稻草和麦草绿液蒸煮过程中各组分变化规律比较

对比了相同蒸煮温度下稻草和麦草绿液蒸煮过程中各组分变化规律。结果表明,稻、麦草原料绿液蒸煮脱木素过程呈明显的两个阶段：主要脱木素阶段木素脱出率约为64%~70%,残余脱木素阶段木素脱出率约为5%~10%。主要脱木素阶段二者脱木素速率相近,残余脱木素阶段稻草脱木素速率略高于麦草;两种原料在主要脱木素阶段和残余脱木素阶段均有聚糖溶出,其中主要脱木素阶段聚糖的溶出率分别为稻草60%、麦草34%,二者脱木素选择性分别为2.1和1.1;残余脱木素阶段聚糖溶出率分别为稻草6%、麦草14%,脱木素选择性分别为0.4和1.7。稻、麦草原料绿液蒸煮过程中硅的变化规律呈现三个阶段,每一阶段稻草浆中硅的保留率都高于麦草原料。150℃保温2 h后,原料中硅的溶出率分别为稻草9.3%和麦草45%。相应地,稻草绿液蒸煮黑液中硅的浓度远低于麦草原料,黑液的临界浓度可达45%,约为麦草的3倍。     

桉树抽出物在硫酸盐法制浆过程中的作用机理

研究了桉木抽出物中多四类化合物在硫酸盐法制浆过程中的作用机理,结果表明：桉水硫酸盐法制浆的蒸煮历程可分为三个阶段。多酚类化合物对破的消耗突出表现在前期和中期,多酚类化合物对得率变化、木素脱除以及碳水化合物溶出的明显影响表现在后期高温保温阶段。桉木蒸煮前预处理除去多酚类化合物对降低减耗和对蒸煮后期脱术素有利。     

枫香树材硫酸盐制浆工艺技术研究

通过对枫香树材硫酸盐蒸煮的用碱量、硫化度、温度和保温时间四因素三水平方差分析工艺技术研究发现,在所选的四因素三水平内,用碱量对浆料得率和卡伯值的影响最大,硫化度对浆料得率和卡伯值的影响最小。枫香树材硫酸盐蒸煮较为适宜的工艺条件为:用碱量17%(Na2O计),硫化度20%,温度165℃,保温时间60 min,液比1∶6。另外,在枫香树材硫酸盐蒸煮过程中添加AQ,对提高蒸煮脱木素选择性具有明显的效果。     

稻草绿液蒸煮与氧脱木素联合制浆工艺研究

采用绿液蒸煮与氧脱木素联合制浆工艺对稻草原料绿液法制浆进行了初步探索。研究结果表明,稻草原料采用绿液蒸煮,在用碱量16%(Na2O计)、硫化度20%左右、最高温度150℃和不保温的蒸煮条件下,可得到卡伯值26的浆料。该浆料继续氧脱木素,在氢氧化钠用量2%～3%、氧压0.7 MPa、最高温度110℃条件下,可将卡伯值降至10左右。绿液蒸煮浆料得率可达60%以上,氧脱木素段得率约90%,联合制浆得率55%以上。绿液与氧脱木素联合制浆工艺可将麦草原料中约65%～75%的硅保留在浆料中,并且浆料的强度性能与常规碱法浆相近。     

硫酸盐制浆过程中硫的分布与变化规律

本文研究了兴安落叶松硫酸盐制浆过程中流在蒸煮液、溶出木素和残余木素中的分布及变化情况。结果表明，蒸煮过程中蒸煮液的活性碱和硫化钠浓度不断下降，硫化度则不断上升，活性碱与硫化钠的消耗主要发生在初始脱水素阶段．溶出木素的含硫量在初始脱木素阶段量最高，随着蒸煮反应的进行，其百分含量逐渐下降，但绝对量却不断上升。蒸煮结束时，约占总用硫量1／5的硫与溶出木素结合在一起。木片或纸浆的含硫量与木素的硫化速率和残余木素的含量密切相关。在残余脱木素阶段，残余木素的硫化对木素的说除已没有促进作用。     

蒸煮助剂对低用碱量硫酸盐法预处理毛竹竹屑的影响

毛竹竹屑经10%低用碱量 (以Na₂O计)、20%硫化度、160 ℃下保温1 h预处理,木质素脱除率达到62.35%,预处理物料酶水解48 h葡萄糖和木糖得率分别为56.04%和53.47%。研究了硼氢化钠、三聚磷酸钠、2-蒽醌磺酸钠3种蒸煮助剂对毛竹竹屑10%用碱量硫酸盐预处理的成分以及糖化效果影响,其中2-蒽醌磺酸钠影响最大。在10%用碱量和20%硫化度的预处理液中添加0.15%的2-蒽醌磺酸时,160 ℃下保温1 h的葡聚糖回收率和木质素脱除率分别为94.93%和68.55%,与空白对比分别提高5.45%和9.94%;预处理物料酶解48 h葡萄糖和木糖得率分别为62.88%和58.97%,与空白对比分别提高12.21%和10.29%。     

