典型碱金属、碱土金属对不同变质程度煤焦溶损反应的催化作用

试验研究发现,添加碱金属、碱土金属对低变质程度煤焦反应性的催化作用小于焦煤等中等变质程度煤焦反应性。它们对焦炭溶损反应的催化作用顺序为：K〉Na〉Ca〉Mg,且随着添加量的增加,催化作用越强。随反应时间和典型金属添加量的增加,以及温度的升高,焦炭转化率越大。     

Fractionation and concentration of kraft black liquor lignin with ultrafiltration

Kraft black liquor lignin is a biofuel that is separated from the cellulose during kraft pulping. Improved technology and energy integration in paper mills have led to an energy surplus at many mills. It is therefore of great interest to extract the lignin from the pulp mill and sell it as fuel to replace fossil fuel in other furnaces. The fractionation of kraft black liquor with a total dry matter content of about 15 wt% has been studied using ultrafiltration. The flux for three polymeric membranes with different cut-offs was investigated as well as their retention of lignin and other process specific substances. The retention of lignin for the three membranes with cut-offs of 4,8 and 20 kDa was 80%, 67% and 45%, respectively. The retention of sulphur and sodium was zero for all three membranes. The purity of the final lignin fuel is of importances as the ash content preferably should be as low as possible. The flux and retention during concentration and diafiltration of the black liquor were therefore studied. The dialfiltration operation was conducted in batch and semicontinuous mode. The lignin purity was 36% in the original kraft black liquor and 78% after semi-continuous dialfiltration.     

红麻硫酸盐法蒸煮中溶出木素的分子量分布及变化

采用凝胶色谱法（GPC）对红麻皮和秆芯硫酸盐法蒸煮过程中溶出木素的分子量及其分布的变化进行了研究。结果表明，随着蒸煮的进行，红麻皮和秆芯溶出木素的平均分子量逐渐增大，多分散性和特性粘数也相应增大。此外，在同一蒸煮条件下，红麻秆芯溶出木素的平均分子量高于红麻皮，这也说明了红麻秆芯比红麻皮更难脱木素。研究还发现，红麻原料木素以及溶出木素的分子量分布曲线都呈单峰现象。     

Molar mass-dependent profiles of functional groups and carbohydrates in kraft lignin

Technical lignins are complex, irregular, polyphenolic compounds obtained in large quantities as by-products of the pulp and paper industries or according to current biorefinery setups. The availability of kraft lignin is increasing due to larger scale retrieval from process liquors, which opens new possibilities for further refining or new applications of such lignins. In the present study, sequential ultrafiltration of kraft lignin was performed to fractionate the lignin and to elucidate molar mass-dependent changes in lignin structure. Two industrial black liquors and three precipitated lignins were fractionated, and their functional groups were determined, providing molar mass-dependent profiles. Interrelations between structural parameters and functional groups, the molecular weight ranges, and the different lignin sources are discussed. This will help to establish structure-property-application relationships (SPARs) for technical lignins which are required for any future large-scale application.     

Behaviour of gaseous chlorine and alkali metals during biomass thermal utilisation

The behaviour of gaseous chlorine and alkali metals of three sorts of biomass (Danish straw, Swedish wood, and sewage sludge) in combustion or gasification is investigated by the chemical equilibrium calculating tool. The ranges of temperature, air-to-fuel ratio, and pressure are varied widely in the calculations (T=400–1800 K, λ=0–1.8, and P=0.1–2.0 MPa). Results show that the air excess coefficient only has less significant influence on the release of gaseous chlorine and potassium or sodium during combustion. However, in biomass gasification, the influence of the air excess coefficient is very significant. Increasing air excess coefficient enhances the release of HCl(g), KOH(g), or NaOH(g) as well as it reduces the formation of KCl(g), NaCl(g), K(g), or Na(g). In biomass combustion or straw and sludge gasification, increasing pressure enhances the release of HCl(g) and reduces the amount of KCl(g), NaCl(g), KCl(g), or NaOH(g) at high temperatures. However, during wood gasification, the pressure enhances the formation of KOH(g) and KCl(g) and reduces the release of K(g) and HCl(g) at high temperatures. During wood and sewage sludge pyrolysis, nitrogen addition enhances the formation of KCN(g) and NaCN(g) and reduces the release of K(g) and Na(g). Kaolin addition in straw combustion may enhance the formation of potassium aluminosilicate in ash and significantly reduces the release of KCl(g) and KOH(g) and increases the formation of HCl(g).     

