Co-hydrothermal carbonization of polyvinyl chloride and lignocellulose biomasses: Influence of biomass feedstock on fuel properties and combustion behaviors.

Co-hydrothermal carbonization (co-HTC) of lignocellulose biomass (LB) and chlorinated waste could produce value-added co-hydrochar while simultaneously removing inorganic metal salts and organic chlorine to the liquid phase. However, there is a lack of understanding of the influence of LB feedstocks on the fuel properties and combustion behaviors of co-hydrochars. Therefore, co-hydrochars derived from co-HTC of pine, bamboo, corncob, wheat stalk, and corn stalk with polyvinyl chloride (PVC) at the mass ratio of 9:1 under 260 °C for 30 min were tested. PVC facilitated the hydrolysis, dehydration, and polymerization of LB compositions (hemicellulose, cellulose, soluble lignin, and insoluble lignin). In turn, these LB compositions could prevent PVC aggregation and promote PVC substitution. Hydrochar fragments could coat the PVC surface and hinder its hydrolysis. Interactions between LB compositions and PVC improved the fuel properties and combustion behaviors of co-hydrochars derived from bamboo, corncob, wheat stalk, and corn stalk while decreasing the fuel properties and combustion behaviors of co-hydrochar derived from pine (HC-PPE). Except for HC-PPE, the fuel ratio (fixed carbon/volatile matter) of co-hydrochars increased to 0.90-1.18 and their HHVs reached approximately 17.5-32.45 MJ/kg without an increased risk of chlorine corrosion. The combustion of co-hydrochars was easier and more stable due to their higher ignition and burnout temperatures and lower activation energies. These findings provide comprehensive knowledge of the LB feedstocks influence on fuel properties and combustion behaviors of co-hydrochars, which would contribute to the cost-effective use of LB and chlorinated wastes.

Co-hydrothermal carbonization of polyvinyl chloride and lignocellulose biomasses for chlorine and inorganics removal.

Co-hydrothermal carbonization (co-HTC) of lignocellulose biomass (LB) and chlorinated waste can simultaneously remove organic chlorine and inorganics, however, the interaction mechanisms are unclear owing to the variety of operating conditions and complexity of biomass compositions. Pine, bamboo, corncob, corn stalk, and wheat straw were co-hydrothermally carbonized with polyvinyl chloride (PVC) at the mass ratio of 9:1 for 30 min under 260 °C to explore the fundamental interactions. The synergistic index (SI) of dechlorination efficiency ranged from -20.3 % to 19.9 %, indicating the interaction depended on the content and composition of cellulose, hemicellulose, and lignin in the LB feedstocks. Hydroxyl functional groups in cellulose and soluble lignin dehydration intermediates promoted PVC substitution. The LB fragments prevented PVC aggregation while promoted PVC fragmentation, thereby facilitating dechlorination. The polyaromatic hydrochar derived from insoluble lignin and polymeric hydrochar derived from hemicellulose, cellulose, and soluble lignin can coat the surface of molten PVC and act as significant dechlorination inhibitors. All SI of removal efficiency of inorganics (RE) were positive, ranging from 0.74 % to 154 %, with large variations for different inorganics, indicating that inorganics contents in LB influenced RE significantly. A large amount of water-insoluble/acid-soluble inorganics was removed via a metathesis reaction. Soluble inorganics were dissolved in the process water by HCl leaching.

Growth mechanism of glucose-based hydrochar under the effects of acid and temperature regulation.

Improving the tailorability of hydrochar synthesis is an effective way to enhance its performance and utilization efficiency. In this study, the growth rate, morphology, and molecular structure of hydrochar were controlled by regulating the pH and temperature of the hydrothermal carbonization process. Growth process analysis indicates that hydrochar has three growth periods: induction, rapid, and stable growth periods. It is mainly controlled by 5-hydroxymethylfurfural (HMF), which is formed by converting glucose and its transformation products. The regulation of acid can significantly shorten the induction period of hydrochar, even under low-temperature conditions (<180℃), and increase the growth rate of hydrochar. However, the degree of hydrochar adhesion varies: the lower the temperature, the greater the degree of its adhesion. Molecular structural analysis demonstrates that hydrochar mainly consists of furan structural domains and aromatic clusters, and its surface is rich in oxygen-containing functional groups. The degree at which hydrochar was aromatized was improved by increasing the reaction temperature (160-220℃); whereas the regulation of acid reduced it and increased the content of oxygen-containing functional groups on the hydrochar surface. Based on these results, it is proposed that hydrochar formation has five stages and three growth periods with or without acid regulation.

