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Resource utilization of solid waste can aid in gradual substitution of fossil fuels while achieving waste recycling. In this study, residual carbon and ash slag from the coal gasification fine slag were separated by froth flotation, and then was used to prepare Ru/C and ZSM-5 dual catalysts with carbon-rich and ash-rich components as raw materials, respectively. The performance of two catalysts for catalytic upgrading of volatiles from pyrolysis of cow manure (CM) to produce light aromatic hydrocarbons was systematically investigated. The direct pyrolysis products of CM mainly included alcohols, ketones, ethers, and other oxygen-containing compounds. When ZSM-5 was used as the catalyst, the yield of monocyclic aromatic hydrocarbons (MAHs) increased significantly due to the better catalytic cracking and aromatization abilities of ZSM-5 catalyst. However, the yield of phenols in the pyrolysis products improved when Ru/C was used as the catalyst due to the cleavage effect of Ru/C on the C-O bond. When Ru/C and ZSM-5 were used as dual catalysts in relay catalytic pyrolysis of volatiles, the increase in MAHs yield in the pyrolysis product was higher than the total increase obtained under Ru/C and ZSM-5 single catalysis. The possible pathways for the generation of MAHs from CM under Ru/C and ZSM-5 relay catalytic pyrolysis were revealed by the pyrolysis experiment performed on model compounds.
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Hidrocarburos Aromáticos , Estiércol , Bovinos , Animales , Pirólisis , Carbón Mineral , Catálisis , CarbonoRESUMEN
The co-gasification of biomass and coal is helpful for achieving the clean and efficient utilization of phosphorus-rich biomass. A large number of alkali and alkaline earth metals (AAEMs) present in the ash system of coal (or biomass) cause varying degrees of ash, slagging, and corrosion problems in the entrained flow gasifier. Meanwhile, phosphorus is present in the slag in the form of PO43-, which has a strong affinity for AAEMs (especially for Ca2+) to produce minerals dominated by calcium phosphates or alkaline Ca-phosphate, effectively mitigating the aforementioned problems. To investigate the changing behavior of the slag flow temperature (FT) under different CaO/P2O5 ratios, 72 synthetic ashes with varying CaO/P2O5 ratios at different Si/Al contents and compositions were prepared, and their ash fusion temperatures were tested. The effects of different CaO/P2O5 ratios on the FT were analyzed using FactSage thermodynamic simulation. A model for predicting slag FT at different CaO/P2O5 ratios was constructed on the basis of the average molar ionic potential (Ia) method and used to predict data reported from 19 mixed ashes in the literature. The results showed that Ia and FT gradually increased with a decreasing CaO/P2O5 ratio, and the main mineral types shifted from anorthite â mullite â berlinite, which reasonably explained the decrease in ash fusion temperatures in the mixed ash. The established model showed good adaptability to the prediction of 19 actual coal ash FTs in the literature; the deviation of the prediction was in the range of 40 °C. The model proposed between FT and Ia based on the different CaO/P2O5 ratios can be used to predict the low-rank coal and phosphorus-rich biomass and their mixed ashes.
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Cow manure (CM) is a kind of biowaste with potential for heat recovery and energy. The effects of different leaching solvents on the physicochemical structure of CM and the catalysis role of AAEMs on the thermal behavior were studied. TGA experiments showed that the maximum weight loss rate and the peak temperature of hemicellulose and cellulose increased after leaching, while the TG/DTG curve moved to a high temperature direction. The devolatilization index (Di) value of the raw and leaching samples increased with the increase of the heating rate, indicating that the higher heating rate promoted the release of volatile. The treatment with leaching not only removed AAEMs in CM effectively, but also led to a larger specific surface area and pore volume, and reduced the crystallinity of cellulose and crystal size in CM. Na salt and K salt were mainly in water soluble state, while Ca salt and Mg salt were mainly in acid soluble salt. Compared with the change of physical and chemical structure caused by leaching, the removal of AAEMs played a dominant role in the pyrolysis characteristics of the samples. The removal efficiency of AAEMs increased with the strength of acid. Based on Kissinger model, the Eα of Raw-CM, H2O-CM, CH3COOH-CM, HCl-CM, HNO3-CM and H2SO4-CM is 171.30 kJ/mol, 187.58 kJ/mol, 190.86 kJ/mol, 292.10 kJ/mol, 287.79 kJ/mol and 280.69 kJ/mol respectively. Both the raw and leaching samples followed the reaction order mechanism and tended to react according to a higher-order reaction model between n = 1.5 and n = 4. In contrast, CH3COOH is an ideal solvent for leaching pretreatment.
