内扩散对煤和石油焦水蒸气气化反应性能的影响

以内蒙褐煤、神府烟煤、遵义无烟煤和石油焦为研究对象,借助热重分析仪,进行了水蒸气气化动力学研究,得到了4种样品焦的本征动力学方程,分析了水蒸气分压和粒径对气化反应的影响。基于幂函数模型得到的动力学参数,结合气固催化理论,提出了计算内扩散效率因子(η)的方法。计算效率因子(ηcal)和实验效率因子(ηexp)的对比结果表明,使用该方法得到的内扩散效率因子可以用于定量评估水蒸气气化反应中内扩散过程的影响程度。     

Kinetic modeling of the ethylbenzene/xylene isomerization reaction over HZSM-5 zeolites revisited

In this article, a binderless dealuminated HZSM-5 zeolite (Si/Al = 41.4) was used as a catalyst for the isomerization of a mixture of ethylbenzene and xylene. The experimental results indicated that at low residence times the catalyst is effective to isomerize the ethylbenzene into xylenes. A comprehensive kinetic model considering chemisorption, surface chemical reactions, and diffusional processes was developed for this reaction. The intrinsic activation energy (71.99 kJ mol⁻¹) for the surface reaction of ethylbenzene into m-xylene was calculated for the first time, and the corresponding intrinsic activation energies for o-xylene to m-xylene and m-xylene to p-xylene surface reactions were calculated to be 59.45 and 50.68 kJ mol⁻¹, respectively. Lower apparent values have been reported in the literature, and we rationalize that they correspond to multistep processes and intrinsically include a negative activation energy pertaining to chemisorption. The results also revealed that the ethylbenzene diffusion within the zeolite channels was four orders of magnitude smaller than p-xylene.     

新型双燃料重整联合循环发电系统

本文提出了一种新型双燃料重整联合循环发电系统。该系统通过重整反应实现了煤和天然气的综合利用,煤的燃烧过程为天然气/水蒸汽重整反应提供了高温反应热,通过双燃料重整煤的部分化学能间接转化到合成气中,然后合成气进入联合循环燃烧作功。研究结果表明双燃料联合循环的供电效率为49.4%-53.2%,煤的折合供电效率为42.4%-44.6%,与IGCC(动力部分相同时为44%-46%)相比供电效率降低1-2个百分点,但是投资大约降低30%。本文的研究开拓性地为煤的清洁高效利用提供了新途径。     

Catalytic gasification of Pakistani Lakhra and Thar lignite chars in steam gasification

采用热重法在常压与700℃~900℃条件下的水蒸气气化过程,对两种巴基斯坦Lakhra和Thar褐煤半焦进行了单一和混合催化剂(即3%钙和5%钠-黑液单一催化剂及一种3%钙和5%钠-黑液混合催化剂)对碳转化率、气化反应速率常数及活化能、有害污染含硫气体相对量的催化效应研究.两者Lakhra和Thar褐煤半焦经直接气化就可获得高的碳转化率,但采用纸浆黑液催化剂可使气化速率变得很快.含灰高的Thar褐煤半焦在纸浆黑液催化气化过程更易生成一些复杂的硅酸盐,从而导致比含灰低的Lakhra褐煤半焦出现一个更低的转化率.在水蒸气气化过程由半焦和纸浆黑液自身所产生的SO2 和 H2S含硫气体可为存在于纸浆黑液中的Ca盐所捕获而完成脱硫过程,但这一过程在低于900℃时更有效.缩芯模型 (SCM)可较好地用来关联转化率与时间的关系并给出不同温度下的反应速率常数k.基于阿累尼乌斯方程预测了反应活化能Ea 和指前因子A.在纸浆黑液和钙混合催化及纸浆黑液催化剂时,Lakhra褐煤半焦的Ea分别为44.7kJ/mol和 59.6kJ/mol明显小于Thar褐煤半焦的Ea=114.6kJ/mol 和 Ea=100.8kJ/mol,同样也小于无催化剂纯半焦气化时Lakhra褐煤半焦的Ea=161.2kJ/mol和Thar半焦的Ea=124.8kJ/mol.     

钙钛矿型甲醇水蒸气重整制氢催化材料的研究

采用溶胶凝胶法合成了钙钛矿复合氧化物,负载氧化铜后得钙钛矿负载型催化材料,通过XRD(X射线衍射分析)、BET(比表面积测试)、H2-TPR(程序升温还原分析)、XPS(X射线光电子能谱)等手段对催化材料进行了表征,考察了不同种类钙钛矿负载纳米铜催化材料的结构、性质对甲醇水蒸气重整制氢性能的影响.结果显示,钙钛矿负载纳...     

晶化温度对SAPO-34结构稳定性的影响

用二乙胺结构导向剂, 分别在473和573 K水热晶化得到两种SAPO-34分子筛材料. SEM和XRD结果表明, 晶化温度升高, SAPO-34晶粒增大, 结晶度提高, 比表面积和孔径增大. 升高晶化温度, 提高了样品的最高焙烧和水蒸汽热处理承受温度.     

