双金属镍-锰／γ-Al2O3催化剂对甲烷二氧化碳重整反应的影响

用浸渍法制备γ-Al2O3负载的Ni-Mn双金属催化剂．在500-700。C按照17：17：2的C02／CHa／N2比例,以36mL／min的载气流速进行甲烷二氧化碳重整反应,利用甲烷二氧化碳的转化率、生成的合成气H2／CO比例以及长期稳定性等指标评价了催化剂的催化性能．实验表明,添加Mn提高催化性能并使双金属催化剂的稳定性更高,比单金属催化剂更好地抑制焦炭生成,Mn最合适的添加量为0．5wt％．通过BET、C02-TPD、TGA、XRD、SEM、EDX和FTIR各种技术对催化剂进行了表征．     

加氢裂化催化剂反应酸性的表征方法及研究

本文报导了用邻二甲苯异构化反应活性表征加氢裂化催化剂及其载体酸性的方法,以邻二甲苯的总转化率表示在反应条件下的反应酸性。用这种方法可将催化剂及载体的反应酸性分成三类:含分子筛或氟的加氢裂化催化剂的反应酸性在55%以上;以无定形硅—铝为载体的加氢裂化催化剂和含氟的无定形硅—铝载体反应酸性大约在10—40%之间;无定形硅—铝载体的反应酸性一般在10%以下。用本方法考察了某些因素对一些加氢裂化催化剂反应酸性的影响。结果表明,硫化型加氢裂化催化剂的反应酸性比氧化型的略低;催化剂上活性金属的含量对反应酸性有明显的影响。     

负载β-Mo2N0.78催化剂上加氢脱硫和加氢脱氮反应行为的研究

在N2-H2下,利用程序升温还原氮化反应制备氧化铝负载的β-Mo2N0.78催化剂,并以苯并噻吩（BT）、二苯并噻吩(DBT)和喹啉为模型化合物,考察该催化剂的加氢脱硫、加氢脱氮活性和选择性。实验结果表明,升高反应温度和压力均提高催化剂的加氢脱硫、加氢脱氮活性;升高温度可同时改善DBT的直接脱硫和氢化脱硫,对选择性没有明显的影响;提高反应压力有利于加氢产物的生成;同时可以使联苯加氢转化为环己基苯。添加喹啉的加氢脱硫反应结果表明,含氮化合物的添加降低了催化剂加氢脱硫反应活性,抑制了氢化脱硫反应的发生。少量硫化合物的添加,使喹啉的转化率提高,还提高了脱氮率。     

DEHYDROGENATION AND AROMATIZATION OF METHANE IN THE ABSENCE OF OXYGEN OVER DOPED Mo/HZSM-5 CATALYSTS

研究了在Ｍｏ／ＨＺＳＭ－５催化剂上添加助剂以及不同的反应预处理温度对甲烷无氧脱氢芳构化反应的影响。实验结果表明，由于第二组分的添加，Ｍｏ／ＨＺＳＭ－５催化剂的活性和选择性都得到了较大程度的改善。预处理温度是影响催化剂反应性能的关键因素。Ｍｏ－Ｒｕ／ＨＺＳＭ－５催化剂经过８７３Ｋ空气预处理后，甲烷在９７３Ｋ的转化率约为１０％，催化剂的稳定性也得到较大程度的提高。ＴＰＳＲ实验结果表明，Ｒｕ的加入降低了芳烃生成的温度。ＴＰＯ和ＤＴＡ实验结果表明，在Ｍｏ－Ｒｕ／ＨＺＳＭ－５催化剂上可生成较多的碳物种，结合反应结果，可以认为反应过程中生成的碳物种对甲烷的无氧脱氢芳构化反应是起积极作用的     

添加Cl离子对V_2O_5-WO_3/TiO_2催化剂低温NO转化率的影响

考察添加不同含量Cl离子对浸渍法制备的Cl-V_2O_5-WO_3/TiO_2催化剂低温NO转化率的影响。随着Cl离子质量添加量从0增加到2.5%,Cl-V_2O_5-WO_3/TiO_2催化剂NO转化率先升高后降低,结合在含有SO_2和H2O的SCR实验结果,确定1.5%Cl-V_2O_5-WO_3/TiO_2为性能最优催化剂。在反应温度为149-362℃,NO转化率大于95%;在145-385℃,NO转化率大于90%。采用XRF、BET、XRD、TG、FT-IR和H2-TPR等方法表征了催化剂的物理化学性能和结构。结果表明,在反应气氛中加入SO_2和H2O后,催化剂比表面积和孔容均减小,副反应产物含有NH+4和SO_2-4。适量Cl离子可以抑制硫物种沉积,减少副反应产物生成,增强催化剂抗中毒能力。     

