邻苯二甲酸二辛脂加氢催化剂的制备

以邻苯二甲酸二辛脂为原料,利用高压加氢反应评价装置,系统考察催化剂载体和活性物质的选择、活性组分负载量及焙烧温度对催化剂活性的影响。结果表明,载体选择大孔γ-Al₂O₃,活性组分选择铑和钌等贵金属,并通过镧改性以降低贵金属使用量,最佳制备条件：活性组分负载质量分数0.2％～0.5％,焙烧温度为550 ℃。催化剂在220 ℃还原2 h,在反应压力10 MPa、反应温度150 ℃、空速0.75 h^-1和氢油体积比1 000∶1条件下,将不低于99.5%的邻苯二甲酸二辛脂转化为环己烷二甲酸二异辛酯。     

Simultaneous Enzymatic Transesterification and Esterification of an Acid Oil Using Fermented Solid as Biocatalyst

This work studied the enzymatic synthesis of fatty acid ethyl esters (FAEE) for potential use as biodiesel via simultaneous esterification and transesterification of acid oil from macaúba in a solvent-free system. A fermented and dry babassu cake with lipase activity from Rhizomucor miehei was used as biocatalyst. FAEE content above 85% was achieved after 96 h of reaction with enzyme loading of 13 U per g of oil, 120 mmol of hydrous ethanol (95% ethanol and 5% water)/20 mmol of oil (molar ratio ethanol:oil of 6:1), at 40 °C. After two consecutive enzymatic reactions, 90.8 wt% FAEE content was obtained. These results demonstrate a promising transesterification/esterification method for FAEE production from an acid and low-cost oil and the process has potential to decrease the costs of enzymatic biodiesel production.     

微量酸催化麻疯树籽油制备生物柴油(英文)

Biodiesel produced from crude Jatropha curcas L.oil with trace sulfuric acid catalyst(0.02%-0.08% oil) was investigated at 135-184 ℃.Both esterification and transesterification can be well carried out simultane-ously.Factors affecting the process were investigated,which included the reaction temperature,reaction time,the molar ratio of alcohol to oil,catalyst amount,water content,free fatty acid(FFA) and fatty acid methyl ester(FAME) content.Under the conditions at 165 ℃,0.06%(by mass) H2SO4 of the oil mass,1.6 MPa and 20:1 methanol/oil ratio,the yield of glycerol reached 84.8% in 2 hours.FFA and FAME showed positive effect on the transesterification in certain extent.The water mass content below 1.0% did not show a noticeable effect on trans-esterification.Reaction kinetics in the range of 155 ℃ to 175 ℃ was also measured.     

Ethanolysis of castor and cottonseed oil: A systematic study using classical catalysts

Several classical catalytic systems for the transesterification reaction have been used to produce FA ethyl esters (FAEE) from castor and cottonseed oils The effects of the amount and nature of the catalyst, and of the reaction temperature, on the yields of FAEE were determined. The most efficient transesterification of castor oil was achieved in the presence of methoxide and acid catalysts, whereas for cottonseed oil, which has a composition that is much more similar to most vegetable oils than is castor oil, the highest yields of FAEE were obtained following base-catalysed ethanolysis.     

KOH/ZrO2催化制备生物柴油新工艺

采用浸渍法,将KOH负载在新型载体氧化锆上,通过高温煅烧得到了固体碱催化剂。探讨了制备条件对催化剂催化酯交换反应活性的影响,获得了催化剂的最佳制备条件,以大豆油和甲醇为原料研究并优化了催化酯交换反应制备生物柴油的工艺条件。结果表明,固体碱催化剂KOH/ZrO₂的最佳制备条件为：KOH负载量20%,煅烧温度600℃,煅烧时间2 h。固体碱催化剂催化酯交换反应的最优反应条件为：醇油比9：1,反应温度75℃,反应时间3 h,催化剂用量4.0%。各因素对产率影响的大小为：醇油摩尔比 > 反应温度 > 反应时间 > 催化剂用量。     

