Carbon dioxide (CO2) is the material substance of plant photosynthesis, yet its concentration remains insufficient to meet plant photosynthesis demands. Therefore, the formation of CO2-enriched regions around leaf stomata is expected to improve the efficiency of plant photosynthesis. Herein, a photoresponsive metal-organic framework (Zr-ABTC) was constructed from azobenzene bonds, while T(n)/Zr-ABTC was prepared by the incorporation of tetraethyl pentamine (TEPA) with an adsorption ability for CO2. The photoresponsive material could capture CO2 in darkness and release it under ultraviolet irradiation, thus establishing a CO2 "enrichment-release" cycle under dark/light cycles. Upon application of Zr-ABTC onto Chinese little green leaves, scanning electron microscopy (SEM) revealed that the material is distributed around plant stomata, resulting in an 87.5% increase in crop yield compared with the blank control group not treated by Zr-ABTC (dry weight). The photothermal responsive materials created in this article may be used to improve the photosynthetic efficiency and enhance agricultural productivity.

Binders play essential roles in fluid catalytic cracking catalysts, and their interaction mechanism with zeolites remains to be explored. The effects of three binders on REUSY zeolite were investigated. The alumina sol most notably blocked the pore channels and destructed the framework of zeolites by removing the framework Al. The silica sol diffused into the silicon hydroxyl nests and form new Si-O tetrahedrons, which enhanced the structural stability and increased the number of Bronsted acid sites in zeolites, rendering the samples’ better hydrothermal stability and higher micro-reaction activity. The influence of the colloidal sol of pseudo boehmite on zeolites was between the two.

Aluminum phosphate sol attracts more and more attention due to its excellent particle size and bonding prop-erties. The structure, morphology and Zeta potential of aluminum phosphate sol during the peptizing process were investigated with NMR, FTIR, Raman, TEM and DLS. The results show that the pseudo boehmite particles were fragmentated, dissolved, and then peptized under the electrostatic repulsion of H+. The peptization process presents three stages: the fragmentation-polymerization stage, the reaction stage, and the stabilization stage. The particle diameter of the stable aluminum phosphate sol ranged from 30 to 50 nm, and the particles with varying sizes were interconnected to form a "hand-in-hand " cyclic system. Meanwhile, the dehydration condensation reaction between H3PO4 and pseudo boehmite was occurring continuously. When 2.1 < n(P)/n(Al) < 3, the proportion of QP10, QP01 and QP11 polymers in the system increased to 25-27 %, the degree of polymerization was deepened, and some cyclic oligomers and polymers appeared. Additionally, the crystal water concentration was increased and the peptization solubility was enhanced.

通过改变分子筛阳离子交换及气相超稳改性的程度工业生产出不同晶胞大小的系列高稳定性分子筛HSZ.为了考察这些分子筛的催化裂化反应性能,分别以所开发的HSZ-3,HSZ-4,HSZ-5分子筛为活性组元中试制备了催化裂化催化剂,并通过固定床自动微反活性评定仪和ACE固定流化床微反装置对其催化裂化反应性能进行了考察比较.结果表明,与以水热法分子筛为活性组元的催化剂相比,以气相法工业制备的高稳定性分子筛为活性组元的催化剂具有较强的重油裂化能力,较高的汽油、轻质油及总液体收率,较好的焦炭选择性.

相比传统ZSM-5分子筛,多级孔ZSM-5分子筛具有空间位阻小、传质效率高、焦炭少等特点,近年来在分子筛领域应用广泛.多级孔分子筛通常可用后处理法和模板剂法制备,相比后处理法,模板剂法能更好地控制介孔的结构和孔道尺寸.概述了采用传统表面活性剂、两亲性的有机硅烷、双功能多季铵盐表面活性剂及高分子聚合物等软模板法合成多级孔ZSM-5分子筛的研究进展.分析不同软模板剂的特点和作用机理,阐述了合成后分子筛的结构特点及催化性能等.指出在今后的研究中,可以设计价格较低的新型功能化模板剂,优化合成过程,致力于在理解合成机理的前提下,寻找操作简单、绿色环保的合成路线,并将其推行到实际工业生产中.

