Effect of ionic liquids on the microstructure and combustion performance of Shengli lignite.

To ensure the safe transportation and efficient utilisation of lignite, it is important to inhibit its spontaneous combustion. In this study, Shengli lignite (SL+) was used as the research object and ionic liquids (ILs) were used to pretreat the lignite to investigate their effect on the combustion performance of lignite. On this basis, the relationship between the structure and combustion performance of lignite with different structures (heat treatment, oxidation) after ILs treatment was investigated. Results indicated that the combustion of lignite treated with ILs shifted towards higher temperatures. The most pronounced effect was observed in coal samples treated with [BMIM]Cl (1-butyl-3-methylimidazolium chloride), with the maximum combustion rate corresponding to a temperature increase of approximately 57 °C compared to that of the untreated lignite. For the heat-treated lignite, the temperature corresponding to the maximum combustion rate was approximately 38 °C higher than that of the untreated lignite. After [BMIM]Cl treatment, the combustion performance of the heat-treated lignite changed very slightly. In contrast, for oxidised lignite, the temperature corresponding to the maximum combustion rate decreased by approximately 54 °C compared with that of the untreated lignite and increased by approximately 135 °C after treatment with [BMIM]Cl. The characterisation results show that the content of aliphatic hydrogen and oxygen-containing functional groups decreased in the heat-treated lignite, while the content of hydroxyl and carboxyl groups increased in the oxidised lignite. The microstructure of the heat-treated lignite after [BMIM]Cl treatment changed slightly. In contrast, in the oxidised lignite after [BMIM]Cl treatment, the content of hydroxyl and carboxyl groups decreased, whereas the content of ether (C-O-) structures increased. The increased content of ether (C-O-) structures improved the stability of the coal samples. It is believed that the inhibition of lignite combustion is mainly attributed to the high stability of the ether (C-O-) structures. The kinetic analysis demonstrated that the ILs treatment increased the activation energy of lignite combustion.

Adsorption mechanism of methylene blue by magnesium salt-modified lignite-based adsorbents.

The rich pore structure and carbon structure of lignite make it a suitable adsorbent for effectively removing methylene blue (MB) from wastewater. This article reports the preparation of lignite-based adsorbents modified by magnesium salts, and the key factors and adsorption mechanism are analyzed to effectively improve the adsorption performance for MB. The results showed that the lignite was modified by magnesium salts, and the Mg2+ in the magnesium salts had a good binding effect on the oxygen-containing functional groups in the lignite. This improved the adsorption performance of the lignite-based adsorbents for MB. The Mg(NO3)2-modified lignite-based adsorbent showed the best adsorption performance and removal rate of MB (99.33%) when prepared with 8 wt % Mg(NO3)2. Characterization analysis showed that a "-COOMg" structure was formed between Mg2+ in the magnesium salts and the carboxylic acid functional group in the lignite, which was postulated to be the absorption site that promoted the adsorption performance for MB. It is speculated that the MB adsorption mechanism of this lignite-based adsorbent is ion exchange.

A novel and highly efficient Zr-containing catalyst supported by biomass-derived sodium carboxymethyl cellulose for hydrogenation of furfural.

Functional use of biomass based on its structural properties is an efficient approach for the valuable utilization of biomass resources. In this work, carboxymethyl cellulose zirconium-based catalyst (Zr-CMC) was constructed by the coordination between the carboxylic groups in sodium carboxymethyl cellulose (CMC-Na) with transition metal Zr4+. The prepared catalyst was applied into the synthesis of furfuryl alcohol (FAL) by catalytic transfer hydrogenation of biomass-derived furfural (FF) using isopropanol as hydrogen donor. Both the preparation conditions and the reaction conditions of Zr-CMC catalyst were investigated and optimized. The results showed that Zr-CMC was efficient for the reaction with the FF conversion, FAL yield and selectivity reaching to 92.5%, 91.5 %, and 99.0%, respectively, under the mild conditions (90°C). Meanwhile, the Zr-CMC catalyst could be reused at least for five times without obvious decrease in efficiency, indicating the catalyst had excellent stability. With the advantages of sustainable raw materials, high efficiency, and excellent stability, the prepared catalyst is potential for application in the field of biomass conversion.

Effect of the Iron Component on Microcrystalline Structure Evolution of Hydrochloric Acid-Demineralized Lignite during the Pyrolysis Process.

