 91 %, 72 %, and 77 % when loaded with nickel (Ni), iron (Fe), and cobalt (Co), respectively, all of which are higher than unmodified HZSM-5 with the yield of 43 %. Among them, the Ni/HZSM-5 has significantly enhanced the yield of BTEX reaching 81.64 %. When using alkali-modified HZSM-5 with a larger pore volume and higher specific surface area, the yield of aromatics can be increased to 60 %. Furthermore, the dual modification of alkali treatment and Ni loading on HZSM-5 simultaneously enhanced catalytic activity and resistance to coke formation. The yield of BTEX reaches 94.47 %. The BTEX formation mechanism can be explained by direct deoxygenation (DDO) of the pyrolytic volatiles of PC and the “phenol pool” mechanisms of primary products on the catalyst surface. This study enriches the understanding of catalytic pyrolysis of PC and provides a theoretical foundation for the harmless treatment of PC.

Effect of polyethylene terephthalate plastics on nitrogen, sulphur and chlorine contaminants via sludge pyrolysis and Pb/Cu adsorption properties of biochar

ABSTRACT Pyrolysis is an effective process for disposing of municipal sewage sludge (SS). Plastics can affect the SS pyrolysis behaviour and pyrolysis products due to their low ash and high hydrocarbon ratio. The secondary pollutants from the pyrolysis process may also be affected. Therefore, polyethylene terephthalate (PET), a typical plastic, was chosen to investigate the release characteristics of pollutants containing nitrogen, sulphur, and chlorine via SS pyrolysis, and the changes of biochar to adsorb two typical heavy metals, Pb and Cu. The pyrolysis of PET plastics facilitates the migration of N toward solid and liquid-phase products, S and Cl to the gas-phase products via pyrolysis. Oxygenated compounds of pyrolytic volatiles decreased from 38.18% to 28.43%, concurrently promoting the formation of phenolic compounds. The co-pyrolysis improved the quality of biochar and the ability to adsorb Pb and Cu. This systematic study can provide some support for the further improvement of SS pyrolysis technology, and will also be beneficial for subsequent applications.

The effects of in situ-produced hydrogen on catalytic upgrading of lignite pyrolysis volatiles over ZSM-5 zeolites to produce light aromatics

The introduction of in situ hydrogen donors to obtain a high H/Ceff ratio is an effective way to upgrade coal pyrolysis volatiles to light aromatics. In this study, the influence of different in-situ hydrogen suppliers in catalytic reforming of coal pyrolysis vapors was explored. The abilities of active hydrogen donation were greatly corresponded to structures of hydrogen donors. Isopropanol showed the best catalytic performance due to the release of a large amount of active α-H as a result of negative inductive effect of hydroxyl. Whereas tertbutanol showed the poorest catalytic performance owing to the lack of α-H. Meanwhile, the effect of in-situ hydrogen production via steam reforming with different alcohols on light aromatic yields was investigated. The highest BTEXN yield was obtained under in-situ hydrogen production from isopropanol steam reforming. Two circumstances of hydrogen supply were further compared. Relatively higher BTEXN yield was presented in the reaction of methanol steam reforming than that of using methanol solely. However, higher BTEXN yield was contrarily obtained from sole isopropanol as a hydrogen donor despite lower H2 production was gained compared to the case of isopropanol steam reforming. The fact was probably ascribed that high electron-withdrawing effect of hydroxyl for isopropanol promoted the cleavage of α-C-H bond and favored the transfer of active hydrogen to reactants over acid sites.

Leaching char with acidic aqueous phase from biomass pyrolysis: Valorization of the leachate via catalytic hydrothermal gasification

Aqueous phase of bio-oil (APB) is a general stream of waste produced from biomass pyrolysis and fractional condensation of pyrolytic volatiles and has very limited applications. We have demonstrated a sequence of leaching of alkali and alkaline earth metallic species (AAEMs) from char and catalytic hydrothermal gasification (CHTG) for valorizing char and APB, respectively. The majority of AAEMs can be removed from the char by leaching with APB and the removal rates were almost equivalent to those leached with HCl (1.0 M). CHTG of an aqueous solution of the spent APB with a total organic carbon of 14,450 ppm was performed in a continuous flow reactor, employing an activated carbon-supported Ru catalyst (Ru loading, 4.6 wt%). The catalyst exhibited a stable activity for carbon conversion of 98.8 % at 350 °C for at least 360 min while gaseous product consisting of H2, CH4, and CO2 was produced with a cold gas efficiency of 101–103 %, on a higher heating value basis. The cold gas efficiency exceeding 100 % is mainly because of the generation of H2 from water through water-gas shift reaction. The CHTG performance of APB was enhanced by char leaching through the uptake of coke-forming precursors of APB onto char and the enrichment of AAEMs in the spent APB. These AAEMs played roles in suppressing coke formation and deposition onto the catalyst and maintaining Ru particle size by providing a less acidic hydrothermal environment.

