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CHEMICAL ENGINEERING JOURNAL · 2025 · IF 13.2

Co-pyrolysis behavior of spent bleaching clay and dealkaline lignin: An investigation into TG-FTIR, kinetics, and interaction mechanisms

Chenguang Zhang,Zilu Zhang,Chuancheng Dongye,Xiaofei Xu,Zhihe Li,Weiming Yi,Xiaobo Chen,Shaoqing Wang

Spent bleaching clay (SBC) and lignin wastes are generated from oil refining and paper industries, respectively. The complementary properties of these two types of waste enable synergistic effects in co-pyrolysis, thereby mitigating limitations characteristic of single-component pyrolysis. In this study, the co-pyrolysis behavior of the two wastes was explored at the microscopic molecular level using simultaneous TG-FTIR technology, coupled with fixed-bed pyrolysis experiments. The co-pyrolysis behavior was systematically investigated at the mass ratio of lignin and SBC (0 %L, 30 %L, 50 %L, 70 %L, and 100 %L) and different reaction temperatures (450, 500, 550, 600, and 650 °C). The results showed that the activation energy required for co-pyrolysis decreased at 50 %L and 70 %L ratios, as determined using FWO and KAS methods. The Ea required for co-pyrolysis decreased at 50 %L and 70 %L ratios. Specifically, the addition of 30 % SBC reduced the activation energy of lignin from 141.67 kJ/mol (KAS) and 146.41 kJ/mol (FWO) to 120.25 kJ/mol (KAS) and 126.04 kJ/mol (FWO), respectively. Furthermore, the 50 %L radio infrared absorbance of CH 4 and CO 2 was relatively strong due to the enhanced decarboxylation and demethoxylation reactions. Meanwhile, the fixed-bed co-pyrolysis experiment showed that the relative content of non-methoxy phenolics increased from 7.0 % to 10.6 % with bio-oil yield increasing from 27 % to 40 %, after adding 50 % SBC. Additionally, the interaction mechanism was proposed based on the TG-FTIR and fixed-bed pyrolysis experimental results. SBC served as a hydrogen donor to promote the thermal decomposition of lignin and improved the yields of phenol and alkylphenols. This work offers guidance for the synergistic conversion of renewable carbon sources with oily solid wastes.

CAS / MDL: 9005-53-2
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CANADIAN JOURNAL OF CHEMICAL ENGINEERING · 2018 ·Vol. 96 ·期 12 ·2586-2592 · IF 1.265

Highly selective preparation of valuable dinitronaphthalene from catalytic nitration of 1-nitronaphthalene with NO2 over HY zeolite

Renjie Deng,Kuiyi You,Fangfang Zhao,Pingle Liu,He'an Luo

In this work, a simple method for the highly selective preparation of valuable dinitronaphthalene from 1-nitronaphthalene employing NO 2 as a nitrating agent has been developed. The results demonstrated that HY zeolite as an eco-friendly and stable catalyst exhibits good catalytic performances. The total selectivity to valuable dinitronaphthalene compounds including 1,5-, 1,4-, and 1,3-dinitronaphthalene can reach 87.6 % in our present nitration reaction. Meanwhile, the physico-chemical properties of catalysts were characterized by XRD, FTIR, TG/DTG, BET, and NH 3 -TPD, and the probable nitration reaction mechanism was also suggested in this paper. The present nitration process seems to be a mild, eco-friendly, and economical route for the preparation of valuable dinitronaphthalene compounds.