马尾松硫酸盐浆分段加碱氧脱木素性能的研究

研究了不同用碱量分四段加碱对马尾松硫酸盐浆氧脱木素的影响。研究结果表明:在总用碱量为4.5%时,分段加碱OOOO比两段氧脱木素OO能脱除更多的木素,木素脱除率达到68%～71%,而黏度仅降低26%～28%,纸浆的白度由27.1%提高到46.4%ISO。     

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。     

枫香树材清洁制浆技术

对速生阔叶木枫香树材的纤维形态、主要化学组成、清洁制浆及绿色漂白工艺进行了一系列探讨。结果显示,枫香木纤维平均长度较长,长宽比均比杨木大,且其综纤维素和戊聚糖含量高而Klason木素含量低,是一种很有发展潜力的制浆造纸原料。采用硫酸盐法制浆,蒸煮后所得细浆得率为49.9%,卡伯值为23.0,白度为23.8%ISO,黏度为734.7 mL/g。利用环境友好型漂白法——氧脱木素技术处理该枫香树材硫酸盐浆,并在此过程中创造性地使用助剂蒽醌。四因素三水平正交试验结果表明:用碱量、氧压、温度和时间对枫香树材硫酸盐浆添加蒽醌氧脱木素后浆料的性能均有很大的影响。其中,温度对得率、卡伯值、白度和黏度等的影响最大,时间对卡伯值、白度和黏度的影响最小。枫香树材硫酸盐浆添加蒽醌氧脱木素的较为适宜的工艺为:用碱量3%,氧压0.7 MPa,温度105℃,保温时间90 min,浆浓20%,MgSO4用量0.5%,蒽醌用量0.1%。在该条件下所得浆料得率90.7%,卡伯值7.0,黏度545.1 mL/g,白度51.0%ISO,脱木素选择性8.42×10-2。与相同条件下常规氧脱相比,卡伯值和白度相近,但得率、黏度和脱木素选择性都有所提高。蒽醌在枫香树材硫酸盐浆氧脱木素过程中可保护碳水化合物,提高脱木素选择性,是一种良好的氧脱木素助剂。     

麦草绿液和氧脱木素联合制浆工艺研究

采用绿液蒸煮和氧脱木素联合制浆工艺对麦草原料绿液法制浆进行了初步探索。研究结果表明,麦草原料采用绿液蒸煮,在用碱量16%～20%、硫化度30%左右、最高温度150～170℃和短保温的蒸煮条件下,可得到卡伯值40～50的浆料,该浆料继续进行氧脱木素,在氢氧化钠用量4%～5%、0.5 MPa的氧脱木素条件下,可将卡伯值降至10左右。蒸煮段浆料得率约45%～50%,氧脱木素段得率约90%。绿液与氧脱木素联合制浆工艺可将麦草原料中约30%的硅保留在浆料中,并且浆料的强度性能与常规碱法浆相近。     

麦草氨法制浆工艺及动力学

1 INTRODUCTION Under the pressure of rising consumption on wood resource, more attention has been paid to using non-wood raw materials in papermaking industry. Pulping on non-wood fiber material is expected to increase from 7%—8% at the present to 10%—15% in 2010 in the world[1]. Non-wood material, particularly wheat straw, are exploited as the main raw material for papermaking in China because of the limited wood resource with a forest coverage of only 13.94%[2]. The main problem that …     

Soda Pulping of Hardwoods Catalyzed by Anthraquinone and Methyl Substituted Anthraquinones

Abstract

Black liquor gasification (BLG) as well as the recovery of lignin and other organic compounds from pulping black liquor would be aided if an efficient sulfur‐free pulping process could be developed. This has provided new impetus for research on soda pulping with redox catalysts instead of sodium sulfide that is presently used in the kraft process. Soda/anthraquinone (AQ) pulping afforded white birch (Betula papyrifera) and sugar maple (Acer saccharum) pulps with equal if not superior strength to kraft pulps. However, the delignification rate was significantly lower for soda/AQ pulping. When AQ was replaced by 2‐methylanthraquinone (2‐MAQ) a delignification rate only slightly lower than that of kraft pulping was obtained at the same effective alkali (EA). At a kappa number of ～20, a soda/2‐MAQ pulp was produced from sugar maple at a higher yield (1.2% on chips) than for a kraft pulp. 2‐MAQ was synthesized, as a powder, at 75% yield using an AlCl₃–mediated Friedel‐Crafts reaction that is one of the methods used for commercial production of AQ.     

