水-乙醇中碱木质素的催化解聚

通过元素分析仪和X射线荧光光谱对碱木质素组成进行了分析。在水-乙醇〔V(水)∶V(乙醇)=50∶50〕溶剂中280℃,2 MPa初始氢压下降解碱木质素。利用傅里叶变换红外光谱(FTIR)对反应前后碱木质素结构进行了表征,反应后醚键减少,碳氢键增加。利用凝胶渗透色谱对二氯甲烷可溶产物进行了分析。利用气相色谱-质谱联用仪(GC-MS)和配有氢火焰离子化检测器的气相色谱(GC-FID)对单体产物进行定性定量分析,无催化剂时单酚收率为4.57%。磷化镍催化剂的加入可使单酚收率翻倍,磷化钼作为催化剂时单酚收率与磷化镍作为催化剂时相似,但出现苯甲醇类物质和大量的直链含氧有机物,单酚质量分数很低。     

水-乙醇中碱木质素的催化解聚研究

通过元素分析仪和X射线荧光光谱对碱木质素组成进行了分析。在水-乙醇〔V(水)∶V(乙醇)=50∶50〕溶剂中280℃,2 MPa初始氢压下降解碱木质素。利用傅里叶变换红外光谱(FTIR)对反应前后碱木质素结构进行了表征,反应后醚键减少,碳氢键增加。利用凝胶渗透色谱对二氯甲烷可溶产物进行了分析。利用气相色谱-质谱联用仪(GC-MS)和配有氢火焰离子化检测器的气相色谱(GC-FID)对单体产物进行定性定量分析,无催化剂时单酚收率为4.57%。磷化镍催化剂的加入可使单酚收率翻倍,磷化钼作为催化剂时单酚收率与磷化镍作为催化剂时相似,但出现苯甲醇类物质和大量的直链含氧有机物,单酚质量分数很低。     

木质素在超临界甲醇和乙醇溶剂中液化过程分析

通过研究木质素分别在超临界甲醇和乙醇溶剂中的液化过程，分析反应温度（260～340℃）及反应时间（0～120min）对木质素在两种溶剂中的转化率、生物油收率及其组分差异的影响。实验表明，木质素在超临界乙醇中的转化率及产物收率均高于甲醇。当反应温度340℃，反应时间60min，木质素在超临界乙醇中的转化率和生物油收率比在甲醇中分别提高了16.23%和11.54%，残渣收率降低了16.23%。通过GC-MS和FTIR对生物油和残渣分析，发现生物油组分中芳香族化合物相对含量较高，在甲醇和乙醇溶剂中分别达到66.13%和58.84%；随着反应时间的延长，甲醇溶剂中残渣的醚键官能团逐渐增强，而在乙醇溶剂中则先增强后减弱。分析认为在木质素降解过程中，超临界乙醇和甲醇均可产生氢自由基作为供氢体，攻击木质素及其大分子片段中的官能团，同时使液化产物中的活性片段减活，减弱重聚合反应，从而更利于芳烃产物的生成。而甲醇在液化过程中容易与木质素断键产生的苯酚中间体发生脱氢缩合反应，通过醚键聚合产生长链芳香族化合物，形成残渣，降低生物油收率。     

二苯醚类除草剂的进展(下)

降解途径二苯醚类除草剂通过动物、植物、微生物、日光等作用,发生硝基还原、醚键断裂、环裂解、脱氯、核羟基化等反应而降解。 (一)光解除草醚水悬液在日光下醚键迅速裂解而形成2,4-二氯酚与对-硝基酚以及对苯二酚、4-硝基邻苯二酚等产物,其他光解途径包括氯被羟基或氢置换、环羟基化、醚键裂解前通过氢氧化物而脱硝基以及分子重排而变成联二苯(图1),这些反应都是光亲核置     

