不同硅铝比Co/ZSM-5催化剂对费托合成汽油馏分烃选择性的调控

以ZSM-5分子筛为载体,通过等体积浸渍法制备了Co/ZSM-5系列催化剂,用于费托合成反应一步法制汽油馏分烃(C_5^C_(11)烷烃)。考察了不同硅铝比(Si O_2/Al_2O_3=25,38,50,80和200)的ZSM-5分子筛对Co/ZSM-5催化剂费托合成汽油馏分选择性的影响。采用氮气物理吸附-脱附、X射线衍射、氢气程序升温还原(H_2-TPR)和氨气程序升温脱附(NH_3-TPD)等手段对载体和催化剂进行了表征,并在高压固定床反应器上对催化剂的费托合成催化性能进行了测试。结果表明,对比Co/ZSM-5(Si O_2/Al_2O_3=25,38,50和80)催化剂,Co/ZSM-5(Si O_2/Al_2O_3=200)催化剂表现出最高的汽油馏分烃类选择性,高达52.8%,这主要归功于Co/ZSM-5(Si O_2/Al_2O_3=200)催化剂上较小钴颗粒尺寸、较优的还原性能以及适量弱酸位的协同作用。分子筛的酸性为催化剂的加氢裂解转化提供活性位,促进重质烃产物发生裂解和异构等二次反应,较小的钴颗粒尺寸和较优的还原性能有利于提高C_5C_(11)烷烃)。考察了不同硅铝比(Si O_2/Al_2O_3=25,38,50,80和200)的ZSM-5分子筛对Co/ZSM-5催化剂费托合成汽油馏分选择性的影响。采用氮气物理吸附-脱附、X射线衍射、氢气程序升温还原(H_2-TPR)和氨气程序升温脱附(NH_3-TPD)等手段对载体和催化剂进行了表征,并在高压固定床反应器上对催化剂的费托合成催化性能进行了测试。结果表明,对比Co/ZSM-5(Si O_2/Al_2O_3=25,38,50和80)催化剂,Co/ZSM-5(Si O_2/Al_2O_3=200)催化剂表现出最高的汽油馏分烃类选择性,高达52.8%,这主要归功于Co/ZSM-5(Si O_2/Al_2O_3=200)催化剂上较小钴颗粒尺寸、较优的还原性能以及适量弱酸位的协同作用。分子筛的酸性为催化剂的加氢裂解转化提供活性位,促进重质烃产物发生裂解和异构等二次反应,较小的钴颗粒尺寸和较优的还原性能有利于提高C_5⁺烃选择性。     

合成气一步法制汽油馏分烃费托合成催化剂研究进展

围绕对费托合成产物分布的有效调控,综述了近年来有关合成气一步法制汽油馏分烃(C5^C11烷烃)费托合成催化剂的研究进展。重点分析了铁、钴、钌基分子筛催化剂对C5C11烷烃)费托合成催化剂的研究进展。重点分析了铁、钴、钌基分子筛催化剂对C5^C11烃选择性的影响,并对费托合成一步法制汽油馏分烃催化剂的未来发展方向进行了展望。     

合成气一步法制汽油馏分烃费托合成催化剂研究进展

围绕对费托合成产物分布的有效调控,综述了近年来有关合成气一步法制汽油馏分烃(C5~C11烷烃)费托合成催化剂的研究进展。重点分析了铁、钴、钌基分子筛催化剂对C5~C11烃选择性的影响,并对费托合成一步法制汽油馏分烃催化剂的未来发展方向进行了展望。     

Co基费托合成催化剂载体的研究进展

综述了近年来钴(Co)基催化剂载体在费托合成反应中的研究进展.重点评述了柱撑蒙脱土、新型介孔分子筛等载体对钴基催化剂活性和选择性等方面的影响,概述了Co/Al_2O_3催化剂在费托合成反应中的催化机理,对今后Co基费托合成催化剂的研究提出了一点建议.     

