基于纤维素的固体酸催化剂的制备及其催化高酸值废油脂生产生物柴油

以廉价的纤维素为原料,经不完全炭化和磺化制得含高密度(1.69 mmol/g) SO3H基团的固体酸催化剂Cellulose-SO3H.结果表明,该催化剂适宜的制备条件为:在400℃炭化15h,再在150℃磺化15h.所得催化剂在油酸与甲醇的酯化反应中表现出明显高于其它几种典型固体酸催化剂(铌酸,Amberlyst- ...     

固体酸改质生物油的研究

利用乙酸和乙醇生成乙酸乙酯的酯化反应为模型反应,筛选得到催化活性最好的固体酸催化剂40％SiO2/TiO2SO42－。 在一定的反应条件下,添加固体酸催化剂和溶剂,生物油的品质得到提高,热值提高了50.7％,运动黏度降低到原来的10％,密度降低了22.6％。生物油改质前后的GC MS分析表明,固体酸可以将生物油中含有的有机羧酸转化为酯类,如甲酸酯、乙酸酯等,使生物油中的羧酸组分发生了催化酯化反应,改善了生物油的品质,生物油物理化学性能得到明显的提高。3A分子筛对生物油的脱水作用不显著,对酸性、密度、黏度等方面影响较小。     

高酸值生物柴油原料甘油酯化脱酸研究

利用共沉淀-浸渍法制备了Al改性固体酸催化剂SO₄^2-/ZrO₂,考察了催化剂在甘油酯化脱酸制备生物柴油原料反应中的催化活性、重复利用性和再生性能,并对使用前后的催化剂进行了红外光谱分析。研究表明,添加适量Al(1%,以Al₂O₃的质量分数计)不但提高了催化剂的活性,还改善了催化剂的重复利用性和再生性能。添加Al使ZrO₂上SO₄^2-的量增加,SO₄^2-结合强度增强,减少了在酯化脱酸反应过程中SO₄^2-的流失。在SO₄^2-/ZrO₂-Al₂O₃催化剂用量为7％、甘油与酸物质的量比为6:1、反应温度为140 ℃、反应时间为4 h的条件下,酯化率可达91%以上,可将高酸值油脂的酸值从31 mg_KOH/g降低到2.8 mg_KOH/g以下,可满足生物柴油原料的要求。     

柴油溶剂中脂肪酶催化高酸值废油脂酯化制备生物柴油

采用0＃柴油作为反应溶剂,利用固定化脂肪酶催化高酸值废油脂与甲醇酯化反应制备生物柴油。来源于Candida antarctica的固定化脂肪酶Novozym435在0＃柴油溶剂中具有极高的催化活性。以酸价高达157×10-3的废油脂为原料,废油脂质量比10%的Novozym435,甲醇与废油脂初始摩尔比2∶1,0＃柴油与废油脂质量比5∶1,摇床摇速170r/min,50℃下反应2h甲酯化率可达95.10%。0＃柴油作为反应溶剂有效地溶解了高酸值废油脂和甲醇,降低了反应体系的黏度和消除了甲醇对Novozym435的负面影响,提高了Novozym435的稳定性。同时,0＃柴油溶剂对未脱胶废油脂中残留的对脂肪酶有害的磷脂等胶类物质具有一定的稀释作用。该工艺省却了溶剂蒸馏的繁琐工序,直接得到脂肪酸甲酯和石化柴油的混合燃料。     

固体酸催化剂催化酯化反应研究：Ⅰ.催化剂的制备及性能

酯化反应是基本有机化学中的一个重要反应,传统上使用的浓H_2SO_4催化剂常常引起一些严重问题.如:设备腐蚀严重,引起副反应及产生大量难以处理的含酸残液等.近年来,采用各种分子筛,氧化物及超强酸等作为该过程的催化剂的研究工作多见报道,这些工作无疑具有重要意义,但主要问题在于低温催化活性不高.     

固体酸燃料电池

固体酸燃料电池(SAFCs)具有不渗透燃料、较高电极催化活性和抗一氧化碳中毒的特点,作为燃料电池领域一个崭新的研究方向,具有良好的发展前景.本文概述了固体酸燃料电池的发展背景及目前的研究状况,较详细地介绍分析以固体酸为电解质膜的燃料电池反应机理及其研究进展,展望了固体酸燃料电池的发展前景,提出了固体酸燃料电池能得以应用必须解决的一些瓶颈因素.     

催化合成丙烯酸高级醇酯的新型固体酸催化剂

丙烯酸高级醇是重要的精细化工产品和高分子聚合物单体，在涂料、石油降凝剂、建筑、造纸及皮革、化工等领域都有广泛的用途［１，２］。以往工业上用浓硫酸等作为催化剂合成，有腐蚀设备、产品难分离等弊端。本文采用的两种固体催化剂，具有活性高、性能稳定、价格便宜、...     

