泵注入方式进料催化菊芋根茎溶液制备多元醇

以硝酸镍和偏钨酸铵为前驱体,活性炭(AC)为载体,通过等体积浸渍氢气还原法分别制备Ni-W2C/AC和Ni/AC催化剂,利用N2吸附仪、XRD、TEM、TG和XRF等对催化剂及原料进行表征。釜式反应器中,对催化剂催化果糖或果糖基能源植物菊芋根茎制备多元醇高附加值化合物进行评价。结果表明,相同反应温度下,与间歇进料方式相比,泵注入方式能进一步提高1,2-丙二醇和乙二醇收率。以果糖为底物,泵速0.5 m L·min-1条件下,氢气起始压力4.0 MPa、温度245℃时,1,2-丙二醇和乙二醇收率分别为41.4%和18.7%,二者总收率较间歇进料增加17.9个百分点;以菊芋根茎为底物,氢气起始压力3.5 MPa、温度255℃时,1,2-丙二醇和乙二醇收率分别为37.7%和27.4%,二者总收率较间歇进料增加10.7个百分点。结合果糖、葡萄糖分子在氢气气氛下进行的逆羟醛缩合和加氢过程,分析泵注入进料提高1,2-丙二醇和乙二醇收率的主要原因。     

生物质多元醇选择性催化氢解制小分子二元醇研究进展

乙二醇、1,2-/1,3-丙二醇等小分子二元醇在精细和有机化工、生物医药等领域应用广泛。与石化路径相比,以可再生的生物质多元醇（丙三醇、山梨醇/木糖醇）为原料选择性催化氢解制取上述小分子二元醇具有过程简单、绿色高效等显著优势,已成为生物质催化转化的研究热点。本文综述了典型生物质多元醇山梨醇/木糖醇和丙三醇选择性催化氢解为乙二醇、1,2-/1,3-丙二醇等小分子二元醇,重点阐述了丙三醇选择性氢解制1,2-丙二醇、1,3-丙二醇和山梨醇/木糖醇选择性氢解制小分子二元醇的催化剂体系和反应机理,并对该领域的发展前景作了展望,提出开发高效稳定的催化剂体系和工艺是未来的研究重点。     

高分子量聚醚多元醇的研制

在高压反应釜中，采用双金属催化剂，以丙三醇和环氧丙烷为原料，制备了高分子量（Mn≥8000）聚氧化丙烯三醇，其不饱和度为0．010~0．017mol／kg。结果表明，在该体系中，反应最佳条件为：反应温度（85±5）℃，反应时间4~6h，环氧丙烷与丙三醇投料质量比为120／1~200／1，催化剂质量分数为0．12％~0．18％，加适量的溶剂有利于提高聚醚的分子量。     

以丙三醇和氯化氢为原料制备环氧氯丙烷的工艺研究

介绍了以丙三醇和氯化氢为原料制备环氧氯丙烷的工艺,以己二酸为催化剂进行丙三醇的氯化反应,生成的二氯丙醇再和碱反应生成环氧氯丙烷。对影响反应的因素进行了研究,得出了最佳工艺条件：氯化反应温度120℃,氯化氢的通气量326．4mL／min,反应时间20h,催化剂物质的量为丙三醇的16％,环化反应采用1．9mol／L的氢氧化钠在30℃下进行较为合适。在此条件下得到的环氧氯丙烷收率为91．79％。     

一种新型可生物降解聚酯压敏胶的制备与性能

以丁二酸、己二酸、1,3丙-二醇、1,4丁-二醇为单体,C-94为催化剂,丙三醇为交联剂,制备了一种新型的、可生物降解的四元无规共聚酯压敏胶,使用核磁共振波谱仪测定了共聚酯中各单元的组成比例,并对其黏弹性、初黏性、持黏性、180°剥离强度等进行了表征,考察了交联剂用量对压敏胶性能的影响。实验结果表明,丙三醇质量分数为0.6%时,压敏胶性能较佳。     