Transformation of alkali and alkaline earth metals in low rank coal during gasification

Transformation of alkali and alkaline earth metals (AAEM) in low rank coals during gasification was examined by combining computer-controlled scanning electron microscopy (CCSEM) and inductively coupled plasma-atomic emission spectroscopy (ICP-AES). Two sub-bituminous coals were pyrolyzed at 1500 °C using a drop tube furnace, and the resultant chars were then gasified in CO₂ atmosphere at the same temperature. Total amounts of AAEM species in the raw coals and the chars were determined by ICP-AES. Minerals in the raw coals and ash particles in the chars were analyzed by CCSEM.AAEM species were mainly present in the raw coals as dispersed species, organically associated cations or fine mineral particles (<1 μm), which cannot be quantified by CCSEM. It was found that the dispersed Ca species were first converted into fine ash particles upon the devolatilization and then most of the particles interacted with inherent clay minerals to form complex aluminosilicates. In the case of Na and K, the dispersed species mostly vaporized and the interaction with inherent minerals was not observed.     

Speciation and distribution of alkali,alkali earth metals and major ash forming elements during gasification of fuel cane bagasse

Gasification of fuel cane bagasse, the waste residue from fuel cane, a hybrid of wild and commercial clones of sugar cane, was carried out in a novel 50 kWe air-blown autothermal downdraft gasifier. The speciation and distribution of alkali, alkali earth metals and major ash forming elements during gasification were investigated to evaluate the extent of volatilisation of these elements into the syngas and to determine the likely impact on syngas fuelled solid oxide fuel cell systems. Also assessed was the potential for defluidisation of the fuel bed due to agglomerate and deposit formation. Chemical fractionation studies showed that 30% of the potassium was captured by aluminosilicates and was retained in the ash, thereby reducing the alkali loading in the syngas and that more than 50% of the alkali earth metals were released to the syngas. In contrast, although the major ash forming elements were transformed from acid insoluble to acid soluble forms during gasification they remained hard bound in the ash and less than 30% of each one was released into the gas phase. The composition of clinkers and agglomerates produced during gasification was investigated by SEM-EDX and XRD which confirmed the presence of the eutectic systems KAlSi₂O₆–SiO₂, KAlSi₂O₆–CaMgSi₂O₆–SiO₂ and CaMgSi₂O₆–NaAlSi₃O₈. A preliminary model of the distribution behaviour during gasification of the ash forming elements has been developed.     

n-alkylbenzenes and ω-phenylcarboxylic acids from the thermal treatment of fatty acids with kraft lignin

A series of homologousn-alkylbenzenes and ω-phenylcarboxylic acids were detected and identified from the pyrolysis reaction of tall oil fatty acids and several pure fatty acids, respectively, with kraft lignin. Different reaction conditions (e.g., varying amounts of lignin) and different reaction times were applied. Temperatures were kept constant at 280 C. Products were distilled at 0.1 Pa and 150 C. After methylation, the distilled fractions were analyzed by gas chromatography-mass spectrometry (GC-MS). The method of detection and identification of the different substances by GC-MS is described. Pure singly and double unsaturated fatty acids (99.9% gas chromatographic purity) showed reactions to the title products (up to 4% total amount), whereas saturated fatty acids did not react at all. A possible reaction scheme taking quantitative parameters into account is suggested.     