Pulping with organic acids: 3-acetic acid pulping of Bagasse

Bagasse was subjected to acetic acid pulping; the effects of the addition of 0.5% H₂SO₄ to the pulping solutions (50, 70 and 90% acetic acid) and varying the liquor ratio, on pulp yield, delignification %, pentosan content and strength properties of the pulps obtained were evaluated. Addition of H₂SO₄ improved the delignification but at the expense of yield and pentosan content. The breaking length and burst deteriorated, whereas the tear was slightly improved. Raising the liquor ratio from 5:1 to 10:1 also reduced the strength properties of the pulps. Delignification of Casuarina was easier than bagasse. IR studies of the acetic acid lignins obtained from both raw materials showed that Casuarina lignins contained more syringyl nuclei than bagasse lignin; the latter resembled softwood lignins. Addition of H₂SO₄ to bagasse changed the syringyl-deficient to guaiacyl-deficient lignin. A relationship was found between the ease of delignification for both raw materials and the relative intensity of the bands corresponding to syringyl groups.     

氧脱木素效率的改善途径

氧脱木素被认为是除了硫酸盐蒸煮脱木素外,成本最低且最简单的脱木素方法,所以氧漂可以把制浆与漂白结合起来。且氧脱木素技术具有环境污染小、漂后纸浆质量高等优点,现已成为ECF和TCF漂白的主体工艺。氧脱木素是以分子氧为漂白剂,酚型木质素与O2反应从而消除侧链,打开苯环,脱甲基化而被氧化降解。该过程受到用碱量、反应温度、时间、氧压、浆浓等许多工艺参数的影响。为改善氧脱木素效果,研究者提出了多种方法,如两段氧脱木素、助剂强化氧脱木素及氧脱木素前预处理等。氧脱木素在我国的应用前景是很广阔的,而且环境保护法规的日益严格对实施氧脱木素技术也十分有利,因此对于氧脱木素的研究还需继续。     

The Influence of Sulfidity in Kraft Pulping on the Nature of Residual Lignin

The influence of sulfidity in kraft pulping of Norway spruce chips on the characteristics of residual lignin has been examined at two levels 25 and 40%. Comparing with the reference kraft cook at similar kappa number, the high sulfidity pulp lignin displayed a significantly lower phenolic hydroxyl group content, and a lower response to O₂ delignification, but it gave a slightly higher yield of nitrobenzene oxidation products, and was more responsive to a neutral sulfite treatment.     

Mechanistic Differences Between Kraft and Soda-AQ Pulping of Hardwoods with Regard to Lignin–Carbohydrate Complexes (LCC)

The literature on biomass research contains many references to lignin–carbohydrate complexes (LCC) decreasing the rate of delignification in chemical pulping, decreasing the yield of cellulosic ethanol via fermentation, and decreasing forage digestibility. Regarding wood delignification, there are a few reports on the formation and/or cleavage of lignin–carbohydrate (L–C) bonds during alkaline pulping. The behavior of LCC was investigated to find a potential explanation for the differences between the soda-anthraquinone (soda-AQ or SAQ) and kraft processes with regard to delignification rate in the residual phase of pulping and in the bleaching process. Enzymatically isolated lignin (EL) was prepared from two soda, nine SAQ, and twelve kraft pulps from sugar maple, a hardwood. The range of kappa numbers, after correction for hexenuronic acid (HexA), was 10–60. The bound sugars on each EL were hydrolyzed and converted to monomers by H₂SO₄ at 121°C. There was evidence in the data suggesting that the bound glucan and xylan on the ELs from soda, SAQ, and kraft pulps were native to the wood. The bound galactan data were somewhat ambiguous, and there was no detection of bound mannan on any EL. The reproducibility and repeatability of bound arabinan attached to ELs (BA) were excellent. Although not conclusive, the totality of the data is suggestive of both L–C bond formation and cleavage involving arabinose units during both kraft and SAQ pulping. There was no decrease in BA when SAQ was used to lower the c-kappa number (HexA-corrected) from ～60 to ～25. The case was similar when kraft was used in the range of ～60 to ～40. However, there were significant decreases in BA content when c-kappa number was lowered below ～25 by both SAQ and kraft. A common mechanism was proposed to explain essentially no decrease in BA content at higher kappa numbers, but distinctly different mechanisms were proposed to explain BA cleavage at c-kappa number <25. A mechanism favorable to subsequent bleaching was proposed for kraft, but an unfavorable mechanism was proposed for SAQ.     

Modification of Alkaline Pulping to Facilitate the Isolation of Aliphatic Acids Part 1. Sodium hydroxide pretreatment of pine wood

Pretreating pine chips (Pinus sylvestris) with sodium hydroxide prior to the alkaline delignification (kraft, kraft-anthraquinone, and soda-anthraquinone) can facilitate the recovery of the carbohydrate degradation products from alkaline pulping liquors. Under suitable pretreatment conditions large amounts of carbohydrate degradation products (aliphatic acids) were formed relative to lignin. The lignin fraction was composed of comparatively low-molecular-weight fragments. Although the delignification was considerably retarded and the yield (based on wood) was decreased by 1–3%, the properties of the resulting pulp were essentially maintained despite pretreatment. Finally, data are given for the composition of aliphatic acids in liquors resulting from pretreatments.