Corrosion behavior of co-gasification slag of furfural residue and coal on alumina-silica refractories

Gasification of furfural residue with coal can realize its efficient and clean utilization.But the high alkali metal content in furfural slag is easy to cause the corrosion of gasifier refractory.Two gasification coals with different silica alumina ratio and a furfural residue were selected in the study.The effects of furfural residue additions on corrosion of silica brick,corundum brick,high alumina brick and mullite brick were investigated by using XRD,SEM-EDS and Factsage Software,and the corrosion mechanism was analyzed.With increasing furfural residue addition,the permeability of the slags to high-aluminium-bearing refractories first decreases and then increases,while the permeability on silica brick shows a slight decrease trend.Leucite(KAlSi_(2)O_(6))with high-melting temperature is generated from the reaction of K_(2)O and SiO_(2)in slag with Al_(2)O_(3)in refractories after furfural residue is added,which hinders the infiltration of slag in refractories.Kaliophilite(KAlSiO_(4))of low-melting point is formed when K_(2)O content increases,and this contributes to the infiltration of slag in refractories.The acid-base reaction between slag and silica brick is distinctly occurred,more slag reacts with SiO_(2)in the silicon brick,resulting in a decrease in the amount of slag infiltrating into the silicon brick as furfural residue is added.The corrosion of silica brick is mainly caused by the acid-base reaction,while the corrosion of three alumina based refractory bricks of corundum,mullite and high alumina brick is determined by slag infiltration.A linear correlation between the percolation rate and slag viscosity is established,the slag permeability increases with decreasing viscosity,resulting in stronger permeability for the high Si/Al ratio slag with lower viscosity.

A critical review on direct catalytic hydrogasification of coal into CH_(4):catalysis process configurations,evaluations,and prospects

Coal catalytic hydrogasification(CCHG)is a straightforward approach for producing CH_(4),which shows advantages over the mature coal-to-CH_(4) technologies from the perspectives of CH_(4) yield,thermal efficiency,and CO_(2) emission.The core of CCHG is to make carbon in coal convert into CH_(4) efficiently with a catalyst.In the past decades,intensive research has been devoted to catalytic hydrogasification of model carbon(pitch coke,activated carbon,coal char).However,the chemical process of CCHG is still not well understood because the coal structure is more complicated,and CCHG is a combination of coal catalytic hydropyrolysis and coal char catalytic hydrogasification.This review seeks to shed light on the catalytic process of raw coal during CCHG.The configuration of suitable catalysts,operating conditions,and feedstocks for tailoring CH_(4) formation were identified,and the underlying mechanisms were elucidated.Based on these results,the CCHG process was evaluated,emphasizing pollutant emissions,energy efficiency,and reactor design.Furthermore,the opportunities and strategic approaches for CCHG under the restraint of carbon neutrality were highlighted by considering the penetration of“green”H2,biomass,and CO_(2) into CCHG.Preliminary investigations from our laboratories demonstrated that the integrated CCHG and biomass/CO_(2) hydrogenation process could perform as an emerging pathway for boosting CH_(4) production by consuming fewer fossil fuels,fulfilling the context of green manufacturing.This work not only provides systematic knowledge of CCHG but also helps to guide the efficient hydrogenation of other carbonaceous resources such as biomass,CO_(2),and coal-derived wastes.

Recycling and utilization of coal gasification residues for fabricating Fe/C composites as novel microwave absorbents

Under the background of a transformation of the global energy structure,coal gasification technology has a wide application prospect,but its by-product,the coal gasification residue(CGR),is still not being efficiently utilized for recycling.The CGR contains abundant carbon components,which could be applied to the microwave absorption field as the carbon matrix.In this study,Fe/CGR composites are fabricated via a two-step method,including the impregnation of Fe^(3+)and the reduction process.The influence of the different loading capacities of the Fe component on the morphology and electromagnetic properties is studied.Moreover,the loading content of Fe and the surface morphology of the Fe/CGR can be reasonably controlled by adjusting the concentration of the ferric nitrate solution.Meanwhile,Fe particles are evenly inserted on the CGR framework,which expands the Fe/CGR interfaces to enhance interfacial polarization,thus further improving the microwave-absorbing(MA)properties of composites.Particularly,as the Fe^(3+)concentration is 1.0 mol/L,the Fe/CGR composite exhibits outstanding performance.The reflection loss reaches-39.3 dB at 2.5 mm,and the absorption bandwidth covers 4.1 GHz at 1.5 mm.In this study,facile processability,resource recycling,appropriately matched impedance,and excellent MA performance are achieved.Finally,the Fe/CGR composites not only enhance the recycling of the CGR but also pioneer a new path for the synthesis of excellent absorbents.

