Using ultrafiltration to analyze the molar mass distribution of kraft lignin at ph 13

We used deliberately calibrated ultrafiltration membranes to analyze the molar mass distribution (MMD) of kraft lignin in alkaline solution. The membranes were first tested with probe macromolecules to obtain sieving curves at the same conditions as the lignin analysis. Using a restricted transport model, we calculated the average effective membrane pore sizes. The results were different from the nominal cut-off values. The MMD of a lignin sample at pH 13 was analyzed by separating the lignin solution into five fractions; the MMD using the calibrated cut-off values was confirmed by gel permeation chromatography.     

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。     

Effect of irradiation on the composition and thermal properties of softwood kraft lignin and styrene grafted lignin

Lignin is an abundant, underutilized natural resource that has potential to be used as a biomaterial but is currently hampered in its use by not being uniform in structure and composition and is thermally unstable due to phenolic group. To address these issues and modify its thermal properties, softwood kraft lignin was modified using γ‐irradiation at low doses with and without styrene present and characterized. Irradiation of kraft lignin alone with γ‐radiation shows an initial decrease in molecular weight due to chain scission up to about 10 kGy followed by an increase in molecular weight due to crosslinking. NMR results indicate a decrease of about 15% in the OH content of the lignin with 30 kGy irradiation. Thermal properties such as T_g, free volume and ΔC_p follow accordingly. Irradiation at very low dosages was determined to facilitate the grafting of styrene monomer to lignin, decreasing the OH content by 23%. This effect increased the hydrophobicity of the material, depressed the value of T_g, increased the ΔC_p, increased the mobility in the liquid state, and made the material more thermally stable relative to the lignin alone, thus improving its processability at high temperatures. Both the irradiation of lignin alone and the grafting of styrene to lignin increased the yield of mass during pyrolysis and the activation energy for mass loss relative to untreated lignin alone. This work has demonstrated that the application of low dosages of γ‐irradiation is a promising method to attach functional molecules onto lignin for use in various applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39743.     

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.     

Tailoring the molecular and thermo–mechanical properties of kraft lignin by ultrafiltration

This study has shown that ultrafiltration allows the selective extraction from industrial black liquors of lignin fraction with specific thermo‐mechanical properties, which can be matched to the intended end uses. Ultrafiltration resulted in the efficient fractionation of kraft lignin according to its molecular weight, with an accumulation of sulfur‐containing compounds in the low‐molecular weight fractions. The obtained lignin samples had a varying quantities of functional groups, which correlated with their molecular weight with decreased molecular size, the lignin fractions had a higher amount of phenolic hydroxyl groups and fewer aliphatic hydroxyl groups. Depending on the molecular weight, glass‐transition temperatures (T_g) between 70 and 170°C were obtained for lignin samples isolated from the same batch of black liquor, a tendency confirmed by two independent methods, DSC, and dynamic rheology (DMA). The Fox–Flory equation adequately described the relationship between the number average molecular masses (M_n) and T_g's‐irrespective of the method applied. DMA showed that low‐molecular‐weight lignin exhibits a good flow behavior as well as high‐temperature crosslinking capability. Unfractionated and high molecular weight lignin (M_w >5 kDa), on the other hand, do not soften sufficiently and may require additional modifications for use in thermal processings where melt‐flow is required as the first step. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40799.     

高温磺甲基化碱木质素染料分散剂的制备及性能研究

以酸析碱木质素(AL)为原料,通过高温磺甲基化改性反应制备不同磺酸基含量的磺甲基化碱木质素(SAL),研究了各反应工艺条件对产物磺酸基含量的影响,并测定了产物用作染料分散剂的高温稳定性和对纤维的沾污性。通过优化得到以下工艺条件:w(AL)=25.0%,反应温度为180℃,反应时间为4 h,反应体系p H=11.0,n(亚硫酸钠)∶n(甲醛)=3.5∶1。在该工艺条件下,通过调节亚硫酸钠用量制备不同磺酸基含量的SAL。对SAL的性能测定结果表明,SAL磺酸基含量为1.2~1.4 mmol/g时具有较优的综合性能,尤其是高温稳定性出色,130℃高温处理后染料分散液的平均粒径最低为14.347μm,明显优于商品染料分散剂UNA(86.125μm)和NNO(59.886μm),但是对纤维还具有一定的沾污性。     

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.     

