马尾松木质素快速热解及产物分析

以针叶材马尾松木质素(Pinus massoniana)为快速热解的原料,采用热解-气相色谱-质谱联用(PyGC-MS)技术,分别对磨木木素(MWL)、碱木素(AL)以及酸不溶木素(Klason木素)三种不同种类的木质素及磨木木素在不同热裂解温度下进行了热裂解实验,分析了不同条件下热裂解产物中主要酚类组分相对含量的变化。结果显示,裂解温度为500℃时,马尾松不同类型木质素热裂解产物存在较大差异,磨木木素、碱木素和酸不溶木素裂解产物中总酚相对含量分别为62.3%、44.86%和16.25%,结果说明磨木木素最易裂解,碱木素次之,酸不溶木素最难裂解。热裂解温度从400℃升高到500℃再升高到600℃的过程中,磨木木素裂解产物中总酚相对含量仅从59.78%升高到62.31%再升高到65.72%,主要酚类组分为愈创木酚及其衍生物,各酚类组分相对含量随温度升高呈现出不同的变化趋势。     

木质素CP-GC-MS法裂解行为研究

采用居里点热裂解-气相色谱-质谱(CP-GC-MS)联用分析技术,以碱木质素为原料,研究了裂解温度对木质素快速裂解产物组成及其含量的影响。结果表明,木质素居裂解主要生成酚类化合物,GC含量可达60%。低温主要生成愈创木酚结构单元为主体的酚类化合物;在300~360℃之间,酚类化合物GC含量随裂解温度升高而提高,愈创木酚基本单元类化合物占主体,占酚类化合物的90%左右;裂解温度进一步提高,酚类化合物GC含量稳定在60%左右,而愈创木酚基本结构单元类化合物GC含量随温度升高而降低,主要由于愈创木酚基本结构单元断裂成其他酚类和小分子化合物。     

竹材居里点快速热裂解研究

利用JHP-5型居里点裂解仪,在358、445、590和670℃4种居里点温度下快速热裂解竹材,通过GC-MS在线分析裂解产物。结果表明竹材居里点裂解液相主要产物为糠醛和酚类物质,其中445℃时2,3-二氢苯并呋喃的相对含量多达21%,并且液相主要产物的相对含量随温度的提高呈现先增后减的变化规律,裂解温度为445~590℃更利于液相产物的生成。裂解机理分析得知糠醛是由纤维素和半纤维素裂解产生,而酚类物质则来源于木质素。     

在Ru/C和甲酸(甲酸盐)体系中碱木质素水热解聚特性研究

在Ru/C和甲酸(甲酸盐)的共同作用下,275~350℃的亚临界水中,进行碱木质素的水热解聚反应。通过GC-MS定性分析和GC-FID定量分析,探究了供氢试剂及用量、反应温度、木质素分子级分对木质素水热解聚的影响。结果表明:在甲酸和Ru/C条件下,木质素解聚液相产物得率最高,组成较简单,具有较好催化降解效果;在甲酸添加量为0.8 mol/L,反应30 min时,木质素解聚液相产物最多,其中含量最高的单酚类物质为4-甲基愈创木酚,在主要单酚类物质中占32.77%,木质素水热解聚液相产物得率随温度升高而先增后减,并在325℃时取得峰值;L1、L2和L3是碱木质素的3个不同的分子级分,L1级分对木质素解聚液相产物得率贡献最大,达61.80%,且产物中单酚类物质总得率最高,为112.71 mg/g。其中,愈创木酚与4-甲基愈创木酚所占比例最高,可分别为35.38和35.52 mg/g;对木质素进行分级分离处理后再进行水热转化反应,有利于液相产物和单酚类物质得率的进一步提高。     

β-蒎烯裂解制取月桂烯的技术

月桂烯是香料产业中最重要的化学品原料和中间体之一,主要来自于β-蒎烯的裂解。本研究设计了β-蒎烯裂解月桂烯的装置,并以此装置进行了β-蒎烯裂解制取月桂烯的工艺研究,得出β-蒎烯最佳的裂解工艺参数为:预热温度400℃,裂解温度500℃,真空度60 mmHg,进料速度35 L/h,此条件下β-蒎烯转化率98.4%,月桂烯含量83.3%。本研究的β-蒎烯裂解制取月桂烯生产条件较温和,成本相对较低,适用于规模化生产。     

高酚类含量生物油喷动循环流化床快速热解工艺

采用喷动循环流化床快速热解系统对落叶松树皮进行快速热解制备高酚类物质含量生物油,考察反应温度、粒径、进料速率和气体流量对生物油中酚类物质含量的影响,以生物油中酚类物质含量为目标,优化快速热解工艺.结果表明:反应温度、粒径是影响生物油中酚类物质含量的关键因素;制备高酚类物质含量生物油的喷动循环流化床快速热解最佳工艺为:反应温度823K,粒径0.3～ 0.45mm,进料速率50 r/min,气流量15 m3/h.     

