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.     

Kraft black liquor recovery in a fluidized bed: Part I — A review

The Tomlinson recovery boiler has been the mainstay of the kraft pulping industry for over fifty years. It is clear, however, that the main drawbacks to this process are the large capital costs of new plant and the smelt-water explosion hazard. This paper examines some of the fundamental scientific information which supports the concept of fluid bed gasification as an alternative to the Tomlinson boiler. It is shown that a knowledge of thermodynamics is useful but insufficient to completely understand the behaviour of the inorganic sulfur species during pyrolysis and gasification of kraft black liquor. Recent key experimental investigations at McGill have demonstrated that solid state reduction of sodium sulfate to sodium sulfide is feasible.     

Hydropyrolysis of kraft hardwood and softwood black liquor

The hydropyrolysis of hardwood and softwood derived black liquor was studied to develop material balance data and to investigate the potential yield of phenolic oils that might be obtained as chemical by-products of a kraft pulp mill. Hydropyrolysis reactions on softwood liquors were found to be more efficient in char formation than those on hardwood liquors. The yield of extractible phenolic oils was low, around 20–30 percent of black liquor organics, but the yields of simple phenols determined by gas chromatography were found to be even lower at 1–5 percent on black liquor organics.     

Reaction kinetics of gasification of black liquor char

CO₂ gasification of black liquor char, prepared from kraft spent pulping liquor is studied thermogravimetrically up to 775°C. The gasification rate is described by Langmuir-Hinshelwood type kinetics and activation energy is similar to that found for alkali metal impregnated porous carbons. However the rate is about 20 times larger than that of coal char mixed with 10-20% Na₂ CO₃. CO inhibition is relatively small and the rate is first order in carbon up to 80% conversion. The behavior is explained by a fine and three-dimensional dispersion of sodium salts in the char. The rate is insensitive to pulping conditions over the range of industrial practice.     

Optical pyrometric measurements of surface temperatures during black liquor char burning and gasification

Surface temperatures of single black liquor droplets in high temperature furnace environments were measured using a two-colour optical pyrometer with a quartz optical fibre probe. The experimental conditions were 750–900 °C and in oxidizing and gasifying environments. Surface temperatures were calculated based on measurements at 650 and 1050 nm using an algorithm which accounted for reflection of radiation from the particle surface. The method gave reliable temperatures under combustion conditions during char burning. The droplet temperature during this period reached a maximum which depended upon droplet size and oxygen content. The flame which appeared during the early part of the devolatilization stage apparently contained enough soot particles to obscure the droplets; this resulted in unreliable indicated temperatures. The indicated surface temperature during the latter half of devolatilization was probably closer to the actual surface temperature, but may have been influenced by the combustion of volatile gases near the particle surface. The surface temperature during drying was too low relative to the surrounding furnace temperature to be measured.     

预水解强度对相思木硫酸盐法制浆黑液性质的影响

经水热预水解技术处理木质纤维素,木片的主要成分发生变化,对后续的化学制浆性能及制浆黑液性质带来影响。本实验采用不同预水解强度（P因子）处理相思木片,并对其硫酸盐制浆行为和黑液性质进行分析。研究结果表明,随着P因子的增大,粗浆得率和细浆得率逐渐降低;浆料的卡伯值逐渐升高。当P因子＜200时,水解后木片的黑液固形物含量由空白组的138.48 g/L升高到162.86 g/L;木素含量由58.57 g/L升高到72.68 g/L;残碱量由4.37 g/L迅速降低到2.07 g/L。当200＜P因子＜600时,黑液固形物含量由162.86 g/L降低到142.71 g/L;黑液中木素含量由72.41 g/L降低到59.16 g/L;残碱量由2.07 g/L降低到1.26 g/L。当P因子＞600时,黑液中固形物含量由142.71 g/L升高到156.95 g/L;木素含量由59.16 g/L升高到62.16 g/L;残碱量由1.26 g/L升高到1.37 g/L。不同条件下,黑液中无机物含量变化不大;黑液固形物的热值由对照组的13.71 MJ/kg提高到14.63~15.09 MJ/kg。     

Ultrafiltration of kraft cooking liquors from a continuous cooking process

Two cooking liquors and a black liquor were fractionated by ultrafiltration. The liquors were withdrawn from different stages in a kraft pulp mill employing continuous digestion. The ultrafiltration was performed at 90°C with two ceramic membranes with cut-offs of 5 kDa and 15 kDa. Only small differences in membrane performance were observed when concentrating the three liquors to 90% volume reduction. The average flux was 55 l/m² h for the 5 kDa membrane and about 115 l/m² h for the 15 kDa membrane. The concentration of lignin was on average 230 and 155 g/L in the retentate from the 5 kDa and 15 kDa cut-off membranes. The ash content was reduced from 37–40 g/g total dry solids to 20–30 g/g after ultrafiltration.     

