碳酸甘油酯的合成研究及产业化进展

碳酸甘油酯是一种颇具吸引力的高附加值甘油衍生物，研究以甘油为反应底物制备高附加值的碳酸甘油酯，已成为实现生物柴油副产物甘油综合利用的有效途径之一。本文简述了包括光气法、CO氧化羰化法、酯交换法、尿素醇解法、CO ₂转化法等在内的碳酸甘油酯合成方法，总结了现有碳酸甘油酯合成的主要催化剂及催化合成反应机理，并简要介绍了我国原料甘油市场现状及国内外碳酸甘油酯合成的产业化进展。最后，从技术研发和产业化发展两个方面对碳酸甘油酯合成的未来发展进行了展望，指出一方面应在开发具有高性能催化剂的同时注重催化基础理论的研究，另一方面应在优化工艺流程、降低产品成本的同时注重下游产业应用与替代，并提出我国应推进生物柴油副产物甘油合成碳酸甘油酯的规模化生产与应用示范，加快培育具有国际竞争力的生物质能源与废弃物资源化利用产业。     

Glycerol carbonate synthesis from glycerol and dimethyl carbonate using guanidine ionic liquids

A large number of surplus glycerol from the biodiesel production can be used as renewable feedstock to produce glycerol carbonate.In this paper,a series of guanidine-based ionic liquids were synthesized to catalyze the transesterification of glycerol and dimethyl carbonate.The tunable basicity and the anion-cation cooperative effect were responsible for the obtained results.The [TMG][TFE] showed the best activity turnover frequency (TOF) of 1754.0 h-1,glycerol (GL) conversion of 91.8％,glycerol carbonate (GC) selectivity of 95.5％) at 80 ℃ with 0.1 mol％ catalyst for 30 min.The reaction mechanism of the transesterification was also proposed.     

粗甘油高值化利用研究现状及发展趋势

粗甘油是生物柴油生产过程的副产品，对其进行绿色处理和应用已成为迫切研究的课题。本文分类介绍了粗甘油生物、化学和电化学转化方法的研究现状。在此基础上分别对粗甘油通过生物转化方式生产1,3-丙二醇、氢气等化学品，利用化学转化方式生产丙烯醛和聚氨酯高分子材料和电化学转化方式制备燃料电池的研究现状进行了综述，并分析了粗甘油高值化利用研究及发展趋势。粗甘油生物转化存在培养基成本较高、产物分离困难等不足，限制了目前的工业化应用；化学转化方式还处于初期研究阶段；电化学转化方式作为新兴技术，具有良好的发展空间。本文指出粗甘油可以作为一种新型的生物质资源，粗甘油基化学品与新材料的开发研究具有广阔的发展前景。     

生物柴油副产物甘油产1,3-丙二醇

在生物柴油的生产过程中会产生10%的副产物甘油,随着对生物柴油的大量需求与规模化生产,导致副产物甘油的产量也大幅增加。为了降低生物柴油的生产成本,充分利用副产物甘油是一个非常有效的途径。目前,国内外以甘油为原料通过化学法生产1,3-丙二醇等技术路线已经比较成熟,但其传统化学法存在高温高压操作、释放有毒有害物质等系列问题,而生物催化法以其高产率及高回收率、绿色环保等优势,受到了越来越多的关注。本文主要介绍以甘油为原料,利用生物发酵途径生产1,3-丙二醇的生产技术。     

Synthesis of acrolein by gas‐phase dehydration of glycerol over silica supported Bronsted acidic ionic liquid catalysts

BACKGROUND: Glycerol has become readily available as a byproduct from the biodiesel industry. High functionality and relatively low price make it a potential building block to produce value‐added derivatives such as acrolein. RESULTS: Dehydration of glycerol to acrolein was performed over several silica supported Brønsted acidic ionic liquids as catalysts. All the catalysts prepared were active for the synthesis of acrolein (conversion of glycerol was observed in the range 35–90% with selectivity to acrolein in the range 29–58%). CONCLUSIONS: Catalyst prepared from triphenyl (3‐sulfopropyl) phosphonium 4‐methylbenzenesulfonate gave good activity and selectivity at 4 h reaction time. The conversion of glycerol decreased with increase in glycerol concentration. Higher temperature (325 °C) resulted in significantly lower conversion as well as selectivity to acrolein. With the use of two additional traps cooled to ? 7 °C, the selectivity to acrolein increased significantly for good catalysts. Copyright © 2010 Society of Chemical Industry     

尿素与甘油反应制甘油碳酸酯的绿色合成工艺

以甘油和尿素为原料,探讨了低甘油含量的甘油碳酸酯环境友好的合成工艺。考察了催化剂的结构、反应条件等因素对甘油转化率的影响,结果表明在390℃煅烧3 h的硫酸锌催化效果最好。采用甘油与尿素反应后再与碳酸酯反应的偶合反应方式,所得甘油碳酸酯中甘油的含量仅为0.6%,降低了合成成本。     

Investigation on a green synthetic approach for glycerol carbonate： The reaction of glycerol with urea