Free radicals trigger the closure of open pores in lignin-derived hard carbons toward improved sodium-storage capacity

The chemical activation of various precursors is effective for creating additional closed pores in hard carbons for sodium storage.However,the formation mechanism of closed pores under the influence of pore-forming agents is not well understood.Herein,an effective chemical activation followed by a high-temperature self-healing strategy is employed to generate interconnected closed pores in lignin-derived hard carbon(HCs).By systematic experimental design combined with electron paramagnetic res-onance spectroscopy,it can be found that the content of free radicals in the carbon matrix influences the closure of open pores at high temperatures.Excessively high activation temperature(>700 C)leads to a low free radical concentration,making it difficult to achieve self-healing of open pores at high tempera-tures.By activation at 700°C,a balance between pore making and self-healing is achieved in the final hard carbon.A large number of free radicals triggers rapid growth and aggregation of carbon microcrys-tals,blocking pre-formed open micropores and creating additional interconnected closed pores in as-obtained hard carbons.As a result,the optimized carbon anode(LK-700-1300)delivers a high reversible capacity of 330.8 mA h g^(-1) at 0.03 A g^(-1),which is an increase of 86 mA h g^(-1) compared to the pristine lignin-derived carbon anode(L-700-1300),and exhibits a good rate performance(202.1 mA h g^(-1) at 1 A g^(-1)).This work provides a universal and effective guidance for tuning closed pores of hard carbons from otherprecursors.

Alkyl-tetralin base oils synthesized from coal-based chemicals and evaluation of their lubricating properties

Naphthenic base oil is an important lubricating base oil and very scarce in the global petroleum resources.Herein,a series of alkylated tetralin fluids similar to naphthenic base oils were produced by the alkylation of tetralin and a-olefins(n-hexene,n-octene,n-decene)with ionic liquid Et_3NHCl/AlCl_(3)as the catalyst,where the applied raw materials are totally derived from the coal chemical industry.The product composition could be controlled by adjusting the feeding ratio of tetralin and olefin.The synthetic fluids were evaluated as lubricating base oils to reveal the structure-property correlations.Their principal physicochemical and tribological properties depend on the chain-length of a-olefins and the number of alkyl groups onto the aromatic rings.Bis-(octyl-or decyl-)alkyl tetralin exhibited good properties in terms of viscosity,thermo-oxidation stability and pour point,as well as friction-reducing and anti-wear performance,showing great potential for producing naphthenic base synthetic oils from coal-based chemicals.

Dealuminated Hβ zeolite for selective conversion of fructose to furfural and formic acid

The fructose-to-furfural transformation is facing major challenges in the selectivity and high efficiency. Herein, we have developed a simple and effective approach for the selective conversion of fructose to furfural using Hβ zeolite modified by organic acids for dealuminization to regulate its textural and acidic properties. It was found that citric acid-dealuminized Hβ zeolite possessed high specific surface areas, wide channels and high Brønsted acid amount, which facilitated the selective conversion of fructose to furfural with a maximum yield of 76.2% at433 K for 1 h in the γ-butyrolactone(GBL)-H_(2)O system, as well as the concomitant formation of 83.0% formic acid. The^(13)C-isotope labelling experiments and the mechanism revealed that the selective cleavage of C1–C2 or C5–C6 bond on fructose was firstly occurred to form pentose or C5 intermediate by weak Brønsted acid, which was then dehydrated to furfural by strong Brønsted acid. Also this dealuminized Hβ catalyst showed the great recycling performance and was active for the conversion of glucose and mannose.

