Quantitative study on cross-linking reactions of oxygen groups during liquefaction of lignite by a new model system

Cross-linking reactions (CLR) of oxygen groups during liquefaction of lignite were quantitatively studied by a new model system. Chinese Yitai lignite (YT) was first oxidized by nitric acid at 70 °C and about 98% of the oxidized sample could be dissolved in tetrahydrofuran (THF) at room temperature. Then benzyl alcohol, PhCH₂OH (BA), as a model compound was added into the oxidized coal, also acted as solvent in the subsequent liquefaction. Temperature-programmed reactions (TPR) at liquefaction conditions under hydrogen atmosphere were performed to evaluate the CLR by quantitative analysis of THF-insoluble solid products (THFI) after reaction. Extensive CLR were observed even under high pressure of H₂ at 200-400 °C, and more than 51.7% and 81.2% of the THFS fraction was converted into the THFI at 300 °C with tetralin (TET) and BA as solvent, respectively. The THFI fraction was almost solely caused by the CLR, which makes it possible to quantitatively study the CLR by analyzing the amount of the cross-linked solid products (CSP). The pyrolysis behaviours of CSP and oxidized coal were examined by TG. Other model compounds containing oxygen-functional groups (alcohol, phenol, carboxyl, carbonyl and ether groups) can also be used in this model system to study CLR of oxygen groups in low-rank coals.     

Co-liquefaction of lignite and sawdust under syngas

Individual and co-liquefaction of lignite and sawdust (CLLS) under syngas was performed in an autoclave and the effects of temperature, initial syngas pressure, reaction time and ratio of solvent to coal and biomass on the product distribution of CLLS were studied. Sawdust is easier to be liquefied than lignite and the addition of sawdust promotes the liquefaction of lignite. There is some positive synergetic effect during CLLS. In the range of the experimental conditions investigated, the oil yield of CLLS increases with the increase of temperature, reaction time (10-30 min) and the ratio of the solvent to the feedstock (0-3), but varies little with the increase of initial syngas pressure. Accordingly, the total conversion, the yield of preasphaltene and asphaltene (PA + A) and gas, changes by the difference in operation conditions of liquefaction. The gas products are mainly CO and CO₂ with a few C₁-C₄ components. The syngas can replace the pure hydrogen during CLLS. The optimized operation conditions in the present work for CLLS are as follows: syngas, temperature 360 °C, initial cold pressure 3.5 MPa, reaction time 30 min, the ratio of solvent to coal and sawdust 3:1. Water gas shift reaction occurs between CO in the syngas and H₂O from coal and sawdust moisture during the co-liquefaction, producing the active hydrogen which increases the conversion of liquefaction and decreases the hydrogen consumption.     

Study of the preasphaltenes of coal liquefaction and its hydro-conversion kinetics catalyzed by SO4/ZrO2

The investigation of hydro-conversion behavior of the heavy intermediate products derived from coal direct liquefaction is advantageous to optimize the technological conditions of direct coal liquefaction and improve the oil yield. In this paper, the hydro-conversion of preasphaltenes catalyzed by SO₄²⁻/ZrO₂ solid acid was investigated based on the structural characterization of preasphaltenes and its hydro-conversion products, and the determination of products distribution and the kinetics of preasphaltenes hydro-conversion. The results indicated that the content of condensed aromatic rings increased, and the contents of hydrogen, oxygen and aliphatic side chains of preasphaltenes decreased with the increase of coal liquefaction temperature. The preasphaltenes showed higher hydro-conversion reactivity while SO₄²⁻/ZrO₂ solid acid was used as catalyst. Higher temperature and longer time were in favor of increasing the conversion and the oil + gas yield. The conversion of preasphaltenes hydro-conversion under 425 °C, for 40 min reached 81.3% with 51.2% oil + gas yield. SO₄²⁻/ZrO₂ solid acid was in favor of the catalytic cracking rather than the catalytic hydrogenation in the hydro-conversion of preasphaltenes. The activation energy of preasphaltenes conversion into asphaltenes was 72 kJ/mol. The regressive reactions were only observed at a higher temperature.     