The Use of Pyrolytic Char Derived from Waste Tires in the Removal of Malachite Green from Dyeing Wastewater.

The organic dye malachite green (MG) poses a potential risk of cancer and fertility loss in humans and aquatic organisms. This study focused on a modified pyrolytic char (PC) derived from waste tires to efficiently remove MG from wastewater. Modified PC has rich -OH functional groups, higher BET (Brunauer-Emmett-Teller) surfaces of 74.4, 64.95, and 67.31 m2/g, and larger pore volumes of 0.52, 0.47, and 0.62 cm3/g for NaOH, Na2CO3, and CaO modification, respectively. The pseudo-second-order model fit the adsorption well, and the maximum equilibrium adsorption capacity was 937.8 mg/g for PC after CaO activation (CaO-PC). NaOH-modified PC (NaOH-PC) showed the best fit with the Langmuir model (R2 = 0.918). It is suggested that alkali-modified waste tire pyrolytic char could be a potential adsorbent for removing MG from dye-containing wastewater.

Interaction of lignin and xylan in the hydrothermal synthesis of lignocellulose-based carbon quantum dots and their application in in-vivo bioimaging.

The complex interaction of lignin, cellulose, and hemicellulose in the hydrothermal degradation progress of lignocellulose, has led to uncertainty in the hydrothermal synthesis of lignocellulose-based CQDs (LC-CQDs). This makes it difficult to identify the specific formation mechanism of LC-CQDs. To simplify the reaction system and comprehensively describe the formation of LC-CQDs, both lignin and hemicellulose, the main hydrothermal degradation products of lignocellulose, were used as precursor to simulate and explore the synthesis of LC-CQDs at different time intervals (2-12 h). First, different lignin models were employed for preparing CQDs to determine the key lignin structure that govern CQDs formation. G-type lignin-model based CQDs were shown to have higher fluorescence intensity than H- and S-type. Then, G-type lignin model and hemicellulose model (xylan) were used simultaneously hydrothermal to prepare LC-CQDs. The analysis shows that the carbon nucleus preferentially formed by the lignin provides growth sites for small molecules degraded from hemicellulose, which gradually grow around the carbon core over time, thus forming a "sunflower" structure of CQDs. The presence of a lignin model could effectively guide the small molecules toward CQDs formation instead of carbonization. Additionally, the CQDs exhibit good in-vivo imaging performance.

Enhancing thermal conductivity and toughness of cellulose nanofibril/boron nitride nanosheet composites.

Generally, the thermal conductivity (TC) of composite based on cellulose nanofibrils (CNF) is improved by adding thermal conductive filler, which inevitably leads to the loss of its mechanical properties. In this work, it is the first to simultaneously improve the toughness and TC of CNF/boron nitride nanosheets (BNNS) composite from the perspective of thermal conductive filler addition and CNF crystal change. The hydrophilic-modified BNNSs were successfully prepared by xylose-assisted ball-milling prior to adding into CNF. Compared with that of CNF film (1.34 W/(m·K)), the in-plane TC of CNF/BNNS composite (12.68 W/(m·K)) increased significantly by 846 % with loading 30 % BNNS. Afterwards, both toughness (8.0 MJ·m-3, increased ~250 %) and TC (14.7 W/(m·K), increased ~16 %) of CNF/BNNS composite were further enhanced significantly by mercerization with 12.5 % NaOH solution. The simultaneously improvement of toughness and TC is unprecedented in related studies, which contributes to the effective preparation of thermal management materials.

Preparation, Properties, and Application of Lignocellulosic-Based Fluorescent Carbon Dots.

Carbon dots (CDs) are a relatively new type of fluorescent carbon material with excellent performance and widespread application. As the most readily available and widely distributed biomass resource, lignocellulosics are a renewable bioresource with great potential. Research into the preparation of CDs with lignocellulose (LC-CDs) has become the focus of numerous researchers. Compared with other carbon sources, lignocellulose is low cost, rich in structural variety, exhibits excellent biocompatibility,[1] and the structures of CDs prepared by lignin, cellulose, and hemicellulose are similar. This Review summarized research progress in the preparation of CDs from lignocellulosics in recent years and reviewed traditional and new preparation methods, physical and chemical properties, optical properties, and applications of LC-CDs, providing guidance for the formation and improvement of LC-CDs. In addition, the challenges of synthesizing LC-CDs were also highlighted, including the interaction of different lignocellulose components on the formation of LC-CDs and the nucleation and growth mechanism of LC-CDs; from this, current trends and opportunities of LC-CDs were examined, and some research methods for future research were put forward.