纸浆黑液对福建无烟煤水蒸气催化气化的动力学和补偿效应

在常压热分析仪上,采用纸浆黑液催化剂对福建无烟粉煤的水蒸气气化反应动力学进行了研究,在850～950℃温度范围内测定了催化剂浓度由0增至10％时的碳转化率随气化时间的变化。结果表明,纸浆黑液具有显著提高碳转化率和气化速率的作用,进而确定了实验条件下的纸浆黑液催化剂加载饱和浓度;在此基础上采用缩芯模型关联出无烟粉煤水蒸气催化气化反应动力学参数,分析表明,该催化气化过程存在明显的补偿效应,最后给出纸浆黑液对无烟粉煤水蒸气催化气化包括补偿效应的动力学方程。     

福建无烟粉煤-纸浆黑液小型流化床水蒸汽催化气化表观动力学研究

在内径为26mm的实验室小型流化床反应器中进行福建尤溪无烟粉煤与纸浆黑液(BL)浸渍混合后的水蒸气催化气化实验.考察了4g/min水蒸汽流量下,不同催化剂加载浓度及不同温度对碳转化率的影响,并对催化气化表观动力学参数进行拟合与计算.研究结果表明:气化温度的升高和催化剂加载浓度的增大能显著提高碳转化率和产气速率,催化剂加载浓度从0%到8%的增加明显降低了催化气化反应的活化能,而从8%到10%的增加又令活化能有增加的趋势.在本实验条件下,BL作为催化剂的饱和加或浓度为8%.     

Pyrolysis of black liquor

Concentrated black liquor was pyrolysed in a semi-batch reactor in an inert atmosphere of nitrogen at 873–993 K. The effects of temperature and reaction time on the gas yields and compositions were studied. The main components of the gaseous product were hydrogen, methane, carbon monoxide, carbon dioxide and sulphur-containing gases. The percentage recovery of energy was also determined. On the basis of the experimental runs, a reaction model was proposed for the kinetics of the pyrolysis reaction, and the activation energies and frequency factors of the rate constants were determined.     

造纸黑液综合治理的研究进展

造纸废水污染十分严重,其综合治理一直是国内外造纸工业和环保界的研究热点。作者对近几十年国内外造纸废水,尤其是造纸黑液治理的方法,如黑液碱回收法、酸析法、絮凝法、膜分离法、生物法、氧化法等进行了详细评述．认为生物法是解决我国造纸工业水污染的最终出路。同时首次提出将超临界水氧化技术应用于造纸黑液的治理,具有潜在的可行性和十分重大的意义。     

Biodegradation of wood-pulp black liquor hydroxyacids by Micrococcus lylae

When Micrococcus lylae grew on the black liquor from wood pulping, glucoisosaccharinic and acetic acids were completely used in 48 h, 2-hydro-xybutanoic acid decreased by 67%, lactic acid by 45% and glycolic acid by 38%. Conditions of the utilization of glucoisosaccharinic acid were optimized.     

纸浆黑液和钙混合催化剂进行高变质无烟煤水蒸气气化的研究

The catalytic effects of single and mixed catalysts, i.e. single 3%Ca and 5%Na-BL（black liquor） catalysts and mixed 3%Ca＋5%Na-BL catalyst, on carbon conversion, gasification reaction rate constant and activation energy, relative amount of harmful pollutant like sulphur containing gases have been investigated by thermogravimetry in steam gasification under temperature 750℃ to 950℃ at ambient pressure for three high-metarnorphous anthracites （Longyan, Fenghai and Youxia coals in Fujian Province）. The mixed catalyst of 3%Ca＋5%Na-BL increases greatly the carbon conversion and gasification rate constant by accelerating the gasification reaction C＋H2O→CO＋H2 due to presence of alkali surfacecompounds [COM], [CO2M] and exchanged calcium phenolate and calcium carboxylate （-COO）2. By adding CaCO3 into BL catalyst in gasification, in addition to improving the catalyst function and enhancing the carbon conversion, the effective desulphurization is also achieved, but the better operating temperature should be below 900℃. The homogenous and shrinking core models can be successfully employed to correlate the relations between the conversion and the gasification .time .and to estimate the reaction rate constant, The reaction acUvaUon energy and pre-exponential factor are estimated and the activation energy for mixed catalyst is in a range of 98.72-166.92 kJ·mol^-1, much less than 177.50-196.46 kJ·mol^-1 for non-catalytic steam gasification for three experimental coals.     

造纸黑液超临界水气化制氢与高附加值化学品回收研究进展

造纸黑液的无害化资源化利用对造纸工业减少环境污染、缓解能源短缺具有重要意义。超临界水气化技术是一种新型且高效的有机废水无害化资源化利用技术,利用水在超临界状态下的特殊性质使其在无害化资源化处理造纸黑液时具有独特的优势。回顾了近年来造纸黑液超临界水气化制氢与高附加值化学品回收的进展,介绍了制氢反应机理,系统总结了温度、压力、浓度、停留时间和催化剂等因素对黑液超临界水气化制氢的影响,介绍了造纸黑液里各类有用无机盐在超临界水条件下的反应、分离回收及造纸黑液超临界水气化反应装置的发展现状。针对现存问题对造纸黑液超临界水气化制氢和资源化无害化处理回收有用成分进行了展望。     