A review of the catalytic preparation of mesophase pitch

Because of its high purity and excellent orientation, mesophase pitch is a superior precursor for high-performance car-bon materials. However, the preparation of top-notch mesophase pitch faces challenges. Catalytic polycondensation at low temperat-ures is more favorable for synthesizing mesophase pitch, because it circumvents the high-temperature free radical reaction of other thermal polycondensation approaches. The reaction is gentle and can be easily controlled. It has the potential to significantly im-prove the yield of mesophase pitch and easily introduce naphthenic characteristics into the molecules, catalytic polycondensation is therefore a preferred method of synthesizing highly spinnable mesophase pitch. This review provides a synopsis of the selective pre-treatment of the raw materials to prepare different mesophase pitches, and explains the reaction mechanism and associated research advances for different catalytic systems in recent years. Finally, how to manufacture high-quality mesophase pitch by using a cata-lyst-promoter system is summarized and proposed, which may provide a theoretical basis for the future design of high-quality pitch molecules.

The relationship between the high-frequency performance of supercapacitors and the type of doped nitrogen in the carbon electrode

Nitrogen doping has been widely used to improve the performance of carbon electrodes in supercapacitors,particularly in terms of their high-frequency response.However,the charge storage and electrolyte ion response mechanisms of different nitrogen dopants at high frequencies are still unclear.In this study,melamine foam carbons with different configurations of surfacedoped N were formed by gradient carbonization,and the effects of the configurations on the high-frequency response behavior of the supercapacitors were analyzed.Using a combination of experiments and first-principle calculations,we found that pyrrolic N,characterized by a higher adsorption energy,increases the charge storage capacity of the electrode at high frequencies.On the other hand,graphitic N,with a lower adsorption energy,increases the speed of ion response.We propose the use of adsorption energy as a practical descriptor for electrode/electrolyte design in high-frequency applications,offering a more universal approach for improving the performance of N-doped carbon materials in supercapacitors.

An efficient and mild recycling of waste melamine formaldehyde foams by alkaline hydrolysis

Melamine formaldehyde foam(MFF)generates many poisonous chemicals through the traditional recycling methods for organic resin wastes.Herein,a high MFF degradation ratio of ca.97 wt.%was achieved under the mild conditions(160℃)in a NaOH–H2O system with ammelide and ammeline as the main degradation products.The alkaline solvent had an obvious corrosion effect for MFF,as indicated by scanning electron microscopy(SEM).The reaction process and products distribution were studied by Fourier-transform infrared spectroscopy(FTIR),X-ray photoelectron spectroscopy(XPS),and ^(13)C nuclear magnetic resonance(NMR).Besides,the MFF degradation products that have the similar chemical structures and bonding performances to those of melamine can be directly used as the raw material for synthesis of melamine urea-formaldehyde resins(MUFs).Moreover,the degradation system demonstrated here showed the high degradation efficiency after reusing for 7 times.The degradation process generated few harmful pollutants and no pre-or post-treatments were required,which proves its feasibility in the safe removal or recovery of waste MFF.

Qualitative analysis of aromatic compounds via 1D TOCSY techniques

The aromatic compounds,including o-xylene,m-xylene,p-xylene,and ethylbenzene,primarily originate from the catalytic reforming of crude oil,and have a wide variety of applications.However,because of similar physical and chemical properties,these compounds are difficult to be identified by gas chromatography(GC)without standard samples.With the development of modern nuclear magnetic resonance(NMR)techniques,NMR has emerged as a powerful and efficient tool for the rapid analysis of complex and crude mixtures without purification.In this study,the parameters of one-dimensional(1D)total correlation spectroscopy(TOCSY)NMR techniques,including 1D selective gradient TOCSY and 1D chemicalshift-selective filtration(CSSF)with TOCSY,were optimized to obtain comprehensive molecular structure information.The results indicate that the overlapped signals in NMR spectra of nonpolar aromatic compounds(including o-xylene,m-xylene,p-xylene and ethylbenzene),polar aromatic compounds(benzyl alcohol,benzaldehyde,benzoic acid),and aromatic compounds with additional conjugated bonds(styrene)can be resolved in 1D TOCSY.More importantly,full molecular structures can be clearly distinguished by setting appropriate mixing time in 1D TOCSY.This approach simplifies the NMR spectra,provides structural information of entire molecules,and can be applied for the analysis of other structural isomers.