Synthesis of hollandite-type LixMnO2 by Li ion-exchange in molten salt and lithium insertion characteristics

The Li⁺ ion-exchange reaction of K⁺-type α-K_0.14MnO_1.93·nH₂O containing different amounts of water molecules (n = 0-0.15) with a large (2 × 2) tunnel structure has been investigated in a LiNO₃-LiCl molten salt at 300 °C. The Li⁺ ion-exchanged products were examined by chemical analysis, X-ray diffraction, and transmission electron microscopy measurements. The K⁺ ions and the hydrogens of the water molecules in the (2 × 2) tunnels of α-MnO₂ were exchanged by Li⁺ ions in the molten salt, resulting in the Li⁺-type α-MnO₂ containing different amounts of Li⁺ ions and lithium oxide (Li₂O) in the (2 × 2) tunnels with maintaining the original hollandite structure.The electrochemical properties and structural variation with initial discharge and charge-discharge cycling of the Li⁺ ion-exchanged α-MnO₂ samples have been investigated as insertion compounds in the search for new cathode materials for rechargeable lithium batteries. The Li⁺ ion-exchanged α-MnO₂ samples provided higher capacities and higher Li⁺ ion diffusivity than the parent K⁺-type materials on initial discharge and charge-discharge cyclings, probably due to the structural stabilization with the existence of Li₂O in the (2 × 2) tunnels.     

Additive effect of cobalt-exchanged coal on the liquefaction of subbituminous coal

In comparison with the liquefaction (420 °C, with tetralin and elemental sulfur) of the proton-exchanged Adaro subbituminous coal with complex (metallocene or metal carbonyl) of cobalt, nickel or iron, the coal liquefaction was enhanced significantly on the liquefaction of cation (Co²⁺, Ni²⁺ or Fe²⁺) exchanged Adaro coal. However, for several kinds of subbituminous coal, metal cations hardly exchange due to the small content of carboxyl group in coal. Therefore, the simultaneous liquefaction of subbituminous coal and cobalt-exchanged coal were carried out in this study. Further, the simultaneous liquefaction of lower rank and subbituminous coals with Co₂(CO)₈ was carried out to compare the catalytic effect of cobalt derived from either the exchanged coal or Co₂(CO)₈. The catalytic effect of cobalt in the exchanged Morwell brown coal was appeared as the decrease of residue yield on the liquefaction with Yilan subbituminous coal. On the other hand, there was little enhancement on the simultaneous liquefaction of cobalt-exchanged Adaro and Yilan subbituminous coals. Accordingly, it is clarified that the hydroliquefaction of subbituminous coal, which was exchanged cation hardly, was enhanced by the addition of cobalt-exchanged brown coal.     

Pressurised flash drying of Yallourn lignite

A previously developed 1D model of lignite drying for pulverised lignite feeding into a conventional pulverised fuel boiler during the coal milling process is applied to lignite in an entrained flow configuration at elevated pressure. A combustor fired with diesel and air was used to produce a flue gas at 800 °C and 10 atm to flash dry Yallourn lignite at a nominal feed rate of 725 kg/h along a 50 m duct. A coal feeder arrangement was also developed which provides a simple positive feeding device for feeding against a back pressure. The feeder takes as an input coal which is nominally <50 mm and discharges it as a finely divided product with a mean particle size of approximately 1.0-1.5 mm. The comparison between model predictions and measured temperature profiles for the flue gas and final moisture content of the dried coal product showed excellent agreement. Coal moisture was reduced from 67 wt% to between 30 and 40 wt%, depending upon on the coal feed rate and particle size. The small variation in the final outlet temperature observed between the model and experimental results is due to heat losses from the exposed duct work to the environment.     

Preparation of carbon nanofibers/carbon foam monolithic composite from coal liquefaction residue

Carbon nanofibers/carbon foam composites that are made by growing carbon nanofibers (CNFs) on the surface of a carbon foam (CF) have been prepared from coal liquefaction residues (CLR) by a procedure involving supercritical foaming, oxidization, carbonization, and catalytic chemical vapour deposition (CCVD) treatment. These new carbon/carbon composites were examined using SEM, TEM and XRD. The results show that the as-made CF has a structure with cell sizes of 300-600 μm. X-ray diffraction studies show that iron-containing contaminates are present in the CLR. However, these species may act as a catalyst in the CCVD process as established in the literature. After the CCVD treatment, the cell walls of CF are covered by highly compacted CNFs that have external diameters of about 100 nm and lengths of several tens of micrometers. This work may open a new way for direct and effective utilization of the CLR.     

Release of alkali and alkaline earth metallic species during rapid pyrolysis of a Victorian brown coal at elevated pressures

Possible reaction mechanisms responsible for the release of Na and Mg during pyrolysis at elevated pressures are described in this paper. In order to evaluate these mechanisms a Victorian brown coal, Loy Yang coal, was pyrolysed in a wire-mesh reactor at pressures up to 6.1 MPa at a heating rate of 1000 °C s⁻¹. Release of Na and Mg were quantified as functions of temperature and pressure. The results demonstrated that increasing pressure suppresses or promotes release of Na and Mg depending on the combination of pressure and temperature. The results obtained have been explained qualitatively by the proposed reaction mechanisms. At temperatures of 600 °C and lower, the release of Na and Mg from the pyrolysing coal/char particles, as light carboxylates, other organic salts and/or metals, was controlled by their diffusion through the pore system of the particles and, therefore, was suppressed by increasing pressure. At higher temperatures, the release of Na and Mg seems to be affected by the changes in intra-particle mass transfer mechanism due to increasing pressure as well as by chemical reactions responsible for the formation of volatile Na and Mg species.     

