Effects of ion-exchanged calcium, barium and magnesium on cross-linking reactions during direct liquefaction of oxidized lignite

In this work the influences of alkaline earth metals on cross-linking reactions (CLRs) during direct liquefaction of lignite were investigated. The oxidized lignite, which has been proved to be appropriate for quantitatively examine the extent of CLR during direct liquefaction, was used as a model coal to study the effects of ion-exchanged calcium, barium and magnesium on CLR during direct liquefaction of the oxidized lignite. The amounts of tetrahydrofuran (THF) insoluble solid products after liquefaction were used to quantitatively evaluate the CLR during liquefaction of the ion-exchanged coal. The results show that the oxidized coal is appropriate to quantitatively examine the extent of CLR and the targeted ions are exchanged to the oxidized coal in the form of highly-dispersed ion. The ion-exchanged Mg^2 + suppresses the CLR during direct liquefaction of coal at both low and high temperature. However, the exchanged Ca^2 + always promotes the CLR at the selected temperatures. While the exchanged Ba^2 + promotes the CLR at low temperature, but suppresses it at high temperature.     

Approach for promoting liquid yield in direct liquefaction of Shenhua coal

Single and multi-stage liquefaction of Shenhua (SH) bituminous coal and re-liquefaction of its liquefaction residue (SHLR) were carried out in an autoclave reactor to investigate the essential approach for promoting oil yield and conversion in SH coal direct liquefaction (SHDL). The multi-stage liquefaction includes pretreatment, keeping the reactor at 250 °C for 40 min before heating up to the reaction temperature, and two-stage liquefaction processes consisting of low temperature stage, 400 °C, and high temperature stage, 460 °C. The results show that the pretreatment has slight effect on oil yield and conversion of SHDL, especially for liquefaction at 460 °C. There is a positive function of two-stage liquefaction in shortening reaction time at high temperature. Increasing ratio of solvent to SHLR can promote the oil yield and abate reaction condition in SHLR re-liquefaction, that is, it can promote the conversion from preasphaltene and asphaltene to oil. The primary factor to inhibit coal liquefaction is the consumption of hydrogen free radical (H·) from solvent or H₂ and condensation of free radicals from coal pyrolysis after a period of reaction. So the essential approach for increasing oil yield and conversion of SHDL is to provide enough H· to stabilize the free radicals from coal pyrolysis.     

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.     

Synergies in co-pyrolysis of Thai lignite and corncob

The results from TGA experiments at the temperature range of 300–600 °C evidently distinguished the different pyrolysis behaviours of lignite and corncob; however, no clear synergistic effects could be observed for the mixture. The investigation of co-pyrolysis in a fixed-bed reactor, however, found significant synergies in both pyrolysis product yields and gas product compositions. The solid yield of the 50:50 lignite/corncob blend was much lower (i.e. 9%) than expected from the calculated value based on individual materials under the range of temperatures studied, and coincided with the higher liquid and gas yield. The synergistic effect in product gas composition was highly pronouncing for CH₄ formation, i.e. three times higher than the calculated value at 400 °C. Possible mechanisms were described including the interaction between corncob volatiles and lignite particles, and the effect of the heat profiles of lignite and corncob pyrolysis on the temperature dependent reactions. The enhanced devolatilisation of the blend was explained by the transfer of hydrogen from biomass to coal as well as the promotion of low-temperature thermal decomposition of lignite by exothermic heat released from corncob pyrolysis. Moreover, water, which was one of the major components in corncob volatiles produced mainly at around 200–375 °C, can also be expected to act as a reactive agent to promote the secondary tar cracking producing more CH₄.     

Additive effect of tyre constituents on the hydrogenolyses of coal liquefaction residue

A numerous amount of waste tyre is landfilled or dumped all over the world, which causes environmental problems. The coal liquefaction residue (CLR) produced in 30% yield through the process supporting unit of the NEDOL coal liquefaction process. As one of the effective method for processing both CLR and waste tyre, simultaneous hydrogenolyses of these materials was carried out. The synergistic effects to upgrading, such as the increase of oil yield and the decrease of asphaltene yield, were appeared on the hydrogenolyses. However, the interaction between tyre and CLR to synergistic effects was not clarified. In this study, the effects of hydrogen donatable solvent (tetralin) and pressurized gas on the hydrogenolyses of CLR and tyre constituents are discussed. As a result, it was clarified that both tetralin and the pressurized H₂ gas were necessary for the simultaneous hydrogenolyses of CLR and tyre. The hydrogen shuttling from H₂ gas and tetralin was enhanced by the aromatic compounds derived from tyre rubber constituents (styrene-butadiene rubber and natural rubber). The hydrogenation of the heavy oil constituent in CLR was enhanced by carbon black and the inorganic constituents in tyre, such as zinc oxide and sulfur. Accordingly, the synergistic effects on the simultaneous hydrogenolyses of CLR and tyre were appeared because the hydrogen shuttling occurred by the aromatics from tyre rubber constituents, and the hydrogenation was enhanced by carbon black and the inorganic constituents in tyre.     

