燃料电池氢源技术——汽油氧化重整制氢反应实验研究

本文对汽油氧化重整制氢反应工艺条件进行了实验研究,研究了双金属M－N／Al2O3预还原与否对烃类制氢反应的活性、生成氢气的选择性及催化剂的稳定性的影响。实验结果表明,催化剂的活性组分价态不同,对烃类部分氧化重整制氢反应催化活性、生成氢的选择性影响不同,还原态的好于非还原态的双金属催化剂;该催化剂的还原态与氧化态在烃类氧化重整制氢反应中稳定性均较好,即预还原与否对其稳定性影响不大。     

辛普森膜分离器提纯重整氢气

济南炼油厂利用辛普森膜分离器提纯重整氢气，使原料氢气纯度由９４％。左右提高到９９．９９％，且不含烃类。用此提纯氢进行重整催化剂还原，提高重整催化剂活性，Ｃ＾＋５液体收率和催化剂寿命，获得了良好经济效益。     

CH4,CO2与O2催化氧化重整制合成气的研究：催化剂中C …

考察了添加稀土Ｃｅ后的镍基催化剂在ＣＨ４，ＣＯ２与Ｏ２催化氧化重整制合成了气反应中的催化性能，发现添中适量的Ｃｅ可以显著催化的活性和选择性，ＴＰＲ，ＸＲＤ，ＸＰＳ结果显示，ＣｅＯ２的加入能够增强活性组分与载体的相互作用，调变催化剂中镍物种的组成，可提高催化剂的活性及稳定性。     

CH_4、CO_2与O_2催化氧化重整制合成气的研究——催化剂中CeO_2的作用及影响

考察了添加稀土Ｃｅ后的镍基催化剂在ＣＨ４、ＣＯ２与Ｏ２催化氧化重整制合成气反应中的催化性能，发现添加适量的Ｃｅ可以显著提高催化剂的活性和选择性。ＴＰＲ、ＸＲＤ、ＸＰＳ结果显示，ＣｅＯ２的加入能够增强活性组分与载体的相互作用，调变催化剂中镍物种的组成，可提高催化剂的活性及稳定性。     

甲烷氧化偶联反应中氢气生成机理的研究

研究了石英、陶瓷和不锈钢等材质空管反应器中及催化剂上甲烷氧化偶联反应中氢气生成的现象。考察了氢气生成量随反应温度、反应气流速、烷氧比反应条件的变化规律。考察了催化剂存在与不存在下甲烷、乙烷、乙烯的蒸汽重整反应、ＣＯ－Ｈ２Ｏ的水气变换反应，进而研究和讨论了甲烷氧化偶联反应中氢气生成的主要途径和机理     

干燥和还原过程中气相组成对重整催化剂金属功能的影响

模拟常用的工业开工和再生条件处理ＣＢ－５Ｂ，ＣＢ－６，ＣＢ－７，ＣＢ－８等工业用铂铼重整催化剂，考察了干燥和还原阶段不同气体组成对催化剂金属功能的影响，试验结果表明，干燥和还原过程中存在的烃类将在催化剂上生焦使之减活，即使是小分子烃类的存在也有不可忽视的影响。     

正十六烷在Pt/SAPO-11上的临氢异构反应

制备了Pt/SAPO-11双功能催化剂,采用XRD、NH_3吸附-脱附等分析方法对制备的催化剂进行表征,对正十六烷在Pt/SAPO-11双功能催化剂上的临氢异构反应进行了研究,考察了氢分压、反应温度、氢烃体积比和液态空速等反应条件对催化剂性能的影响,探讨了催化剂的焙烧温度和还原温度对催化剂性能的影响。表征结果显示,Pt/SAPO-11双功能催化剂的孔结构对性能影响较小,而催化剂的弱酸性有利于异构选择性。实验结果表明,氢分压高对于烷烃临氢异构反应活性有不利的影响,而反应温度的选择需兼顾异构活性及选择性,氢烃体积比对反应无明显影响;催化剂的焙烧温度、还原温度对催化剂的活性和异构选择性有较大影响,在适当的温度范围内制备的催化剂有较好的活性和选择性。     