造纸黑液超临界水气化制氢与高附加值化学品回收研究进展

造纸黑液的无害化资源化利用对造纸工业减少环境污染、缓解能源短缺具有重要意义。超临界水气化技术是一种新型且高效的有机废水无害化资源化利用技术,利用水在超临界状态下的特殊性质使其在无害化资源化处理造纸黑液时具有独特的优势。回顾了近年来造纸黑液超临界水气化制氢与高附加值化学品回收的进展,介绍了制氢反应机理,系统总结了温度、压力、浓度、停留时间和催化剂等因素对黑液超临界水气化制氢的影响,介绍了造纸黑液里各类有用无机盐在超临界水条件下的反应、分离回收及造纸黑液超临界水气化反应装置的发展现状。针对现存问题对造纸黑液超临界水气化制氢和资源化无害化处理回收有用成分进行了展望。     

草浆黑液热解和燃烧碱回收过程硅元素的分布

热解作为一种生物质能源利用技术,有望为草浆黑液的碱回收提供新途径。利用10 kg·h^-1搅拌热解实验装置对麦草浆黑液开展了研究,分析热解半焦浸取与燃烧熔融物溶解两种绿液制备方式在总碱回收及硅元素分布方面的差异。结果表明：热解浸取法所获得绿液中包括碳酸钠和硅酸钠在内的总碱量与燃烧溶解法相比基本相等或稍高;浸取完成后有30%～40%的硅元素未溶入绿液而留存于固相即炭粉之中,主要赋存形态为Al、Ca、Fe和Mn等非过程元素的复合硅酸盐;由于数量可观的硅元素留存于固相,因此热解浸取法相比燃烧溶解法绿液硅含量较低,也因此碳酸钠与硅酸钠之比较高。热解浸取法的硅元素分布特性有利于后续的石灰苛化操作。     

厌氧处理棉浆粕黑液废水中试实验

采用水力循环UASB和IC两种厌氧反应器处理黑液的中试试验,研究了CODcr去除率和CODcr容积负荷。实验表明：用H2SO4来调节pH值时,厌氧反应会受到抑制;用HCl代替H2SO4来调节pH值,可以消除硫酸盐的抑制。     

利用草浆黑液制备两性木质素絮凝剂

用硫酸沉淀回收造纸黑液中的木质素,经与Na2SO3磺化和季铵盐接枝聚合,合成出两性木素基絮凝剂.研究表明:用制备出的两性絮凝剂处理蒙脱土悬浮液和印染废水,可有效降低浊度和色度,当絮凝剂质量浓度分别为25mg/L和300 mg/L时,除浊率和脱色率均＞85%.     

Catalytic methanol synthesis via black liquor gasification

Biofuel production from gasified black liquor is an interesting route to decrease green house gas emissions. The only pressurised black liquor gasifier currently in pilot operation is located in Sweden. In this work, synthesis gas was taken online directly from this gasifier, purified from hydrocarbons and sulphur compounds and for the first time catalytically converted to methanol in a bench scale equipment. Methanol was successfully synthesised during 45 h in total and the space time yield of methanol produced at 25 bar pressure was 0.16-0.19 g methanol/(g catalyst h). The spent catalyst exposed to gas from the gasifier was slightly enriched in calcium and sodium at the inlet of the reactor and in boron and nickel at the outlet of the reactor. Calcium, sodium and boron likely stem from black liquor whereas nickel probably originates from the stainless steel in the equipment. A slight deactivation, reduced surface area and mesoporosity of the catalyst exposed to gas from the gasifier were observed but it was not possible to reveal the origin of the deactivation. In addition to water, the produced methanol contained traces of hydrocarbons up to C₄, ethanol and dimethyl ether.     

福建无烟煤CO2气化过程纸浆黑液和钙混合物的催化活性

CO2 gasification of Fuijian high-metamorphous anthracite with black liquor （BL） and/or mixture of BL and calcium stuff （BL＋Ca） as catalyst was studied by using a thermogravimetry under 750-950℃ at ambient pressure. When the coal was impregnated with an appropriate quantity of Ca and BL mixture, the catalytic activity of CO2 gasification was enhanced obviously. With a loading of 8%Na-BL＋2%Ca, the carbon conversion of three coal samples tested reaches up to 92.9%-99.3% at 950℃ within 30min. The continuous formation of alkali surface compounds such as （[-COM], [-CO2M]） and the presence of exchanged Ca, such as calcium phenolate and calcium carboxylates （COO）2Ca, contribute to the increase in catalytic efficiency, and using BL＋Ca is more efficient than that adding BL only, The homogeneous model and shrinking-core model were applied to correlate the data of conversion with time and to estimate the reaction rate constants under different temperature. The corresponding reaction activation energy （Ea） and pre-exponential factor of three anthracites were estimated. It is found that Ea is in the range from 73.6 to 121.4kJ·mol^-1 in the case of BL＋Ca, and 74.3 to 104.2kJ·mol^-1 when only BL was used as the catalyst, both of which are much less than that from 143.5 to 181.4kJ·mol^-1 if no catalyst used. It is clearly demonstrated that both of BL＋Ca mixture and BL could be the source of cheap and effective catalyst for coal gasification.