阐述了催化裂化(FCC)催化剂中常用黏结剂的发展现状,重点介绍了铝溶胶、胶溶拟薄水铝石、硅溶胶、硅铝溶胶和磷铝溶胶的组成、制备方法及胶溶机理,并对FCC催化剂黏结剂的发展前景进行了展望,指出未来复合黏结剂的运用将会越来越广泛.复合黏结剂属于亚稳体系,对于它的稳定性、聚合度、胶溶机理等有待进一步研究.

采用XRD、X射线荧光光谱、N2吸附-脱附和SEM等手段分析了REUSY、Hβ和ZRP-1分子筛的物理化学性质,考察了REUSY、REUSY+Hβ和REUSY+ZRP-1分子筛催化剂对原料油的催化裂化性能和产物碳四烯烃选择性的影响.结果表明:高稀土含量的REUSY分子筛具有较强的重油裂化能力和较高的汽油选择性,但是碳四烯烃选择性较低;Hβ分子筛对产物的碳四烯烃选择性优于REUSY和ZRP-1分子筛.在此基础上,提出采用催化材料目标导向技术开发选择性增产碳四烯烃催化剂的方案.

为了提高催化裂化催化剂的活性组元分子筛的稳定性和活性,通过改变分子筛阳离子交换及气相超稳改性的程度,设计并且工业制备5种不同晶胞大小的高稳定性分子筛HSZ-1,HSZ-2,HSZ-3,HSZ-4,HSZ-5,采用X射线衍射、N2吸附-脱附及傅里叶变换红外光谱等方法对其结构与性能进行分析表征.结果表明:所开发的H SZ系列分子筛具有结晶度高、比表面积大以及热稳定性和水热稳定性高的特点;并且,随着分子筛超稳程度的提高,分子筛的晶胞常数减小、SiO2含量升高、总酸量降低、B酸与L酸酸量比值降低、小笼羟基减少、末端硅羟基增多,但是,不同超稳程度的分子筛的大笼羟基均保持完好的结构.另外,H SZ系列分子筛均含有骨架四配位铝及非骨架六配位铝物种,超稳程度的提高使得非骨架铝含量增加;超稳程度最高的H SZ-1分子筛除具有4种Si配位状态以外,还有Si碎片存在.

在固定床微反装置上对4种不同结构的分子筛HZSM-5,HIM-5,HEU-1,HAl-ITQ-13的石脑油催化裂解(NCC)反应性能进行对比评价.采用XRD、SEM、N2吸附-脱附及Py-IR等方法表征各分子筛的孔道结构和酸性质.结果 表明:与HZSM 5相比,石脑油在HIM 5,HEU 1,HALITQ13作用下催化裂解反应的转化率均有所提高;孔径较小、酸量较低的HAl-ITQ-13和HEU-1具有较高的催化活性,其作用下的低碳烯烃(乙烯十丙烯十丁烯)收率分别比HZSM 5提高13.3百分点和8.6百分点;而在HIM 5作用下的低碳烯烃收率则比HZSM-5降低3.5百分点.同时,考察了NCC反应条件下丙烯的反应性能,发现丙烯在NCC反应条件下具有非常高的反应活性,可通过催化反应转化为乙烯、丙烷、丁烯等产物.抑制氢转移反应有利于提高低碳烯烃的收率,开发NCC新型催化材料时,应综合考虑分子筛的酸性质和孔道结构对低碳烯烃二次反应的抑制作用.

The negative influences caused by frequent shift of FCC catalyst species in current production mode were summarized. Through pilot test and practical statistics on industrial production line, the advantages of longer production term which could be obtained by adopting base catalysts blending technology, such as energy and raw material saving, higher production efficiency and improved catalyst quality, were comparatively discussed.

Increasing production of light raw chemical materials such as light olefins and aromatics is an inevitable trend in the development of catalytic pyrolysis technology. Reaction conditions are the crucial factors which affect the catalytic pyrolysis process and product distribution. This review introduces reaction mechanism of catalytic pyrolysis. Some typical reaction conditions including reaction temperature, mass ratio of catalyst to oil, residence time (space velocity), mass ratio of water to oil are being systemically discussed. Additionally, different reactor types and raw oil properties are also under discussion. Finally, we illustrate industrial applications to analyze the effect of reaction conditions.