几种甲基磺酸盐催化合成缩醛(酮)的研究

以甲基磺酸盐为催化剂合成了苯甲醛缩乙二醇和环己酮缩乙二醇。考察了影响收率的因素,优化合成条件为n醛（酮）：n二醇：n催化剂：V带水剂为0．2mol：O．3mol：3．2mmol：15mL,反应在回流温度下进行2．5h。当以甲基磺酸锌为催化剂时,苯甲醛缩乙二醇的收率可达87．7％。甲基磺酸锌等甲基磺酸盐对缩醛（酮）的合成反应具有较高的催化活性。     

具有C2轴对称的吡啶类手性醇、醚配体的合成

以2,6-二甲基吡啶为原料,在丁基锂作用下分别与手性酮、手性醇合成了具有C2轴对称的手性醇和手性醚化合物。所有化合物经IR、1HNMR、13CNMR等进行了表征及结构确证,为制备具有手性配体的金属催化剂以及探索其在手性二级醇的选择性催化氧化方面打下了良好基础。     

直接酯化法合成1,3-丙三醇二丙烯酸酯

以丙三醇和丙烯酸为原料直接酯化合成1,3-丙三醇二丙烯酸酯,并系统地研究了带水剂、阻聚剂、催化剂、醇酸比、反应时间等对酯化反应的影响。研究表明,带水剂与阻聚剂显著地抑制了反应过程中副产物的生成,且在70 mL环己烷为带水剂,1.5 g对甲苯磺酸为催化剂,对甲氧基苯酚与吩噻嗪复配成的复合阻聚剂1.5 g,丙三醇与丙烯酸的物质的量之比为1∶2.4,反应时间为9 h的条件下酯化生成1,3-丙三醇二丙烯酸酯的产率可达88.1%。     

氯化铁催化合成二乙酸乙二醇酯

利用氯化铁水合物为催化剂,从乙二醇和冰醋酸制备了二乙酸乙二醇酯,在最佳条件下其收率达９２％ 。     

卷烟烟丝中1,2-丙二醇和丙三醇含量测试方法的改进

为了快速测定卷烟烟丝中1,2-丙二醇和丙三醇的含量,通过气相色谱-质谱联用仪(GC-MS)结合内标法建立了上述两种保润剂的定量分析方法。结果表明:1,2-丙二醇和丙三醇的相对标准偏差(RSD)均在5%以内,回收率分别在98.59%～103.87%和95.12%～104.76%范围内,检测限和定量限分别为3.28、10.95μg/g和15.95、53.18μg/g,表明该法具有较好的重现性和准确性。与行业标准方法相比较,两种方法之间没有显著性差异,表明该法可用于快速地测定卷烟烟丝中1,2-丙二醇和丙三醇的含量。     

Isocyanate-modified dehydrated castor oil

Esters of dehydrated castor oil fatty acids with polyhydric alcohols like ethylene glycol, propylene glycol, glycerol, pentaerythritol and sorbitol have been prepared. The esters, having hydroxyl value ranging from 78.5 to 167, were reacted with toluene diisocyanate. The scratch hardness and other film properties of the resulting urethanes have been studied. Urethanes obtained from various mixtures of the above esters also have been studied. The best results have been obtained when a mixture of ethylene glycol ester and plenaerythritol ester of dehydrated castor oil fatty acids in the ratio of 4:1 are reacted with one equivalent of toluene diisocyanate. One equivalent of glycerol ester (hydroxyl value 78.5), ethylene glycol ester (hydroxyl value 167), or propylene glycol ester (hydroxyl value 159.4) of DCO fatty acids when reacted with 1.25 equivalent of toluene diisocyanate also gave satisfactory products.     

回收PET醇解催化剂的研究及机理分析

采用回收PET制备不饱和聚酯,探讨了不同催化体系中最佳醇解条件。当控制醇解产物分子量在600左右时,在相同温度(185℃),相同丙二醇/PET摩尔比(1.6)和相同催化剂用量(0.5%,质量比)的情况下,在乙酸锌催化体系中,乙酸锌/二环己胺为0.4(摩尔比),反应2h;在乙酸锰催化体系中,乙酸锰/环己胺为0.2(摩尔比),反应4h。     

Anodic Oxidation of Polyhydric Alcohols on a Pt Electrode in Alkaline Solution

The electrochemical oxidation of various polyhydric alcohols, ethylene glycol, glycerol, meso-erythoritol, and xylitol, on a platinum electrode was investigated systemematically in acidic H₂SO₄, and in alkaline KOH and K₂CO₃ solutions to evaluate the potential of these polyhydric alcohols as fuels in micro-fuel cells for portable electronic devices. All polyhydric alcohols tested in the present study showed high reactivities in both alkaline solutions. Ethylene glycol showed the highest reactivity. Although the reactivity of ethylene glycol was lower in K₂CO₃ than in KOH, the carbonate solution is a potential candidate as an electrolyte solution due to its resistance to solution carbonation. Furthermore, ethylene glycol showed much less significant electrode poisoning by adsorbed CO upon oxidation in alkaline solution.     