新型高效乙酸丁酯合成固体酸催化剂及其反应工艺

酯化反应是精细化学工业中极为重要的一类反应 ,目前工业上均在硫酸液相催化下直接酯化制取。硫酸腐蚀反应器 ,污染环境 ,随着环保法规的不断完善 ,开发可替代硫酸的新型催化体系已成为现代化学工业中普遍关注的新趋势。目前的研究工作主要集中在以固体酸 (尤其是 SO2 - 4/Mx Oy 型固体酸 )替代硫酸催化酯化反应 [1～ 8]。我们制得了一种新型 SO2 - 4/Fe2 O3- Zr O2 - Si O2 催化剂[9] ,该催化剂催化乙酸 /丁醇酯化反应表现出良好的转化率、选择性、酯收率。考察了反应温度、反应时间、催化剂加入量等对乙酸 /丁醇酯化反应的影响 ,并考…     

生物质炭基固体酸催化剂的制备

 以生物质木粉为原料, 采用炭化-磺化法制备了炭基固体酸催化剂, 并用于油酸与甲醇的酯化反应, 考察了制备条件对炭基固体酸催化剂活性的影响. 采用 X 射线衍射、红外光谱、热重分析、高分辨透射电子显微镜及元素分析等手段对催化剂进行了表征. 结果表明, 由生物质木粉制备的炭基固体酸催化剂具有较高催化酯化反应活性, 在 400 oC 下炭化 0.5 h, 135 oC 下磺化 1 h 制备的炭基固体酸催化剂在精馏分水连续酯化装置中催化油酸与甲醇的酯化反应 2 h 时, 酯化转化率达到 96%. 采用炭化-磺化法制备的生物质炭基固体酸催化剂具有蠕虫状的无序乱层炭结构, 磺酸基 (－SO3H) 含量高达 13.25%, 并且在 220 oC 以下时具有良好的热稳定性.     

填料型固体酸的制备及其催化性能

用阳极氧化法制备了填料式Al₂O₃-Al载体,经浸渍H₂SO₄后再焙烧制得SO₄^2-/Al₂O₃-Al固体酸催化剂.用SEM,BET,XRD和NH3-TPD等手段对其进行了表征,结果显示,载体Al₂O₃膜为无定形结构,SO₄^2-/Al₂O₃-Al为中等酸强度的固体酸.用乙酸-乙醇酯化催化反应评估了该固体酸的催化性能,显示出催化剂具有较高的催化活性,且稳定性较好.     

Heterogeneous Solid Acid Catalysts for Esterification of Free Fatty Acids

Use of low-quality (and inexpensive) feedstock such as waste oils and animal fats for biodiesel synthesis has been continuously researched as a prospective means of improving the economic efficiency of the process. Pretreatment of free fatty acids by catalytic esterification is necessary for achieving this purpose. This paper reviews some relevant studies on heterogeneous acid catalysts that have been shown to be effective for this reaction.     

Esterification by ZrO2 and Mo-ZrO2 ECO-Friendly Solid Acid Catalysts

Esterification of mono-and dicarboxylic acids catalysed by single (ZrO₂) and mixed oxide (Mo-ZrO₂) eco-friendly solid acid catalysts is described. The Mo-ZrO₂ catalyst exhibits better catalytic performance than ZrO₂.     

Al_2O_3掺杂SO_4~(2-)/SnO_2固体酸催化剂上的酯化和酯交换反应

用共沉淀法制备了一系列不同Al2O3掺杂量(0.5%-3.0%,摩尔分数)的SO24-/SnO2催化剂.采用N2吸附、热重(TG)分析、X射线粉末衍射(XRD)、X射线光电子能谱(XPS)、漫反射红外光谱(DRIFTS)、拉曼(Raman)光谱、魔角旋转固体核磁共振(27AlMASNMR)对催化剂的结构和织构性质进行了表征,用正丁胺电位滴定法测定了催化剂的酸量,并评价了这些催化剂对月桂酸与甲醇的酯化和三乙酸甘油酯与甲醇的酯交换反应性能.实验结果表明SO24-/SnO2催化剂中掺杂少量Al2O3能明显提高催化活性,这是由催化剂的酸性位增加而引起的,添加Al2O3的摩尔分数为1.0%的催化剂表现出最高的反应活性,在酯化反应中6h后月桂酸转化率高达92.7%,在酯交换反应中8h后三乙酸甘油酯转化率高达91.1%.     