Study on the liquefaction of Shengli lignite with NaOH/methanol

The behavior of liquefaction of Shengli (SL) lignite with NaOH-methanol was studied. Based on high content of water in lignite and the economy of the process (amounts of NaOH used), the effects of NaOH concentration, methanol content and water content on the liquefaction behavior of SL lignite were preliminarily investigated. The results show that SL lignite has a good reaction activity, and its conversion and product yield reach 98% and 99% at 300 °C for 1 h respectively, when the ratio of SL lignite, NaOH and methanol is for 1 g:1 g:10 ml. NaOH participates in the reaction. The increase of the amount of NaOH significantly increases the amount of tetrahydrofuran soluble (THFS) fraction. Methanol plays a promotion role in the liquefaction, which makes the product yield increase for about 16-23%. Water content has little effect on the SL lignite conversion, product yield and the product distribution. Solvent-extraction components of liquefaction products of SL lignite with NaOH-methanol are mainly THFS, toluene soluble (TS), hexane soluble (HS) and water soluble fractions (WS). The FTIR analyses of solvent-extraction components show that all of the fractions contain OH group, aromatic structure, carbonyl group and aromatic ether oxygen group.     

An investigation of mercury distribution and speciation during coal combustion

A multi-field electrostatic precipitator (ESP) and a two-stage condensing heat exchanger (CHX^®) have been added to the pilot scale Vertical Combustion Research Facility (VCRF) in CETC-O to further research into integrated emissions control for coal fired power plants. A series of combustion trials were conducted on the VCRF with three different coals (bituminous, sub-bituminous and lignite) to study mercury distribution and speciation at various VCRF locations. Results showed that, with the bituminous coal, as the flue gas cools down from 700 to 200 °C, 80% of total mercury in the gas phase existed in oxidized form and 20% in elemental form. For sub-bituminous and lignite coals, elemental mercury was the dominant form throughout the system. Analysis of deposited ash samples showed that oxidized mercury can be absorbed on carbon-rich ash deposits, although overall only a very small percentage of total mercury was absorbed on the ash. The potential of the CHX^® at removing mercury from the flue gas was also explored. Results indicated that, using wet scrubbing, the CHX^® was able to remove 98% of oxidized mercury. Though elemental mercury went through the system unabated, it is suggested that, with appropriate agent to oxidize elemental mercury in the CHX^®, it is conceivable to use CHX^® to remove both oxidized and elemental mercury. Finally, mercury balance was performed and good mercury balance was obtained across the VCRF, validating our sampling procedures and analysis methods.     

Study on NO heterogeneous reduction with coal in an entrained flow reactor

The effects of coal types with a wide range of volatile matter content including lignite, bituminous coal, and lean coal, as well as the effects of reaction temperature, coal particle size, the primary-zone stoichiometry (SR1) and reburning-zone stoichiometry (SR2), etc. on NO reduction efficiency were carried out systematically in an entrained flow reactor. The heterogeneous NO reduction mechanism was analyzed. The results indicate that the NO reduction efficiencies increase with decreasing SR2 and coal particle size, and with increasing reaction temperature. The char contributions to the total NO reduction efficiency increase with increasing proximate volatile matter, coal particle size, and with decreasing reaction temperature. The char contribution can be reached more than 40% when SR2 is larger than 1.06 or less than 0.92 for XLT lignite. The char contribution at the conditions of SR1 = 1.0 and SR1 = 1.2 is significantly larger than that at SR1 = 1.1 for coals with high-volatile matter at a fixed reburning fraction.     