Catalytic upgrading of Naomaohu coal pyrolysis volatiles over CaO catalyst

Catalytic upgrading of coal pyrolysis volatiles is one the promising way to achieve high quality tar and gas. In this study, catalytic upgrading of volatiles from Naomaohu (NMH) coal pyrolysis has been conducted in a two-stage fixed bed reactor using CaO as catalyst. The aim of this work was to investigate the catalytic effect of CaO on the gas and liquid product distribution, as well as the variations in gas and coal tar components. Simulated distillation and GC-MS analysis has been used to understand the distribution of tar component. On the one hand, CaO exhibits selective cleavage of large molecules, such as long-chain esters, leading to the production of aromatics through the processes of dehydrocyclization and aromatization. CaO has the ability to stabilize free radicals that are generated during the cleavage of large molecules, thereby promoting the formation of light aromatic hydrocarbons. Consequently, the light tar fraction (boiling point <360 °C) increased from 64.4 % to 74.6 %, while the heavy tar fraction (boiling point＞360 °C) decreased from 35.6 % to 25.4 % in the pyrolysis tar. The compounds with long ester chains in the tar composition decreased by 24.4 %. The content of light components, such as benzenes, naphthalene, and phenols, increased significantly with the increasing catalytic temperature. Specifically, the content of benzenes, naphthalene, and phenols increased by 11.83 %, 17.73 %, and 4.41 % respectively at the coal to CaO ratio of 1/0.5 and the catalytic temperature of 600 °C. On the other hand, the CaO absorbs the CO2 pyrolysis gas leading to an elevation in the concentration of CH4 and H2 in the pyrolysis gas. The concentration of CO2 decreased from 37.9 % to 16.58 % compared to without the catalyst while the concentrations of H2 and CH4 increased to 26.24 % and 31.15 % at the catalytic temperature of 450 °C. The CO2 absorption ratio reached a maximum value of 97.16 % at a coal to CaO ratio of 1/2. These findings suggest that the CaO catalyst beneficial both for improving the tar and gas quality.

Regulation of co-pyrolysis behavior of Naomaohu coal and polypropylene by controlling the cracking of polypropylene pyrolysis volatiles

Pyrolysis is one of the technologies for clean and efficient conversion and utilization of coal, however, low yield and poor quality of tar restrict its utilization. Waste polypropylene (PP) could be efficiently used to improve tar yield of low-rank coal via co-pyrolysis. To strengthen the generation and transfer of hydrogen-rich radicals, modified HZMS-5 (HZ5) catalyst was used to regulate the composition of PP pyrolysis volatiles. Results show that close contact between HZ5 catalyst and coal favors the formation of light components, which reaches the maximum value of 72.45 wt%. In the presence of zeolite catalysts modified with 0.2 mol/L NaOH (0.2Na-HZ5), light oil in tar exhibits an obvious increase of 12.78 % compared with HZ5. A synergetic effect analysis clarifies that C2-C3 produced from PP pyrolysis under the action of the catalyst participate in the formation of tar. And the reactive intermediates from secondary cracking of PP volatiles over 0.2Na-HZ5 promote the cleavage of O-containing groups in coal, leading to the increase of phenols and alcohols in tar. The co-pyrolysis behavior of benzyl phenyl ether /bibenzyl and PP is shown that the transfer of oxygenated compounds into liquid is enhanced, confirming a positive synergetic effect. Meanwhile, the clear inhibition of C2-C3 components further indicates their contribution to tar formation.

In-situ catalytic upgrading of lignin pyrolysis volatiles over red mud

Red mud (RM) is a solid waste of Bayer's alumina industry production process, which comprises a mixture of diverse minerals. After calcination, the minerals in RM are present in the form of oxides, exhibiting remarkable catalytic performance for biomass pyrolysis. It is thought that pyrolysis of lignin generates renewable aromatic chemicals. In this paper, the effect of in-situ catalysis of calcinated RM on the distribution of lignin pyrolysis volatile products is investigated. In addition, upgrading of tar by components in RM, including SiO2, Al2O3, Fe2O3, and Na2O is also discussed. The results show that the addition of RM in lignin pyrolysis leads to lower char yield and higher gas yield. RM catalyzes the breaking and rearrangement of methoxy groups and induces the generation of hydroxyl groups, which leads to an increase from 1.96 to 3.96 wt% in monophenol content of the tar. Furthermore, the activation of C-O bonds by Fe2O3 and the redox properties of Fe2O3 (FeSi) combine to stimulate the production of monophenols and aldehydes by 30.8 % and 148.2 %, while Al2O3 (AlSi) boosts the production of guaiacols by 32.0 % comparing with SiO2 (Si). It is found that synergistic effect between multiple species improves the catalytic performance, the yield of tar reaches 24.5 wt% and the selectivity of oxygenated compounds achieves 94.4 % (FeAlSiNa). The catalytic performances of RM for product yield and tar component distribution are similar to that of FeSi, indicating that Fe2O3 and SiO2 play a main catalytic role in RM.