β-5型木质素模型化合物热解机理研究

木质素作为三维网状无定形高聚物,其化学结构非常复杂。为探究热解过程中产物的分布及形成路径,利用PyGC/MS联用仪在不同的热解温度下对软木木质素中最典型的C—C键(β-5型)模型化合物的热解产物进行详细研究。结果表明:β-5型化合物在低温下主要发生C—O键的开环断裂,热解产物仍以二聚体的酚类和酮类化合物为主。随着热解温度的升高,二聚体继续发生二次裂解反应,形成大量的小分子芳香族化合物,相对含量约占15%～30%;当热解温度为900℃时,热裂解生成的化合物之间能够通过缩聚反应形成萘和茚,其相对含量约占产物含量的9%。同时,反应路径也进一步揭示了热解过程中的转化机理。     

醋酸水溶液预处理对柳杉木材炭化的影响

杉木(日本柳杉)经醋酸水溶液处理后，重量减少。将处理前后柳杉木材在4℃下进行炭化，得到了木醋液、木焦油和木炭。与未处理材相比，处理材木醋液的收率增加，而木焦油和木炭的收率减少。处理液的醋酸浓度增加后，木醋液和木焦油的收率几乎不变，但木炭的收率稍微减少了。用毛细管气相色谱法对木醋液的成分进行了定量分析。与未处理材相比，处理材木醋液中糠醛(呋喃甲醛)及5-羟甲基糠醛的收量增加，而羧酸类、苯酚类、邻苯二酚、愈创木酚类及麦芽酚的收量几乎不变。当醋酸浓度从0增至3％时，糠醛的收量随着增加，但是当醋酸浓度从3％增至30％时，其收量却几乎不变。     

生物质与塑料共热解协同作用研究

利用固定床反应器研究了木屑与低密度聚乙烯(LDPE)共热解时的热解行为,并以木屑、LDPE单独热解为对照,考察了热解温度对共热解行为的影响,结果表明:木屑与LDPE共热解可以提高液体产率,当热解温度为600℃时液体产率达到最大值56.84%,比理论值高6.44个百分点。通过GC-MS对生物质与LDPE共热解液体产物组成进行了分析,发现共热解产生的生物油组分主要为脂肪烃、醇类及酚类,共热解过程中还生成了某些特定组分,如十一醇、庚烯醛等含氧长链化合物,这是生物质与LDPE共热解时自由基相互作用的产物。通过热重-红外联用实验研究了木屑与LDPE共热解的协同作用,结果发现:共热解时最大反应速率温度为490℃,相比LDPE单独热解时的512℃降低22℃;木质素裂解过程中产生的羟基自由基会与LDPE裂解产生的小分子产物结合形成十一醇、辛基苯酚等物质,而纤维素热解过程中生成的呋喃类、醛类会与LDPE裂解产生的CnHm分子结合形成2-丁基四氢呋喃、庚烯醛、十二醛等物质。     

废轮胎与生物质共热解特性研究

采用热重分析(TG-DTG)对废轮胎和生物质的热解特性进行了分析,研究了原料配比、升温速率及粒度对热解的影响,并采用HSC计算模拟软件对热解气体的分布规律进行了模拟。研究结果表明:废轮胎与生物质共热解过程主要分为干燥阶段(20~200℃)、气化裂解阶段(200~500℃)和二次裂解阶段(500~800℃) 3个阶段。废轮胎掺混比例由100%下降至0时,热解初始温度由358.0℃下降至288.5℃,热解终止温度由473.0℃下降至361.6℃。随着升温速率和原料粒度的增加,废轮胎热解反应的最大失重速率增大,热解终温逐渐升高,反应向高温方向移动。采用Coats-Redfern法得到的废轮胎与生物质共热解阶段(250~500℃)活化能为18.61~40.86 k J/mol,生物质掺混比例增加时反应所需要的活化能减小。HSC计算模拟发现:热解过程气体产物主要为H_2、CO、CH_4和CO_2,随着废轮胎掺混比例下降,H_2、CO和CO_2产量增加,CH_4产量减小。通过可燃性气体总量与CO_2产量比值及热解特性分析发现:废轮胎掺混比例控制在40%~60%时获取的可燃性气体产量较高。     