Dynamic experimental simulation of hydrogen oriented underground gasification of lignite

The main goal of the study presented in the paper was to experimentally demonstrate the feasibility of lignite gasification to hydrogen-rich gas under the underground conditions simulated in the ex situ reactor. The in situ gasification conditions were simulated both in respect to the coal seam and the surrounding stratum. In the 54-h experiment the process of lignite gasification with oxygen and steam as gasifying medium was tested. The experiment was initially divided into three stages: the ignition stage, the oxygen stage and the steam stage.The gas produced in the steam gasification stage was characterized by the calorific value of 7.8 MJ/m³ and average hydrogen content of 46.3 vol.%. Unfortunately a rapid decrease in the temperature levels and in the amount of produced gas proved that the tested lignite of 53 vol.% moisture content was not suitable for steam gasification. A great amount of thermal energy was consumed for water evaporation which led to a considerable heat loss. An addition of stoichiometric amount of water in the system by adding steam caused the seam to extinguish. Thus only oxygen could be used as the gasifying medium in the gasification of the tested lignite. The average calorific value of gas produced in the stable operation during oxygen gasification stage equaled 5.2 MJ/m³ with the average gas production rate of 16.0 m³/h and the average hydrogen content in the produced gas of 26.4 vol.%.     

Hydration of freestanding Nafion membrane in proton and sodium ion exchanged forms probed by infrared spectroscopy

Transmission infrared spectroscopy was used to follow the uptake of water into Nafion 112 (∼50 μm thick) membrane under conditions that enabled detection of vibrational bands for water in different environments inside membrane pores and channels. The evolution of infrared features for interfacial and weakly hydrogen bonded water were followed upon exposure of initially vacuum dried membranes, exchanged by either Na⁺ or H⁺, to low humidity atmospheres. The rapid uptake of water into H⁺ exchanged Nafion 112 precluded time resolved spectral measurements. However, the considerably slower timeframe for water incorporation into Na⁺ exchanged membrane enabled the evolution of different environments for water to be observed. Under approximately 10% relative humidity, the time dependent increases in absorbance for a mode of interfacial water near 3674 cm⁻¹ and a mode of more bulk-like, weakly hydrogen bonded water at 3525 cm⁻¹ in Na⁺ exchanged Nafion 112 could be fit by a pore diffusion model. The results provide a foundation for the application of multivariate analysis techniques to identify different structures that develop in metal cation exchanged Nafion during changes in hydration state.     

Preparation of CuY catalyst using CuCl2 as precursor for vapor phase oxidative carbonylation of methanol to dimethyl carbonate

Cu^IY catalyst was prepared by heating the mixture of CuCl₂ and acidic Y zeolite under flowing nitrogen and characterized by TG/DTG, XRD and elementary analysis techniques. The experimental result indicate that when the heating temperature was from 350 °C to 500 °C, the CuCl₂ of the CuCl₂ and acidic Y zeolite mixture sample decompose to CuCl and Cl₂ gas, then the produced CuCl reacted with the Brønsted acid center H⁺ of Y zeolite to form Cu^IY catalyst by the solid-state ion-exchanged reaction. The amount of ion-exchanged Cu^I in the Cu^IY catalyst reached the maximum of 0.1 mol/g when the heating temperature was 650 °C, and the catalyst exhibited the best catalytic activity, the conversion of methanol (C_MeOH), the selectivity and the space-time yield of dimethyl carbonate (S_DMC and STY) reached 4.36%, 74.55% and 97.32 mg/(g h), respectively.     

水热处理对不同变质程度煤加氢液化反应性的影响

分析了4个温度下水热处理对不同变质程度煤加氢液化反应性的影响。结果表明:(1)200℃²50℃为褐煤和长焰煤加氢液化较好的水热处理温度。(2)在实验条件下,水热处理温度200℃250℃为褐煤和长焰煤加氢液化较好的水热处理温度。(2)在实验条件下,水热处理温度200℃²50℃,褐煤总转化率和油、气产率可达到84.70%和79.29%,沥青烯和前沥青烯产率为5.41%;长焰煤相对应的数据分别为78.2%、70.72%和7.48%。(3)水热处理温度>250℃或<200℃,褐煤和长焰煤液化反应性均降低。     

Combined effects of pressure and ion-exchangeable metallic species on pyrolysis of Victorian lignite

A set of ion-exchanged samples prepared from Loy Yang lignite was pyrolyzed in a wire-mesh reactor at elevated pressures from 1 to 36 bar. The tar yields from the pyrolysis of H-form (acid-washed) sample at a fast heating rate of 1000 °C s⁻¹ were drastically reduced by increasing pressure to 6 bar and then remained unchanged with further increase in pressure to 36 bar. This behavior of the tar yield was in sharp contrast to that from the raw lignite which showed a minimum with increasing pressure. The sensitivities of the tar yields to changes in the heating rate were also suppressed by increasing pressure. The tar yields from Ca-form and Na-form samples (prepared by ion-exchanging Ca and Na on the H-form sample, respectively) were not very sensitive to changes in the heating rate and pressure up to 11 bar. At 20 bar, the tar yields from the Na-from sample nearly doubled whereas from the Ca-form sample nearly halved compared to those respective values at 1 bar. Although increasing pressure is thought to cause changes in the intra-particle mass transfer processes of volatile precursors, the rate of formation of volatile precursors tends to dictate the kind of mass transfer process responsible for the release of volatiles. Therefore, depending on the pyrolysis condition, bulk diffusion or forced flow would dominate the mass transfer processes for the release of volatiles. The introduction of cations is thought to result in irreversible changes in the lignite structure and not only control the process of formation but also the amount of volatile precursors and in turn alter the effects of pressure. Valence and catalytic activity of cations seem to play important roles in determining pyrolysis products distribution at elevated pressures.     