Biomass source influence on hydrogen production through pyrolysis and in line oxidative steam reforming.

This study evaluates the potential of several biomasses differing in nature and composition for their valorization by pyrolysis and in-line oxidative steam reforming. The first task involved the fast pyrolysis of the biomasses in a conical spouted bed reactor at 500ºC, in which product yields were analyzed in detail. Then, the oxidative steam reforming of pyrolysis volatiles (gases and bio-oil) was approached in a fluidized bed reactor. The reforming experiments were performed at 600 ºC, with an steam/biomass (S/B) ratio of 3 and catalyst (Ni/Al2O3) space times of 7.5 and 20 gcat min gvol-1. Concerning equivalence ratio (ER), a value of 0.12 was selected to ensure autothermal operation. Remarkable differences were observed in H2 production depending on the type of biomass. Thus, pine wood led to a H2 production of 9.3 wt%. The lower productions obtained with rice husk (7.7 wt%) and orange peel (5.5 wt%) are associated with their higher ash and fixed carbon content, respectively, which limit the efficiency of biomass conversion to bio-oil. However, in the case of the microalga, the poor performance observed is due to the lower conversion in the reforming step toward gases due to the composition of its pyrolysis volatile stream.

The application of Ni and Zr modified ZSM-5 nanosheet in upgrading of lignite pyrolysis volatiles coupling with methanol to light aromatics

Ni and Zr modified nanosheet ZSM-5 zeolites as tandem catalysts were designed using co-impregnation method (Zr-Ni/S-Z5) or combining in-situ hydrothermal synthesis of Ni@S-Z5 and sequential impregnation of Zr (Zr/Ni@ S-Z5). Their applications in upgrading of lignite pyrolysis volatiles coupling with methanol to light aromatics were investigated. The results demonstrated that nanosheet zeolites with larger surface areas and shorter b-axis length benefited the production of light aromatics due to exposing more active sites and improved diffusion limitation compared with conventional ZSM-5 zeolites. Adding Ni and Zr into tandem catalysts further enhanced BTEXN yields, which was attributed to the induction of oxyphilic ZrO2 for activating CAr-O bonds combining the promotion of Ni for hydrogenation. Comparing to Zr-Ni/S-Z5 catalyst, lower BTEXN yield was observed due to the decrease in exposing active sites over Zr/Ni@ S-Z5 catalyst. Moreover, enhancing diffusion behaviors in shorter b-axis length and the presence of more fractions of external coke indicated less effective in blocking pore channels, thus nanosheet zeolite series showed lower deactivation rates.

Catalytic upgrading of Naomaohu coal pyrolysis volatiles over NiAl and NiLiAl oxides

Catalytic upgrading of volatiles is an essential technology to improve the product distribution of pyrolysis for the clean and efficient utilization of low-rank coals. In this work, novel acid-base bifunctional catalysts composed of Ni/Li/Al oxides were designed and prepared using LDH precursors with tunable chemical composition and structural properties. The catalysts were systematically characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA), physisorption, NH3-temperature programmed desorption (NH3-TPD), CO2-temperature programmed desorption (CO2-TPD), H2-temperature programmed reduction (H2-TPR), and scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS). A two-stage fixed bed reactor was employed to evaluate the performance of the catalysts. Characterization results suggest that the crystal size of NiO and the surface area of the catalyst decreased with increasing Li content and decreasing Ni content in the catalyst, while the pore volume and pore diameter were positively correlated with Li content. Moreover, the addition of Li reduced the amount of weak acid sites and raised the amount of total basic sites. Consequently, the bifunctional catalysts boosted the yield of light tar and the contents of aromatics and phenols in tar. Specifically, with the highest total acid sites (569 μmol/g) promoting the cracking of heavy pitch components, Ni2.5Li0.5Al1 decreased the content of pitch in tar to 23.8 wt%, representing a 42.7 % drop from the corresponding non-catalytic pyrolysis. Accordingly, it improved the light tar yield to 7.2 wt%, which was 18 % higher than non-catalytic pyrolysis. 450 °C is identified as a suitable temperature for the catalytic upgrading of volatiles from Naomaohu coal; higher catalysis temperatures at 500 °C and 550 °C led to lower tar yield and lower phenols content, along with higher gas yield and more carbon deposition.

