Synthesis of ZSM-22/SAPO-11 composite molecular sieve-based catalysts with small crystallites and superior n-alkane hydroisomerization performance

To improve oil quality,ZSM-22/SAPO-11 composite molecular sieves were synthesized by adding ZSM-22 into a synthetic gel of SAPO-11 for n-decane hydroisomerization.The mass ratios of ZSM-22/(ZSM-22+SAPO-11)in the composite molecular sieves were optimized and the optimal ZSM-22/SAPO-11 composite(ZS-9)was obtained.The electrostatic repulsions between the ZSM-22 precursors and the SAPO-11 crystalline nuclei produced small ZSM-22 and SAPO-11 crystallites in ZS-9,which increased the specific surface area and mesopore volume and thereby exposed more acid sites.In comparison with conventional SAPO-11,ZSM-22 and their mechanical mixture,ZS-9 with smaller crystallites and the optimal medium and strong Brønsted acid centers(MSBAC)content displayed a higher yield of branched C_(10) isomers(81.6%),lower cracking selectivity(11.9%)and excellent stability.The correlation between the i-C_(10) selectivity and the MSBAC density of molecular sieves indicated that the selectivity for branched C_(10) isomers first increased and then decreased with increasing MSBAC density on the molecular sieves,and the maximum selectivity(87.7%)occurred with a density of 9.6×10^(−2)μmol m^(−2).

The synthesis of Co-doped SAPO-5 molecular sieve and its performance in the oxidation of cyclohexane with molecular oxygen

Silicoaluminophosphate（SAPO） molecular sieves doped with cobalt（Co-SAPO-5） were synthesized hydrothermally with different concentrations of Co.Each sample was characterized by X-ray diffraction,N2 adsorption-desorption,scanning electron microscopy,ultraviolet-visible spectroscopy,temperature-programmed desorption of NH3（NH3-TPD）,and infrared spectrascopy of adsorbed pyridine（Py-IR）.The results showed that Co was highly dispersed in the Co-SAPO-5 samples.In addition,a part of the Co content had been incorporated into the SAPO-5 framework,while the remainder existed on the surface as extra-framework Co.The surface areas of the Co-SAOP-5 samples were similar to the SAPO-5 sample.However,the pore volumes of the Co-SAOP-5 samples were lower than that of the SAOP-5 sample.As the concentration of Co increased,the pore volume gradually decreased because extra-framework cobalt oxide was present on the catalyst surface.NH3-TPD and Py-IR results revealed that the amount of Br（？）nsted acid and the total amount of acid for the Co-SAPO-5 samples were higher than that for the SAPO-5 sample.These values were also higher for samples with higher Co content.The catalytic activity of the Co-SAPO-5 samples was evaluated for the oxidation of cyclohexane with molecular oxygen.When Co was added to the SAPO-5 catalyst,the catalytic activity of the Co-SAPO-5 catalysts improved.In addition,the conversion of cyclohexane increased as the Co content in the Co-SAPO-5 catalysts increased.However,with a high conversion of cyclohexane（6.30%）,the total selectivity of cyclohexanone（K） and cyclohexanol（A） decreased sharply.The K/A ratio ranged from 1.15 to 2.47.The effects of reaction conditions（i.e.,reaction temperature,reaction time,initial oxygen pressure,and the catalyst amount） on the performance of the Co-SAPO-5 catalysts have also been measured.Furthermore,the stability of the Co-SAPO-5 catalyst was explored and found to be good for the selective oxidation of cyclohexane by molecular oxygen.

A SAPO-11 Silicoaluminophosphate Molecular Sieve with Stable Crystal Structure

A SAPO-11 silicoaluminophosphate molecular sieve with stable crystal structure was synthesized for the first time. After removing template by calcination, its crystal space group still retains Icm2 which the as-synthesized has. The catalyst deriving from the present SAPO-11 materials shows higher isomerization selectivity and higher paraffin hydroisomerization yield than those reported elsewhere.