Effects of phosphoric acid on liquefaction of wood in phenol and optimum liquefaction processing parameters

To clarify the influencing factors of liquefaction of wood in phenol using phosphoric acid as a catalyst and get its liquefaction technology, a study on the liquefaction technology of Chinese fir (Cunninghamia lanceolata) and poplar (triploid Populus tomentosa Carr) under different conditions was conducted. The results indicate that the residue rate decreases with the increase of liquefaction temperature, liquefaction time, catalyst content or liquid ratio. It is also found that the optimum condition of liquefaction for poplar is estimated as: the reaction temperature of 180 ℃, the reaction time of 2.5 h, liquid ratio (phenol/wood ratio)of 4.5 and catalyst content of 8%, and 4.2% residue rate could be obtained. Under the processing parameters of temperature 180 ℃, the reaction time of 2.5 h, liquid ratio (phenol/wood ratio) of 4 and catalyst content of 10%, the residue rate of Chinese fir can reach 5.6%.     

Rapid wood liquefaction by supercritical phenol

Wood was rapidly liquefied at the supercritical temperature of phenol. Under these conditions, wood was liquefied by over 90% for 0.5 min, and the combined phenol content of the obtained liquefied wood reached about 75%. The effects of various reaction conditions on liquefaction were investigated. With increases in reaction temperature, phenol/wood weight ratio, and the charged mass-to-reactor capacity (w/v) ratio, the amount of methanol-insoluble residue decreased and combined phenol content increased. The range of molecular weights and polydispersity of the products obtained after the time at which sufficient liquefaction was achieved were from 400 to 600 and from 1.5 to 2.5, respectively. Wood showed a marked decomposition to low molecular weight components early in the reaction, and then the molecular weight increased slightly with increasing reaction time. The properties of liquefied wood were investigated and compared with those obtained with conventional liquefaction methods. Combined phenol content was similar to that obtained by other liquefaction methods, except the sulfuric acid–catalyzed method, which resulted in flow properties comparable to those of other liquefaction methods. The flexural strength of moldings prepared using liquefied wood was also comparable to those prepared by other liquefaction methods.     

水蒸气氛围下木薯渣气化的研究

在水蒸气氛围下,对酒精工业的生产废弃物--木薯渣进行热解气化.研究了木薯渣的热失重情况,并分析温度、升温速率等工艺条件对三相产物产率及组成情况的影响.气体产物主要以H2、CO、CH4和CO2为主;焦油中主要是苯酚类物质,2,6-二叔丁基-4-甲基苯酚(BHT)含量最高,占42.27%.实验结果表明,木薯渣可以通过气化生产可燃气、炭、苯酚类物质,变废为宝.     

Reactivity of lignin in supercritical methanol studied with various lignin model compounds

Behavior of lignin in supercritical methanol (250–270°C, 24–27 MPa) was studied by using lignin model compounds at the tin bath temperature of 270°C with a batch-type reaction vessel. Guaiacol and veratrole were selected as a guaiacyl type of aromatic ring in lignin, while 2,6-dimethoxyphenol and 1,2,3-trimethoxybenzene as a syringyl one. In addition, biphenyl and β-O-4 types of dimeric lignin model compounds were, respectively, studied as condensed and ether linkages between C₆-C₃ phenyl propane units. As a result, both guaiacyl and syringyl types of aromatic rings were very stable, and the biphenyl type was comparatively stable under supercritical conditions of methanol. However, β-ether linkage in the phenolic β-O-4 model compound was cleaved rapidly into guaiacol and coniferyl alcohol, which was further converted to its γ-methyl ether. Non-phenolic β-O-4 model compound was, on the other hand, converted initially into its α-methyl ether and degraded further to produce guaiacol. These lines of evidence imply that in lignin macromolecules, the new phenolic residues are continuously formed and depolymerized repeatedly in supercritical methanol into the lower molecular products, mainly by the cleavage of the dominant β-ether structure in lignin.     