Na-Fe_3O_4/ZSM-5催化剂上CO_2加氢反应汽油烃产物的组成调控

CO_2加氢直接合成汽油不仅有利于CO_2减排,还可减轻人们对化石能源的依赖。汽油馏分烃产物组成是决定汽油燃料品质的重要因素,其调控是该过程具有挑战性的研究热点。研究NaFe_3O_4/ZSM-5催化剂中分子筛的金属(La,Ga,Zn,Cu,Co)改性对CO_2加氢产物中汽油馏分烃组成的影响,结果表明,与其他金属相比,Cu改性ZSM-5分子筛组分可在保持较高汽油收率前提下,明显提高汽油产物中异构烷烃选择性。优化改性分子筛中Cu质量分数8%时,汽油馏分烃产物中异构烷烃含量最高。当Na-Fe_3O_4和Cu-ZSM-5采用分层填装方式时,汽油馏分烃产物中异构烷烃含量达50.5%,组成调控后富含异构烷烃汽油产品更符合汽油品质升级趋势需求。     

南京黄马化工有限公司

<正> (专业生产各类特种分子筛和催化剂) 南京黄马化工有限公司位于南京市东郊,是国内规模较大的专业生产各类ZSM-5沸石分子筛、丝光沸石、β分子筛、其它介孔沸石分子筛等的特种分子筛和催化剂厂。特种分子筛主要产品有:不同硅铝比ZSM-5分子筛,从低硅(SiO_2/Al_2O_3=25～30)、常规(SiO_2/Al_2O_3=32～40)、中硅(SiO_2/Al_2O_3=50～120)到高硅(SiO_2/Al_2O_3=260～300);不同晶粒度ZSM-5分子筛从大晶粒(1～4μm)、小晶粒(200～500 nm)到纳米级(100～200 nm)ZSM-5分子筛;钠型和氢型丝光沸石;     

Co/Al_(2)O_(3)固定床费托合成催化剂水热稳定性研究

考察不同水热条件对Al_(2)O_(3)载体、Co/Al_(2)O_(3)催化剂稳定性的影响。表征结果表明,在苛刻水热条件下,即使高温焙烧的Al_(2)O_(3)载体也存在水热不稳定性现象。在接近工业固定床费托合成条件下运行,蛋壳型Co/Al_(2)O_(3)催化剂水热稳定性好。少量Co、Si改性能明显提高载体水热稳定性。     

Co/Al_2O_3催化剂制备及其合成重质烃的反应性能

以不同孔道结构Al_2O_3作载体,甲醇、乙醇和柠檬酸作分散剂,通过等体积浸渍法制备系列Co/Al_2O_3费托合成催化剂。采用XRD、TG-DSC和H2-TPR等考察制备方法对催化剂结构的影响,并在固定床反应器中对催化剂进行性能评价。结果表明,采用具有适宜孔道结构Al_2O_3作载体才能获得综合性能较好的催化剂,3种分散剂的加入,促进了钴物种在载体上的分散,增强了钴与载体间的相互作用,改善了催化剂费托合成反应活性,显著提高了重质烃时空收率。     

ZSM-23/活性氧化铝复合催化剂在甲醇脱水反应中的应用研究

在常规的合成方法中,进一步优化了制备拟薄水铝石的pH及老化时间等条件,并对合成得到的拟薄水铝石做了X射线衍射(XRD)、N_2物理吸附、扫描电镜(SEM)等表征。结果表明,pH=7~8、老化时间为2 h是较适宜的拟薄水铝石合成条件。采用优化条件下制备得到的拟薄水铝石,通过干燥、焙烧等后处理可得到用于甲醇脱水制二甲醚的活性Al_2O_3催化剂。通过向活性Al_2O_3中加入ZSM-23分子筛,得到了ZSM-23/活性Al_2O_3复合催化剂。通过NH_3程序升温脱附表征(NH_3-TPD)及反应性能评价发现,相比纯活性Al_2O_3,ZSM-23/活性Al_2O_3分子筛复合催化剂具有更高的甲醇脱水反应活性和稳定性。     

