Catalytic pyrolysis of cellulose in sulfolane with some acidic catalysts

Catalytic pyrolysis of cellulose in sulfolane (tetramethylene sulfone) with sulfuric acid or polyphosphoric acid gave levoglucosenone, furfural, and 5-hydroxymethyl furfural (5-HMF) up to 42.2%, 26.9%, and 8.8% (as mol% yield based on the glucose unit), respectively. Pyrolysis behaviors of the intermediates indicated the conversion pathways, and the conversion: levoglucosenone → furfural was found to require water. The control of the water content in the pyrolysis medium was quite effective in controlling the product selectivity between levoglucosenone and furfural: mild vacuum conditions to remove the product water dramatically enhanced the levoglucosenone yield, while steam distillation conditions increased the furfural and 5-HMF yields.     

糠醛连续精制新流程的研究

本文为糠醛连续精制技术的系列报告之一。本研究所采用的流程系在原研究基础上提出的新流程,具有第二代连续精制流程的性质。研究属中间试验性质,在生产规模下进行;研究的主要目的是为了对新流程的可行性及有关技术经济指标进行测定及论证。新流程的主要特点是:①从脱水塔顶馏份水层脱去低沸点杂质并回收糠醛;②连续回收精制塔釜液所含糠醛;③从中和前粗醛水层中回收糠醛;④利用玉米芯为原料生产糠醛时精制塔精馏过程可以省略。测试结果表明新流程在技术上是可行的,较原流程可节约设备投资20.0％及金属材料11.9％。产品质量符合工业糠醛国家标准GB 1926-80所规定的优级品指标。     

Acid prehydrolysis of pinus pinaster bark with dilute sulfuric acid

Summary The influence of temperature (100–150°C) and acid concentration (0–5 wt%) on the prehydrolysis of pine bark and its alkaline-extracted residues was studied (the latter were obtained by vigorously stirring the bark for 15 min with a solid/liquid ratio of 1:10). Optimal prehydrolysis conditions were established by the sectioning method with a solid/liquid ratio of 1:10. For milled bark these conditions were: temperature 125°C, sulphuric acid concentration 2 wt%, duration of prehydrolysis 4.5 h; and for alkali-extracted residues, temperature 125°C, sulphuric acid concentration 3 wt%, duration of prehydrolysis 5 h. These treatments removed respectively 90% and 75% of non-glucose sugars in the hydrolysate while solubilizing less than 20% (respectively 10%) of the potential glucose yield. Enzymatic digestion of bark successively alkali-extracted and prehydrolysed under optimal conditions gave poor results, with yields similar to those obtained after other pretreatments.This work was supported by the CAICYT (Pr. 0030/85)     

催化木糖制备 呋喃甲醛的研究

为了使呋喃甲醛的制备过程绿色化,以ZrOCl2为原料,利用沉淀-浸渍法初步制备了SO42-/ZrO2固体酸,并应用于催化木糖制备呋喃甲醛的反应。采用L9(34)正交试验确定了适宜的反应条件:木糖质量浓度10 g/L、催化剂用量20 g/L、反应温度220℃、反应时间3 h。之后采用单因素试验考察了催化剂制备条件对呋喃甲醛产率的影响。得到的催化剂最佳制备条件为:H2SO4浸渍浓度1.0 mol/L、焙烧温度550℃、焙烧时间5 h,呋喃甲醛产率达最大值47%。实验结果表明:SO42-/ZrO2固体酸在催化木糖制备呋喃甲醛方面,具有较大发展潜力。     

锯木屑蒸汽爆破预处理制备糠醛的研究

以锯木屑为原料,采用蒸汽爆破进行预处理,然后酸催化提取糠醛。探讨了预处理温度、爆破压力、预处理时间及液料比等因素对糠醛得率的影响。采用响应面法建立二次回归模型,并对预处理工艺进行了优化。研究结果表明:预处理能有效的促进锯木屑的降解,提高糠醛的得率。在预处理温度为216℃、爆破压力1.8 MPa、预处理时间6 min、液料比3∶1(mL∶g)时,糠醛的得率(79.13%)比相同条件下未进行蒸汽爆破预处理的试样(55.35%)提高了23.78个百分点。     

玉米秸秆蒸汽爆破降解产物的分析

采用高效液相色谱(HPLC)和气质联用(GC-MS)色谱技术对玉米秸秆蒸汽爆破降解产物进行分析.玉米秸秆经蒸汽爆破预处理后,其纤维素、半纤维素和木质素降解损失分别为9.60%、47.98%和17.55%.采用HPLC对碳水化合物降解和分解产物定量分析,100g玉米秸秆预处理后,产生甲酸2.10g、乙酸2.00g、乙酰丙酸0.10g、5-羟甲基糠醛0.08g和糠醛0.13g.采用GC-MS对木质素和提取物降解产物定性分析,共检测出14种芳香类化合物、22种脂肪酸类化合物和5种呋喃化合物.     