The conversion of the heavy fractions of crude oil into transportation fuels and chemical feedstocks is still a severe challenge for fluid catalytic cracking (FCC) technology, in which geometrical parameters of the catalyst are of key importance to the accessibility for reactant and product molecules to travel through the pore space. Here a new core-shell zeolite catalyst with hierarchical pore network from macro- via meso- to micropores is developed by controlling overgrowth of another zeolite shell on the surface of a commercial Y-zeolite. The zeolite shell is a distinctive nano ZSM-5 crystals. The core-shell zeolite catalyst has a high thermal and hydrothermal stability because of high crystallinity, which can meet the industrial requirements. More importantly, the heavy oil can be cracked by the designed zeolite catalyst step-by-step into the required products. The meso- and macroporous shell facilitates pre-cracking the large molecules in heavy oil into moderate ones which can directly diffuse into the micropores of the Y-zeolite to be cracked selectively into the desired products. Both the pore structure network and acid sites distribution of the core-shell zeolite catalyst in the FCC processing are completely harmonious. As a practical example, the catalytic cracking of VGO heavy oil is actualized over the new catalyst. The results showed that the conversion of heavy oil and the yield of gasoline increased by 1.8 wt% and 8.9 wt% respectively, LPG decreased by 6.9 wt%, iso-paraffins and olefins in gasoline fraction increased by 5.21 wt% and 6.31 wt% respectively, aromatics decreased by 11.55 wt%, because of the graduated cracking in core-shell zeolite and returned isomerization in nano ZSM-5, compared with commercially industrial FCC catalyst. (C) 2018 Elsevier Inc. All rights reserved.FCC Core-shell structure Y-zeolite Heavy oil Gradual cracking Industrialization

以某炼油厂催化裂化装置催化剂置换前后的生产运行数据为依据,从原料性质、催化剂以及装置操作条件等方面分析了影响FCC汽油辛烷值变化的主要技术因素.在催化剂方面,控制适宜的稀土氧化物含量和较高的基质活性;在原料性质方面,适度降低饱和烃含量和控制较低的钠含量;在操作条件方面,控制适宜的反应温度和剂油比.通过对汽油辛烷值各个影响因素的系统解析,有助于炼油厂在实际生产中科学有效地进行汽油辛烷值的调节控制.

为实现烟气NOx达标排放,在中国石化安庆分公司DCC装置无烟气脱硝后处理设施上进行了RDNOx助剂工业应用试验.结果表明,在助剂占系统藏量约2.5％(w)、按进料计剂耗0.03 kg/t加注时,可在烟气过剩氧含量不受严格限制的情况下,将烟气中NOx质量浓度稳定控制在小于70 mg/m3(在线仪表),达到国家最新环保标准(特别限值)要求.逐步调整助剂加注量至0.015 kg/t、约占新鲜催化剂补充量的1.5％时,NOx浓度依然保持稳定达标.相对加注脱硝助剂前的NOx质量浓度空白值400～500 mg/m3,NOx浓度降幅达到80％以上.在RDNOx助剂应用过程中,产品分布和主要产品性质基本不变.

常规方法制备的RFS-1硫转移剂MgO含量较低且磨损指数较差,采用铈化合物全部加入成胶过程的方法制备的RFS-2及采用铈化合物全部加入浸渍过程的方法制备的RFS-3硫转移剂在提高MgO含量的前提下保证了催化剂的抗磨损性能,并采用XRF、XRD、DTA、BET、XPS、SEM、TEM等分析手段及FCC再生烟气脱硫性能评价实验对3种不同制备方法得到的硫转移剂进行表征和性能考察。结果表明:RFS-3为MgAl 2 O 4 表面负载金属CeO 2 且富集MgO的结构、镁铝尖晶石晶体结晶保留度高,具有较为优良的热稳定性、孔道结构及表面、体相元素分布状态;具有较好催化剂外观形貌,且催化剂球形度好、破损黏联少;烟气脱硫效果最好,吸附时间500 s之内烟气SO 2 体积分数最低,且烟气脱硫效果及性能保留时间最长。