研究领域: 化学工程 · 催化 · 环境化学
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HIGH PERFORMANCE POLYMERS · 2017 · IF 1.179

Synthesis of high Tg and organosoluble poly(N-arylene benzimidazole ether imide) copolymers by C–N/C–O coupling reaction

Lala Rukh Sidra,Nafeesa Mushtaq,Guofei Chen,Xingzhong Fang

A series of poly(N-arylene benzimidazole ether imide) copolymers PEIBIs were prepared from 1H,3′H-5,5′-bis-benzimidazole, bisphenol-A and 4,4′-bis(4-fluorophthalimido)diphenyl ether by nucleophilic displacement polymerization. The resulting copolymers PEIBI(10–90) demonstrated moderate to good solubility in polar aprotic solvents and high glass transition temperatures (Tgs) of 228–336°C, good thermal stability with 10% weight loss temperatures in the range of 503–548°C. All copolymer films showed good mechanical properties with tensile strengths of 101–130 MPa, tensile moduli of 3.3–4.0 GPa, elongations at break of 5–7%, and also presented low water uptake (0.15–0.34%). The wide-angle X-ray diffraction results revealed the amorphous nature of copolymers. The copolymer PEIBI-80 showed good balance in solubility, thermal and mechanical properties.

研究领域: 材料科学 · 高分子化学
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GREEN CHEMISTRY · 2026 · IF 10.6

Fully-biobased Monomers Containing Monopyrrolidone Ring Towards the Synthesis of Renewable Polyesters with High Tg and Hydrolyzable Closed-loop Recycling

Yumeng Zhang,Yang Yu,Ziyi Feng

The development of fully bio-based polyesters with distinguished performance and facile chemical closed-loop recycling in aqueous environment still faces a challenge. Herein, a series of N-substituted pyrrolidone carboxylic acid monomers (xPCA) were synthesized from renewable itaconic acid (IA) with six amino acids with solvent-free and water-catalyzed conditions. xPCA was polymerized with ethylene glycol to prepare biobased six homopolyesters with number average molecular weights (Mn) up to 37.8 kDa. These polyesters exhibited high glass-transition temperatures (Tg) in the range of 47.8-106.2 ℃. Among these, L-tryptophan imparts the highest Tg (106.2 ℃) due to the addition of the indole heterocycle, which was higher than that of most of the commercial polyesters, such as polyethylene terephthalate (PET). In addition, these amorphous polyesters display excellent UV shielding properties with UV shielding cut-off values up to 241-323nm. The pyrrolidone structure improves the hydrophilicity of the polyester, thereby promoting the chemical cycle using deionized water at 80 ℃ as the solvent and low-toxicity zinc acetate as the catalyst. The recovered monomer can be polymerized again to obtain the original polyesters, which still retains its original properties. In addition, this polyester exhibits significant tolerance to common organic solvents and possesses long-term stability in water. Overall, this series of fully bio-based polyesters realizes the greening of the whole chain from raw material synthesis, product preparation to recycling treatment.

CAS / MDL: 97-65-4
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International Journal of Pharmaceutics-X · 2026 · IF 7.9

Solvent-free aqueous spray drying of poorly soluble drugs enabled by hot-feed micellar solubilization and high-Tg polymer matrices

Wenling Zheng,Hui Chen,Rongrong Xue,Ziqing Wu,Yongming Liu,Fenghua Chen

Poor aqueous solubility limits the oral bioavailability of many BCS II drugs, while conventional spray drying of amorphous solid dispersions (ASDs) often relies on organic solvents. Here we develop an aqueous spray-drying (AQSD) strategy that couples temperature-boosted solubility with poloxamer-enabled micellar solubilization and a high-Tg polymer matrix. Using celecoxib (CEL) as a model drug, heating increased intrinsic solubility and poloxamer 407 (P407) further raised apparent solubility to a ≥ 1 mg·mL −1 feed window suitable for atomization. Binary CEL–P407 produced wax-like solids, whereas adding soluble starch (SS) or polyvinylpyrrolidone (PVP) improved solidification and yielded powdery, amorphous products. PXRD and vibrational spectroscopy supported amorphization and a P407-rich hydrophobic microenvironment in the hot feed. Compared with the binary, ternary systems improved powderability/yield (e.g., ∼50% for CEL–P407–SS vs ∼40% for CEL-P407), maintained target drug loading with minimal net loss during drying, and enhanced non-sink dissolution, with CEL remaining amorphous after storage. The framework was further validated using indomethacin, sulfamerazine, and aripiprazole, while highlighting limitations for thermally labile compounds. Overall, AQSD provides a practical green rule—hot-feed micellar solubilization coupled with a Tg-raising matrix—for early ASD formulation screening and solvent-free manufacturing.