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.     

Mechanisms leading to process improvements in lignite liquefaction using CO and H2S

Optimum distillate yields from US lignites can be as high on a dry, ash-free basis as those obtained from bituminous coals, but only if the vacuum bottoms are recycled. Lignites are more readily liquefied if the reducing gas contains some carbon monoxide and water, which together with bottoms recycle has proven to yield the highest conversions and the best bench-unit operability. The recycle solvent in the reported tests consisted of unseparated product slurry, including coal mineral constituents. Variability in coal minerals among nine widely representative US low-rank coals did not appear to correlate with liquefaction behaviour. Addition of iron pyrite did, however, improve yields and product quality, as measured by hydrogen-to-carbon ratio. Future improvements in liquefaction processes for lignite must maintain high liquid yields at reduced levels of temperature, pressure, and reaction time whilst using less reductant, preferably in the form of synthesis gas (CO + H₂) and water instead of the more expensive pure hydrogen. Understanding the process chemistry of carbon monoxide and sulphur (including H₂S) during lignite liquefaction is a key factor in accomplishing these improvements. This Paper reviews proposed mechanisms for such reactions from the viewpoint of their relative importance in affecting process improvements. The alkali formate mechanism first proposed to explain the reduction by CO does not adequately explain its role in lignite liquefaction. Other possible mechanisms include an isoformate intermediate, a formic acid intermediate, a carbon monoxide radical anion, direct reaction with lignite, and the activation of CO by alkali and alkaline earth cations and by hydrogen sulphide. Hydrogen sulphide reacts with model compounds which represent key bond types in low-rank coal in the following ways: (1) hydrocracking; (2) hydrogen donor; (3) insertion reactions in aromatic rings; (4) hydrogen abstraction, with elemental sulphur as a reaction intermediate; and (5) catalysis of the water-gas shift reaction. It appears that all of these reaction pathways may be operative when catalytic amounts of H₂S are added during liquefaction of lignite. In bench recycle tests, the addition of H₂S as a homogeneous catalyst reduced reductant consumption as much as three-fold whilst maintaining high yield levels when the reaction temperature was reduced by 60°C. Attainment of the high distillate yield at 400°C was accompanied by a marked decrease in the production of hydrocarbon gases, which normally is a major cause of unproductive hydrogen consumption and solvent degradation via hydrocracking. Processing with synthesis gas and inherent coal moisture using bottoms recycle and H₂S as a catalyst appears to be the most promising alternative combination of conditions for producing liquids from lignite at reduced cost.     

Prediction of coal liquefaction reactivity by solid state 13C NMR spectral data

A method for the deconvolution of ¹³C NMR spectra of coals has been developed by using coal-like model compounds and various lithotypes separated from Yallourn brown coal which is rich in various types of oxygen-functional groups. The spectrum of coal was resolved into 24 peaks which were classified into nine types of carbon-functional group. This analytical method can be applied to all ranks of coal from lignite to anthracite. In addition, the liquefaction data of seven kinds of coal collected from five different countries were obtained by the operation of 1 t/d process support unit and 150 t/d pilot plant NEDOL process liquefaction plants. A good correlation was obtained for every reaction product between structural data derived from solid state ¹³C NMR spectra and liquefaction data of coals. This means that the yields of liquefaction products could be predicted from ¹³C NMR spectral data of coal.     

Kinetics of coal liquefaction during heating-up and isothermal stages

Direct liquefaction of Shenhua bituminous coal was carried out in a 500 ml autoclave with iron catalyst and coal liquefaction cycle-oil as solvent at initial hydrogen of 8.0 MPa, residence time of 0–90 min. To investigate the liquefaction kinetics, a model for heating-up and isothermal stages was developed to estimate the rate constants of both stages. In the model, the coal was divided into three parts, easy reactive part, hard reactive part and unreactive part, and four kinetic constants were used to describe the reaction mechanism. The results showed that the model is valid for both heating-up and isothermal stages of liquefaction perfectly. The rate-controlled process for coal liquefaction is the reaction of preasphaltene plus asphaltene (PAA) to oil plus gas (O + G). The upper-limiting conversion of isothermal stage was estimated by the kinetic calculation.     

