甲烷部分氧化制合成气反应中的氘同位素效应

近几年来,甲烷部分氧化制合成气过程重新引起了人们的极大兴趣。该过程是温和的放热反应,生成的合成气中H_2/CO比约为2,非常适合作甲醇、f-T合成的原料气。该过程使用的催化剂主要是负载型第Ⅷ族过渡金属,如nI,ru,rH,Pd,PT等。关于该过程的催化反应机理,文献中还存在诸多的争论。许多研究者认为反应中部分甲烷首先发生完全氧化反应生成CO_2和H_2O,而后剩余甲烷由生成的CO_2和/或H_2O重整为合成气。与上述观点不香港研究基金委员会资助项

Study on CO_2 catalytic hydrogenation For methanol synthesis

用TPd、TPSr-MS活性评价等方法，用Cu-zn-Al催化剂，对CO2加氢合成甲醇的原料气掺入适量CO进行了研究。结果表明，CO能占据催化剂表面部分CO2的吸附位，能抑制CO2加氢的逆水汽变换反应和促进甲醇含成，从而大大提高了CO2加氢合成甲醇的选择性和收率。The eFFects of CO on methanol synthesis From CO2 hydrogenation using Cu-Zn-Al as catalysts were studied by TPD,TPSR-MS techniques and catalytic per Formance evaluation method.The results indicated that CO could occupy some of the CO2 adsorption sites on the catalyst surFace, suppress the reverse water-gas shiFt reaction and promote methanol synthesis, thereFore methanol selectivity with CO2 conversion increased obviously.香港研究基金!RGC/96-97/02;厦门大学固体表面物理化学国家重点实验资

非平衡条件下的甲烷直接氧化制合成气的研究

将甲烷转化成重要的化工原料是过去15年最富挑战性的课题之一.尽管人们对甲烷氧化偶联制乙烯进行了大量的研究,但由于其收率较低、反应温度高等缺点,实际应用还有很大困难.近年来,人们开始注意甲烷直接氧化制合成气,该反应具有高活性、高选择性、高时空收率和相对低的反应温度等特点,有可能替代水煤气变换反应,成为制取FL合成和甲醇合成等工业过程原料的途径.Choudhary等人报道,在Ni,Co等催化剂上,大空速的情况下,当反应温度高于700℃时,甲烷直接氧化制合成气的活性和CO选择性接近热力学平衡值;

Temperature Programmed Decomposition of NO over Er 2O 3/Bi 2O 3 Catalysts

nOX是造成大气污染的化学物质之一，因此，消除nOX是环境保护的一项重要任务.目前比较成熟的消除nOX工艺是用氨为还原剂和V2O5/TIO2为催化剂的选择催化还原（SCr）法［1］，但其成本过高.其后发展了用CH4等低碳烷烃作还原剂，在O2共存下用C...The Face centered cubic(Fcc) phases of n (Er 2O 3)/ n (Bi 2O 3)=5%￣40%, molar Fraction) which is an oxygen ion conductor were prepared.The decomposition of NO over these Er 2O 3/Bi 2O 3 catalysts was examined by means of temperature programmed surFace reaction.The results showed that the surFace adsorbed NO decomposed to N 2 and O 2 at ca.600 ℃.The plot of NO conversion and Er composition showed that there was an optimum decomposition rate at ca.23%(molar Fraction).Comparing to the data of conductivity, one can conclude that the rate of NO decomposition increases with the increase in the number of oxygen vacancies.This has been contributed to the similar electronic structure between O 2 and NO.国家自然科学基金;香港研究基

提高CO_2加氢合成甲醇选择性和收率的一种方法

提高CO2加氢合成甲醇选择性和收率的一种方法李基涛张伟德付金印古萍英（厦门大学化学系物理化学研究所361005）区泽棠（香港浸会大学化学系九龙塘）关键词CO2加氢合成甲醇CO的作用提高选择性和收率随着工业发展和人类利用石化能源的增加，大气中CO2浓度...香港浸会大学科研基金;厦门大学固体表面物理化学国家重点实验