The application of molecular simulation in ash chemistry of coal

One of the crucial issues in modern ash chemistry is the realization of efficient and clean coal conversion.Industrially,large-scale coal gasification technology is well known as the foundation to improve the atom economy.In practice,the coal ash fusibility is a critical factor to determine steady operation standards of the gasifier,which is also the significant criterion to coal species selection for gasification.Since coal behaviors are resultant from various evolutions in different scales,the multi-scale understanding of the ash chemistry is of significance to guide the fusibility adjustment for coal gasification.Considering important roles of molecular simulation in exploring ash chemistry,this paper reviews the recent studies and developments on modeling of molecular systems for fusibility related ash chemistry for the first time.The discussions are emphasized on those performed by quantum mechanics and molecular mechanics,the two major simulation methods for microscopic systems,which may provide various insights into fusibility mechanism.This review article is expected to present comprehensive information for recent molecular simulations of coal chemistry so that new clues to find strategies controlling the ash fusion behavior can be obtained.

Mineralogy,distribution,occurrence and removability of trace elements during the coal preparation of No.6 coal from Heidaigou mine

Optical microscopy and scanning electron microscopy in conjunction with energy dispersed X-ray spectrometry(SEM–EDX)were used to study the minerals and the concentrations of 33 trace elements in No.6 coal from Heidaigou mine.The distributions,organic affinity and removability of 18 trace elements were studied by float-sink experiments.A determination of the maceral groups was also undertaken.A high mineral content,dominated by kaolinite,was found in No.6 coal from Heidaigou mine.The bauxite content was relatively high and it was mainly present as individual particles in fusinite lumens or was intimately intergrown with carbonate minerals.The pyrite and quartz contents were low.Some marcasite with a parallel twin structure was observed by cross-polar reflected light.A small amount of bean-like goyazite was present in the calcite.The weighted trace element content in Heidaigou formations is relatively low,which is beneficial for coal processing and utilization.The concentrations of Ga,Hg,Pb,Se,Th,Ta are relatively high compared with the average values of Chinese coals.As,Hg,Mo,Ge,Ga,Ta,Ti,W,Mn are mainly present in minerals while B,Be,Th,P,Sc,Sr,V,Y,Yb are mainly found in organic matter.As,Ge,Hg,Mo are mainly present in sulfides and Be,Th,P,Sc,Sr,Y,Yb are mainly present in inertinite.B and V are mainly present in vitrinite.The high organic affinity and the low theoretical removability of most trace elements cause difficulties in removing them during coal preparation.

Influence of coal blending on mineral transformation at high temperatures

Transformation of mineral matter is important for coal utilization at high temperatures.This is especially true for blended coal.XRD and FTIR were employed together to study the transformation of mineral matter at high temperature in blended coals.It was found that the concentration of catalytic minerals, namely iron oxides, increases with an increasing ratio of Shenfu coal, which could improve coal gasification.The transformation characteristics of the minerals in blended coals are not exactly predictable from the blend ratio.This was proved by comparing the iron oxide content to the blending ratio.The results from FTIR are comparable with those from XRD.FTIR is an effective method for examining variation in mineral matter.

Mechanisms and characteristics of mesocarbon microbeads prepared by co-carbonization of coal tar pitch and direct coal liquefaction residue

DCLR-P was prepared by direct coal liquefaction residue (DCLR) with ash removal.In the present experiments,mesocarbon microbeads (MCMBs) were prepared by co-carbonization of coal tar pitch (CTP) and DCLR-P.With the increase of DCLR-P content,the yield of MCMBs increased from 47.8% to 56.8%.At the same time,the particle sizes distribution of MCMBs was narrowed,resulting in the decrease of D9o/D10 ratio from 154.88 to 6.53.The results showed that DCLR-P had a positive effect on the preparation of MCMBs.1H-NMR,FTIR,SEM and XRD were used to analyze the mechanisms and characteristics of MCMBs prepared by co-carbonization of CTP and DCLR-P.The results showed that the Proton Donor Quality Index (PDQI) of DCLR-P was 13.32,significantly higher than that of CTP (0.83).This indicated that DCLR-P had more naphthenic structure than CTP,which leads to hydrogen transferring in polycondensation reaction.The aliphatic structure of DCLR-P can improve the solubility and fusibility of mesophase,thereby making the structure of MCMBs more structured.The microstructure of the graphitized MCMBs had a substantially parallel carbon layer useful for its electrical performance.The performance of graphitized MCMBs as a negative electrode material for Li-ion batteries was tested.The particle sizes,tap density,specific surface area and initial charge-discharge efficiency of graphitized MCMBs met the requirements of CMB-I in GB/T-24533-2009.However,the initial discharge capacity of graphitized MCMB was only 296.3 mA h g-1 due to the low degree of graphitization of MCMBs.