合成气费托合成制重质烃Ru-Co/SiC催化剂的制备及性能

费托合成是以合成气生产清洁燃料和其他化学品的重要途径。传统费托合成产物遵循A-S-F分布,只有甲烷和重质烃的选择性没有极限值。因此,费托合成研究以最大程度地合成重质烃,提高合成产物中重质烃的选择性为目标。基于此,首先详细探究了Al₂O₃、SiO₂和SiC载体对费托反应性能的影响。结果表明 Co/SiC催化剂具有最高的CO转化率（83.5%）和C₅₊选择性（80.3%）。与浸渍法相比,原位还原法更为有效地引入Ru到Co/SiC催化剂,将C₅₊选择性提高至90.1%。Ru助剂能在保持较高催化活性不变的前提下,有效提高Co/SiC催化剂C₅₊选择性。催化剂表征（XRD、H₂-TPR、XPS、H₂-化学吸附和TEM）结果表明,Ru能与Co发生相互作用,提高了催化剂的可还原性和活性组分的分散性,进而改善了Co/SiC催化剂重质烃的选择性。     

Self-organized nano-crystallisation of BaF2 from Na2O/K2O/BaF2/Al2O3/SiO2 glasses

In glasses with the compositions (100 ? x)(2Na₂O·16K₂O·8Al₂O₃·74SiO₂)xBaF₂ (with x = 0 to 6), the glass transition temperature decreases with increasing BaF₂-concentration. Samples with x = 6 were thermally treated at temperatures in the range from 500 to 600 °C for 5–160 h. This leads to the crystallisation of BaF₂. The quantity of crystalline BaF₂ increases with increasing time of thermal treatment, while the mean crystallite size remains constant within the limits of error. The glass transformation temperature of partially crystallised samples increases with increasing crystallisation time and approaches a value equal to the temperature, at which the samples were treated. This is explained by the formation of a highly viscous layer enriched in SiO₂ which is formed during crystallisation. This layer acts as a diffusion barrier and hinders further crystal growth.     

Prediction of Immiscibility Boundaries of the Systems K2O-SiO2, K2O-Li20-SiO2, K20-Na2O-Si02, and K2O-BaO-SiO2

In earlier work, a prediction method of the immiscibility boundary of a ternary silicate glass system was developed involving two known binary immiscibility boundaries and a measured immiscibility temperature of one ternary glass composition. In the present work, the method is extended to the case where one of the two binary immiscibility boundaries is not known and is applied as an example to ternary silicate systems containing K₂O. First, the immiscibility boundary of the system K₂O-SiO₂ is estimated by measuring the immiscibility temperatures of three glasses in the system K₂O-Li₂O (or Na₂O)-SiO₂. Using this result the immiscibility boundaries of the systems K₂O-Li₂O-SiO₂, K₂O-Na₂O-SiO₂, and K₂O-BaO-SiO₂ are estimated. The results agree reasonably well with the experimentally determined immiscibility temperatures at selected compositions.     

Some Properties of the System Na2O-NaF-B2O2-H2O

It was first shown that the enamel slips which have the best suspnding characteristics contain equal amounts of Na₂O and B₂O₃ and at least a moderate amount of NaF. The solubilities of mixtures of Na₂O, NaF, and B₂O₃ were then investigated. The pH of these solutions and the primary crystalline phases separating on evaporation also were determined. The solubility data obtained at room temperature were summarized. When the solutions were evaporated, NaF was the first crystalline phase to separate from a large proportion of the mixtures investigated. It was concluded that the desirable handling characteristics of enamels whose mill liquors contain the proper proportion of Na₂O, NaF, and B₂O₃ are not due to the formation of complex salts but to the following combination of properties: (1) the presence of salts with a moderate solubility which changes very slightly with temperature, (2) a moderate pH of about 10 in a probably well-buffered solution, (3) a relatively stable crystalline material, NaF, as a primary phase, and (4) a secondary phase which crystallizes slowly with relatively little shrinkage.     