贫燃条件下铜离子改性铝交联蒙脱土汽车尾气净化催化剂的研制

以铝交联蒙脱土为载体,研制铜离子改性铝交联蒙脱土催化剂,在贫燃条件下考察其选择性还原NO的催化活性,并与Cu/ZSM-5做了比较。结果表明:采用浸渍法Cu2+负载量以w(Cu2+)=3%为最佳,可使NO转化率达52 25%;采用SO2-4改性能较大幅度提高催化活性,使NO转化率提高15 42%,同时能使操作温度范围更宽,500℃NO转化率仍达到22 16%,优于Cu/ZSM-5。     

Presence of Fatty‐Acid Ethyl Esters in Krill Oil Dietary Supplements

Krill oil dietary supplements are increasingly used for their high concentrations of phospholipids (PL), which offer reportedly greater bioavailability of n‐3 polyunsaturated fatty acids (PUFA) than those of triacylglycerols or fatty‐acid ethyl esters (FAEE) commonly found in fish oils and fish‐oil concentrates. This work evaluated the lipid composition of 22 commercial krill oil (CKO) supplements available in the US market, and found ten products (i.e. 45%) contained significant amounts of FAEE, varying from 41% to 75%, by weight. These concentrations of FAEE differed from the minor abundances of FAEE (<3%, by weight) found in manufacturer‐supplied krill oil. The potential clinical and regulatory implications for these findings warrant further investigation.     

半焦基催化剂裂解煤热解产物提高油气品质

利用上段热解下段催化的两段固定床反应器,针对府谷煤研究了半焦和半焦负载Co催化剂对煤热解产物的催化裂解效果。结果表明,半焦和半焦负载钴对热解产物催化裂解后,热解气收率增加,焦油收率降低,但焦油中沸点低于360℃的轻质组分含量提高,轻质焦油收率基本保持不变或略有增加。与煤在600℃直接热解相比,在热解和催化温度均为600℃,采用煤样质量20%的半焦为催化剂时焦油中轻质组分质量含量提高了约25%,轻质组分收率基本不变,热解气体积收率增加了31.2%;在热解温度600℃,催化温度500℃时,采用煤样质量5%的半焦负载钴催化剂,焦油中轻质组分质量收率和含量分别提高了约8.8%和28.8%,热解气体积收率增加了21.5%。煤热解产物的二次催化裂解的总体效果是将焦油中重质组分转化为轻质焦油和热解气。     

新型生物柴油催化剂性能研究

以精制菜籽油为原料,考察了项目组自行开发的新型催化剂SXL的催化效率,反应条件是所用甲醇质量为原料油质量的56%,最优条件下,催化剂质量为原料油质量的3%,反应时间为60 min,反应温度为40—60℃,转化率和产率可达98%以上。以精制菜籽油为原料油,考察催化剂的抗中毒性,结果表明:该催化剂对游离脂肪酸耐受性可以达到7%,并可耐受10%的水分,可直接用于未经精炼的粗植物油,将显著降低生产成本,显现出良好的应用前景。     

铜绿假单胞菌脂肪酶无溶剂催化棕榈油甘油解Ⅰ.单甘酯酶促合成工艺的研究

以自产铜绿假单胞菌脂肪酶为催化剂 ,通过无溶剂法棕榈油甘油解反应催化合成了单脂肪酸甘油酯。实验结果表明 :适宜加酶量为 50 0u g棕榈油 ,甘油相适宜水质量分数为w (H2 O)=3%～ 4 5% ,反应物量比宜设定为 n(甘油 )∶n(棕榈油 ) =( 2 0～ 2 5)∶1。反应器材质对单甘酯产率有影响 ,31 6L型不锈钢为适宜材质。最佳反应温度为 38～ 42℃ ,在此温度区间内适宜反应时间为 2 4h。临界反应温度为 44℃。     

聚氨酯丙烯酸酯预聚体的合成与性能研究

合成了聚氨酯丙烯酸酯预聚体,配制了紫外光固化胶粘剂,研究了预聚体含量和种类对紫外光固化胶粘剂固化膜性能的影响。确定了预聚体合成的最佳条件为：反应温度75-80℃、催化剂用量0.45%左右。预聚体在胶粘剂配方中的最佳含量为50%-60%;芳香族预聚体剪切强度明显高于脂肪族预聚体,但胶层较硬,韧性较差;脂肪族预聚体柔顺性较好,180°剥离强度和附着力高于芳香族预聚体;不挥发物含量越高则固化得越完全,综合强度越好;芳香族预聚体的玻璃化温度高于脂肪族预聚体,二者分别贡献胶粘剂固化膜的剪切强度和剥离强度。     