SAPO-18分子筛在丁烯裂解中的应用

选用磷源、硅源、铝源、去离子水以及有机模板剂作为原料,采用水热合成法制备了SAPO-18分子筛。采用XRD、SEM和BET表征手段对分子筛进行了特性分析,考察了SAPO-18分子筛在丁烯裂解催化反应中的催化性能。SAPO-18分子筛初期催化效果比较稳定,很好的控制了催化反应中氢转移副反应的发生,并且得到了较高的丙烯收率。

核壳型SAPO-34/AlPO-18分子筛的制备及生长机理

采用水热法制备了核壳型SAPO-34/AlPO-18分子筛,并运用X射线衍射、扫描电镜和超高分辨场发射扫描电镜等方法对样品进行了表征.结果表明,通过改变实验条件可有效调控壳层AlPO-18纳米晶在SAPO-34晶体表面的生长,从而得到具有不同生长区域、生长取向及紧密度的核壳型SAPO-34/AlPO-18分子筛.超高分辨场发射扫描电镜结果发现,核相SAPO-34晶体的外表面结构与壳层AlPO-18纳米晶的生长性质紧密相关,从而推测出核相晶体外表面微细结构诱导壳层分子筛生长的晶化机理.

SAPO-18分子筛研究进展

介绍了SAPO-18分子筛的合成、结构组成、酸性表征及其在催化甲醇制烯烃(MTO)反应中应用的最新研究情况。由于其特有的结构和B酸中心分布特点,SAPO-18分子筛在MTO反应中具有良好的应用前景。

SAPO-34/18分子筛合成的影响因素研究

采用水热合成法,以四乙基氢氧化铵(TEAOH)为模板剂,合成了SAPO-34/18共晶分子筛。利用XRD、SEM手段对合成样品进行表征,考察了反应条件对SAPO-34/18共晶分子筛合成的影响。结果表明分子筛的合成受晶化时间、晶化温度、晶化方式、升温速率、模板剂含量影响较大。确定了合成SAPO-34/18共晶分子筛最佳工艺条件为晶化时间72h、晶化温度165℃、动态晶化方式、升温速率5℃/h、n(SiO_2):n(Al_2O_3):n(P_2O_5):n(H_2O):n(TEAOH)=0.15:1:1:35:1.2。

SAPO-18分子筛在丁烯催化裂解反应中催化性能的研究

以磷酸、拟薄水铝石、气相二氧化硅、去离子水以及有机模板剂为原料,采用水热合成法合成SAPO-18分子筛,采用XRD、SEM和NH3-TPD表征手段对分子筛结构特性进行分析。同时考察了反应温度以及反应空速对SAPO-18分子筛在丁烯催化裂解反应中催化性能的影响。试验结果表明,在丁烯催化裂解反应中反应温度为500℃且反应空速为3.5 h^(-1)时,催化剂的催化性能最好,具有较高的丙烯收率和丙烯选择性,同时兼有较高的乙烯收率、较高的丙烯与乙烯收率比(P/E比)和较高的原料转化率。

SAPO-5/SAPO-18的合成及其在甲醇制烯烃中的应用

合成了系列具有不同SAPO-18/SAPO-5比例的微孔分子筛SAPO-18与大孔型微孔SAPO-5生长在一起的复合分子筛,并考察其催化甲醇制烯烃反应性能。复合分子筛呈现出较高的催化活性和优异的丙烯、丁烯选择性。SAPO-18和SAPO-5具有不同的酸性和孔结构,复合分子筛中SAPO-18/SAPO-5比例变化会影响产物分布。SAPO-18有利于生成乙烯和丙烯,而大孔的SAPO-5可大幅提高丙烯和丁烯选择性。SAPO-5/SAPO-18复合分子筛的协同作用,有利于根据市场需求调整甲醇制烯烃产品结构。