以甘油和尿素为原料,探讨了低甘油含量的甘油碳酸酯环境友好的合成工艺。考察了催化剂的结构、反应条件等因素对甘油转化率的影响,结果表明在390 ℃煅烧3 h的硫酸锌催化效果最好。采用甘油与尿素反应后再与碳酸酯反应的偶合反应方式,所得甘油碳酸酯中甘油的含量仅为0.6%,降低了合成成本。     

Production of biodiesel with glycerol carbonate by non‐catalytic supercritical dimethyl carbonate

New biodiesel production processes comprising one‐step and two‐step supercritical dimethyl carbonate methods have been pioneered. The use of dimethyl carbonate allows the reaction conditions to be mild and thus avoid unwanted deterioration of substrates during reaction. In this process, without any catalyst applied, supercritical dimethyl carbonate converts triglycerides (rapeseed oil) into fatty acid methyl esters (FAME) along with glycerol carbonate as a value‐added by‐product, instead of glycerol. Free fatty acids could be also converted into FAME so that the total yield of biodiesel for both methods resulted in over 96 wt%. In addition, the produced FAME satisfy the fuel requirements for the international standards of biodiesel specification.     

超临界制备生物柴油及副产甘油工艺研究

利用植物油和超临界甲醇制备生物柴油及副产甘油,增加了油相在其中的溶解度,提高了原料转化率和产品收率。实验考察了醇油摩尔比、压力、温度、时间等对生物柴油及副产物甘油产率的影响,结果表明:醇油摩尔比、压力、温度、时间等因素对生物柴油及甘油产率影响较为显著。通过正交实验设计得出的超临界甲醇制备生物柴油的工艺条件为醇油摩尔比30∶1,压力20 MPa,温度280℃,保温时间60 m in,生物柴油和甘油产率可分别达到89.14%和88.73%。     

A Robust and Scalable Continuous Flow Process for Glycerol Carbonate

With glycerol being a bulk waste product, the interest in converting it to other value‐added products is steadily increasing. A scalable continuous flow process was developed for the synthesis of glycerol carbonate (2‐GLC) from glycerol and dimethyl carbonate on a hydroxide functional resin. High conversion and selectivity were obtained while the residence times were typically shorter than 10 min. Continuous production of 2‐GLC was achieved in high throughput and with improved processing metrics, creating the foundations for a production level process.     

微生物转化粗甘油制备高附加值产品的研究进展

随着生物柴油产业的发展,其主要副产物粗甘油的产量也逐年增加。大量粗甘油的产生不仅给环境造成了污染,也使精制甘油的市场价格大幅度下降。甘油是一种稳定的多功能化合物,可用作精细化工合成的基本原料。利用微生物转化甘油生产各种生物基化学品,因其具有绿色环保、可持续发展等特点,越来越受到人们的重视。本文简单介绍了甘油经微生物发酵的有氧代谢途径和厌氧代谢途径,重点分析了微生物发酵技术在粗甘油转化为1,3-丙二醇、生物乙醇、乳酸、1,3-二羟基丙酮的应用,旨在为平台化合物的工业化生产提供参考。     

甘油水相重整制氢研究进展

甘油作为生物柴油的副产物,当前的产能严重过剩。甘油制氢,尤其是通过水相重整（APR）制取可以供燃料电池直接使用的高品质氢气,是提高甘油附加值、降低生物柴油成本的重要途径和手段。本文简述了当前生物柴油及其副产物甘油的生产,阐述了甘油的水相重整制氢反应,详细介绍了甘油水相重整制氢反应的热力学和动力学影响因素。分别从催化剂的贵金属活性组分、非贵金属活性组分和载体等三方面对甘油水相重整制氢反应进行了详细的综述,最后提出了双金属催化剂可能具有优异的催化甘油水相重整制氢性能。     

甘油脱水制丙烯醛催化剂的研究进展

伴随着生物柴油的产量不断增大,大量副产的甘油导致了市场过剩。甘油脱水制取丙烯醛是提高生物柴油经济性的一条有效途径。本文结合近年来甘油脱水制丙烯醛的研究进展情况,分析了液相、气相以及超（亚）临界条件下该反应的特点,重点阐述了气相脱水催化剂的研究进展,讨论了催化剂的微观结构、活性组分的酸碱性和氧化还原位等对催化剂活性、选择性和寿命等的影响,分析了催化剂失活的原因。此外,还讨论了甘油脱水过程的反应机理,指出了今后甘油脱水制丙烯醛的研究方向。     

Determination of free glycerol in biodiesel

Within the biodiesel production process, glycerol arises as a side product. This free glycerol is included also in biodiesel in small amounts. Several methods are known to determine it. Some of them are based on gas chromatography (GC). In this paper, a new method is introduced that is based on the extraction of free glycerol into water and its subsequent determination in water solution by high‐performance liquid chromatography (HPLC) with refractometric detection. Comparison of the GC and HPLC methods showed that they led to the same results. The new method is reliable and comparatively fast for the determination of free glycerol in biodiesel.     