In this work, nickel metal supported on different supports (SiO2, Al2O3, ZSM-5) were prepared by spraying nickel nitrate on the supports and calcined at 873 K. Then, they were characterized by XRD, XRF, N-2 adsorption-desorption, NH3-TPD, MCH-TPD, H-2-TPR, and pyridine-FTIR, and tested as catalysts for the dehydrogenation aromatization and isomerization of methylcyclohexane (MCH) under the conditions of S-Zorb catalytic adsorption desulfurization (T = 673 K, P = 1.5 MPa, WHSV = 5 h(-1)). The H-2-TPR results showed that the interaction of NiO with support decreased in the order of NiO/ZSM-5-Fe < NiO/ZSM-5 < NiO/Al2O3 < NiO/SiO2. The decrease of the interaction appeared to facilitate the reduction of Ni and therefore to promote the dehydrogenation aromatization of MCH. It was found that a direct correlation existed between the gasoline components yields, cracking activity and the total number of different supports acid sites measured by NH3-TPD tests. Higher total acidity of ZSM-5 resulted in gasoline loss because of higher cracking activity of MCH. The number of total acid sites of NiO/ZSM-5-Fe decreased and the medium strong Bronsted acid sites necessary for MCH isomerization increased after the modification of ZSM-5 by iron metal. So, NiO/ZSM-5-Fe exhibited enhanced MCH conversion, aromatic and isomerization yields when compared to NiO/ZSM-5 and other Ni-based catalysts. This study shows that NiO/ZSM-5-Fe catalyst may be possible to be integrated into the S-Zorb system achieving the recovery of the octane number of gasoline. (C) 2018, Institute of Process Engineering, Chinese Academy of Sciences. Publishing services by Elsevier B.V. on behalf of KeAi Communications Co., Ltd.

将NiO∕γ-Al2 O3催化剂制成自支撑的薄片,采用原位红外光谱方法探究了噻吩分子在Ni上的吸附模式.将稀土Ce引入,对NiO∕γ-Al2 O3催化剂改性,发现Ce可以改善NiO的还原性能,并增强噻吩吸附时的S-金属直接作用,改善了噻吩脱硫的选择性.

随着原料油重质化、劣质化程度逐渐增高,催化裂化催化剂基质不仅需要保证催化剂有良好的磨损性能和流化性能,还需要具有适当的孔和一定的酸性对原料油中的大分子进行预裂化.半合成催化裂化催化剂中的高岭土系黏土对催化剂性能有重要影响.高岭土可直接或经酸、碱改性作为催化剂基质,也可通过原位晶化技术合成分子筛或含有Y型分子筛的催化剂.累托石通过交联反应可以合成层柱分子筛用于催化裂化催化剂制备.埃洛石因其管状结构,作为基质时催化剂具有孔体积和比表面积大及活性高的特点.对催化裂化催化剂中高岭土系黏土结构、改性方法及在催化裂化催化剂中应用进行综述,并对今后高岭土在催化裂化催化剂中的研究方向进行展望.

Main technologies of producing ethylene, such as, steam cracking, naphtha deep catalytic cracking, heavy oil deep catalytic cracking, separating of refinery dry gas, C4 deep catalytic cracking, methanol to olefins, ethanol to olefins, methane to ethylene, syngas to ethylene, biology technology and so on were summarized. Especially, technology characteristics, reaction mechanism, catalysts and typical technologies were compared. According to the comparison, coal based technologies were more developed than the oil based because difference of feed stock. By taking advantage of the coal based technologies, the oil based technologies would become more important and applicable.

在蓝星石油有限公司济南分公司催化裂化装置上进行新型RFS09烟气硫转移剂的工业应用.结果表明,在原料硫质量分数0.7％ ～0.9％和RFS09硫转移剂加注量5％情况下,再生烟气SO2≤100 mg·m-3,达到环保法规要求,按空白SO2浓度约1200 mg·m-3计算,再生烟气SO2脱除率大于90％.RFS09硫转移剂试用期间,总液收和油浆收率等主要产物分布未出现异常变化,再生烟气粉尘浓度和油浆固含量保持稳定.