The distribution and occurrence of mercury in Chinese coals

Mercury is one of the most concerned hazardous elements in coals. 1018 coal samples of different coal-forming periods, coal-accumulating areas and coal ranks all over the country were collected to study the distributions of mercury in Chinese coals. The modes of occurrence of mercury were studied with float-sink experiments of 10 coals from different basins in China and correlation analyses were conducted between concentrations of mercury and maceral and sulfur contents, as well as the ash yield. The theoretic concentrations and affinities of mercury in vitrinite, inertinite, clay and pyrite were then calculated following the methods proposed by Solari. The weighted average concentration of mercury in Chinese coals is 0.154 ~tg/g, which is similar to that in the word coals in general. The mercury concentrations vary largely in the coals of different coal-forming period and coal-accumulating areas as geological settings play key roles in deter- mining the geochemistry of mercury. The concentrations of mercury in coals from south and southwest China and those from North China of C3-P1 are relatively higher while those from North China of Jm-a and Northeast of J3-K1 relatively lower. The general distribution trends of mercury are very similar to that of ash yield, sulfur contents in coals. Pyrite is the dominant carrier of mercury in most coals, especially in some high-sulfur coals with abundant epigenetic pyrite formed during diagenesis and metamorphism. Mercury has higher affinity to vitrinite than to inertinite in most coals, which accords with the geological origin of macerals and geochemistry of mercury.

Modification of ash flow properties of coal rich in calcium and iron by coal gangue addition

Flow property of coal ash and slag is an important parameter for slag tapping of entrained flow gasifier.The viscosity of slag with high contents of calcium and iron exhibits the behavior of a crystalline slag,of which viscosity sharply increases when temperature is lowered than temperature of critical viscosity(TCV).The fluctuation in temperature near the TCVcan cause an accumulation of slag inside the gasifier.In order to prevent slag blockage,it is necessary to adjust the ash composition by additive to modify the flow property of coal rich in calcium and iron.Main components of coal gangue are Al_(2)O_(3) and SiO_(2),which is a potential additive to modify the ash flow properties of these coals.In this work,we investigated the ash flow properties of a typical coal rich in calcium and iron by adding coal gangue with different SiO_(2)/Al_(2)O_(3)ratio.The results showed that the ash fusion temperatures(AFTs)firstly decreased,and then increased with increasing amount of coal gangue addition.Chemical composition of coal ash rich in calcium and iron moved from gehlenite primary phase to anorthite,quartz and corundum primary phases.The slags with coal gangue addition behaved as a glassy slag,of which the viscosity gradually increased as temperature decreased.Besides,a high SiO_(2)/Al_(2)O_(3)ratio of coal gangue was beneficial to modify the slag viscosity behavior.Addition of coal gangue with a high SiO_(2)/Al_(2)O_(3)ratio impeded formation of crystalline phases during cooling.This work demonstrated that coal gangue addition was an effective way to improve the ash flow properties of the coal rich in calcium and iron for the entrained flow gasifier.