Fluorescence Enhancement of Lignin-Based Carbon Quantum Dots by Concentration-Dependent and Electron-Donating Substituent Synergy and Their Cell Imaging Applications.

Black liquor is an important pollutant in the pulp industry, but it also has the potential for high-value utilization. In this study, lignin extracted from black liquor was hydrothermally prepared into lignin-based carbon quantum dots (L-CQDs) using a one-pot method. Physicochemical characterization suggested that the L-CQDs exhibited a lamellar core-shell multilayered graphene structure surrounded by oxygen-containing functional groups. The fluorescence intensity of the L-CQDs was strengthened depending on their own concentration dependence and the doping of external groups. The fluorescence intensity of L-CQDs varied between 89.09 and 183.66 under different concentrations, and the most intense fluorescence (183.66) was obtained at 0.1 mg mL-1. At hydroxyl and amino adsorption capacities of 11.08 and 0.98 mmol g-1, the hydroxylated RL-CQDs-5 and aminated NL-CQDs-3 exhibited the highest fluorescence intensities at 689.22 and 605.39, respectively. Moreover, when pristine L-CQDs were sequentially aminated and hydroxylated, the NRL-CQDs' fluorescence intensity reached 1224.92. Cell imaging experiments proved that cells cultivated with NRL-CQDs have brighter fluorescence compared with L-CQDs. The results will render L-CQDs more suitable for practical applications.

Effect of endoglucanase and high-pressure homogenization post-treatments on mechanically grinded cellulose nanofibrils and their film performance.

In this study, the effects of mechanical grinding (G) assisted by endoglucanase (E) and high-pressure homogenization (H) post-treated cellulose nanofibrils (CNFs) and its film properties were investigated. Compared to only mechanical grinding, these two post-treatment processes improved the size uniformity of CNFs in width. The crystallinity of GECNFs was increased by 4.3 % and the resulting film exhibited low oxygen permeability rate (6.33 mL/m2·day). Moreover, the combination post-treatments of enzyme and homogenization improved the tensile strength and transparency of CNFs films from 132.31 MPa, 27.52 %- to 177.99 MPa, 61.75 %, respectively. Besides, a composite of acrylic resin ABPE-10 and GEHCNFs film under negative pressure improved the transparency (85.68 %) and water contact angle (104.11°) of film. This work also provides insight on the relationship between the CNFs morphology and their film properties, which can be used to improve the CNFs film performance and promote future applications of CNFs.

Synergistic Effect and Chlorine-Release Behaviors During Co-pyrolysis of LLDPE, PP, and PVC.

Plastic wastes are environmentally problematic and costly to treat, but they also represent a vast untapped resource for the renewable chemical and fuel production. Pyrolysis has received extensive attention in the treatment of plastic wastes because of its technical maturity. A sole polymer in the waste plastic is easy to recycle by any means of physical or chemical techniques. However, the majority of plastic in life are mixtures and they are hard to separate, which make pyrolysis of plastic complicated compared with pure plastic because of its difference in physical/chemical properties. This work focuses on the synergistic effect and its impact on chlorine removal from the pyrolysis of chlorinated plastic mixtures. The pyrolysis behavior of plastic mixtures was investigated in terms of thermogravimetric analysis, and the corresponding kinetics were analyzed according to the distributed activation energy model (DAEM). The results show that the synergistic effect existed in the pyrolysis of a plastic mixture of LLDPE, PP, and PVC, and the DAEM could well predict the kinetics behavior. The decomposition of LLDPE/PP mixtures occurred earlier than that of calculated ones. However, the synergistic effect weakened with the increase of LLDPE in the mixtures. As for the chlorine removal, the LLDPE and PP hindered the chlorine removal from PVC during the plastic mixture pyrolysis. A noticeable negative effect on dechlorination was observed after the introduction of LLDPE or PP. Besides, the chlorine-releasing temperature became higher during the pyrolysis of plastic mixtures ([LLDPE/PVC (1:1), PP/PVC (1:1), and LLDPE/PP/PVC (1:1:1)]. These results imply that the treatment of chlorinated plastic wastes was more difficult than that of PVC in thermal conversion. In other words, more attention should be paid to both the high-temperature chlorine corrosion and high-efficient chlorine removal in practical. These data are helpful for the treatment and thermal utilization of the yearly increased plastic wastes.