酶解木质素的碱催化温和水热降解

针对木质素相对分子质量大、空间位阻大、反应活性低、难于利用的缺点,以氢氧化钠作催化剂对酶解木质素进行温和水热降解。研究了反应条件对降解木质素产率的影响,并以红外光谱（FT-IR）、核磁共振谱（¹H NMR）、凝胶渗透色谱（GPC）来表征降解木质素产物。优化后的水热降解条件为反应温度200℃,反应时间120 min,氢氧化钠与木质素的质量比值为0.2,木质素的质量分数为8%,此条件下降解木质素的产率为71%。FT-IR分析表明,在温和的水热降解条件下,木质素的芳环结构得以保留。¹H NMR分析结果表明,水热降解使木质素的部分醚键断裂,酚羟基增多。GPC分析表明,木质素相对分子质量明显下降,证明在此过程中木质素发生了降解。     

酸性助水溶剂脱除木质素机理分析

系统探讨了酸性助水溶剂对甲苯磺酸(p-toluenesulfonic acid,TSA)和马来酸(maleic acid,MA)分离桉木各组分的工艺过程,并对其中木质素脱除机理进行了研究。通过分析对比两种优化后的工艺发现：(1)两种酸性助水溶剂都可以高效脱除木质素,TSA木质素脱除率为67.94%,MA为65.14%;(2)在相同质量分数下,TSA的木质素脱除率比MA更高;(3)在温和条件下,TSA木质素的β-芳醚键含量比MA的高,随着反应条件的加剧,TSA和MA处理后木质素产品中β-芳醚键含量逐渐减少;(4)两种酸性助水溶剂处理后,纤维素保留率都较高,可保持90%以上;但是半纤维素的降解程度随着反应条件的加剧而增加;(5)酸性助水溶剂质量分数越高,在疏水表面的接触角越小,对木质素的助溶作用越明显,脱除木质素效率越高,溶液中木质素聚集体的粒径越小。综上所述,酸性助水溶剂对木质素的脱除基于润湿溶解、木质素芳醚键断裂、半纤维素降解等的综合作用。相关研究可为后续实现温和条件脱木质素工艺优化及机理提供参考。     

甲醇介质中制备阳防子淀粉醚

以精制淀粉（Ⅰ）与3－氯－2－羟丙基三甲基氯化铵（Ⅱ）为原料,甲醇为溶剂,在碱性条件下合成季铵型阳离子淀粉醚。采用凯氏滴定分析产品中氮的质量分数,得出制备季铵型阳离子淀酚醚的最佳反应条件：m(Ⅰ):m(CH3OH)=1:1,m(Ⅰ):m(Ⅱ)=100:6.96,n(Ⅱ):n(NaOH)=1.0:1.5,反应温度80℃,反应时间8h,在此条件下制备的季铵型阳离子淀粉醚中氮的质量分数为0．324％,取代度为0．0388,反应效率为64．8％,甲醇回收率为75％。     

Ni-P/HZSM-5催化木质素降解制备酚类化学品

采用Ni-P复合改性HZSM-5催化剂催化木质素降解制备高附加值的单酚类化学品,探讨了催化剂种类、金属负载量、反应温度、反应时间以及溶剂种类对木质素催化降解制备酚类化合物的影响。同时采用X射线衍射仪（XRD）、比表面积和孔径分析仪（BET）、化学吸附仪（NH₃-TPD）、热重分析仪（TG）以及气相色谱质谱联用仪（GC/MS）对催化剂以及液相产物进行分析表征,同时探讨其催化失活以及再生机制。结果表明：Ni、P高度分散在HZSM-5催化剂的表面,Ni的添加有效地弱化了C－C键,致使β-O-4和α-O-4发生断裂,有效地提高了木质素加氢解聚的活性,减少了焦炭的生成,但催化剂的再生水热稳定性较差,重复使用性较低。当采用甲醇为供氢试剂,在反应温度为220℃,氢气压力为2MPa,反应时间为8h,催化剂负载量为10%,NaOH为共催化剂时,其木质素的转化率为98.6%,酚类化合物的含量达到74.97%。产物以苯酚、愈创木酚和紫丁香酚为主,低温促进了紫丁香酚的产生。     