Distribution and occurrence of trace elements in the No.14 coal from the Huolinhe mine

Optical microscopy, and scanning electron microscopy in conjunction with energy dispersed X-ray spectrometry （SEM-EDX）, have been used to study the minerals and the concentrations of 12 trace elements in the No.14 coal from the Huolinhe mine, Inner Mongolia China. The distribution, affinity and removability of the trace elements were studied by float-sink experiments and petrological methods. A high mineral content, dominated by clay minerals, was found in the No.14 coal from the Huolinhe mine. The concentrations of As, Sb and Hg are relatively high compared to the average values for Chinese coals. As, Cr, Hg, Li, Mn, Pb are mainly associated with the minerals while Cd, Co, Ni, Sb, and Se are evenly distributed between the minerals and the organic matter. Be and Ba are mainly distributed in the minerals with a minor proportion in the organic matter. Most elements have a low organic affinity, although Sb, Se, Co, Cd, Ni are closely integrated with the organic matter. High theoretical removabilities are indicated for most trace elements. So it may be possible to lower the concentrations of trace elements during coal preparation.

Composition of phenolic compounds in wastewater from the fixed-bed gasification of Baishihu coal

Crude phenols extracted using organic solvent from the wastewater of a typical fixed-bed gasification process was used as a raw material,and the distillation range was analyzed.The wide and narrow fractions of the raw material derived from distillation range analysis were cut using a real boiling point distillation device.The phenolic compounds in the different fractions were then qualitatively and quantitatively analyzed by gas chromatography after derivatization pretreatment.The yield of the<290℃fraction was 68.50%(mass fraction).A total of 33 effective phenolic compounds were identified in this fraction,and the percentage of identified phenols was nearly 80%.The contents of eight phenolic compounds were high,with phenol being the most abundant(26.34%)followed by catechol(13.44%).The contents of the remaining six abundant phenols ranged from 4%to 8%.The sum of the contents of m-cresol and p-cresol exceeded 12%,and the content of 5-indenol was nearly 8%.The yield of the fraction rich in low-grade phenols(<230℃)was 35.40%.The content of phenol in this fraction was more than 40%,the total content of cresol was over 23%,and the total content of m-cresol and p-cresol was nearly 20%.At room temperature,the 235-245℃and 245-260℃fractions were white crystals in which the catechol content was approximately 50%,and the 5-indenol content was more than 10%.The contents of these two high-value-added phenolic compounds are low in typical coal tar,making them difficult to extract.However,due to their strong polarity and good water solubility,catechol and 5-indenol are enriched in gasification wastewater by water selection,allowing their further extraction.

Effects of surface chemical properties of activated coke on selective catalytic reduction of NO with NH_3 over commercial coal-based activated coke

Surface chemical properties of typical commercial coal-based activated cokes were characterized by Xray photoelectron spectroscopy(XPS) and acid-base titration, and then the influence of surface chemical properties on catalytic performance of activated cokes of NO reduction with NH3 was investigated in a fixed-bed quartz micro reactor at 150 ℃. The results indicate that the selective catalytic reduction(SCR) activity of activated cokes with the increase of its surface acidic sites and oxygen content,obviously, a correlation between catalytic activity and surface acidic sites content by titration has higher linearity than catalytic activity and surface oxygen content by XPS. While basic sites content by acid-base titration have not correlation with SCR activity. It has been proposed that surface basic sites content measured by titration may not be on adjacent of acidic surface oxides and then cannot form of NO2-like species, thus the reaction of reduction of NO with NH3 have been retarded.

Study on reaction characteristics of phenolic hydroxyl in coal by using the model compound during direct coal liquefaction

The reaction characteristics of phenolic hydroxyl group were studied under the conditions of direct coal liquefaction. 2-naphthol was used as a coal model compound in this study. Under the conditions of with and without catalysts, a series of experiments were conducted at different temperatures, pressures and reaction time. Gas chromatography-mass spectrometry and gas chromatography were used to identify and quantify the reactants and products respectively. The conversion of 2-naphthol rises with the increase of reaction temperature, initial pressure and catalyst amount. The results indicated that tem- perature had a significant effect on 2-naphthol conversion, which promoted the dehydroxylation reaction. However, initial pressure had an important influence on the hydrogenation of 2-naphthol and naphthalene. The iron catalyst plays a significant role of cracking instead of hydrogenation. It is concluded that the harsh reaction conditions of high temperature, high pressure, and more catalyst are conducive to promoting dehydroxylation of 2-naphthol. The reaction mechanism was put forward based the experimental results, in which 2-tetralone was an intermediate.