镍基整体式催化剂上生物质粗燃气重整调变的特性研究

采用浸渍法制备了Ni基整体式催化剂,考察了不同条件(温度、时间、空速、水蒸气添加等)对催化剂上生物质粗燃气重整反应性能的影响。结果表明,催化剂在较低温度下(≤500 ℃)只具有CO加氢反应活性,随着反应温度的升高粗燃气重整反应逐渐进行,在800 ℃以上,CH₄和C₂转化率均高达95 %以上,CO₂转化率达到92%,但随着反应空速和水蒸气添加量的增加,CH₄和CO₂等转化率呈现缓慢降低的趋势。此外,通过改变水蒸气添加量可对合成气中H₂/CO体积比在0.85~4.00进行较好调节。结合XRD表征发现,Ni基整体式催化剂中Ni°的生成可较好地促进重整反应的进行。     

金属离子对Ru-Pt/γ-Al2O3催化剂上对氯硝基苯选择加氢反应的影响

 采用混合醇还原法制备了聚乙烯吡咯烷酮(PVP)稳定的Ru-Pt/γ-Al2O3双金属催化剂,考察了其催化对氯硝基苯(p-CNB)选择加氢反应的性能,探讨了反应温度、压力、第三金属离子的种类、添加量及添加方式对反应的影响. 结果表明,以Ru-Pt/γ-Al2O3为催化剂,在1.0 MPa和50 ℃的条件下反应1 h,p-CNB的转化率可达48.2%,生成对氯苯胺(p-CAN)的选择性为87.3%. 在反应体系中添加适量的Fe3+或Sn4+离子时,在相同的反应条件下,p-CNB的转化率和p-CAN的选择性分别提高到100%和99.0%. Fe3+或Sn4+的添加量及添加方式对p-CNB的转化率有较大的影响,加入Fe2+,Co2+和Ni2+离子也有利于提高催化剂的活性和选择性. Ru-Pt/γ-Al2O3催化剂体系对其它氯硝基苯的加氢反应也有明显的催化作用.     

大孔强酸型离子交换树脂选择性催化硝化邻二甲苯

以大孔强酸型离子交换树脂-95％硝酸作为硝化剂,利用单因素实验考察了硝化反应的影响因素,并用正交实验优化了硝化反应条件,得到最佳的硝化反应条件为:树脂用量为12g/mL硝酸,硝酸滴加温度为-20℃,搅拌保持3h,然后升温至40℃反应1h,邻二甲苯的转化率为89％,4-硝基邻二甲苯和3-硝基邻二甲苯的质量比为1.81,且树脂具有良好重复使用性能.     

助剂的引入对多组分V-Cs-Cu-Tl催化剂反应性能的影响

在钒基催化剂上考察了助剂铯、铜、铊的引入对制取对叔丁基甲醛的反应性能的影响,并用扫描电镜、ICP等技术对其进行了表征。实验结果表明添加剂铯后,目的产物对叔丁基苯甲醛的选择性提高,而对叔丁基甲苯的转化率影响不大;添加铜后对反应活性和选择性提高都有利;添加铊后的催化剂反应性能更优于添加其它助剂,获得了转化率大于12mol%、选择性大于80mol%的好结果,该催化剂稳定运转365小时后催化性能保持不变,是一种很有工业应用前景的催化剂。     

化学液相沉积与沸石择形催化性能

在经ＳｉＣｌ４化学液相沉积的ＨＺＳＭ－５沸石催化剂上进行了甲茉歧化、Ｃ６烷烃异构体催化裂解和邻二甲苯异构化反应，随着ＳｉＯ２沉积量增加，沸石内表面性质变化不大，而孔径逐渐缩小，甲苯歧化和邻二甲苯异构化反应的对二甲七选择性提高，Ｃ６烷烃异构体中支链烃３－甲基戊烷和２，２－二甲基丁烷的裂解反应转化率下降，实验结果表明，化学液相沉积是改善沸石催化剂对反应物物产物择形性能的一种有效方法。     