Effect of polyhydric alcohols on the mechanical and thermal properties,porosities, and air permeabilities of polyurethane-blended films

Polyurethane (PU) and polyhydric alcohols composites were successfully prepared to be used as coating materials for fabrics. The effects of various polyhydric alcohols on the PU composites properties have been investigated. The tensile strengths, glass-transition temperatures, thermal-mechanical properties, and swelling capacities of the PU/polyhydric-alcohol-blended films are described in detail, along with their surface and cross-sectional morphologies. The tensile strengths and glass-transition temperatures of the PU/polyhydric-alcohol-blended films were found to decrease remarkably with increasing polyhydric-alcohol concentration. The swelling capacities and porosities of the PU/poly(propylene glycol) (PPG)-blended and PU/glycerol-blended films were observed to increase with increasing PPG or glycerol concentration. However, the poly(ethylene glycol) (PEG) concentration in the PU/PEG-blended film did not significantly affect its properties. The air and water-vapor permeability of nonwoven nylon fabrics coated with PU/PPG and PU/glycerol increased with increasing PPG or glycerol contents, while those coated with PU/PEG were unaffected by PEG content. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47429.     

Carbon nanofibers supported Ru catalyst for sorbitol hydrogenolysis to glycols: Effect of calcination

Carbon nanofiber (CNFs) supported Ru catalysts for sorbitol hydrogenolysis to ethylene glycol and propylene glycol were prepared by incipient wetness impregnation, calcination and reduction. The effect of calcination on catalyst properties was investigated using thermal gravimetry analysis, temperature-programmed reduction, X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy and N₂ physisorption. The results indicated that calcination introduced a great amount of surface oxygen-containing groups (SOCGs) onto CNF surface and induced the phase transformation of Ru species, but slightly changed the texture of Ru/CNFs. The catalytic performance in sorbitol hydrogenolysis showed that Ru/CNFs catalyst calcined at 240 °C presented the highest glycol selectivities and reasonable glycol yields. It was believed that the inhibition and confinement effect of SOCGs around Ru particles as well as the high dispersion of Ru particles was the key factor for the catalytic activity.     

Effect of Selected Polyhydric Alcohols on Refining Oil Loss in the Neutralization Step

Alkaline neutralization is a classical method for removal of free fatty acids (FFA) in crude oil. It is generally accompanied by neutral oil loss. Thus, reduction of refining losses associated with alkaline neutralization is very desirable. Refined, bleached and deodorized (RBD) palm oils with different FFA contents were used as oil models in this study. FFA in the oil models were neutralized with sodium hydroxide in polyhydric alcohols as neutralization media. Glycerol, propylene glycol and ethylene glycol in water were effective neutralization media. FFA in the oil models were totally removed in one step of neutralization, while percentages of refining losses were different. The losses were increased in the order of water > propylene glycol > ethylene glycol > glycerol used as neutralization media. Also, a higher concentration of polyhydric alcohol in the neutralizing media significantly reduced the percentage of refining loss (p < 0.05). Glycerol (90% in water) was the most effective neutralization media (p < 0.05). When neutralization was carried out on crude palm oil (containing 7.53% FFA), refining loss was reduced from 36.1% (in water) to 20.0% (in 90% glycerol in water).     