Liquefaction of subbituminous coals with a basic nitrogenous model process solvent

Liquefaction reactions in a tubing-bomb reactor have been carried out as a function of coal, coal sampling source, reaction time, atmosphere, temperature, coal pre-treatment, SRC post-treatment and process solvent. Pyridine as well as toluene conversions ranging from 70 to > 90 wt% involving both eastern bituminous and western subbituminous coals are obtained. 1,2,3,4-Tetrahydroquinoline (THQ) has been extensively used as a process solvent under optimized liquefaction conditions of 2:1 solvent: coal, 7.5 MPa H₂, 691 K and 30 min reaction time. Comparisons of THQ with other model process solvents such as methylnaphthalene and tetralin are described. Liquefaction product yield for conversion of subbituminous coal is markedly decreased when surface water is removed from the coal by drying in vacuo at room temperature prior to liquefaction. The effect of mixing THQ with Wilsonville hydrogenated process solvent in the liquefaction of Wyodak and Indiana V coals is described.     

Cold sintering process of Li1.5Al0.5Ge1.5(PO4)3 solid electrolyte

The recently developed technique of cold sintering process (CSP) enables densification of ceramics at low temperatures, i.e., <300°C. CSP employs a transient aqueous solvent to enable liquid phase‐assisted densification through mediating the dissolution‐precipitation process under a uniaxial applied pressure. Using CSP in this study, 80% dense Li_1.5Al_0.5Ge_1.5(PO₄)₃ (LAGP) electrolytes were obtained at 120°C in 20 minutes. After a 5 minute belt furnace treatment at 650°C, 50°C above the crystallization onset, Li‐ion conductivity was 5.4 × 10^?5 S/cm at 25°C. Another route to high ionic conductivities ~10^?4 S/cm at 25°C is through a composite LAGP ‐ (PVDF‐HFP) co‐sintered system that was soaked in a liquid electrolyte. After soaking 95, 90, 80, 70, and 60 vol% LAGP in 1 M LiPF₆ EC‐DMC (50:50 vol%) at 25°C, Li‐ion conductivities were 1.0 × 10^?4 S/cm at 25°C with 5 to 10 wt% liquid electrolyte. This paper focuses on the microstructural development and impedance contributions within solid electrolytes processed by (i) Crystallization of bulk glasses, (ii) CSP of ceramics, and (iii) CSP of ceramic‐polymer composites. CSP may offer a new route to enable multilayer battery technology by avoiding the detrimental effects of high temperature heat treatments.     

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.     

A comparison of spontaneous combustion susceptibility of coal according to its rank

This study investigated spontaneous combustion susceptibility of coal according to the rank. To estimate the spontaneous combustion susceptibility of coal, both crossing-point temperature (CPT) measurement and gas analysis by using gas chromatography (GC) were performed. For the experiment, Eco coal and Kideco coal, Indonesian lignite, and Shenhua coal that is Chinese bituminous coal were used. The lignite such as Eco coal and Kideco coal contains more functional groups that easily react to oxygen more so than Shenhua coal. For this reason, the lignite is more easily oxidized than bituminous coal at low temperature, which results in high O₂ consumption, increase in CO and CO₂ generation, and low CPT. Although the CPT of Eco coal and Kideco coal is identical to each other as they are the lignite, Kideco coal has a lower initial oxidation temperature (IOT) and maximum oxidation temperature (MOT) than those of Eco coal. This means that although each coal has the same rank and CPT, spontaneous combustion susceptibility of coal may vary because the initial temperature of the coal at which oxidation begins may be different due to the substances that participate in oxidation.     

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.     

Rapid liquefaction of Longkou lignite coal by using a tubular reactor under methane atmosphere

Rapid liquefaction of Longkou lignite coal under methane atmosphere was studied in a novel laboratory scale tubular reactor. Experiments were performed at a temperature ranging from 400 to 800 °C, a residence time ranging from 4.5 to 11.2 s and 10–15 MPa (without catalyst). Reactions were also carried out under a nitrogen gas atmosphere at the same reaction conditions. The results indicate that there are synergistic effects between coal and methane at temperatures higher than 600 °C, and the temperature and residence time are the main factors influencing the coal conversion and products distribution. The oil yields reach a maximum of 21.97 (wt.% daf) at 750 °C during 9.0 s.     