一种制氢预转化催化剂还原的新方法

对上海高桥分公司2×10~4m~3/h(标准状态)制氢装置原设计的预转化催化剂还原流程进行了改进。先跳开预转化反应器,利用转化炉制取氢气,再用自产的高纯氢气代替重整氢,对预转化催化剂进行单独升温还原,避免了催化剂在还原初期因发生甲烷化反应而超温失活的问题,使催化剂具有更好的活性和稳定性。     

正己烷在铂铬重整催化剂上的反应

考察了在连续流动条件下，正己烷在铂铬重整催化剂上的反应行为。结合ＴＰＲ、环己烷脱氢及异丙苯裂解等手段，研究铬的还原特性及其对催化剂双功能的调变。结果表明，低铬质量分数的催化剂（当ｗ（铬）＝３．００％时），不仅能提高铂催化剂的芳构化产率，抑制氢解，且能保持铂催化剂的初活性和稳定性。但催化剂中铬的质量分数较高时，铬破坏了催化剂原有的双功能匹配，使高铬质量分数催化剂性能呈现劣势。铬的这种作用与它本身的可还原程度及其对催化剂的调变功能密切相关。铬的引入使铂催化剂的金属功能略有下降，更主要的是调变了催化剂的酸功能。当双功能相互匹配时，铂铬催化剂才体现较好的催化剂的反应性质。     

助剂对F－T合成Fe－Mn共沉淀催化剂的影响 Ⅳ．催化剂F－T合成反应性能的研究

用微型固定床反应器，在中压（１．１ＭＰａ）条件下考察了助剂Ｌａ、Ｖ、Ｚｎ、Ｋ对共沉淀Ｆｅ－Ｍｎ催化剂ＣＯ＋Ｈ２合成反应性能的影响。反应结果表明，助剂Ｌａ、Ｋ的加入均使ＣＯ＋Ｈ２转化率降低，烃的选择性提高，产物中ＣＨ４减少，Ｃ５＋增多，产物平均分子量增大，同时烯烷比也提高，但是助剂Ｋ使催化剂失活较快；助剂Ｖ使ＣＯ＋Ｈ２的转化率降低，使产物中ＣＨ４增加，Ｃ５＋减少，Ｖ对烯烷比影响不明显，但提高了合成反应的稳定性；助剂Ｚｎ使ＣＯ＋Ｈ２的转化率提高，产物中ＣＨ４和Ｃ５＋的含量都减少，Ｃ２～Ｃ４烃明显增加，烯烷比降低。     

IRON COMPOUNDS AND C0-Mo/Al2O3 CATALYSTS: ACTIVITY IN DIRECT HYDROGENATION OF A SUBBITUMINOUS A COAL WITH AN H-DONOR SOLVENT

The effectiveness of different catalysts were compared in coal liquefaction experiments using a 250 ml stirred autoclave, 10 g of a Spanish Subbituminous A coal, 1 hour reaction time, 17 MPa operating pressure, 400 rpm stirring speed, at 425 and 450 °C with 2/1 and 3/1 tetralin/coal ratio. The liquefaction products were fractionated into oils, asphaltenes, preasphaltenes and solid residue using pentane, toluene and THF as extractive solvents. Three iron-oxide containing catalysts: red mud, an Fe2O3 aerosol and Cottrell ash (by-product of the aluminium industry); and three alumina supported catalysts: CMA, which is a conventional CoMo/Al2O3 catalyst, CZMA which in addition contains Zn as a second promoter, and CZMFA which has the alumina acidified with fluorine and also contains Zn, were compared. It has been reported that the addition of Zn and of F enhances the HDS, cracking, hydrocracking or hydrogenating activities of CoMo/Al2O3 catalysts in experiments with pure compounds. The objective of this study was to determine if the addition of Zn and of F has also a beneficial effect in the catalyst activities in coal liquefaction, and also to compare cheap iron containing catalysts with the more sophisticated and expensive alumina supported ones.