EFFect of CO on CO 2 hydrogenation to methanol over a Cu/Zn/Al/Mn catalyst

：Cu/zn/Al/Mn4组分催化剂对CO2加氢合成甲醇原料气中CO的助催化作用进行研究。结果表明，CO占据了部分催化剂表面起逆水汽变换反应的活性位，从而降低CO2转化率，但甲醇选择性和收率得到了提高。Au Chaktong (Chemistry Department, Hong Kong Baptist University, Kowloon Tong, Hong Kong) The eFFect of adding Co to the Feed gas as a promotor has been investigated For methanol synthesis via CO 2 hydrogenation over a Cu/Zn/Al/Mn catalyst. The results indicate that CO may capture a small amount of active sites on the catalyst surFace which bring about the reverse water gas shiFt reaction.Thus the conversion of CO 2 is suppressed, but the selectivity to and yield of methanol are improved

Studies on preparation of catalyst For light oleFin synthesis via carbon monoxide hydrogenation

采用脉冲反应技术，研究了CH4、CH4/O2（2/1）在还原态和氧化态铑基催化剂上的反应情况。观察到，在第一个CH4/O2（2/1）脉冲反应点中，氧化态催化剂上的甲烷转化率、CO2选择性显著高于还原态催化剂；从第二个脉冲反应点开始，氧化态催化剂上的甲烷转化率、产物选择性均与还原态催化剂上的基本接近，表明在第一个CH4/O2（2/1）脉冲反应点中，氧化态催化剂中的铑氧化物已被甲烷还原至金属态铑；从第二个脉冲反应点开始，CH4＋O2反应实际上在还原态的铑位上进行。由此推断，金属态铑是甲烷部分氧化制合成气的活性位The method of "multiple step reFlux impregnation" is put Forward in this article For preparing high dispersion and high iron content supported catalyst For light oleFin synthesis via carbon monoxide hydrogenation, with Fe 3(CO) 12 being the precursor.Characterization by XRD and other techniques shows that,although the iron content is high at 11%(mass), the state of iron on the surFace of the catalyst support is in high dispersion.EFFects of diFFerent temperatures of decarbonylation, iron contents and supports on catalyst preparing chemistry are also investigated.It is Found that an iron content of 5.4 %(mass),using Y zeolite as a support and decarbonylating at 300℃ are more Favourable and ZSM 5 is a best support.The catalyst using ZSM 5 as support exhibits an excellent selectivity of 99.8% to light oleFin.香港研究基金委员会资

Studies on Increasing Selectivity for Methanol Synthesisin CO2 Hydrogenation

在CO2加氢合成甲醇的原料气中，掺入适量的CO，能相对提高CO2加氢合成甲醇的选择性和产率.它们分别为132%和38%.TPd和TPSr-MS实验表明，CO能占据催化剂表面部分的活性位，并抑制CO2的逆水汽变换反应，从而促进甲醇的合成おhe addition of CO in the feed of CO2 hydrogenation enhanced the selectivity as well as the yield of methanol (132% and 38%, respectively).The results of TPDMS and TPSRMS indicated that CO is able to occupy some of the active sites, supressing the reverse watergas shift reaction, thus promoted the production of methanol.香港研究基金;厦门大学固体表面物理化学国家重点实验

EFFect of CO on Methanol Synthesis From CO_2 Hydrogenation

The eFFect of CO on methanol synthesis From CO2 hydrogenation over Cu-Zn-Al cat-alysts have been investigated by TPSR-MS techniques and evaluated by testing the catalytic per-Formance. The results indicated that CO can Occupy part of CO2 adsorption site on the catalystsurFace to restrain the reverse water gas shiFt reaction and promote methanol synthesis in CO2hydrogenation .ThereFore it inereases the Inethanol selectivity and yield From CO2 hydrogenation.香港研究基金!RGC/96－97/02;厦门大学固体表面物理化学国家重点实验室资