Effect of early stages of coal oxidation on its reaction with elemental sulphur

The present research shows how mild oxidation of coal mostly affects the evolution of H₂S produced in the reaction of coal with elemental sulphur. Coal samples oxidized at 30, 50, 80 and 150°C were reacted with sulphur in a temperature-programmed reactor. The H₂S produced in the reaction is very sensitive to the initial stage of the oxidation of coal. The strongest reduction in the amount of H₂S evolved was observed in the samples oxidized at 30°C. This temperature is lower than the one found in most coal storage places. The reaction with elemental sulphur could be used to monitor the initial stages of coal oxidation, which otherwise would be difficult to follow by conventional analytical methods.     

Synthesis of a carbon nanofiber/carbon foam composite from coal liquefaction residue for the separation of oil and water

A carbon nanofiber (CNF)/carbon foam composite was fabricated from coal liquefaction residue (CLR) through a procedure involving template synthesis of carbon foam and catalytic chemical vapor deposition (CCVD) treatment. The high solubility and high pyrolysis yield make CLR a promising carbon precursor for the synthesis of carbon materials using the template method. The carbon foam has cell size of about 500 μm and a porosity as high as 95 vol.%. Fe species naturally present in the CLR disperse homogeneously on the surface of the carbon foam acting as a catalyst in the CCVD process. After the CCVD treatment, the whole surface of the carbon foam is covered by entangled CNFs with external diameters of 20–100 nm and lengths of several tens of micrometers. The obtained CNF/carbon foam composites are effective selective adsorbents in the separation of oil and water, through a combination of hydrophobicity and capillary action.     

Liquefaction mechanism of Wandoan coal using tritium and 14C tracer methods: 2. Liquefaction using 3H labelled gaseous hydrogen

Tritium labelled gaseous hydrogen was used to clarify the role of gaseous hydrogen in coal liquefaction. Wandoan coal was hydrogenated under 5.9 MPa (initial pressure) of ³H-labelled hydrogen and in unlabelled solvents such as tetralin, naphthalene and decalin at 400 °C and for 30 min in the presence or absence of NiMoAl₂O₃ catalyst. Without a catalyst, liquefaction proceeded by addition of the hydrogen from donor solvent. The NiMoAl₂O₃ catalyst enhanced both hydrogen transfer from gas phase to coal and hydrocracking of coal-derived liquids. With NiMoAl₂O₃ catalyst, liquefaction in naphthalene solvent proceeded through the hydrogen-donation cycle: naphthalene → tetralin → naphthalene. The amount of residues showed that this cycle was more effective for coal liquefaction than the direct addition of hydrogen from gas phase to coal in decalin solvent. The ³H incorporated in the coal-derived liquids from gas phase was found to increase in the following order: oil < asphaltenes < preasphaltenes < residue.     

Effect of pre-swelling of coal on its solvent extraction and liquefaction properties

Effects of pre-swelling of coal on solvent extraction and liquefaction properties were studied with Shenhua coal. It was found that pre-swelling treatments of the coal in three solvents, i.e., toluene (TOL), N-methyl-2-pyrrolidinone (NMP) and tetralin (THN) increased its extraction yield and liquefaction conversion, and differed the liquefied product distributions. The pre-swollen coals after removing the swelling solvents showed increased conversion in liquefaction compared with that of the swollen coals in the presence of swelling solvents. It was also found that the yields of (oil + gas) in liquefaction of the pre-swollen coals with NMP and TOL dramatically decreased in the presence of swelling solvent. TG and FTIR analyses of the raw coal, the swollen coals and the liquefied products were carried out in order to investigate the mechanism governing the effects of pre-swelling treatment on coal extraction and liquefaction. The results showed that the swelling pre-treatment could disrupt some non-covalent interactions of the coal molecules, relax its network structure and loosened the coal structure. It would thus benefit diffusion of a hydrogen donor solvent into the coal structure during liquefaction, and also enhance the hydrogen donating ability of the hydrogen-rich species derived from the coal.     

Study on coal liquefaction characteristics of Chinese coals

The New Energy and Industrial Technology Development Organization (NEDO) has implemented the collaborative research work with China Coal Research Institute (CCRI) on the liquefaction of Chinese coals for about 20 years. A total of 53 runs in a 0.1 t/d bench scale coal liquefaction plant installed at the CCRI were made on 27 kinds of coal selected among coals existing throughout China. The bench plant was operated in a direct hydrogenation (DH) mode and NEDOL mode. In the DH mode, 25 MPa of reaction pressure was employed with decrystallized anthracene oil used as the solvent, while 17 MPa of reaction pressure was employed and hydrogenated solvent was used in the NEDOL mode. This study confirmed that the NEDOL mode, which uses comparatively mild in liquefaction conditions, can liquefy each coal with the high oil yield more efficiently, and is capable of liquefying about 60% of inertinite in high inertinite coals.