煤质对H2/Ar等离子体热解制乙炔的影响

选取12种不同变质程度的煤，通过等离子体热解实验考察了煤的挥发分产率、煤中氧质量分数、灰分产率对乙炔收率和结焦的影响。研究结果表明，挥发分产率为30%～40%的烟煤，热解时具有较高的乙炔收率；含氧量越高的煤，生成的碳氧化物越多，相应的乙炔收率较低；煤中的矿物质与乙炔收率之间并不存在相关性，但煤中的矿物质有利于CO的生成。影响结焦量的主要因素与煤的矿物质密切相关，煤中掺入二氧化硅和天然河沙能够明显增加结焦量，改变结焦形态。     

改性Y沸石上的氢转移反应

本文试图用环已烯和邻二甲苯两典型反应考察改性Y沸石的氢转移反应性能。发现在改性Y沸石上环已烯的氢转移, 异构化和聚合反应时发生。在反应开始时SY沸石的氢转移反应和异构化反应活性与铝含量之间的关系与沸石强酸量和铝含量的关系一致, 呈火山形曲线, 极大值在Al/(Al+Si)为0.15左右, 结焦以后反应总转化迅速下降, 且氢转移活性和异构化活性随铝含量减少而单调下降。USY沸石的氢转移活性大幅度降低。在改性Y沸石上邻二甲苯异构化和歧化反应同时进行, SY沸石的歧化反应变化规律与环乙烯氢转移反应相似。当沸石样品中有大量非质子酸位存在时, 两个反应的数据会出现予盾。     

Synthesis and catalytic performance on methanol conversion of NiAPSO-34 crystals (II): catalytic performance under various reaction conditions

This work has been focused on the catalytic performance for methanol conversion of NiAPSO-34 catalysts which had been synthesized by various preparation methods. The deposited coke during the hydrocarbon transformation was analyzed by temperature-programmed oxidation (TPO) method. For a catalyst with small acid sites and sharp particle size distribution, the catalytic activity and selectivity to ethylene increased compared with other catalysts. It could be confirmed that the catalysts having different acidic densities on external surface and internal surface represented different catalytic activities. Furthermore, it was elucidated that amount of coke formation was strongly related to acidic density on the external crystal surface. On the other hand, catalytic performances under various reaction conditions were exhibited variously and the deposited coke amount was also various. In particular, a surprising result was that the catalytic performance was not changed on the revived catalyst by thermal treatment at 600°C for 3 h.     

Ultraviolet (UV) curing of phosphated polyurethane-acrylic dispersions

Phosphate-containing polyurethane-acrylic dispersions were synthesised for UV curing studies. The effects of light intensity, substrate-dependent temperature increase, soft-segment content and water on conversion were investigated. The effect of the light intensity on conversion was twofold. At first, conversion increased with light intensity. This was attributed to the inability of shrinkage to keep pace with the polymerisation and crosslinking, resulting in the creation of free volume, thereby facilitating reaction and enhanced conversion. At higher intensities, conversion was found to be reversed or, at least, it remained constant, owing to increasing radical-radical termination reactions. Phosphated-polyurethane coatings with high soft-segment content show improved conversion with exposure time. This was found to be related to the chain mobility, caused by the low glass transition temperature of the soft segment. The effect of water on conversion was also twofold. On the one hand, water had a plasticising effect on the UV curing and the polymerisation rate was fast. On the other hand, the gel content was found to be lower when films were cured before the evaporation of water.     