Chemical looping reforming of the micromolecular component from biomass pyrolysis via Fe2O3@SBA-16

AbstractTo solve the problems of low gasification efficiency and high tar content caused by solid–solid contact between biomass and oxygen carrier in traditional biomass chemical looping gasification process. The decoupling strategy was adopted to decouple the biomass gasification process, and the composite oxygen carrier was prepared by embedding Fe2O3 in molecular sieve SBA-16 for the chemical looping reforming process of pyrolysis micromolecular model compound methane, which was expected to realize the directional reforming of pyrolysis volatiles to prepare hydrogen-rich syngas. Thermodynamic analysis of the reaction system was carried out based on the Gibbs free energy minimization method, and the reforming performance was evaluated by a fixed bed reactor, and the kinetic parameters were solved based on the gas–solid reaction model. Thermodynamic analysis verified the feasibility of the reaction and provided theoretical guidance for experimental design. The experimental results showed that the reaction performance of Fe2O3@SBA-16 was compared with that of pure Fe2O3 and Fe2O3@SBA-15, and the syngas yield was increased by 55.3% and 20.7% respectively, and it had good cycle stability. Kinetic analysis showed that the kinetic model changed from three-dimensional diffusion to first-order reaction with the increase of temperature. The activation energy was 192.79 kJ/mol by fitting. This paper provides basic data for the directional preparation of hydrogen-rich syngas from biomass and the design of oxygen carriers for pyrolysis of all-component chemical looping reforming.

Continuous and low-carbon production of biomass flash graphene

Flash Joule heating (FJH) is an emerging and profitable technology for converting inexhaustible biomass into flash graphene (FG). However, it is challenging to produce biomass FG continuously due to the lack of an integrated device. Furthermore, the high-carbon footprint induced by both excessive energy allocation for massive pyrolytic volatiles release and carbon black utilization in alternating current-FJH (AC-FJH) reaction exacerbates this challenge. Here, we create an integrated automatic system with energy requirement-oriented allocation to achieve continuous biomass FG production with a much lower carbon footprint. The programmable logic controller flexibly coordinated the FJH modular components to realize the turnover of biomass FG production. Furthermore, we propose pyrolysis-FJH nexus to achieve biomass FG production. Initially, we utilize pyrolysis to release biomass pyrolytic volatiles, and subsequently carry out the FJH reaction to focus on optimizing the FG structure. Importantly, biochar with appropriate resistance is self-sufficient to initiate the FJH reaction. Accordingly, the medium-temperature biochar-based FG production without carbon black utilization exhibited low carbon emission (1.9 g CO2-eq g−1 graphene), equivalent to a reduction of up to ~86.1% compared to biomass-based FG production. Undoubtedly, this integrated automatic system assisted by pyrolysis-FJH nexus can facilitate biomass FG into a broad spectrum of applications.

Study on the pyrolysis characteristics, kinetics, thermodynamics, volatile products, and chemical reactions of micron polyamide waste, a typical marine plastic microfragment

AbstractThe pollution of waste plastic microfragments to the marine ecosystems is an increasingly serious problem. Pyrolysis is widely recognized as a viable technique for the treatment of such plastic waste materials. The pyrolysis behaviors, characteristic parameters, kinetics, thermodynamics, volatiles, and possible chemical reactions during the pyrolysis of micron polyamide waste (the main component of fishing gear abandoned in the marine environment) are studied in inert atmosphere in the present work. The results show that the pyrolysis of micron polyamide may be regarded as a one‐step reaction. The peak and average reaction rates decrease significantly when the heating rate increases. The calculated kinetic parameters can effectively predict the pyrolysis behaviors of micron polyamide. The pyrolysis of micron polyamide is characterized as an endothermic reaction that occurs non‐spontaneously. Furthermore, the information of volatiles was obtained. The volatiles with higher content were –CH2 groups, CO2, and lactam, and the volatiles with smaller content were: –NH groups, NH3, HCN, H2O, CO, and amide derivatives. In addition, an analysis was conducted to explore the potential chemical reactions.Highlights The pyrolysis of micron polyamide can be considered as a one‐step reaction. The obtained kinetic parameters can well predict the pyrolysis process. Pyrolysis of micron polyamide is a non‐spontaneous and endothermic reaction. Specific volatile products are determined by Fourier transform infrared and mass spectrometry. The chemical reactions that may occur during the pyrolysis have been inferred.