碱木素分子量及其分布的GPC表征

采用水溶性凝胶渗透色谱测定了碱水素的分子量特征,并对影响分子量分布测定的因素进行了探讨。结果发现,所用流动相的酸度对碱木素在凝胶色谱柱上可能发生的吸附影响比较显著。当流动相的碱性不够时,碱水素会发生吸附,并且大分子量木素优先被吸附,当pH升至12时可消除吸附现象。流动相的离子强度增大亦可以部分消除木京的吸附。     

The effect of coal sulfur on the behavior of alkali metals during co-firing biomass and coal

Biomass contains high amounts of volatile alkali metals and chlorine, which can cause deposition, corrosion and agglomeration during combustion. Meanwhile coal contains a certain amount of sulfur that produces serious environmental pollution following combustion. To investigate the effects of sulfur on the migration of alkali metals during biomass and coal co-combustion, thermodynamic equilibrium calculations were applied and experiments were performed in a laboratory scale reactor combining with a scanning electron microscope (SEM), X-ray powder diffraction (XRD) and other analytical approaches. The results indicate that inorganic sulfur FeS₂ addition significantly enhanced the formation of potassium sulfate when the S/K molar ratio was less than 2. Meanwhile increasing FeS₂ dosage reduced the formation of KCl(g) and KOH(g) and increased the release of HCl(g). In addition potassium sulfate can react with silica and aluminum to form potassium aluminosilicates and release HCl at the S/K molar ratio above 4.     

Effect of alkali and alkaline earth metals on nitrogen release during temperature programmed pyrolysis of coal

Formation of HCN, NH₃, and N₂ during fixed-bed pyrolysis at 10K min⁻¹ has been studied using coal samples after partial demineralization followed by addition of metal hydroxides from aqueous systems. Without additives, NH₃ is the predominant product at ≤ 700°C, showing the two peaks in the formation rate profile, whereas N₂ is the only product at ≥ 800°C. The presence of NaOH, KOH and Ca(OH)₂ promotes considerable NH₃ formation between 450 and 600°C, but in contrast suppresses HCN formation in this region. The Ca shows the largest effect on both the promotion and suppression. It is likely that the NH₃ increased by Ca addition arises partly from HCN, but mainly from secondary reactions of tar-N. These hydroxides affect N₂ formation in quite different manners: the Na decreases the rate between 700 and 950°C, and the K changes it less significantly than the Na, but the Ca remarkably increases the rate in a low temperature region of 550–700°C. These different features are discussed in terms of solid-phase reactions of alkali metal carbonates with char-N and secondary decomposition reactions of tar-N on CaO particles. As a result, total conversion of coal-N to HCN, NH₃ and N₂ up to 1000°C increases in the sequence of Na < none < K < Ca.     

Effect of carbon deposition on porosity and reactivity of a lignite char

Carbon deposition from the cracking of methane into the pores of a lignite char occurs at a significant rate at temperatures between 815 and 855 °C. The maximum amount of carbon deposited is much less than the amount of open pore volume within the char which is potentially available to accommodate carbon. Removal of the inorganic impurities from the char by acid washing significantly reduces the extent of carbon deposition. Carbon deposition reduces surface area and open pore volume of the char and accessibility of methane into the pore structure. Deposition of carbon has a large and lasting adverse effect on the subsequent reactivity of the char to air. This has been attributed both to a decrease in active surface area, and deactivation of catalytic inorganic impurities due to coating with carbon. Deposited carbon is much less reactive to air than the lignite char. Results indicate that in order to maximize subsequent char reactivity to oxidizing gases, carbon deposition from volatiles during the conversion of coal to char should be kept to a minimum.     