A1C13／（NH4）2HPO4催化直接法合成乙二醇单甲醚

开发了非石油路线法合成乙二醇单甲醚的新工艺,即以煤制乙二醇为原料和甲醇直接法合成乙二醇单甲醚。以A1Cl3／（NH4）2HPO4做复合催化剂,考察了A1C13／（NH4）2HPO2复合催化剂不同比例、催化剂的用量、反应温度、压力、时间等因素对反应的影响。确定适宜条件为AICl3／（NH4）2HPO4复合催化剂的质量比为1：2．5,催化剂的质量占乙二醇质量的4％,乙二醇／甲醇物质的量比为1：4,反应温度260℃,反应时间4h,反应压力7MPa,此时乙二醇转化率为39％,乙二醇单甲醚选择性84％,乙二醇单甲醚收率32％。并对反应机理进行了初步探讨。     

Bifunctional Materials for the Catalytic Conversion of Cellulose into Soluble Renewable Biorefinery Feedstocks

The combination of Br?nsted acidity with metallic functionality in a mesoporous catalyst offers a potential pathway for the conversion of cellulose into sugar alcohols that may be used as a sustainable source of renewable biorefinery feedstock. Supported Ru catalysts were prepared by evaporative deposition on various ordered mesoporous silicas (SBA-15) with different functionalities and characterized using multiple experimental techniques. The catalytic performance of the supported Ru catalysts was compared to that of the corresponding supports and of Ru/C. We studied the effects of functional group loading, reaction time and temperature on the activity and products yield of the bifunctional catalysts by monitoring the cellulose conversion and the production of sugars and sugar alcohols in a high-pressure batch reactor. Sorbitol is the main product obtained by the hydrolysis of cellulose to glucose followed by the corresponding reduction. Secondary products include sugars, ethylene glycol and glycerol. The activity of mesoporous silica catalysts increases with an increase in acid loading and the addition of Ru allows control of the selectivity towards sugar alcohols. Ruthenium supported on arenesulfonic acid-functionalized mesoporous silica (Ru/SBA-15S) displays the best catalytic performance. Ru/SBA-15S is more hydrothermally stable than SBA-15, but loses a significant fraction of its surface area, crystallinity, acidity and activity after prolonged exposure to water at 483?K.     

A multi-functional Ru Mo bimetallic catalyst for ultra-efficient C3 alcohols production from liquid phase hydrogenolysis of glycerol

Ru and Mo bimetallic catalysts supported on active carbon modified by phosphotungstic acid (PW) were designed and applied in glycerol hydrogenolysis reaction. The physicochemical properties of the catalysts were characterized and the presence of active sites was investigated from the perspective of the glycerol hydrogenolysis performance. The MoO_x is highly selective for the C—O bond cleavage of glycerol molecules, which can reasonably regulate the strong C—C bond cleavage activity of Ru nanoparticles. By using sequential deposition of Ru and Mo supported on mesoporous PW-C, the characterization results show that the combination of isolated low-valence MoO_x with metal Ru particles can form “MoO_x-Ru-PW”, which provides highly catalytic activity toward C—O bond cleavage, selectively producing more C3 alcohols (mainly 1,2(3)-propanediol). The glycerol conversion of 1% Mo/Ru/PW-C catalyst was 59.6%, the selectivity of C3 alcohol was 96.1%, and the selectivity of propanediol (1,2(3)-propanediol) was 94.9%. It is noteworthy that the selectivity of 1,3-propanediol reached 20.7% when the PW was 21.07% (mass). This study provides experimental evidence for the tandem dehydration and hydrogenation mechanism of the multifunctional Mo/Ru/PW-C catalyst.     

乙二醇双琥珀酸烷基聚氧乙烯醚双酯磺酸钠的合成及泡沫性能研究

采用乙二醇、马来酸酐和脂肪醇聚氧乙烯醚(AEO3)为主要原料,采用两步酯化反应和磺化反应,在催化剂的作用下,合成了一种阴非离子型双子表面活性剂。各步反应的最佳条件:酯化反应Ⅰ(反应温度120℃,马来酸酐与乙二醇的摩尔比为2.15∶1,催化剂用量2%,反应时间4 h);酯化反应Ⅱ(AEO3∶酯化产物Ⅰ摩尔比为2.10,反应温度180℃,催化剂用量3%,反应时间6 h);磺化反应(温度100℃,亚硫酸氢钠与酯化产物摩尔比为1∶3,催化剂用量1.5%,反应时间4 h)。产物的临界胶束浓度为0.17 mmol/L,γCMC为35.2 m N/m,浓度750 mg/L时,泡沫性能达到稳定。