煤液化油中低级酚生成的影响因素研究

为了探究反应温度、反应压力、催化剂添加量以及供氢溶剂对褐煤直接液化油中低级酚生成的影响以及低级酚生成的机理,利用模型化合物邻苄基苯酚在煤直接液化条件下进行加氢反应。实验结果表明:邻苄基苯酚在液化条件下主要发生桥键断裂反应生成低级酚,苯环不易被加氢饱和。温度升高对促进邻苄基苯酚桥键断裂有利;压力升高则不利于其桥键断裂;铁系催化剂添加量的增加会促进桥键断裂;供氢溶剂四氢萘相比十氢萘会抑制低级酚的生成。邻苄基苯酚加氢液化的产物以苯酚与甲苯为主,邻甲酚与苯相对较少。     

铁酸铜催化双氧水氧化降解碱木质素

采用双氧水、铁酸盐复合氧化体系,在碱性条件下,探究了麦草碱木质素氧化降解制备单酚类化合物的工艺条件。结果表明以铁酸铜为催化剂能促进木质素醚键的断裂,显著地提高单酚收率,在一定程度上碱浓度的增大以及双氧水量的增加,有利于提高单酚收率。     

Solubility increase of coals by the reaction with alcohol — elucidation of reaction mechanism using model compounds

The reaction mechanism of coal-ethanol reaction was examined using model compounds: phenol, benzylphenylether, diphenylmethane and anthracene. The main reaction for these compounds was the splitting of ether bonds, ethylation of benzene nucleii, hydrogenation of aromatic nucleii and the splitting of methylene linkages. The most important reactions were the first two types. The splitting of ether linkages would reduce the molecular weight of coal and ethylation of aromatic rings would be favorable to the easy dissolution of coal in solvents.     

Condensation Reactions of Softwood and Hardwood Lignin Model Compounds Under Organic Acid Cooking Conditions

In order to examine the condensation reactions of softwood and hardwood lignin during organic acid cooking, mixtures of benzyl alcohol type lignin model compounds with guaiacyl and syringyl units as the sources of benzyl cations and creosol and 5-methoxycreosol as the sources of electron-rich aromatic carbons were cooked under acidic pulping conditions.

From the yield of the condensation products in the initial reactions, it was shown that the carbonium cations of guaiacyl nuclei were more reactive than those of syringyl nuclei.

Syringyl type aromatic ring carbons had higher reactivities than guaiacyl type ones.

The cleavage of the benzyl ether bond in syringyl compounds was slower than that of guaiacyl compounds.

The diphenylmethane structures formed by the condensation reaction between veratryl alcohol and 5-methoxycreosol were found to be unstable under the strong acidic cooking conditions.

It is concluded that the condensation reactions between benzylic cations from the guaiacyl compounds and the electron rich aromatic ring carbons of syringyl ones are very fast, but the condensation products are unstable under the strong acidic pulping conditions.

When the guaiacyl nuclei react as an electron-rich aromatic carbon, the reaction is slower but the condensation product is much more stable.

These differences in reactivities, and the stabilities of the condensation products, may contribute to the resistance of softwood toward complete delignification on acid pulping.     

木质素酚醛树脂的固化动力学及机理研究

通过差示扫描量热法（Dsc）和红外光谱（IR）分别研究了木质素酚醛树脂（LPF）的固化动力学及机理。DSC分析表明,LPF的固化反应起始温度比酚醛树脂高,终止温度及活化能比酚醛树脂低,因此,LPF凝胶点比酚醛树脂高,贮存稳定性比酚醛树脂好,固化速度比酚醛树脂快;IR分析表明,LPF的固化机理与酚醛树脂相似,都是羟基之间及羟基与芳环上的氢之间的缩合反应。不同的是LPF固化后仍有部分醚键结构。     

Aromatic Compounds from Lignin Liquefaction over ZSM‐5 Catalysts in Supercritical Ethanol

A systematic research about the liquefaction of alkali lignin in supercritical ethanol using ZSM‐5 zeolite catalysts is reported, which includes the synergistic effect of temperature, catalytic content, and reaction time on product yield and distribution. Fourier transform infrared and gas chromatography‐mass spectrometry analysis were carried out to evaluate the compositions of bio‐oil and solid residue. Under moderate condition, maximum conversion and yield of bio‐oil were satisfactorily high. With the help of ZSM‐5 catalyst, lignin could be successfully converted into aromatic compounds.     