Dechlorination of PVC wastes by hydrothermal treatment using alkaline additives.

Some chemicals were usually utilized in the hydrothermal dechlorination (HTD) of chlorine-containing wastes without revealing their roles. This work intends to investigate the role of chemical additives in the HTD of PVC (polyvinyl chloride). Several chemicals, including Na2CO3, KOH, NaOH, NH3·H2O, CaO and NaHCO3, were added into the PVC HTD process, which was conducted in subcritical Ni2+-containing water at 220°C for 30 min. The results show the alkalinity of additives had notable effects on the dechlorination efficiency (DE) of PVC due to the neutralization between HCl and additives. The most effective additive is Na2CO3, with the maximum DE of 65.12% at a Na2CO3 concentration of 0.025 M in this study. According to SEM, the hydrochar obtained from the HTD with Na2CO3 become more porous and looser than the others did, which contributed to the acceleration of PVC dechlorination. The DE vibration with the concentration of additives was different. For Na2CO3, it was firstly increased and then decreased with Na2CO3 concentration increasing from 0.01 to 0.04 M. For KOH and NaOH, it kept reducing with the concentration increasing from 0.02 to 0.08 M. The drop in DE was ascribed to surface poisoning and a loss in the supported active phase resulting from the formation of metal chloride species. FTIR analysis shows that the elimination of hydrogen chloride was the main route for HTD of PVC. All the results provide some fundamental data to find some cheap but efficient chemicals with aim to recycle the chlorinated organic wastes effectively.

[Raman Lidar measuring tropospheric temperature profiles with many rotational Raman lines].

Due to lower tropospheric aerosols, the Rayleigh and vibrational Raman methods can't measure lower tropospheric temperature profiles accurately. By using N2 and O2 molecular pure rotational Raman scattering signals, lower tropospheric temperature profiles can be gained without influence of lower tropospheric aerosols. So we decide to use a pure rotational Raman Lidar to get lower tropospheric temperature profiles. At present, because the most light-splitting systems of pure rotational Raman Lidar measure temperature by gaining a single rotational Raman line, the signal to noise ratio (SNR) of these Lidar systems are very low. So we design a new kind of Lidar light-splitting system which can sum different rotational Raman lines and it can improve SNR And we can find the sensitivity of the temperature of the ratios of multi rotational Raman lines is as same as single rotational Raman line's through theoretical analysis. Moreover, we can obtain the temperature profiles with good SNR fromthis new the system with a normal laser and a small telescope up to several kilometers. At last, with the new light-splitting system, the lower tropospheric temperature profiles are measured from 0.3 km to 5 km altitude. They agree well with radiosonde observations, which demonstrate the results of our rotational Raman lidar are reasonable.

[Obtaining aerosol backscattering coefficient using pure rotational Raman spectrum].

Atmospheric aerosol backscattering coefficient ratio can be obtained with the ratio of elastic signal to the total rotational Raman backscattering signal without assuming the ratio of aerosol extinction to backscatter. Generally, the intensity ofpartial rotational Raman spectrum lines instead of the total rotational Raman spectrum lines is measured. The intensity of the total rotational Raman spectrum lines is not dependent on the temperature, but the intensity of the partialrotational Raman spectrumlines is dependent on the temperature. So calculating aerosol backscattering coefficient ratio with the intensity of the partial rotational Raman spectrum lines would lead to an error. In the present paper, the change in the intensity sums of different rotational Raman spectrum lines with temperature was simulated and the errors of aerosol backscattering coefficient ratio derived from them were discussed. A new method was presented for measuring aerosol backscattering coefficient ratio, which needed not to measure the intensity of the total rotational Raman spectrum lines. Aerosol backscattering coefficient ratio could be obtained with the atmospheric temperature and a single rotational Raman spectrum line. Finally, a erosol backscattering coefficient ratio profiles of the atmosphere were acquired with the combined Raman lidar of our lab. The results show that there is no need to assume any relation between aerosol backscattering and extinction or to consider any wavelength calibration to determine the aerosol scattering coefficient.