The results showed that 1) Catalysts effects depend on the operating conditions used, and that with tetralin, a strong H-donor solvent, they never are very pronounced. 2) The supported catalysts have higher activities in coal liquefaction than the iron ones, but there are no significant differences among the catalysts within each group. 3) Zn, which is a cheaper metal than Co, can substitute succesfully for half the amount of Co and retain the activity of the CoMo/Al2O3 catalyst in coal liquefaction. 4) The addition of F to the CoMo/Al2O3 catalyst does not show a benefecial effect     

IRON COMPOUNDS AND C0-Mo/Al2O3 CATALYSTS: ACTIVITY IN DIRECT HYDROGENATION OF A SUBBITUMINOUS A COAL WITH AN H-DONOR SOLVENT

Abstract

The effectiveness of different catalysts were compared in coal liquefaction experiments using a 250 ml stirred autoclave, 10 g of a Spanish Subbituminous A coal, 1 hour reaction time, 17 MPa operating pressure, 400 rpm stirring speed, at 425 and 450 °C with 2/1 and 3/1 tetralin/coal ratio. The liquefaction products were fractionated into oils, asphaltenes, preasphaltenes and solid residue using pentane, toluene and THF as extractive solvents. Three iron-oxide containing catalysts: red mud, an Fe2O3 aerosol and Cottrell ash (by-product of the aluminium industry); and three alumina supported catalysts: CMA, which is a conventional CoMo/Al2O3 catalyst, CZMA which in addition contains Zn as a second promoter, and CZMFA which has the alumina acidified with fluorine and also contains Zn, were compared. It has been reported that the addition of Zn and of F enhances the HDS, cracking, hydrocracking or hydrogenating activities of CoMo/Al2O3 catalysts in experiments with pure compounds. The objective of this study was to determine if the addition of Zn and of F has also a beneficial effect in the catalyst activities in coal liquefaction, and also to compare cheap iron containing catalysts with the more sophisticated and expensive alumina supported ones.

The results showed that 1) Catalysts effects depend on the operating conditions used, and that with tetralin, a strong H-donor solvent, they never are very pronounced. 2) The supported catalysts have higher activities in coal liquefaction than the iron ones, but there are no significant differences among the catalysts within each group. 3) Zn, which is a cheaper metal than Co, can substitute succesfully for half the amount of Co and retain the activity of the CoMo/Al2O3 catalyst in coal liquefaction. 4) The addition of F to the CoMo/Al2O3 catalyst does not show a benefecial effect     

随车制氢甲醇裂解铜水泥催化剂的研究

分别以H2O,H3BO3,C6H8O7,NH3.H2O为溶剂,采用离子交换法制备了铜水泥催化剂,并在固定床上考察了催化剂催化甲醇裂解的性能。实验结果表明,以H2O代替NH3.H2O制得的铜水泥催化剂性能优越,实现了催化剂制备的环保高效。与商用的CuZnAl甲醇裂解催化剂相比,铜水泥催化剂具有较高催化活性和选择性,在常压、300℃、重时空速3.39h-1的条件下,铜水泥催化剂的比活性(甲醇转化率与铜负载量的比值)和CO+H2的选择性分别为2.44和95.9%,CuZnAl催化剂分别为0.64和89.2%;铜水泥催化剂的抗压强度大于45N,而CuZnAl催化剂的抗压强度为20N。铜水泥催化剂具有机械强度高、活性高、CO+H2选择性高的特点,基本满足了随车制氢的要求。XRD,SEM,DTG-DTA,FTIR,H2-TPR表征结果显示,铜水泥催化剂制备过程中形成的CaCO3具有稳定铜物种的作用,有助于保持催化剂的高温活性。     