均相碱催化法生物柴油副产甘油精制的研究进展

介绍了生物柴油生产过程中甘油的产生情况及均相碱催化法得到的生物柴油副产物的相关成分组成。归纳出均相碱催化法得到的生物柴油副产物甘油的精制全过程,并研究了该精制过程中副产物组分的相关变化,同时分析了精制过程中的相关影响因素(稀释剂的种类及用量、酸的种类及pH值)。提出建议:均相碱催化法制备生物柴油的伴生副产物甘油比较适合采用“预处理分离+粗甘油精制”组合工艺制备高纯度甘油,且预处理分离中常采用甲醇作稀释剂,用磷酸调节pH值比较适宜,同时应将pH值调节在2.5～4.0范围内;分离后的粗甘油经减压蒸馏、离子交换、膜分离、萃取或分子蒸馏等技术精制后,用活性炭吸附脱色,可获得高纯度甘油。     

Kinetics of glycerol effect on biodiesel production for optimal feeding of methanol

The enzymatic production of biodiesel has been considered as an eco-friendly process. Candida antarctica lipase B (CalB) has been studied for its application for biodiesel production because of its high activity and stability. Enzyme deactivation caused by alcohol and effect of glycerol has to be resolved for the industrial application of this process. In traditional kinetic studies of biodiesel production, the effects of alcohol and oil were only considered in the kinetic equation, while the effect by glycerol was neglected. A new kinetic model incorporating glycerol effect is proposed in this paper. The proposed kinetic equation is applied by predicting the supplying rate of methanol in a fed-batch addition of methanol. The conversion rate was improved from 59.7% to 94.6% in a fed-batch by considering glycerol effect.     

甘油催化氧化合成二羟基丙酮研究进展

对甘油选择性催化氧化转化为二羟基丙酮的研究进行综述,介绍了负载型催化剂在不同条件下对产物选择性和反应物转化率的影响,以及催化剂的作用机理。阐述了甘油催化氧化存在的问题以及发展前景。从均相到非均相催化,从单金属到双金属负载催化,从金属到非金属催化,甘油氧化反应的研究不断在完善。研究发现用Bi改性的Pt负载催化剂可以有效地将甘油选择性催化氧化为二羟基丙酮,在最优条件下,可获得较高的甘油转化率和二羟基丙酮选择性,但催化剂稳定性较差,有待进一步提高。杂多酸催化剂以及非金属催化剂也存在稳定性差的问题。指出改善催化剂的稳定性将是未来研究的主要方向。     

碘化铯催化二氧化碳与甘油合成甘油碳酸酯

以不同碱金属(铵)卤化物为催化剂,考察了其在二氧化碳与甘油合成甘油碳酸酯反应中的活性。采用环氧丙烷为溶剂及耦合剂,极大提高了反应的转化率。实验结果发现碘化物具有较好的催化活性。以碘化铯为催化剂,考察了反应温度、反应时间、反应压力、反应物摩尔比和催化剂用量对反应结果的影响。在最佳反应条件下(环氧丙烷0.3 mol,甘油0.1 mol,反应温度120℃,反应时间1.5 h,反应压力3.0 MPa,催化剂用量0.15 g),甘油的转化率为86.5%,甘油碳酸酯的产率为81.6%。     

Characterization of ionic liquid‐based biocatalytic two‐phase reaction system for production of biodiesel

The property of a variety of ionic liquids (ILs) as reaction media was evaluated for the production of biodiesel by enzymatic methanolysis of rapeseed oil. The IL Ammoeng 102, containing tetraaminum cation with C₁₈ acyl and oligoethyleneglycol units, was found to be capable of forming oil/IL biphasic reaction system by mixing with substrates, which is highly effective for the production of biodiesel with more than 98% biodiesel yield and nearly 100% conversion of oil. Conductor‐like screening model for real solvent (COSMO‐RS) in silico prediction of substrate solubility and simulation of partition coefficient change vs. reaction evolution indicated that the amphiphilic property of Ammoeng 102 might be responsible for creating efficient interaction of immiscible substrates; while big difference of partition coefficients of generated biodiesel and glycerol between the two phases suggests a large chemical potential to move reaction equilibrium for maximum oil conversion and yield of target biodiesel. The reaction behavior and specificity of oil/IL biphasic system for enzymatic production of biodiesel were theoretically delineated through COSMO‐RS computation with experimental validation. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

KF/C催化甘油酯交换合成碳酸甘油酯

以三嵌段共聚物(EO-PO-EO)F127为结构导向剂,甲阶酚醛树脂为碳源,KF·2H₂O为无机前驱体,用溶剂诱导挥发自组装的方法合成KF/C复合材料。采用XRD、BET和XPS等手段对合成的材料进行结构表征,并考察KF/C在甘油与碳酸二甲酯酯交换合成碳酸甘油酯反应中的性能,结果表明,在甘油加入量为0.184 6 g、碳酸二甲酯加入量为0.900 7 g、溶剂N,N-二甲基乙酰胺为5.426 g、催化剂KF/C加入量为0.1 g、反应温度100 ℃、反应时间2 h和搅拌速率600 r·min^-1条件下,甘油转化率达98.5%,碳酸甘油酯选择性达99.8%,催化剂具有较好的循环使用性能。