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Estiércol , Pirólisis , Animales , Bovinos , Femenino , Cinética , Solventes , TermogravimetríaRESUMEN
CaO modified with acetic acid solution or sodium hydroxide (H-CaO/OH-CaO) was used to explore the relationship between the physical and chemical properties of CaO and the components of bio-oil during the pyrolysis of rice straw (RS) and model compounds via experiment and density functional theory(DFT) simulation. The results showed that the modification changed the properties of CaO, and thus the catalytic performance on production of bio-oil components. H-CaO with the larger number of strong basic sites (1.10 â¼ 2 times than commercial CaO) and the longer Ca-O bond length showed the better selectivity and performance on formation of ketones (the maximum relative content in bio-oil reached 43 %). The conversion pathway of cellulose/hemicellulose was changed by H-CaO, which promoted the formation of ketones. The easier combining of H-CaO with the pyrolysis primary products due to the longer Ca-O bond was the key to its better performance.
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Coal based solid waste has been recognized as a sustainable raw material for the preparation of high added value materials for wastewater treatment. In this paper, a preparation route was designed for the rapid, efficient, and low-cost preparation of MCM-41 zeolite using coal gasification fine slag as raw material. Functionalization modification of MCM-41 was carried out by grafting amino groups on its surface to improve its application performance. Moreover, the prepared functionalized material is used for bidirectional adsorption of anionic and cationic dyes. The experimental results indicate that MCM-41 zeolite with highly ordered pore structure was rapidly prepared using the advantages of fast heating and strong permeability of microwave synthesis method, with a specific surface area of up to 862.03 m2/g. Amine functionalized MCM-41 exhibits strong adsorption capacity for both cationic and anionic dyes, with maximum adsorption capacities for methylene blue and Congo red being 292.40 mg/g and 354.61 mg/g, respectively. The study of adsorption kinetics and adsorption mechanism indicate that the adsorption process is mainly controlled through chemical adsorption, including electrostatic attraction, hydrogen bonding, and π-π interactions. The results of this study will provide useful references for the use of coal based solid waste to prepare functional materials for the treatment of organic wastewater.
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Carbón Mineral , Dióxido de Silicio , Zeolitas , Colorantes , Adsorción , Microondas , Residuos Sólidos , CinéticaRESUMEN
CO2 hydrogenation coupled with renewable energy to produce methanol is of great interest. Carbon coated In2O3 hollow tube catalysts embedded with ultra-low content ZnO quantum dots (QDs) were synthesized for CO2 hydrogenation to methanol. ZnO-In2O3-II catalyst had the highest CO2 and H2 adsorption capacity, which demonstrated the highest methanol formation rate. When CO2 conversion was 8.9%, methanol selectivity still exceeded 86% at 3.0 MPa and 320 °C, and STY of methanol reached 0.98 gMeOHh-1gcat-1 at 350 °C. The ZnO/In2O3 QDs heterojunctions were formed at the interface between ZnO and In2O3(222). The ZnO/In2O3 heterojunctions, as a key structure to promote the CO2 hydrogenation to methanol, not only enhanced the interaction between ZnO and In2O3 as well as CO2 adsorption capacity, but also accelerated the electron transfer from In3+ to Zn2+. ZnO QDs boosted the dissociation and activation of H2. The carbon layer coated on In2O3 surface played a role of hydrogen spillover medium, and the dissociated H atoms were transferred to the CO2 adsorption sites on the In2O3 surface through the carbon layer, promoting the reaction of H atoms with CO2 more effectively. In addition, the conductivity of carbon enhanced the electron transfer from In3+ to Zn2+. The combination of the ZnO/In2O3 QDs heterojunctions and carbon layer greatly improved the methanol generation activity.
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As an industrial solid waste, coal gasification fine slag (CGFS), which consists of many elements, such as silicon, aluminum, and carbon, could be used as an important resource. Therefore, this solid waste was used as a raw material to prepare high-value-added adsorption material for the treatment of industrial wastewater in this study. A hydrothermal synthesis method was applied to convert CGFS into a Y-type zeolite/carbon porous composite. The effects of time and temperature on the synthesis were studied. XRD, SEM, and other techniques were used to analyze the material and its physicochemical properties. Additionally, the adsorption performance of the material for phenol was studied. The results showed that the composite has better adsorption capacity for phenol than CGFS. The Freundlich model and pseudo-second-order kinetics well fitted the adsorption behavior of the composite, which demonstrated that the adsorption of phenol was dominated by chemical adsorption.