碱金属和锌对高炉用SiAlON结合刚玉砖的复合侵蚀

将高炉用SiAlON结合刚玉砖制成外部尺寸为50mm×50mm,内孔尺寸为25mm×25mm的坩埚,分别加入由Na2CO3、K2CO3、ZnO和宝钢高炉现场高炉灰配制的炉渣(其w(Na2O+K2O)=2.75%,w(ZnO)=5.1%)和用K2CO3、ZnO、石墨配制的炉渣(其w(Na2O+K2O)=25%,w(ZnO)=25%),然后分别在还原气氛下于1350℃16h和1100℃40h进行侵蚀试验。将侵蚀后的试样纵向对称剖开,观察渣对试样的侵蚀和渗透情况,进行SEM和EDAX分析。结果表明:碱金属和锌含量不同的两种炉渣对SiAlON结合刚玉砖的侵蚀速度都很小;碱金属侵蚀机理主要是SiAlON与碱蒸气反应生成钾霞石,与渣反应生成铁橄榄石,并参与硅酸盐玻璃相的生成;刚玉颗粒与渣中的FeO、Na2O和K2O反应生成铁铝尖晶石和少量针状β-Al2O3;锌对该砖没有产生明显的化学侵蚀。     

Synthesis and characterization of SBA-15 modified with alkali metals

A synthesis protocol that has not been previously reported in the literature that allows doping a solid of SBA-15 with alkali metals, preserving the structural features of the mesoporous solid has been developed. X-ray diffraction at low angles, Nitrogen adsorption, Electron transmission microscopy, X-ray photoelectron spectra, atomic absorption spectroscopy and Thermal Programmed Desorption of carbon dioxide were used to characterize the solids obtained. The introduction of alkali metals within the channels of the solid generates basic sites of weak and intermediate strength, which do not exist in undoped SBA-15. Without significant changes in the structural and textural properties of the support, only the densification of the channel walls is evidenced. According to the alkali metal used, the order established by the total number of sites obtained is: Li-SBA-15 ? K-SBA-15 ≈ Cs-SBA-15, while the order by force of both types of sites (weak and intermediate) is: Li-SBA-15 > Cs-SBA-15 > K-SBA-15.     

Catalytic roles of metals and supports on hydrodeoxygenation of lignin monomer guaiacol

Hydrodeoxygenation of the lignin monomer guaiacol was performed on the bifunctional catalysts of noble-metals supported on acidic matrices. The catalytic roles of metal nanoparticles and acidic supports were elucidated using the acid-site-measurement-dependent catalysis results, which demonstrated that metals were responsible for the hydrogenation of aromatic rings while metal-deposited acidic supports were indispensable to the deoxygenation of oxygenates. Among various combinations of metals and supports, Rh/SiO₂-Al₂O₃ and Ru/SiO₂-Al₂O₃ exhibited the highest cyclohexane yields.     

Laboratory assessment of alkali contribution by aggregates to concrete and application to concrete structures affected by alkali-silica reactivity

In Phase I, particles from 17 different aggregates, 1.25-5 mm in size, were immersed in continuously agitated solutions at 38 °C: distilled water, Ca(OH)₂-saturated solution, 0.7 M NaOH (measurement of K supply), and 0.7 M KOH (measurement of Na supply). These solutions were periodically analysed for K and/or Na up to 578 days. More alkalies were released in alkaline solutions than in lime-saturated solution, with lower values in water. After 578 days, the aggregates released between <0.01% and 0.19% Na₂O_e, excluding the nepheline-rich aggregate tested (0.68%). This would correspond to a contribution to concrete from <0.1 to 3.4 kg/m³ Na₂O_e (12.7 for the phonolite), based on an aggregate content of 1850 kg/m³. In general, the feldspar-rich aggregates released significantly more alkalies. In Phase II, the water-soluble alkali content of mass concrete elements from many dams was measured using a hot water extraction method. The values obtained often largely exceed the soluble alkali content expected to be released by the cement used. These results thus also suggest that large amounts of alkalies were supplied with time by the aggregates, particularly by feldspar-rich ones.     