CuO-BaO/SiO_2催化剂的表面性质、还原性能及氢解反应性能

研究了在合成气或纯氢气气氛下ＣｕＯ－ＢａＯ／ＳｉＯ２催化剂甲酸甲酯氢解反应活性的变化,并对催化剂进行了ＴＰＲ、ＴＥＭ和ＢＥＴ表征。结果表明,合成气氢解反应活性和甲醇选择性明显低于纯氢氢解反应活性和甲醇选择性,反应温度高对提高催化剂活性有利,但同时也加速了副反应的进行。随着负载量的增加,其比表面积、孔容和孔径逐渐降低;铜载量＜２０％时,催化剂孔结构为单孔型孔道;铜载量＞２０％以后,其孔结构呈双孔型孔道。铜载量对ＣｕＯ－ＢａＯ／ＳｉＯ２催化剂的还原性能影响很大,随着铜载量的增加,还原温度升高;焙烧温度小于５００℃时,催化剂还原性能基本不发生变化,且易于还原;焙烧温度大于５００℃后,催化剂还原温度升高而变得难于还原     

Mo_2N催化剂加氢脱硫性能的研究

在中压反应装置中以环己烷６９％（ｍ），环己烯２０％（ｍ），苯１０％（ｍ），噻吩１％（ｍ）混合液为反应物，考察了不同比表面Ｍｏ２Ｎ的加氢脱硫（ＨＤＳ）、环己烯加氢（ＨＹＤ）和苯加氢（ＢＨＤ）的活性。表面积大的催化剂，ＨＤＳ、ＨＹＤ活性均高，但若用比活性比较，则刚好相反。在一较宽温度范围内测试Ｍｏ２Ｎ催化性能，ＨＤＳ和ＨＹＤ活性随温度升高而增加，但各温区变化幅度差异较大。对Ｍｏ２Ｎ催化剂采用３种预处理方法：（１）４００℃下Ｈ２还原；（２）４００℃下Ｈ２Ｓ／Ｈ２硫化；（３）不处理。结果表明，ＨＤＳ和ＨＹＤ活性顺序为预还原＞不处理＞预硫化。预还原处理的Ｍｏ２Ｎ具有接近硫化态商品ＮｉＣｏＭｏ／Ａｌ２Ｏ３的催化剂性能，此催化剂具有良好的应用前景     

HYDRATION OF BUTENE-1 OVER H.-MORDENITE AND H-MORDENTTE COMPOSITED WITH ZEOLITE-β

The hydration of butene-1 over H-mordenite and H-mordenite composited with different amounts of zeolite-β has been investigated in a batch reactor. The products of the reaction were sec-butanol (SBA), diisobutylether (DIBE) and C₈-oligmer. The reaction was carried out over H-mordenite at different operational conditions of a reaction temperature and built-up pressure. The maximum activity (46% of the thermodynamic equilibrium) of H-mordenhe was observed at 250°C and 180.27 atm with 88% selectivity of SBA and no formation of C« dimmer by-product. The structural characteristics of a H-form of the composited catalysts, containing 10, 15 and 45 wt% of zeolite-β, were studied by means of an electron dispersion system (EDS) technique in order to determine SiO₂/Al₂O₃ ratio and % degree of exchange. It was found that SiO₂/Al₂O₃ ratio ranges between 20.2 and 29.61 indicating that all the catalysts could be considered as siliceous zeolites. The acidic properties of the pure mordenites and those composited with zeolite-β were determined potentiometrically in an aqueous medium. From the results obtained, it is obvious that the catalysts, containing mordenite composited with 15 and 45 wt% of zeolite-β, possess stronger acidic -OH's than pure mordenites. Also, the hydration activity of zeolites seemed to be strongly correlated with their protonic acid strength. The activity and selectivity of the composited zeolites for the hydration reaction were studied at the optimum operational conditions and compared with those of pure mordenite. The binary composited zeolites, containing 15 and 45 wt% of zeolite-β were found to be more active and selective for the hydration of butene -1 than those of pure mordenite. It was suggested that the activity and selectivity of the binary zeolite catalyst system may be due to shape selectivity of β-zeolite, high surface acidity and hydrophobic nature exhibited by the two forms of zeolites.     