高温饱和水密度动态变化探讨

本文分析了高温饱和水在满管流动的爬高过程中,其密度发生明显变化的动态机理,利用此动态特性,就实现低压高温凝结水无泵回收的可能性进行分析讨论.     

超音速两相流极限升压能力的理论与试验研究

采用理论和实验的方法研究了一定汽水参数下的超音速汽液两相流升压装置的极限升压能力以及主要结构参数对其的影响规律。计算与实验的结果表明:超音速汽液两相流升压装置的极限升压能力计算值可达进汽压力的14倍左右,实验值可到进汽压力的2.6倍左右;混合腔和水喷嘴的几何尺寸是影响极限升压能力的最主要的结构参数;极限升压能力随混合腔收缩比增大而增大,随水喷嘴出口与混合腔喉部截面积比增大而减小,随蒸汽喷嘴喉部与出口截面积之比变化不大。计算和实验得到的结构参数对极限升压能力的影响规律是基本一致的。     

Zeolite Catalyzed Alkylation of Biphenyl. Where Does Shape-Selective Catalysis Occur?

Liquid-phase alkylation of biphenyl (BP) was studied over large-pore zeolites. Selective formation of the least bulky products, 4,4-diisopropylbiphenyl (4,4-DIPB) occurred only in the isopropylation of BP over one- or two-dimensional zeolites, H-mordenite (HM), ZSM-12, SSZ-24, SAPO-5, SSZ-31, and CIT-5. These shape-selective catalyses are ascribed to steric restriction of transition state and to easiness of the substrates to enter into the pores. HM gave the highest selectivity among them. The dealumination of HM enhanced catalytic activity and the selectivity for 4,4-DIPB because of the decrease of coke deposition. Non-regioselective catalysis occurs on external acid sites over HM with the low SiO₂/Al₂O₃ ratio because severe coke deposition deactivates the acid sites inside the pores by blocking pore openings. The selectivity of DIPB isomers was changed with propylene pressure and/or with reaction temperature. Selective formation of 4,4-DIPB was observed at moderate temperatures such as 250°C, whereas the decrease of the selectivity of 4,4-DIPB occurred at higher temperatures as 300°C. 4,4-DIPB yielded selectively under high propylene pressure (<0.3 MPa) at 250°C, while the selectivity of 4,4-DIPB decreased under low propylene pressure as 0.2 MPa. However, 4,4-DIPB was almost exclusive isomer in the encapsulated DIPB isomers inside the pores under every temperature and pressure. The decrease of the selectivity of 4,4-DIPB is due to the isomerization of 4,4-DIPB on the external acid sites. The deactivation of external acid sites of HM was examined by the modification with cerium and other rare earth metal oxide on HM. Selectivities of 4,4-DIPB were improved over modified HM even at high temperatures because of the suppression of non-regioselective alkylation and isomerization at the external acid sites. The ethylation of BP to ethylbiphenyls (EBPs) and diethylbiphenyls (DEBPs) was non-regioselective. The ethylation of BP to EBPs was controlled kinetically. However, there was difference in reactivities of EBPs and DEBPs for their further ethylation. 4-EBP was ethylated preferentially among the isomers, although the formation of 4,4-DEBP was less selective. 4-EBP and 4,4-DEBP have the highest reactivities among EBPs and DEBPs for the ethylation to polyethylbiphenyls (PEBPs). These results show that the environments of HM pores are too loose for shape-selective formation of the least bulky isomers, 4-EBP and 4,4-DEBP, in the ethylation of BP, and that HM pores have enough space for the further ethylation of 4,4-DEBP.     

Ethanol production in immobilized-cell bioreactors from mixed sugar syrups and enzymatic hydrolysates of steam-exploded biomass

We investigated ethanol production from mixed sugar syrups. Hydrolysates were prepared from enzymatic saccharification of steam-pretreated aspen chips. Syrups containing 45 g/L of glucose and 12 g/L of xylose were detoxified through two ion-exchange resins and then fermented with Pichia stipitis and Saccharomyces cerevisiae immobilized in Ca-alginate gel beads. Combinations of different gel fractions in the fermentation volume, amount of yeast cells, and ratios of P. stipitis vs S. cerevisiae within each bead were compared. In the best conditions, by using a total beads volume corresponding to 25% of the working volume, we obtained a yield of 0.39 g_ethanol/g_{initial sugars}. This amount of gel entrapped an initial cell concentration of 6×10¹²cells/L with ratio of S. cerevisiae/P. stipitis of 0.25 g/g. Modified stirredtank reactors were obtained either by adding marbles or by inserting a perforated metal cylinder, which reduced considerably the rupture of beads while visibly improving oxygenation of the medium.