硅源用量对SAPO-18分子筛合成及催化性能的影响

采用水热合成法,以N,N-二异丙基乙胺为模板剂合成SAPO-18分子筛,并用X射线衍射、X射线荧光光谱、扫描电子显微镜、NH3程序升温脱附及N2吸附-脱附等对其结构进行表征,系统研究合成凝胶中硅源用量对SAPO-18分子筛合成及其在甲醇制烯烃反应中催化性能的影响。结果表明,在晶化温度453 K、晶化时间96 h和合成凝胶中0.3≤n(Si O2)∶n(Al2O3)≤1.2条件下,能合成出纯相的SAPO-18分子筛,其中,当n(Si O2)∶n(Al2O3)=0.6,在反应时间135 min时,合成的SAPO-18分子筛具有较高的双烯选择性(乙烯+丙烯)。合成凝胶中硅源的用量对SAPO-18分子筛酸性有显著影响,适当增加分子筛中强酸比有助于提高乙烯和丙烯选择性,但缩短催化剂寿命。

SAPO-18/SAPO-5分子筛样品非骨架铝物种表征方法

本文的表征方法是根据SAPO-18/SAPO-5硅铝磷分子筛样品的XRF测试结果中Al原子含量,来初步快速判断是否存在非分子筛骨架铝,然后采用NMR表征进行验证。分别将该方法应用到SAPO-18单一分子筛和SAPO-18/SAPO-5复合分子筛体系中,均能准确判断出分子筛样品中是否存在非分子筛骨架铝。

一种新颖的十八元环超大孔分子筛骨架拓扑结构CJU-18的设计

提出了一种新颖的十八元环超大孔分子筛的拓扑结构模型——CJU-18,它属钙霞石笼作用于六方晶系的P_(63)/mmc空间群.与VPI-5类似,具有平行于c方向的十八元环直孔道结构,但侧面有十元环孔道,通过计算该结构模型各原子间的键长、键角,认为该结构有可能存在,采用POWD-MODELING程序,计算了它的理论XRD谱图并绘制出其立体拓扑结构。

SAPO-34 synthesized with n-butylamine as a template and its catalytic application in the methanol amination reaction

SAPO-34 was synthesized with n-butylamine（BA） as a template for the first time.Crystallization temperature and initial Si amount were important factors leading to successful syntheses.Lamellar AlPO-kanemite tends to form as the major phase or as an impurity of SAPO-34 at lower crystallization temperatures,though a higher initial Si amount may offer a positive effect on the crystallization of SAPO-34 that mitigates the low temperature.Higher temperature（240℃） can effectively suppress the generation of lamellar materials and allow the synthesis of pure SAPO-34 with a wider range of Si incorporation.The crystallization processes at 200 and 240℃ were investigated and compared.We used the aminothermal method to synthesize SAPO-34-BA at 240℃ and also found n-propylamine is a suitable template for the synthesis of SAPO-34.The SAPO-34-BA products were characterized by many techniques.SAPO-34-BA has good thermal stability,crystallinity and porosity.BA remained intact in the crystals with ~1.8 BA molecule per chabazite cage.The catalytic performance of SAPO-34 was tested in the methanol amination reaction,which showed high methanol conversion and selectivity for methylamine plus dimethylamine under the conditions investigated,suggesting that this material is a good candidate for the synthesis of methylamines.

Z-18抗焦活化剂在苏丹炼厂重催装置上的应用

介绍了Z-18催化分子筛抗焦活化剂在苏丹喀土穆炼油有限公司重油催化裂化装置(简称KRC)上的工业应用。应用结果表明,该剂在以通过调节催化裂化剂酸性中心为主的机理下使催化剂反应活性得以有效维持,从而减小了催化剂表面结焦,改善了产品分布及产品质量。

n-Nonane hydroisomerization over hierarchical SAPO-11-based catalysts with sodium dodecylbenzene sulfonate as a dispersant