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BIOMACROMOLECULES · 2026 · IF 5.9

Closed-Loop Recyclable Bio-Based Polyesters Featuring a Tricyclic Diglycolicaldehyde Xylose Diol toward High Tg and Excellent Gas Barrier Performance

Linlin Wang,Yunlong Sun,Lei Song,Lu Li,Yumei Gong,Rui Wang

Biobased degradable polyesters have emerged as a promising alternative to mitigate plastic pollution and reduce dependence on petroleum resources. However, the utilization of tricyclic rigid diols derived from biomass remains limited, which restricts the overall performance of degradable polyesters. In this study, a novel diglycolicaldehyde xylose (DGX) diol containing a rigid tricyclic structure, synthesized from D-xylose and glyoxylic acid hydrate, is reported. Both the single- and multiple-stereoisomer forms of DGX were polymerized with linear diacids of varying carbon chain lengths to produce biobased poly(xylosediethylene alkylenedicarboxylate)s (PXAs) and m-PXAs polyesters. The high rigidity of the single-regioisomer DGX conferred enhanced thermal properties to PXAs, with a 5% weight loss temperature (Td,5%) reaching 372 °C and a glass transition temperature (Tg) of up to 93.8 °C. The structural regularity of the PXAs polymer backbone, combined with their higher molecular weights, resulted in a higher Tg relative to the m-PXAs analogues. Furthermore, the tricyclic unit endowed the polyesters with a superior gas barrier performance. Notably, the PXD film exhibited oxygen (O2) and carbon dioxide (CO2) barrier capabilities that were 3 and 7 times greater than those of polylactic acid (PLA), respectively. All amorphous polyesters allowed efficient recovery of DGX under mild conditions, with a yield of 93% achieved, and the recycled polymers displayed properties comparable to those of the virgin materials, thus demonstrating the potential for closed-loop recycling. This work presents a viable strategy for designing high-performance, sustainable biobased polyesters with end-of-life utility.

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JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS · 2026 · IF 6.7

Integrating TG–FTIR analysis and predictive modeling to elucidate phenolic enrichment in biomass pyrolysis over transition-metal/g-C3N4 catalysts

Yuhang Li,Haifeng Jiang,Jiahao Qi,Junyu Chen,Wenpeng Hong

This study investigated the catalytic pyrolysis of pine sawdust over transition-metal-modified g-C 3 N 4 catalysts (Ni/g-C 3 N 4 , Zn/g-C 3 N 4 , and Co/g-C 3 N 4 ) to enhance phenolic selectivity and elucidate metal–support synergistic effects. Among these catalysts, Co/g-C 3 N 4 exhibited the best performance in enhancing the relative content of phenolic compounds. Compared with non-catalytic pyrolysis at 550 ℃, the phenolic content increased by 24.66%. In addition, the results indicated that a CO 2 atmosphere negatively affected phenolic formation. The temperature-programmed TG-FTIR and evolved-gas analyses revealed that the presence of the Co/g-C 3 N 4 catalyst could promote the formation of CO and limit the generation of CH 4 and C 2 -C 3 hydrocarbons during the catalytic pyrolysis process. The related mechanism analysis showed that the interaction between Co 2 + /Co 3+ species on g-C 3 N 4 and Lewis-basic N sites enabled an interfacial synergistic effect for the selective formation of catechol and methyl-catechol. Furthermore, the exploratory multi-output regression analysis further verified that catalyst type primarily governed phenolic enrichment, whereas temperature mainly influenced syngas formation. Overall, this study provides a deeper understanding of the reaction pathways for the selective generation of phenolic compounds in biomass catalytic pyrolysis, and offers a practical approach for the integration of experimental analysis and data-driven methods.