负载型固体酸催化合成生物柴油

以固体酸TSOH/HY-SBA-15（对甲苯磺酸改性的介孔分子筛）为催化剂,催化大豆油和甲醇制备生物柴油,考察了反应的最适宜条件。结果表明,催化剂为(0.5 mol/L)TSOH/(10 %)HY-SBA-15,反应温度为180 ℃,反应时间为7 h,n(醇)/n(油)为25,催化剂用量为油质量的5 %,溶剂用量为油质量的30 %,生物柴油的收率可达到94.6 %。     

HPW/HY-SBA-15催化剂的制备及氧化脱硫性能研究

采用后合成法合成了HY-SBA-15复合分子筛,并以其为载体,负载不同比例的磷钨酸(HPW)制备催化剂.用XRD对HY-SBA-15复合分子筛及HPW/HY-SBA-15催化剂进行了表征,结果表明:适量磷钨酸的引入并没有改变复合分子筛的介孔结构,但会使其衍射峰的强度有所降低.以硫含量为500 μg/g模拟油进行氧化脱硫反应,考察了反应温度、反应时间、磷钨酸负载比例、剂油比、氧化剂用量等工艺条件对脱硫率的影响.研究结果表明:磷钨酸的负载量为20％(质量分数),活化温度为300℃时的HPW/HY-SBA- 15催化剂效果最好,在模拟油用量为30 mL,反应温度50 ℃,反应时间90 min,剂油比(催化剂与模拟油的质量比)为0.02,n(H2O2)∶n(S)=8,无水乙醇用量3 mL的条件下,脱硫率可达95.7％.     

双端乙烯基氟硅油的研制

以1,3,5-三甲基-1,3,5-三(3,3,3-三氟丙基)环三硅氧烷为原料、四甲基二乙烯基二硅氧烷为封端剂、硫酸为催化剂制得双端乙烯基氟硅油,研究了反应时间、催化剂用量、反应温度对产物黏度和挥发分质量分数的影响;采用红外光谱和核磁共振波谱表征了产物结构.结果表明,产物为双端乙烯基氟硅油.较佳的制备条件为反应时间1 h...     

Pb、Bi改性Pd催化剂合成芳樟醇

反应温度30～75℃,压力0.5～1.0MPa,以Pb、Bi改性的Pd催化剂合成芳樟醇,当催化剂中w(Pd)=1%时,脱氢芳樟醇转化率为99%～100%,合成芳樟醇选择性大于98%。产品经减压精馏,w(芳樟醇)>98%,收率为80%～90%。以Lindlar催化剂合成芳樟醇,脱氢芳樟醇转化率为99%～100%,合成芳樟醇选择性为95%～97%。     

重质松节油直接异构制备异长叶烯的研究

探讨了以重质松节油为原料进行直接异构化制备异长叶烯的新工艺,选出了较为理想的GO₄^n-/TiO₂(A)固体超强酸催化剂,确定了较好的反应条件为:催化剂用量为原料质量的 1%~2%、异构化反应温度190~200℃,反应时间 4 h,异长叶烯得率达到 90% 以上,为工业化生产异长叶烯探索了一条"绿色"新工艺途径。     

异构化反应改善小桐梓油生物柴油的低温流动性

以小桐梓油生物柴油为原料,在固定床连续反应器中,以Hβ型分子筛为催化剂,采用异构化反应改善生物柴油的低温流动性。考察了反应温度、质量空速、助剂(水)加入量等不同条件对生物柴油低温流动性的影响。实验结果表明,催化剂选用硅铝比为25的Hβ分子筛的情况下,反应温度为250℃、质量空速为1.0 h-1、助剂加入量为1.2%为最佳反应条件,小桐梓油生物柴油在最佳反应条件下进行异构化反应,凝点从1℃降低到-5℃,降幅为6℃。对生物柴油和异构化产物进行了色谱、质谱、核磁共振等表征,结果发现,低温流动性改善的原因是生物柴油的主要成分油酸甲酯、亚油酸甲酯发生了异构化反应,产生了带支链的异构体。     