Photocatalytic activity of Cu2O/TiO2, Bi2O3/TiO2 and ZnMn2O4/TiO2 heterojunctions

Cu₂O/TiO₂, Bi₂O₃/TiO₂ and ZnMn₂O₄/TiO₂ heterojunctions were studied for potential applications in water decontamination technology and their capacity to induce an oxidation process under VIS light. UV–vis spectroscopy analysis showed that the junctions-based Cu₂O, Bi₂O₃ and ZnMn₂O₄ are able to absorb a large part of visible light (respectively, up to 650, 460 and 1000 nm). This fact was confirmed in the case of Cu₂O/TiO₂ and Bi₂O₃/TiO₂ by photocatalytic experiments performed under visible light. A part of the charge recombination that can take place when both semiconductors are excited was observed when a photocatalytic experiment was performed under UV–vis illumination. Orange II, 4-hydroxybenzoic and benzamide were used as pollutants in the experiment. Photoactivity of the junctions was found to be strongly dependent on the substrate. The different phenomena that were observed in each case are discussed.     

Crystallization of zeolite L from Na2O-K2O-Al2O3-SiO2-H2O system

Zeolite L powder was prepared from the substrate mixture of Na₂O-K₂O-Al₂O₃-SiO₂-H₂O system at temperatures of 373-443 K. In order to investigate the factors which influence the synthesis outcome, a reference system which yields zeolite L in a reproducible manner was chosen and subjected to controlled changes in synthesis parameters. The crystalline zeolite L samples obtained were characterized by elemental chemical analysis, X-ray diffraction (XRD), and scanning electron microscopy (SEM). It was established that phase purity, morphology, and the size of crystals of crystalline product were affected by molar ratios of the substrate, such as SiO₂/Al₂O₃, (K₂O+Na₂O)/SiO₂, Na₂O/(K₂O+Na₂O), and H₂O/(K₂O+Na₂O). Amorphous silica powder (Zeosil) was the preferred silica source, and the crystallization rate was promoted by introducing gel aging, seeding, and rapid heating rate.     

Chemical Durability of Na2O-K2O-CaO-SiO2 Glasses

The mixed-alkali effect on chemical durability was evaluated for bulk and powdered Na₂O-K₂O-CaO-SiO₂ glasses. Two contributions to this effect are discussed, i.e. those of glass structure and corrosion solution. The magnitude of the mixed-alkali effect depends on the pH of the corroding solution. For pH<9, alkali-ion leaching is the major mode of glass corrosion, and the mixed-alkali effect is large. However, for pH≥9 congruent glass dissolution is the rate-controlling corrosion mechanism, and the effect is diminished. When ion exchange is the rate-controlling corrosion mechanism the magnitude of the mixed-alkali effect depends on the extent of reaction. Since the kinetics of corrosion are influenced by the ratio of glass surface area to solution volume ( SA/V ), results obtained when this ratio is large may be misleading if extrapolated to smaller ratios. Physical evidence of the mixed-alkali effect in bulk glasses was obtained using scanning electron microscopy and ir reflection spectroscopy.     

O_2/N_2、O_2/CO_2和O_2/CO_2/NO气氛下煤粉燃烧NO_x排放特性

利用滴管炉研究了O2/N2、O2/CO2和O2/CO2/NO气氛下煤燃烧过程中NOx的排放特性。实验结果表明,在O2/N2和O2/CO2气氛下,高温或高O2浓度均使NO排放量增加。O2/CO2气氛下NO排放量比O2/N2气氛下NO排放量低大约30%~40%。在O2/CO2/NO气氛下,温度不同时,O2浓度变化对NO排放量的影响规律不同,对循环NO降解的影响规律也不同。高温不利于循环NO降解。随停留时间的延长NO排放量出现两个峰值。     

复合固体超强酸SO42-/ZrO2-Al2O3催化合成乳酸正丁酯的研究

合成了几种不同Zr、Al原子比的SO42-/ZrO2-Al2O3复合固体超强酸,将其用于催化乳酸与正丁醇的酯化反应,均有较好的催化活性,尤以ZrAl=12的催化效果最好,经济性优于ZrO2超强酸催化剂.其最佳反应条件为酸醇摩尔比为13,催化剂用量为乳酸质量的10%,反应时间2～2.5h,酯化率达96.9%.该催化剂具有制备容易、催化活性高、不污染环境、可重复使用的优点.