Hydrochloric acid-demineralized Shengli lignite (SL+) and iron-added lignite (SL+-Fe) were thermally degraded using a fixed-bed device to better understand the effect of the iron component on the microcrystalline structure transformation properties of lignite during the pyrolysis process. The primary gaseous products (CO2, CO, H2, and CH4) were detected by pyrolysis-gas chromatography. X-ray diffraction and Raman spectra were adopted to analyze the microcrystalline structure of lignite and chars. The results indicated that the iron component had a catalysis effect on the pyrolysis of SL+ below 602.6 °C. The pyrolysis gases released in the order of CO2, CO, H2, and CH4, and the addition of the iron component did not change the sequences. The iron component promoted the generation of CO2, CO, and H2 in the low-temperature stage. During the high-temperature stage, the iron component inhibited the formation of CO and H2. The formation of CH4 was inhibited by the iron component throughout the pyrolysis process. The evolution characteristics of -OH, C=O, C=C, and C-H functional groups were not significantly affected, and the fracture of aliphatic functional groups and C-O functional groups was inhibited by the iron component during the pyrolysis process. The iron component restricted the spatial regular arrangement tendency of aromatic rings and facilitated the decrease in the small-sized aromatic ring but inhibited the formation of large aromatic rings (≥6 rings) and the content decrease in side chains during the pyrolysis process. Notably, the effects of the iron component on the formation of gaseous products were associated with the microstructure evolution of lignite.

Reusability Investigation of a Ruthenium Catalyst during Ruthenium Ion-Catalyzed Oxidative Depolymerization of Lignite for the Production of Valuable Organic Acids.

A clean and efficient conversion process is essential for the utilization of low-rank coals. Lignite, a typical representative of the low-rank coal family, has huge potential for the production of valuable chemicals via the oxidative depolymerization reaction. Ruthenium ion-catalyzed oxidation (RICO) is an effective route for lignite depolymerization under mild conditions, but the high cost of precious Ru limits the potential large-scale application of RICO. How to recycle and reuse Ru is critical to promote the application of RICO. In this work, a novel and efficient approach for reusing Ru through recycling the solvent mixture containing Ru was established for RICO. First, the influence of different reaction parameters on the depolymerization degree of lignite and benzene polycarboxylic acid (BPCA) yields was investigated. Second, the distribution of Ru in the organic phase (OP), aqueous phase (AP), and residual solid phase (RSP) was analyzed after the RICO reaction. Finally, based on the distribution of Ru in different phases, a novel route of recycling Ru by reusing the Ru-containing solvents was proposed. The results showed that the dosage of RuCl3 and NaIO4 had a significant influence on both the depolymerization degree of lignite and BPCA yields. The distribution of Ru had a close relationship with the depolymerization degree of lignite and the dosage of NaIO4. After the depolymerization reaction, the CCl4 phase containing Ru was reused directly as the solvent for the next run, which could fulfill the reuse of both CCl4 and Ru. The results proved that the Ru-containing CCl4 phase could maintain catalytic performance for 5 runs. This work provides an efficient route to reuse Ru for the RICO depolymerization of lignite into valuable organic acids. As far as we know, this is the first report concerning the recycling and reuse of Ru during the RICO of lignite. This work is important for the application of RICO in lignite depolymerization.

Effects of Water-Soluble Sodium Compounds on the Microstructure and Combustion Performance of Shengli Lignite.

Different water-soluble sodium compounds (NaCl, Na2CO3, and NaOH) were used to treat Shengli lignite, and the resulting effects on the microstructure and combustion performance of the coal were investigated. The results showed that Na2CO3 and NaOH had a significant impact on combustion performance of lignite, while NaCl did not. The Na2CO3-treated lignite showed two distinct weight-loss temperature regions, and after NaOH treatment, the main combustion peak of the sample moved to the high temperature. This indicates that both Na2CO3 and NaOH can inhibit the combustion of lignite, with the latter showing a greater effect. The FT-IR/XPS results revealed that Na+ interacted with the oxygen-containing functional groups in lignite to form a "-COONa" structure during the Na2CO3 and NaOH treatments. It is deduced that the inhibitory effect on combustion of lignite may be attributed to the stability of the "-COONa" structure, and the relative amount is directly correlated with the inhibitory effect. The XRD/Raman analysis indicated that the stability of the aromatic structure containing "-COOH" increased with the number of "-COONa" structures formed. Additionally, experiments with carboxyl-containing compounds further demonstrated that the number of oxygen-containing functional groups combined with Na was the main reason for the differences in the combustion performance of treated lignite.