CAS / MDL: 57-13-6
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POLYMER · 2026 · IF 5.1

1, 3‐Propanediol (PDO)-based biodegradable copolyesters with elevated Tg, improved mechanical properties and spinnability as intrinsic alternatives to PBAT

Chang Liu,Yuming Cui,Yunbo Mo,Qian Xu,Kai Wang,Jianwu Lan,Shaojian Lin

Commercial poly(butylene adipate-co-terephthalate) (PBAT), a biodegradable aromatic–aliphatic copolyester, is considered a promising alternative to conventional plastics in various fields. However, its relatively low mechanical strength and low glass transition temperature (T g ) often restricts broader applications. In this study, bio-based 1,3-propanediol (PDO) was employed to completely replace 1,4-butanediol in PBAT, and a series of poly(trimethylene terephthalate- co -trimethylene adipate) (PPAT) copolyesters were synthesized via melt polycondensation. Structural characterization confirmed the targeted copolyester compositions and random chain segments (R ≈ 1), with intrinsic viscosities of 0.89-1.01 dL/g. Crystallographic analysis revealed that the crystallinity of PPATs varied with the adipic acid/dimethyl terephthalate molar ratio while preserving a monoclinic crystal structure. Notably, PPAT55 exhibited a significantly higher T g (−7.8 °C) than PBAT (−26.1 °C), and all copolyesters showed good thermal stability for melt processing. Importantly, PPAT55 fibers achieved a tensile strength of 0.71 cN/dtex after threefold drawing, representing a 51.06% enhancement over PBAT fibers. Furthermore, the increased aliphatic segment content promoted by hydrolytic susceptibility, as demonstrated by enzymatic degradation tests, with PPAT55 showing a 9.93% mass loss after 42 days, demonstrating satisfactory biodegradability comparable to PBAT. The degradation mechanism was further elucidated at the molecular level through theoretical calculations. This work provides a feasible strategy for developing high-performance sustainable polyester materials with good spinnability.

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PROGRESS IN REACTION KINETICS AND MECHANISM · 2026 ·Vol. 51 ·期 1 · IF 13.8

Pyrolysis kinetics and backbone decomposition mechanisms of nylon 6/6: insights from TG-FTIR-GC/MS and density functional theory

Donghua Xu,Haoyu Xiao,Shengwei Feng,Yingquan Chen,Xianhua Wang,Hanping Chen,Haiping Yang

A limited understanding of the pyrolysis mechanisms hinders the efficient thermochemical conversion and recovery of nylon waste. This study investigates the pyrolysis behavior, volatile evolution, and backbone degradation mechanisms of nylon 6/6 by integrating thermogravimetry-Fourier transform infrared spectroscopy-gas chromatography/mass spectrometry (TG-FTIR-GC/MS) and density functional theory (DFT) calculations. According to TG analysis, nylon 6/6 undergoes pyrolysis mainly in the range of 390–515 °C, with a mass loss of 95.86 wt%, and exhibits the most intense degradation at approximately 480 °C. Kinetic analysis using the Coats-Redfern integral and Achar differential methods indicates that nylon 6/6 pyrolysis follows the first-order reaction model with an apparent activation energy of 278 kJ/mol. Online FTIR and offline GC/MS identify the characteristic gaseous products, including CO2, NH3, 1-amino-5-hexene (13.54%), and cyclopentanone (79.64%). Furthermore, DFT calculations elucidate the electrostatic potential (ESP) distribution, Fukui function indices, and bond dissociation energies (BDEs) of the nylon 6/6 model molecule. Results demonstrate that the nucleophilic attack of the terminal amino group and the free radical attack of H· facilitate the cleavage of the amide structure. The generated hexamethylenediamine and adipic acid segments subsequently undergo deamination and cyclization reactions to form 1-amino-5-hexene and cyclopentanone, respectively. By elucidating the backbone degradation mechanisms and product formation pathways during nylon 6/6 pyrolysis, the multi-scale study provides a theoretical basis for the recovery of high-value fuels and chemicals from nylon waste.