思茅松的苯酚液化及树脂化研究

研究了硫酸催化条件下,将恩茅松在苯酚中液化用于制备酚醛树脂的技术工艺,分析了各工艺参数对思茅松液化效率的影响,测定了由液化产物制备的液化木基酚醛树脂的物理化学性质和胶合强度。结论如下：1）．液比、反应温度、时间和木粉目数是影响液化反应效率的重要因素,液化产物的残渣率均随上述工艺参数值的升高而降低。2）．残渣含量对树脂物化性质和胶合强度均有影响,残渣含量降低,树脂粘度减小,聚合时间缩短,游离酚含量降低,胶合强度升高。3）．甲醛／苯酚摩尔比对树脂的物化性质和胶合强度也有影响,甲醛／苯酚摩尔比增加,树脂粘度增加,聚合时间减少,游离酚含量减低,胶合强度升高。     

落叶松锯屑液化技术的研究

以兴安落叶松锯屑、苯酚为主要原料,以硫酸为主要催化剂,采用均匀设计试验方法和单因子试验法,研究液化温度、液化时间以及硫酸等催化剂的用量对落叶松锯屑液化率的影响。结果表明,酚木比为2.8∶1的前提下,硫酸用量为4%,TSA用量为硫酸的5%,液化温度为135℃,液化时间为120 min时,兴安落叶松锯屑的液化率为95.60%,且液化物中游离酚含量为39.88%,可被溴化物含量为49.33%。     

木材阻燃剂FRW的阻燃机理

在综合分析热分析法、锥形量热仪法和FTIR法获得的FRW阻燃机理研究结果并吸收木材阻燃机理研究现有成果的基础上,推导进而提出了木材阻燃剂FRW的阻燃机理。其主要内容是:1)FRW阻燃木材受热时,阻燃剂FRW分解产生不燃性气体和不挥发的酸性熔融物质,具有降低体系温度和氧气浓度及屏蔽热辐射的作用,降低了木材的热解速度;2)FRW的组分硼酸和GUP的酸性分解产物催化木材脱水、降解,以及木材热解产物的缩合、聚合、芳构化等反应,能改变木材的热解途径并使其向着有利于炭化的方向变化,FRW显著的催化成炭作用,使阻燃木材的燃烧放热量大大降低,这是FRW阻燃机理的主要方面;3)硼酸与GUP起阻燃作用的温度和方式不同,并且有相互补充的作用,因而表现出阻燃协同效应。     

Effects of inorganic acid catalysts on liquefaction of wood in phenol

In order to obtain the effects of acid catalysts on wood liquefaction in phenol, we investigated the liquefaction of wood powder from Chinese fir (Cunninghamia lanceolata) and poplar (Triploid Populus tomentosa Carr) in the presence of phenol with the following weak inorganic acids as catalysts: phosphoric acid (85%), sulfuric acid (36%), hydrochloric acid (37%) and oxalic acid (99.5%). Results show that phosphoric acid (85%) and sulfuric acid (36%) are better than the other catalysts. It was found that lower residue ratios can be obtained under defined reaction conditions: phenol/wood ratio is 4, a 10% catalyst based on the weight of phenol, a temperature of 150°C for 2 h and phosphoric or sulfuric acid. The residue ratios are 3.2% and 4.0%, respectively. __________ Translated from Journal of Beijing Forestry University, 2004, 26(5) [译自: 北京林业大学学报, 2004, 26(5)]     

Preparation of sulfuric acid-catalyzed phenolated wood resin

Summary Birch wood meal was phenolated in the presence of sulfuric acid used as a catalyst by changing several reaction conditions, such as, phenol-to-wood ratio, temperature, time, and catalyst concentration to make novolak-type resin. A phenol-to-wood ratio of 2–5, reaction temperature of 60–150 °C, time of 60–120 min, and acid concentration of 1–3% were found to be usable values for obtaining good enough amounts of combined phenol and less amounts of unreacted wood residue. The flow properties (flow temperature and apparent melt-viscosity) of the phenolated wood obtained increased with the increase in the amount of combined phenol, however, decreased with the increase in the moisture content and free phenol in the phenolated wood. Furthermore, it was found that the solubility of the phenolated wood in the organic solvents depended, greatly, on the hydrogen bonding strength of the solvents.