A General Route of Using Lignite Depolymerized Derivatives for Catalyst Construction: Insights into the Effects of the Derivative Structures and Solvents.

Depolymerization is an emerging and promising route for the value-added utilization of low-rank coal (LRC) resources, and how to use the complex depolymerized mixtures efficiently is of great importance for this route. In this work, we designed the rational route of using depolymerized mixtures from lignite via ruthenium ion-catalyzed oxidation (RICO) depolymerization directly without complex separation to construct a Zr-based hydrogenation catalyst. The prepared catalyst was applied into the catalytic transfer hydrogenation of biomass-derived carbonyl compounds. Meanwhile, a copper-based oxidation catalyst was also constructed via a similar route to investigate the universality of the proposed route. Special insights were given into how the depolymerized components with different structures influenced the performances of the catalysts. The effects of the solvents used during the catalyst preparation (H2O and DMF) were also studied. The results showed that the proposed route using the depolymerized mixtures from lignite via RICO to construct catalysts was feasible for both Zr-based and Cu-based catalysts. The two catalysts prepared gave high efficiency for their corresponding reaction, i.e., the Zr-based catalyst for catalytic transfer hydrogenation of biomass-derived carbonyl compounds and the Cu-based catalyst for selective oxidation of alcohols into aldehydes. Different depolymerized components contributed differently to the activity of the catalyst, and the solvents during the preparation process could also influence the activity of the catalyst. The depolymerized components and the solvents influenced the activities of the Zr-based catalyst mainly via changing the Zr contents, the microenvironment of Zr4+, and the specific areas of the catalyst.

Direct use of the solid waste from oxytetracycline fermentation broth to construct Hf-containing catalysts for Meerwein-Ponndorf-Verley reactions.

The oxytetracycline fermentation broth residue (OFR) is an abundant solid waste in the fermentation industry, which is hazardous but tricky to treat. The resource utilization of the waste OFR is still challenging. In this study, a novel route of using OFR was proposed that OFR was used as the organic ligands to construct a new hafnium based catalyst (Hf-OFR) for Meerwein-Ponndorf-Verley (MPV) reactions of biomass-derived platforms. The acidic groups in OFR were used to coordinate with Hf4+, and the carbon skeleton structures in OFR were used to form the spatial network structures of the Hf-OFR catalyst. The results showed that the synthesized Hf-OFR catalyst could catalyze the MPV reduction of various carbonyl compounds under relatively mild reaction conditions, with high conversions and yields. Besides, the Hf-OFR catalyst could be recycled at least 5 times with excellent stability in activity and structures. The prepared Hf-OFR catalyst possesses the advantages of high efficiency, a simple preparation process, and low cost in ligands. The proposed strategy of constructing catalysts using OFR may provide new routes for both valuable utilization of the OFR solid waste in the fermentation industry and the construction of efficient catalysts for biomass conversion.

Investigation on carbide slag catalytic effect of Mongolian bituminous coal steam gasification process.

Carbide slag may pollute the environment because it is difficult to handle. In this paper, carbide slag without pretreatment served as the new source of calcium and was added to bituminous coal for gasification experiments to realize waste utilization. The gasification experiment after adding carbide slag to bituminous coal enhances H2 production, which reduced the activation energy of the gasification reaction. The results show that the catalytic effect on steam gasification was evident when the carbide slag was added to Mongolian bituminous coal. The coal char at reaction temperature was prepared and characterized by X-ray diffraction (XRD), Raman, Scanning electron microscope (SEM), Transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), and FT-IR spectroscopy. The carbon structure evolution and calcium structure changes of coal char under reaction temperature were studied, and the influence of coal char structure changes on gasification performance was analyzed. The results show that in the coal char added with carbide slag, the oxygen-containing functional groups generated by the polycondensation reaction interacted with calcium to form a calcium-oxygen-carbon complex. The existence of this structure not only leads to the highly uniform dispersion of CaO in the char but also hinders the graphitization process of the char. Highly dispersed CaO and disordered carbon structure significantly improved the reactivity of bituminous coal steam gasification. Si and Al in the bituminous coal affected the dispersion of Ca during steam gasification.

The construction of novel and efficient hafnium catalysts using naturally existing tannic acid for Meerwein-Ponndorf-Verley reduction.