K~+/CaO催化糠醛与甲基异丁基酮缩合制备生物航空燃料中间体

将K_2CO_3溶于去离子水后,室温下负载到活化后的CaO上,采用"等体积浸渍-焙烧法"制备了负载型固体碱催化剂K~+/CaO,并用XRD和CO_2程序升温脱附(CO_2-TPD)对催化剂进行表征。研究了无溶剂条件下K~+/CaO催化糠醛与甲基异丁基酮缩合制备生物航空燃料中间体——亚糠基甲基异丁基酮(F-MIBK)的反应,考察了催化剂种类、K~+/CaO负载量、反应温度、反应时间及物料比等因素对目标产物收率和选择性的影响。结果表明:糠醛与甲基异丁基酮的缩合反应是在催化剂的强碱性位上进行的,K~+的加入明显提高了CaO的碱性,K_2CO_3负载量为1%时,催化剂K~+/CaO表现出了最优的催化性能;当甲基异丁基酮与糠醛的物质的量比值为2,催化剂用量为物料质量的10%,温度140℃,反应时间3 h时,糠醛的转化率为99.1%,F-MIBK的选择性和收率分别为98.2%,97.1%。     

First results on synchrony between seasonal pattern of pheromone trap captures of cotton bollworm, <Emphasis Type="Italic">Helicoverpa armigera</Emphasis> and appearance of freshly emerged larvae on developing cobs of corn hybrids

Synchrony between development of five corn hybrid varieties of various seasonal growing rates (FAO numbers), seasonal flight pattern of male cotton bollworm, Helicoverpa armigera Hb. (Lepidoptera: Noctuidae), as monitored by pheromone traps, and the subsequent appearance of newly hatched larvae on developing cobs were studied at Mezőhegyes, South-Hungary, in 2003 and 2004. The phenological stages of corn hybrids were evaluated using the Iowa State University Scale (R₁–R₅), the flight of male moths was monitored by large capacity, funnel type of pheromone traps and the appearance of freshly hatched larvae on developing cobs were counted by visual inspection. The synchrony between the flight peak of male moths and the peak apperance of L₁ larvae on cobs was investigated by cross-correlation. In 2003 (average daily temperatures 20.7°C, average daily relative humidity 59.9% for the period of 4–18 July) “DK 391”, “DK 443” and “Maraton” hybrid varieties already reached silking stage (R₁) by the time when pheromone traps indicated a peak, at 7 July (peak capture at 3-day intervals 755.5 males/traps). The number of L₁ larvae peaked on developing cobs of these varieties also at 7 July (7.0, 4.0 and 3.8 larvae/50 cobs, respectively). The synchrony between the flight peak of male moths and the peak appearance of L₁ larvae on cobs was proven (LAG = 0). A rather similar trend was observed in “Vilma” hybrid variety: it reached R₁ stage at 7 July, and L₁ larvae appeared only a few days later (11 July, 3.8 larvae/50 cobs) (LAG = −1). However, “Maxima” hybrid variety reached R₁ stage 1 week later (14 July) than the time of peak captures. Here L₁ larvae peaked as late as at 18 July (0.8 larvae/50 cobs), i.e., only after the cob had reached R₁ stage (LAG = −3). A reverse order of dates of R₁ stage and peak capture was observed in “Maxima” in 2004 (average daily temperatures; 22.5°C, average daily relative humidities 72.6% for the period of 15 July–6 August): it reached R₁ stage at 19 July, while peak trap captures were recorded at 6 August (peak capture at 3-day intervals 20.5 males/traps). L₁ larvae were found in the highest numbers on 2 August (1.5 larvae/50 cobs), practically in synchrony with peak caputres (LAG = 0). “Káma” reached R₁ stage in 16 July, and L₁ larvae peaked at 2 August (1.3 larvae/50 cobs) (LAG = 0). On the rest of the corn varieties larvae were found only in too numbers for performing statistical analysis. We conclude that in order to predict the appearance of L₁ larvae, the phenological stage of the corn variety and the seasonal flight pattern of moths, as measured by large capacity pheromone traps, should be considered in combination. If the corn variety already reached R₁ stage, L₁ larvae appear on cobs as early as the time of peak flight of moths. However, no young larvae appear on cobs despite of high trap captures, until the corn reaches the R₁ stage. These findings are discussed in the view of specifying optimal timing of a pesticide application.     

蒸汽爆破木质纤维原料的乙醇脱毒研究

以乙醇为溶剂,采用抽提的方法去除蒸汽爆破玉米秸秆中的甲酸、乙酸、糠醛及羟甲基糠醛等抑制物,比较了动态和静态两种不同的抽提方法对抑制物和糖的抽提效果,考察了温度、固液比和时间等因素对不同条件下乙醇静态抽提效果的影响。以总抑制物抽提率/总糖抽提率为评价指标,通过正交试验,对温度、固液比、时间3个因素在不同水平下的乙醇静态抽提效果进行直观分析和方差分析,确定了乙醇静态抽提的最佳试验条件为:温度80℃,固液比1∶10(g∶mL),抽提时间60 min。在最佳试验条件下,两种最重要的抑制物甲酸和乙酸的抽提率分别达到84%和98%。     

固体酸水解玉米秸秆制备糠醛的研究

为了减少使用液体酸制备糠醛时对环境的影响,以玉米秸秆为原料,以SO42--TiO2/黏土固体酸为催化剂制备糠醛.对水解温度、时间和固体酸用量等主要影响因素进行了分析,采用响应面法对制备工艺进行了优化,并建立了二次回归模型.当玉米秸秆的粒度为O.45mm、固液比1:10(g:mL)、水解温度为158℃,水解时间为3.8 ...