高沸醇木质素吸附苯酚研究

研究了搅拌时间、苯酚初始浓度、溶液pH值、温度等因素对高沸醇木质素吸附苯酚吸附性能的影响,并与工业碱木质素对苯酚吸附性能进行了比较。结果表明：高沸醇木质素对苯酚的吸附随时间的延长在25min左右趋于稳定,苯酚初始浓度越高,吸附量越大;随pH值升高,吸附量降低,升高温度对吸附苯酚不利。在初始搅拌阶段,高沸醇木质素与碱木质素对苯酚的吸附性能差异不明显,但随吸附时间延长,高沸醇木质素对苯酚的吸附能力与碱木质素相比明显提高;在相同苯酚初始浓度下,随苯酚初始浓度的提高,高沸醇木质素对苯酚的吸附量比碱木质素的吸附量约高一倍。     

Coal liquefaction by in-situ hydrogen generation.: 2. Zinc-water model compound reactions

Model compound studies were carried out to elucidate the reaction mechanisms taking place during the liquefaction of coal with the hydrogen produced from the reaction of zinc and water. In compounds of the type Ph-(CH₂)_n-Ph the splitting of the aliphatic bridge was easier with higher n values. Ether type compounds such as diphenylether were unreactive although the C-O bond in dibenzylether was easily cleaved. Condensed ring aromatic compounds gave low conversion with hydrogenation being facilitated by an increase in ring number. Phenolic compounds such as phenol did not react well, but the reactivity increased with increase in aromatic ring size. The cleavage of the aliphatic bridge was accelerated by the OH group, for example, in the case of 4-hydroxydiphenylmethane bond scission was about 15 times higher than that of diphenylmethane. Heterocyclic compounds were unreactive.     

蔗渣碱木素的热裂解特性

利用热重分析法研究了蔗渣碱木素的热解特性,并利用TG-FTIR和Py-GCMS对碱木素的热解产物种类及分布规律进行了分析。结果表明,木素热解呈现宽温度区域,可分为4个阶段,主要裂解温度范围为200～500℃,在400℃左右失重率最大,残余物得率较高。TG-FTIR分析显示了木素热解过程中气体产物的释放规律,300～500℃为主要热解挥发阶段,大部分气体产物在400℃左右产率达到最大。Py-GCMS分析表明,木素的热解产物大致可分为杂环、苯类芳香族、酚类芳香族、酯和酸等化合物,在主要热分解阶段,随着热解温度的升高,苯类和酚类芳香族化合物的含量增多,600℃时酚类物质的含量最高。     

Properties of phenol‐formaldehyde resins prepared from phenol‐liquefied lignin

In this study, alkaline lignin (AL), dealkaline lignin (DAL), and lignin sulfonate (SL) were liquefied in phenol with sulfuric acid (H₂SO₄) or hydrochloric acid (HCl) as the catalyst. The phenol‐liquefied lignins were used as raw materials to prepare resol‐type phenol‐formaldehyde resins (PF) by reacting with formalin under alkaline conditions. The results show that phenol‐liquefied lignin‐based PF resins had shorter gel time at 135°C and had lower exothermic peak temperature during DSC heat‐scanning than that of normal PF resin. The thermo‐degradation of cured phenol‐liquefied lignin‐based PF resins was divided into four temperature regions, similar to the normal PF resin. When phenol‐liquefied lignin‐based PF resins were used for manufacturing plywood, most of them had the dry, warm water soaked, and repetitive boiling water soaked bonding strength fitting in the request of CNS 1349 standard for Type 1 plywood. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011