Mass spectrometric investigations on the release of inorganic species during gasification and combustion of Rhenish lignite

To reduce problems such as fouling, slagging and corrosion, which can occur during thermal utilisation of lignite, an enhanced understanding of the underlying release mechanisms for the involved Na-, K-, Cl-, and S-species is needed. Therefore basic investigations have been performed in an atmospheric tube furnace at 1400 °C under gasification and combustion like conditions in lab-scale experiments. Molecular beam mass spectrometry has been used for on-line qualitative and semi-quantitative analysis of the hot product gas. ³⁴H₂S⁺ has been formed during gasification experiments, while has been formed during combustion experiments. ³⁶HCl⁺, ⁵⁸NaCl⁺, ³⁹K⁺ (assumed to be partly a fragment of KCl) have been the main alkali and chlorine species and have been released mainly during pyrolysis phase. Linear correlation analysis has been undertaken to investigate the dependence of coal composition on the release of Na-, K-, Cl, and S-species. The correlations have been found to be similar for both gasification and combustion experiments. The release of ³⁴H₂S⁺ and is in high negative correlation with the Ca/S ratio and in high positive correlation with the S-content of the coals. The release of ³⁶HCl⁺ shows a negative correlation with the Na/S ratio and the Na/Si ratio of the lignite under investigation. The release of ⁵⁸NaCl⁺ depends with negative correlation on the S/Cl ratio and the content of Al + Si of the investigated lignite. The experimental results have been compared with thermodynamic equilibrium calculations. The release of H₂S, SO₂, and NaCl could be predicted with sufficient accuracy, though the release of HCl and K-species could not satisfactorily be predicted.     

Gasification of lignite and hard coal with air and oxygen enriched air in a pilot scale ex situ reactor for underground gasification

The main goal of the study presented in the paper was an experimental comparison of the underground lignite and hard coal seams air gasification simulated in the ex situ reactor. In the study lignite and hard coal were gasified with oxygen, air and oxygen enriched air as gasification agents in the 50- and 30-h experiments, respectively, with an intrinsic coal and strata moisture content as a steam source. Application of air as a sole gasification agent was problematic for a resulting rapid decrease in temperatures, deterioration of gas quality and, finally, cessation of gasification reactions. Use of oxygen/air mixture of an optimum ratio led to valuable gas production. In lignite seam gasification with oxygen/air (of 4:2 volume ratio) the average H₂ and CO contents in product gas were 23.1 vol.% and 6.3 vol.%, respectively, and the calorific value was 4.18 MJ/m³, whereas in hard coal gasification with the oxygen/air ratio (of 2:3 volume ratio) the average H₂ and CO contents in produced gas were 18.7 vol.% and 17.3 vol.%, respectively, and product gas calorific value equaled 5.74 MJ/m³.     

Mesoporous carbon prepared from direct coal liquefaction residue for methane decomposition

Mesoporous carbons (MCs) were directly prepared from direct coal liquefaction residue (CLR) by KOH activation, and used as catalysts for methane decomposition. The results indicated that the prepared MCs were of a narrow pore size distribution centered at about 3.5 nm. The mineral matters in the CLR and their salts formed during KOH activation process served as templates for mesopore formation, through washing off the mineral matters and the salts occupied in the inner space of the carbon. The resultant MCs showed higher and more stable activity in methane decomposition reaction than commercial coal-based activated carbon and carbon black catalysts.     

Preparation of carbon microfibers from coal liquefaction residue

Carbon microfibers (CMFs) were synthesized directly from coal liquefaction residue (CLR) by arc-jet plasma method at atmospheric pressure, and were examined using scanning electron microscopy and EDX spectroscopy. It has been found that the as-synthesized CMFs are smooth in surface and quite uniform in diameter that is smaller than 1 μm and centers at 700 nm. The possible mechanism involved in the formation process of CMFs is proposed and discussed in terms of the special chemical composition of CLR and the process parameters. This work may open a new way for direct and effective utilization of the CLR.