重金属对重油热转化过程生焦特性的影响

以委内瑞拉减渣、辽河减渣、克拉玛依减渣三种劣质减压渣油为原料,在微型反应釜中进行反应,研究重金属等因素对重油热转化过程生焦特性的影响。结果表明,重油中重金属含量越高,其在热转化过程中的生焦诱导期越短。随着重金属总含量的增加,重油的生焦量明显增多,生成的焦颗粒也逐渐变大。延迟焦化产物分析结果进一步表明,重金属含量越高的重油,焦产率越高,导致液体产物收率下降。     

Effect of Dimethyl Ether Co-feed on Catalytic Performance of Methane Dehydroaromatization over Mo／HZSM-5 Catalyst

The effect of dimethyl ether (DME) co-feed on the catalytic performance of methane dehydroaxomatization (MDA) over 6Mo/HZSM-5 catalyst was investigated as a function of DME concentration under reaction conditions of T=1023 K, p=101 kPa and SV=1500 ml/(g.h). A high benzene yield wasobtained and the stability of the catalyst was improved by adding 1.5%DME to the CH4 feed. The C6H6 yield was as high as ca. 10% even after reaction for 6 h. The stability of the catalyst was further improved when DME concentration in the co-feed gas was increased to an appropriate value. TGA and TPO results of the used 6Mo/HZSM-5 catalyst showed that the amount of coke on the used catalyst was reduced and the chemical nature of the coke was changed. When 1.5%DME was added to the CH4 feed, the coke formed on the catalyst could be burned off more easily than that when only CH4 was used as reactant. It is supposed that the oxygen in DME may play a role in preventing the coke burnt off at lower temperature from transforming into the coke burnt off at higher temperature, which results in the improvement of the stability of the catalyst.     

大庆催化油浆受热相分离行为的研究

借助于热台显微镜,对大庆油浆受热相分离行为进行了考察。通过在有氧、无氧条件及不同温度下对大庆油浆受热相分离行为的研究,并与之基本物性相互关联,从微观上探讨油浆的生成机理。实验表明,油浆中重组分含量高时,有氧条件下生焦就会加剧;同时高温短时间或是低温长时间下生焦倾向就会加大,而油浆的芳香性分布较宽条件下生焦可以得到减缓。     

焦煤与不同种类废塑料共焦化的研究

采用10g常压固定床反应器、热天平和偏光显微镜,对太钢炼焦煤中添加不同种类废塑料（如HDPE,LDPE,PP和PS）后热解的产品分布、半焦的光学特性以及热重行为进行了研究。结果表明：煤和塑料的热解温度范围和峰温的差异决定二者协同作用的程度;四种塑料的添加对净焦煤的半焦收率无明显影响;当添加HDPE、LDPE、PP时,焦煤的焦油收率增加,热解水收率下降,但添加PS时的情况正相反;除了PP外,添加其它各类的塑料能增加半焦中的光学各向异性组织的含量。     

Conversion of Methane and Carbon Dioxide in a DBD Reactor: Influence of Oxygen

A continuous plug flow reactor supported by a dielectric barrier discharge (DBD) is used to study the conversion of methane, carbon dioxide, and oxygen at different compositions. The three studied gases were diluted with helium to 3 % with an overall flow rate of 200 sccm. The 13.56 MHz plasma was ignited at atmospheric pressure. The product stream and the inlet flow were analyzed by a FTIR spectrometer equipped with a White-cell and by a quadrupole mass spectrometer. The DBD reactor generates hydrogen, carbon monoxide, ethane, ethene, acetylene, formaldehyde, and methanol. Additional oxygen in the feed has positive effects on the yield of methanol, formaldehyde and carbon monoxide and reduces the total consumed energy. The hydrogen yield reaches its maximum at medium amounts of oxygen in the inlet flow. The conversion of methane increases to a limiting value of about 35 %. Methane rich feeds increase the yield of hydrogen, ethane and methanol. On the other hand, additional oxygen has a negative influence on the produced amount of C2 hydrocarbons. The conversion of methane and carbon dioxide as well as the yield of synthesis gas components and C2 hydrocarbons increases by changing the plasma power to higher values.     

7—氮杂降冰片二烯衍生物光诱导电子转移敏化异构化反应研究

本文以结晶紫、吖啶橙为光敏化剂，以Ｎ—对甲苯磺酰基－７－氮杂－双环［２．２．１］－２，５－庚二烯－２，３－二羧酸二甲酯（ＮＮＢＤ）为反应底物，测定了ＮＮＢＤ光敏异构化反应的转化率及量于产率。通过荧光谱和ＮＮＢＤ对敏化剂的荧光猝灭试验，根据ｗｅｌｌｅｒ电子转移理论对ＮＮＢＤ的光敏异构化机理进行了探讨。