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Fatigue crack fracture is one of the main reasons for the failure of a refractory lining in a coal-water slurry gasifier. To explore the fracture failure behavior of a refractory lining during the operation of a gasifier, the stress intensity factor (SIF) and J-integral at crack front were calculated by the finite element method, and a crack growth model for the refractory was established. At the same time, the effects of different crack length, depth, and angle on the stress and SIF, as well as J-integral distribution around the crack-tip, were presented. The simulation results demonstrated that very large stresses occurring at the crack tip and the distribution regulation of K I and J-integral along the crack front for surface cracks were similar. The maximum values occurred near the two ends of the crack (θ = 0°, 180°), and the minimum values appeared near the deepest crack front (θ = 90°). K I and J-integral values at the same position increase with increasing crack length and depth and decrease with the angle of crack when the a/c was kept constant. Furthermore, J-integral results indicated that excessive crack depths were likely to cause destabilizing crack growth. These results have provided a reliable theoretical basis for fracture analysis and life prediction of the refractory lining in a gasifier.
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As special waste biomass, cow manure (CM) is also the main pollutant in agricultural production. The combination of cow manure and coal is conducive to the sustainable development of energy and the solution to pollution problems. This work aims to investigate the co-gasification reactivity and synergy of cow manure and Meihuajing (MHJ) bituminous coal blends at 800-1100 °C using a thermogravimetric analyzer, and the correlation between char gasification reactivity and its structural characteristics is performed. The results indicate that the sensitivity of gasification reactivity to temperature is gradually weakened with the proportion of CM increasing. The synergistic effect on reactivity was observed in the co-gasification process of CM/MHJ. The addition of CM promoted the synergistic effect obviously at the low carbon conversion level, and the inhibitory effect with the CM addition on the order degree of char carbon structure was enhanced during the co-gasification process according to Raman spectroscopy analysis. The addition of CM promoted the porous structure evolutions, which make the pore size distribution and the specific surface developed remarkable. The changes in carbon and pore structures can be well related to the gasification reactivity. The findings in this study would be helpful in the understanding of the co-gasification synergy mechanism of cow manure and coal blends.
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In this study, the co-pyrolysis characteristics of cow manure (CM) and Meihuajing bituminous coal (MHJ) blends were investigated in detail. The mass loss behavior and gas evolution characteristics of the blends were analyzed online by thermogravimetry-mass spectrometry (TG-MS), and kinetic analysis was performed. The results demonstrate that the addition of CM to the MHJ increases the reactivity of blends, indicating that interaction between the CM and MHJ occurred during co-pyrolysis. For conventional gases, the release order of gases during CM and MHJ blend pyrolysis is H2O, CO2, CO, CH4, H2. For sulfur-containing gases, with increasing proportion of CM, the emissions of H2S, COS, and C4H4S increase and that of SO2 decrease, and the release temperature interval shifts to lower directions. The Coats & Redfern model was used, an increase of activation energy with CM addition was observed. The optimum blending ratio based on the lowest activation energy is CM:MHJ = 1:3 and the activation energy is 41.9 kJ/mol.
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Carbón Mineral , Pirólisis , Animales , Bovinos , Femenino , Cinética , Estiércol , Espectrometría de Masas , TermogravimetríaRESUMEN
A modified high performance liquid chromatographic (HPLC) method was developed for the determination of the five nucleotides (uridine monophosphate (UMP), adenosine monophosphate (AMP), inosine monophosphate (IMP), guanosine monophosphate (GMP) and cytidine monophosphate (CMP)) in infant formula milk powder. The samples were extracted by water, deproteinized by acetic acid and purified with an HLB SPE cartridge. The analytes were separated by a Waters XBrigde Amide column (150 mm×4.6 mm, 3.5 µ m). Acetonitrile, 10 mmol/L sodium dihydrogen phosphate aqueous solution and 0.12%(v/v) phosphoric acid aqueous solution were used as mobile phases with gradient elution. The detection wavelength of photodiode array detector was set at 254 nm. Five linear calibration curves were obtained with correlation coefficients (r2) of 0.9999. The recoveries were determined at three spiked levels ranging from 86.9% to 105.7%. The limits of quantification (LOQs) were from 5.6 mg/kg to 8.0 mg/kg. The intra-day and inter-day precisions were 0.5%-1.7% (n=5) and 0.6%-1.9% (n=9), respectively. The method is simple, effective, accurate and repeatable. It is suitable for thedetermination of the five nucleotides in infant formula milk powder.