Mesoporous Solid Acid Catalysts

Solid acids have been employed as one of the most important catalysts for chemical processes. However, relatively low surface area and small micropores of conventional solid acids have strongly limited their practical applications. This article systemically reviews the synthesis and catalysis performance of mesoporous solid acids including (1) mesoporous aluminosilicates, (2) mesoporous zeolites, (3) mesoporous sulfated zirconia, (4) mesoporous hybrid inorganic–organic materials, and (5) mesoporous resins.     

固体磷酸催化剂的活性相

研究了固体磷酸催化剂活性与其自由磷酸聚合态及磷酸硅晶型的关系，指出高活性磷酸催化剂应具备的条件，即自由磷酸中应为正磷酸和焦磷酸的混合物，结合态磷应具有“Ｃ”晶型。     

Trimerization of Isobutene Over Solid Acid Catalysts

Oligomerization of isobutene is a very promising reaction not only for the production of isobutene oligomers such as trimers but also for the separation of isobutene from C₄ mixtures. Several solid acid catalysts have been applied for the continuous oligomerization of isobutene in liquid phase. This review analyzes the trimerization of isobutene over various solid acid catalysts such as zeolites, oxides (zirconias and titanias) and acid resins. Trimers selectivity increases with increasing isobutene conversion, irrespective of catalysts such as zeolites and acid resins. Very stable operation with high trimers selectivity is accomplished with WO _x /ZrO₂ catalyst having tetragonal zirconia or various zeolite catalysts with high Lewis acid site-to-Brønsted acid site ratio (LA/BA ratio). For a good performance, acid resins should be macroporous and strong acid (sulphonic acid group) with high acid concentration. Inorganic catalysts are superior to acid resins because the deactivated inorganic materials can be regenerated by simple calcination. The WO _x /ZrO₂ catalyst may be applied to a commercial process because about several thousand tons of isobutene can be oligomerized per one ton of zirconia catalyst in a catalytic cycle without regeneration. The oligomerization of isobutene may be improved further because the reaction has been started only recently and no research has been done for the optimization of the reaction and catalysts. It is expected to develop a new inorganic catalyst having suitable acidity, LA/BA ratio and phase, etc. by further research. The isobutene trimers, with or without hydrogenation, may be used for various purposes, and the importance of this trimerization reaction will be increased considering the expected surplus of isobutene due to the banned use of methyl-tert-butyl ether.     

Al2O3掺杂SO2-4/SnO2固体酸催化剂上的酯化和酯交换反应

用共沉淀法制备了一系列不同Al2O3掺杂量(0.5%-3.0%, 摩尔分数)的SO2-4/SnO2催化剂. 采用N2吸附、热重(TG)分析、X射线粉末衍射(XRD)、X射线光电子能谱(XPS)、漫反射红外光谱(DRIFTS)、拉曼(Raman)光谱、魔角旋转固体核磁共振(27Al MAS NMR)对催化剂的结构和织构性质进行了表征, 用正丁胺电位滴定法测定了催化剂的酸量, 并评价了这些催化剂对月桂酸与甲醇的酯化和三乙酸甘油酯与甲醇的酯交换反应性能. 实验结果表明SO2-4/SnO2催化剂中掺杂少量Al2O3能明显提高催化活性, 这是由催化剂的酸性位增加而引起的, 添加Al2O3的摩尔分数为1.0%的催化剂表现出最高的反应活性, 在酯化反应中6 h后月桂酸转化率高达92.7%, 在酯交换反应中8 h后三乙酸甘油酯转化率高达91.1%.     

Sulfonic Acid-Functionalized Solid Acid Catalyst in Esterification and Transesterification Reactions

The recent development of an environmentally benign solid acid catalyst has been a relatively cutting-edge area of research in the synthesis of value added esters and biodiesel. Solid acid catalysts are economically viable, effective, and environmentally amicable than conventional homogeneous catalysts and reusability of the catalyst is another advantage of these catalysts. The applicability of sulfonic acid-functionalized solid acid catalysts in the well-known esterification and transesterification reactions for the synthesis of esters and biodiesel, respectively along with their reusability aspect are discussed in this review.     

Synthesis of Ethyl Methyl Ether Over Solid Acid Catalysts

The alkylation of methanol by triethylamine to form ethyl methyl ether was studied in the temperature range 310-330°C using γ-alumina and silica-aluminas differing in their silica content. The effect of treating γ-alumina with hydrochloric and boric acid on the reaction rate was also investigated. The results obtained for ether formation over γ-alumina show that the reaction is first order for methanol and zero orde for triethylamine. Alumina-H₃BO₃ was found to be the most active catalyst whereas alumina-HCl is the least active towards ether formation. The activity of silica-alumina is proportional to its silica contents.