Effects of hemicellulose extraction on the kraft pulp mill operation and energy use: Review and case study with lignin removal

The implementation of wood extraction prior to pulping (pre-hydrolysis), with subsequent recovery of hemicellulose, is expected to affect the operation of a conventional kraft pulp mill. The magnitude of impacts will depend especially on the extraction conditions. In this specific work, the consequences of integrating the auto-hydrolysis process are studied using a detailed mill balance. A softwood pulp mill in Finland was used as a reference. With 14.1% of wood extracted, the wood demand increased by 15.5% and the steam generation in the recovery boiler by 13.5%. The removal of approximately 17% of lignin from black liquor would put the flue gas side of the boiler back to the original required capacity. In turn, this would enable the simultaneous recovery of lignin and hemicellulose. To make this process economically feasible, the extra revenue from the sales of lignin and hemicellulose products would need to compensate for the additional operating costs in the pulp mill.     

Zero-point potentials of metals in molten alkali halides and their binary mixtures

The zero-point potentials of liquid bismuth, lead, and indium in molten alkali halides and their binary mixtures were determined by electrocapillary-curve method, using the same led reference electrode. They are found to grow more electropositive as temperature and alkali cation radii increase and those of halide anions decrease. Such dependence is supposed to be caused by the changing of work function as a result of capturing the emitted electrons by alkali cations and of the existence of the potential jumps to which the dipoles induced by the cations on the halide anions give rise on the interface metal/salt melt. The zero-point potential of bismuth in the binary molten mixtures with common halide anions is shown to reach the values characteristic of the heavier components when their contents in the mixtures amount to about 40 mol% and to remain nearly constant by the further increase of their concentration.s But in the mixtures with common alkali cations the zero-point potential changes fairly monotonously by substituting one halide anion for another. The difference in behaviour of these two groups of the binary mixtures gives evidence that in the molten alkali halides and their mixtures most of the halides anions are bound by the cations in (auto)complexes or associates whereas most of the alkali cations remain relatively loose among them.     

Synthesis and optic properties of titanium dioxide nanostructures doped with alkali metals

The synthesis of nanotubes and faceted nanocrystals of titanium dioxide doped with alkali metals cations has been performed. It has been established that TiO₂ nanotubes with lengths of up to 100 nm and thicknesses of 50–500 nm obtained by solvothermal synthesis have an anatase structure in the direction of crystal growth. Faceted TiO₂ particles with sizes of 80–150 nm doped with Na and K cations (2–7 at % calculated to a yield of TiO₂ yield) preserve the anatase structure, whereas doping with Li induces the formation of a mixture of anatase and rutile. An analysis of the diffuse reflectance spectra showed that dopants had an insignificant effect on optic properties of TiO₂ nanoparticles. The high activity of these catalysts is explained by a decrease in the rate of recombination of charge carriers, rather than by the increase of their photo-generation yield.

     

Effect of cellulose, lignin, alkali and alkaline earth metallic species on biomass pyrolysis and gasification

Fundamental pyrolysis/gasification characteristics of natural biomass and acid-washed biomass without alkali and alkaline earth metals (AAEM) were investigated by a thermogravimetric analyzer (TGA) and a fixed-bed reactor. In these experiments, six types of biomass were used and the contents of cellulose, lignin and AAEM species in the biomass were measured. It was observed that the characteristic of biomass pyrolysis and gasification was dependent on its components and AAEM species on the basis of TGA experiments. During biomass pyrolysis, the tar and gas yields increased with the growth of cellulose content, but the char yield decreased. There were two reactions indicating two major decomposition mechanisms. The first stage of decomposition showed rapid mass decrease due to the volatilization of cellulose, while the second stage became slow attributed to the lignin decomposition. The higher the cellulose content, the faster the pyrolysis rate. In contrast, the pyrolysis rate of biomass with higher lignin content became slower. In addition, the rises of cellulose content elevated the peak temperature of gasification and prolonged the gasification time. Meanwhile, the effect of AAEM species on gasification behavior was studied by comparing unwashed and acid-washed biomass. AAEM species increased the peak gasification value, whereas decreased initial gasification temperature. It revealed that the activity of biomass gasification was attributed to the interaction between AAEM-cellulose/lignin.