负载型二(2-乙酰基-1-萘酚氧基)二氯化钒催化剂的制备及其催化乙烯聚合反应

分别以活性MgCl2和无水MgCl2为载体,采用浸渍法制备了负载型二(2-乙酰基-1-萘酚氧基)二氯化钒催化剂(简称负载型催化剂),并采用元素分析、红外光谱、X射线光电子能谱、X射线衍射、核磁共振和氮吸附静态容量法等手段对载体和负载型催化剂的结构进行了表征。表征结果显示,采用浸渍法制备的负载型催化剂没有改变催化活性组分的化学结构。研究负载型催化剂对乙烯聚合的性能时发现,负载型催化剂比二(2-乙酰基-1-萘酚氧基)二氯化钒均相催化剂的活性提高约一倍,所得聚乙烯的黏均相对分子质量增大;以活性MgCl2为载体的负载型催化剂的活性高。聚合动力学研究表明,负载型催化剂活性中心的稳定性好于二(2-乙酰基-1-萘酚氧基)二氯化钒均相催化剂,负载型催化剂活性中心的衰减速率较慢。     

LaFeO3甲烷氧化催化剂的表征及反应性能评价

采用高温熔融法制备出LaFeO3系列催化剂,利用XRD,BET,XPS等分析手段对催化剂样品进行了表征,并通过CH4/O2切换反应考察了催化剂的反应性能.结果表明,纯LaFeO3催化剂具有2个O1s峰,低结合能的氧归属为晶格氧,高结合能的氧归属为吸附氧;负载型的催化剂除了含有晶格氧和吸附氧外,还含有大量与Al2O3结合的表面氧;加入助剂会降低各种结合状态氧的结合能;高温熔融致使催化剂中晶格氧的结合能降低.采用挤条法制备的活性组分质量分数为40％的Al基新鲜LaFeO3催化剂反应性能最佳,其CH4转化率、CO选择性分别为87.9％,97.1％,且产物H2/CO（摩尔比）为2.     

CO_2氧化丙烷脱氢制丙烯Pd-Cu/MoO_3-SiO_2催化剂研究

以MoO3 SiO2复合物作载体,采用等体积浸渍法制得了Pd Cu催化剂,采用BET、TPR、IR对催化剂结构及CO2、C3H8在催化剂上的吸附位、吸附态进行了分析。实验结果证明,CO2在催化剂上存在卧式吸附态,丙烷以亚甲基和其中一个甲基上的氢吸附在Mo=O双键的端基氧上。在微型反应装置上测试了催化剂在CO2氧化丙烷脱氢制丙烯反应中的催化性能,常压和600℃条件下,C3H8转化率达26 94%,C3H6选择性达78 34%。通过催化剂的物化性质、化学吸附性质与反应性能的关联,讨论了反应机理和影响催化剂性能的基本因素。     

甲烷部分氧化制甲醛──不同种类含硅化合物催化剂的研究

用纯氧作氧化剂，研究了甲烷在各种含硅化合物催化剂上的直接氧化反应。结果表明，不同的含硅化合物对部分氧化产物甲醛有不同的活性，在最佳条件下，用１号催化剂，ＣＨ２Ｏ产率最高可达２．１４％（４９．７２ｇ／ｍ３．ｈ）。对各种含硅化合物催化剂的红外和热重分析发现，不同催化剂上所含─ＯＨ量不同，这可能是催化剂活性差异的原因。