碱木质素/聚乙烯亚胺碳点的制备及其对pH敏感性

以碱木质素（alkali lignin，AL）、聚乙烯亚胺（polyethylenimine，PEI）为碳源，其中PEI不仅作为碳源还作为表面钝化剂，在H₂O₂氧化下通过一步水热法绿色、高效制备高荧光、寿命长和多氨基化功能碳点（alkali lignin/polyethylenimine carbon dots，AL/PEI-CDs）。探究了碱木质素/PEI质量比、水热温度和水热时间等因素对碳点荧光强度的影响，确定了最佳的反应条件，同时考察了AL/PEI-CDs对pH的敏感性及稳定性。采用紫外分光光度计（ultraviolet spectrophotometer，UV-vis）、荧光分光光度计、原子力显微镜（atomic force microscope，AFM）、高分辨透射显微镜（high resolution transmission electon microscopy，HRTEM）、傅里叶红外光谱仪（Fourier transform infrared spectroscopy，FTIR）和X射线衍射仪（X-ray diffractometer，XRD），对AL/PEI-CDs的光学性质、形貌结构、化学结构和晶体结构等进行了表征分析。结果表明，在碱木质素/PEI质量比为1∶12、水热温度190℃、水热时间12h的条件下，合成的AL/PEI-CDs荧光量子产率为25.53％，荧光寿命为5.06ns，表面含有丰富的氨基和羟基，且粒径均一、水溶性好，有良好的稳定性，在最佳激发波长为ex=313nm下对应的发射峰位为405nm，稀释液在紫外灯下发出明亮的蓝光。本研究制备的碳点在离子监测和细胞代谢过程监测质子传感器中可能具有良好的应用前景。     

碱法分离回收水稻秸秆中木质素

中国是一个农业大国,拥有丰富的秸秆。农作物秸秆中的木质素是一种天然可再生芳香高聚物,具有良好应用价值。研究秸秆中木质素的分离回收方法对秸秆资源的有效利用有重大意义。目前木质素的分离方法多样化,不同处理方法对木质素的分离具有较大的影响。本文结合木质素与某些金属离子螯合呈可溶性盐这一特点,采用碱法与亚硫酸钠法复合处理秸秆,提出一种简单新型分离秸秆中木质素的方法。通过正交试验研究了氢氧化钠、亚硫酸钠、硫酸锌添加量及pH对木质素分离的影响,并找出一种最佳的木质素分离方案。研究表明氢氧化钠添加量及pH对木质素分离影响显著,随着氢氧化钠浓度及pH的增加,木质素的分离效果增加。其最佳方案中木质素的提取率最高可达97.14%,冻干后木质素回收率为88.97%,制备的木质素磺酸锌盐中锌质量分数为2.4%。本研究为秸秆中木质素的分离回收及秸秆有效利用提供了一种简单的新途径。     

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.     

Lignin–polypropylene composites. II. Plasma modification of kraft lignin and particulate polypropylene

Indulin kraft lignin and polypropylene were subjected to plasma treatments in a rotating electrodeless plasma reactor at 13.56 MHz radio frequency, with the goal of improving the strength properties of the composites made from these materials. It was shown that efficient surface modification could be achieved by these plasma treatments, avoiding long reaction times and large volumes of reactants for modification by conventional wet chemistry. SiCl₄‐plasma treatments of lignin at 100 and 200 W resulted in silicon implantation in the range of 4–10% that depended on the treatment time. However, the effect of power in the treatments was minimal, given that changes in silicon implantation were not observed for changes in this parameter. SiCl₄‐plasma treatment of polypropylene at 80 W, 1 and 10 min, resulted in silicon implantation in the order of 10–15%, for the two different treatment times, showing that low power and short treatment times were sufficient to significantly alter the polypropylene surface. However at high power (250 W), the longer treatment time of polypropylene apparently led to formation of oligohalosilanes. Other plasma treatments in the rotating reactor such as plasma‐induced copolymerization of acryloyl chloride on both lignin and polypropylene, and plasma‐state polymerization of acryloyl chloride on polypropylene under pulsing conditions, resulted in thin film depositions. Evaluation of composites from these treated materials is described in the next contribution (Part III) from this series. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1920–1926, 2004     

Quantitative determination of phases in the alkali activation of fly ash. Part I. Potential ash reactivity

The various (vitreous and crystalline) components of two type F fly ashes are quantified in this paper using three techniques: chemical analysis with selective solutions, X-ray powder diffraction combined with the Rietveld method and nuclear magnetic resonance. The findings confirm the suitability of the techniques to pursue the objectives while providing further insight into the chemical composition of the vitreous phase of the ash as well as an understanding of the thermal history of these materials. Finally, the paper corroborates the grounds established in prior research for regarding the glassy constituents of an ash to be instrumental in the control of its alkali reactivity during the manufacture of ‘alkaline cements’.