The conversion of carbonyl compounds into alcohols or their derivatives via the catalytic transfer hydrogenation (CTH) process known as Meerwein-Ponndorf-Verley reduction is an important reaction in the reaction chain involved in biomass transformation. The rational design of efficient catalysts using natural and renewable materials is critical for decreasing the catalyst cost and for the sustainable supply of raw materials during catalyst preparation. In this study, a novel hafnium-based catalyst was constructed using naturally existing tannic acid as the ligand. The prepared hafnium-tannic acid (Hf-TA) catalyst was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and thermogravimetry (TG). Hf-TA was applied in the conversion of furfuraldehyde (FD) to furfuryl alcohol (FA) using isopropanol (2-PrOH) as both the reaction solvent and the hydrogen source. Both preparation conditions and the effects of the reaction parameters on the performance of the catalyst were studied. Under the relatively mild reaction conditions of 70 °C and 3 h, FD (1 mmol) could be converted into FA with a high yield of 99.0%. In addition, the Hf-TA catalyst could be reused at least ten times without a notable decrease in activity and selectivity, indicating its excellent stability. It was proved that Hf-TA could also catalyze the conversion of various carbonyl compounds with different structures. The high efficiency, natural occurrence of tannic acid, and facile preparation process make Hf-TA a potential catalyst for applications in the biomass conversion field.

The catalytic effect of calcium and potassium on CO2 gasification of Shengli lignite: the role of carboxyl.

The CO2 gasification of Chinese Shengli lignite (SL) catalysed by K+ and Ca2+ was studied. The results showed that calcium could greatly decrease the gasification reaction temperature of SL, and the gasification reaction rates of acid-treated SL catalysed by calcium were significantly higher than that catalysed by potassium. Kinetic analysis showed that the activation energy of the reaction catalysed by calcium was much lower than that catalysed by potassium, which was the reason for the higher catalytic activity of calcium. Fourier transform infrared characterization showed that, compared with acid-treated SL, the addition of K+/Ca2+ resulted in the significant weakening of C=O bond, and new peaks attributed to carboxylate species appeared. X-ray photoelectron spectroscopy results indicated that the numbers of C=O decreased after the metal ions were added, indicating the formation of metal-carboxylate complexes. Raman characterization showed that the I D1/I G values increased, suggesting more structural defects, which indicated that the reactivity of coal samples had a close relation with amorphous carbon structures. Ca2+ could interact with the carboxyl structure in lignite by both ionic forces and polycarboxylic coordination, while K+ interacted with carboxyl structure mainly via ionic forces.

[Coal Combustion Reactivity of Different Metamorphic Degree and Structure Changes of FTIR Analysis in Pyrolysis Process].

The combustion reaction of raw coals in the air was analyzed withThermal Gravimetric Analyzer 6300 and FTIR (Fourier Transform infrared spectroscopy). The raw coals came from three different sources which were SL lignite, SH bitumite and TT anthracite. The chars were prepared by fixed bed pyrolysis equipment in different reaction temperature. The overlapping peaks were fitted into some sub-peaks by Gaussian function. The aromatic index (R), aromatic structure fused index (D) and organic maturity index (C) were calculated through sub-peaks areas. It showed that three kinds of ignition temperature of SL, SH and TT were 299.3, 408.2 and 441.0 ℃ respectively. The peak temperature of maximum weight loss rate were 348.6, 480.5 and 507.0 ℃ respectively. With the increase of coal rank, both ignition temperature and peak temperature of maximum weight loss rate increased in some degree. The result showed that coal structure was very complex. Vibration absorption peaks of hydroxyl (­OH), aliphatic hydrocarbons (­CH2，­CH3), aromatic (CC), oxygen-containing functional group(CO, C­O) and other major functional groups could be observed in the infrared spectral curves of all samples. With the increase of pyrolysis temperature, infrared vibration absorption peaks of aliphatic hydrocarbons (­CH2­, ­CH3) were gradually decreased. the stretching vibration peak of CO which was at 1 700 cm-1 almost disappeared after coked at 550 ℃. SL samples' absorption peak area infrared curve of oxygen functional groups at 1 000～1 800 cm-1 was more complex. With the increase of coking temperature they changed more significantly compared with others. While peak position and peak intensity for aromatic CC absorption peaks of SH and TT did not change apparently when temperature was changing. Variation trends of main functional groups among three ranks of coals were obviously different with changes of R, D and C values.