CAS / MDL: 32131-17-2
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FUEL · 2019 · IF 5.128

A novel method for precise measurement of unburnt carbon in boiler fly ash by ECSA® based on TG-MS

Rongbin Li,Kai Wei,Qian Huang,Hongde Xia

The unburnt carbon content of fly ash is an important index for evaluating the combustion efficiency of boilers. Measurement by traditional loss-on-ignition (LOI), approximate and elemental analyses causes large errors due to mixing minerals such as portlandites, carbonates, or sulfates with the unburnt carbon. In this paper a new method of Equivalent Characteristic Spectrum Analysis (ECSA®) based on Thermogravimetric Mass Spectrometry (TG-MS) was adopted to determine the unburnt carbon in fly ash. The measuring mechanism, accuracy, superiority, sensitivity, and reliability of ECSA® were discussed. The intrinsic measuring mechanism of ECSA® and its sensitivity were explored through analyzing the reaction characteristics of model compounds that were used to simulate the real fly ash. Five types of real fly ashes collected from boiler plants were used to calibrate and verify the reliability and accuracy of ECSA® method. The ECSA® was finally validated to be more precise and accurate by improving 2 to 3 orders of magnitude in error compared with the LOI and elemental analysis on determining the unburnt carbon in fly ash, and can provide reliable information to assess the operating status of boilers.

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CHEMICAL ENGINEERING SCIENCE · 2026 · IF 5.1

A universal biomass screening model for skeleton activated carbon based on TG data using CR method and peak-splitting technique

Hao Chen,Huimin Gao,Wenbo Jiang,Xiaohua Lu,Hongliang Qian

Skeleton activated carbon retains the natural cellulose skeleton structure of biomass, resulting in a large surface area and green preparation. However, various biomass types make it difficult to obtain which biomass under what conditions the skeleton can be preserved through experiments. Seeking the temperature range where oxidants react preferentially with carbonized lignin over carbonized cellulose is the key to the successful preparation of skeleton activated carbon. Herein, based on the assumption that combining kinetic modeling with peak-splitting technique and generalizing the model enables prediction of whether the biomass can be prepared into skeleton activated carbon and the preparation conditions based solely on its composition. The combination of the CR method and peak-splitting technique can be used to fit biomass’s pyrolysis process and obtain the reaction temperature window between oxidants and carbonized cellulose/lignin. To enhance universal applicability, modified parameters E’ and n were incorporated into the predictive model. Finally, a universal biomass screening model was established by correlating modified parameters with biomass composition, eliminating the need for extensive experimentation in traditional screening processes.

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EUROPEAN POLYMER JOURNAL · 2022 · IF 5.546

Synthesis and characterization of poly(amide-imide)s with high Tg and low CTE derived from isomeric amide-containing diamines

Ge Zhu,Haoji Lao,Feng Feng,Minyan Wang,Xingzhong Fang,Guofei Chen

Two series of poly(amide imide)s (PAIs) based on two novel isomeric amide-containing diamine monomers and different commercial aromatic dianhydrides were synthesized via thermal imidization. These PAIs exhibited excellent T g s ranging from 368 to 431 °C, low coefficients of thermal expansion (CTE) of 6.7–47.2 ppm/K, and good 5% weight loss temperatures ( T d5% s) in N 2 of 494–540 °C, which was attributed to the introduction of rigid backbone and strong intermolecular hydrogen bonding resulted from amide bond. In particular, PAI-1a and PAI-1b displayed well-balanced performance with T g s in the range of 419–431 °C, CTE in the range of 6.7–9.0 ppm/K, and mechanical properties with tensile strengths of 116–125 MPa, tensile moduli of 8.4–8.7 GPa, which could be probably used in flexible displays. In addition, the effects of two isomeric monomers on the properties of films were compared, and it was found that PAI-(1 – 3)a showed higher T g, T d5% and CTE, but lower tensile strength and transparency than PAI-(1 – 3)b .

CAS / MDL: 2351-37-3 122-04-3
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