V_2O_5-WO_3/TiO_2催化剂的制备及其烟气脱硝性能

以活性成分负载量、负载顺序和焙烧温度等关键制备参数因素进行正交实验设计制备了V_2O_5-WO_3/TiO_2催化剂,对其进行XRD和TPR表征,并在自行设计搭建的SCR烟气脱硝实验平台上评价其(300~390)℃的SCR脱硝性能。结果表明,活性成分钒和钨绝大多数以非晶态形式存在于载体表面,且具有良好的分散性;主要活性成分V_2O_5负载量越高,脱硝率越高;400℃焙烧温度可以形成催化反应所需的晶相,且维持催化剂较高的比表面积;催化剂低温活性和高温活性是由表面富集和各种成分之间相互作用共同产生的结果,活性组分与载体之间的相互作用对315℃低温脱硝活性影响明显,以先钒后钨负载顺序为宜,表面富集对390℃高温脱硝活性起主要作用,以钒钨同时负载或先钒后钨负载顺序较好;随着m(WO_3)∶m(V_2O_5)的增加,在7.5∶1处催化剂的脱硝率升至最高,随后迅速下降,WO_3负载质量分数以6%为宜。在优化条件V_2O_5负载质量分数0.8%、WO_3负载质量分数6%、先钒后钨负载和400℃焙烧温度下制备了催化剂并进行脱硝性能验证,315℃低温脱硝活性达到69.56%。     

高黏度、高黏度指数和低凝点聚α-烯烃润滑油基础油的合成

在Al Cl3催化剂作用下,将癸烯与1-n C18按不同比例合成高性能聚α-烯烃基础油,考察反应温度、反应时间和C10与C18质量分数对混合齐聚反应的影响,采用响应面法设计实验,并对实验条件进行最优选择。结果表明,在实验条件下,用癸烯与1-n C18烯烃混聚可制备高性能的润滑油基础油。响应曲面法分析中,对黏度交互影响最显著的因素是时间A和温度B,最佳取值为3 h和50℃;对黏度指数交互影响最显著的因素是时间A和温度B,最佳取值为3 h和75℃;对倾点交互影响最显著的因素是时间A和温度B,最佳取值为3 h和25℃;对收率交互影响最显著的因素是时间A和C10与C18质量分数C,最佳取值为3 h,C10与C18质量分数分别为100%和15%。     

Optimization of Cottonseed Oil Ethanolysis to Produce Biodiesel High in Gossypol Content

Transesterification of cottonseed oil was carried out using ethanol and potassium hydroxide (KOH). A central composite design with six center and six axial points was used to study the effect of catalyst concentration, molar ratio of ethanol to cottonseed oil and reaction temperature for percentage yield (% yield) and percentage initial absorbance (%A _385nm) of the biodiesel. Catalyst concentration and molar ratio of ethanol to cottonseed oil were the most significant variables affecting percentage conversion and %A _385nm. Maximum predicted % yield of 98% was obtained at a catalyst concentration of 1.07% (wt/wt) and ethanol to cottonseed oil molar ratio of 20:1 at reaction temperature of 25 °C. Maximum predicted %A _385nm of more than 80% was obtained at 0.5% (wt/wt) catalyst concentration and molar ratio of 3:1 at 25 °C. The response surfaces that described % yield and %A _385nm were inversely related. Gossypol concentration (% wt), oxidative stability and %A _385nm of biodiesel were found to be highly correlated with each other. Hence, color %A _385nm is a measure of the amount of pigments present in biodiesel fuels that have not yet been subjected to autoxidation. High gossypol concentration also corresponds to a fuel with high oxidative stability. The fatty acid ethyl esters (FAEE) produced from cottonseed oil had superior oxidative stability to fatty acid methyl esters (FAME) produced from cottonseed oil.