To enhance the gasoline octane number,low-octane linear n-alkanes should be converted into their high-octane di-branched isomers via n-alkane hydroisomerization.Therefore,hierarchical SAPO-11-based catalysts are prepared by adding different contents of sodium dodecylbenzene sulfonate(SDBS),and they are applied in n-nonane hydroisomerization.When n(SDBS)/n(SiO2)is less than or equal to 0.125,the synthesized hierarchical molecular sieves are all pure SAPO-11,and as the SDBS content increases,the submicron particle size decreases,and the external surface area(ESA)increases.Additionally,these hierarchical SAPO-11 have smaller submicron particles and higher ESA values than conventional SAPO-11.When n(SDBS)/n(SiO2)is greater than 0.125,with increasing SDBS content(n(SDBS)/n(SiO2)=0.25),the synthesized SAPO-11 contains amorphous materials,which leads to a decline in the ESA;with the further increase in SDBS content(n(SDBS)/n(SiO2)=0.5),the products are all amorphous materials.These results indicate that in the case of n(SDBS)/n(SiO2)=0.125,the synthesized SAPO-11 molecular sieve(S–S3)has the most external Brønsted acid centers and the highest ESA of these SAPO-11,and these advantages favor generation of the di-branched isomers in hydrocarbon hydroisomerization.Among these Pt/SAPO-11 catalysts,Pt/S–S3 displays the highest selectivity to entire isomers(83.4%),the highest selectivity to di-branched isomers(28.1%)and the minimum hydrocracking selectivity(15.7%)in n-nonane hydroisomerization.

Rice Husk Ash:A New Silicon Source for Preparing SAPO-34 Catalysts Used in the Methanol-to-Olefins Reaction

SAPO-34 molecular sieves were synthesized directly by hydrothermal method with rice husk ash(RHA)used as the silicon source.The crystal structure,composition,surface morphology and acidity of the synthesized products weresieves had a high crystallinity,without any impure phase.Compared with the SAPO-34 prepared by the silica sol,RHA-SAPO-34 had similar acid properties in strength.The methanol to olefins(MTO)experiments showed that the SAPO-34molecular sieve synthesized from RHA exhibited both a good catalytic activity and ethylene selectivity.

Conversion of methanol to propylene over SAPO-14:Reaction mechanism and deactivation

Methanol to olefins(MTO)reaction as an important non-oil route to produce light olefins has been industrialized,and received over 80% ethylene plus propylene selectivity.However,to achieve high single ethylene or propylene selectivity towards the fluctuated market demand is still full of challenge.Small-pore SAPO-14 molecular sieve is a rare MTO catalyst exhibiting extra-high propylene selectivity.It provides us a valuable clue for further understanding of the relationship between molecular sieve structure and MTO catalytic performance.In this work,a seconds-level sampling fixed-bed reactor was used to capture real-time product distributions,which help to achieve more selectivity data in response to very short catalytic life of SAPO-14.Changes in product distribution,especially during the low activity stage,reflect valuable information on the reaction pathway.Combined with in situ diffuse reflectance infrared Fourier-transform spectroscopy,in situ ultraviolet Raman measurements and ^(12)C/^(13)C isotopic switch experiments,a reaction pathway evolution from dual cycle to olefins-based cycle dominant was revealed.In addition,the deactivation behaviors of SAPO-14 were also investigated,which revealed that polymethylbenzenes have been the deactivated species in such a situation.This work provides helpful hints on the development of characteristic methanol to propylene(MTP)catalysts.

Cu-SAPO-17:A novel catalyst for selective catalytic reduction of NOx

The high-temperature(HT) and low-temperature(LT) hydrothermal stabilities of molecular-sieve-based catalysts are important for the selective catalytic reduction of NOx with ammonia(NH3-SCR). In this paper, we report a catalyst, Cu2+ loading SAPO-17, synthesized using cyclohexylamine(CHA), which is commercially available and inexpensive and is utilized in NH3-SCR reduction for the first time. After systematic investigations on the optimization of Si and Cu2+ contents, it was concluded that Cu-SAPO-17-8.0%-0.22 displays favorable catalytic performance, even after being heated at 353 K for 24 h and at 973 K for 16 h. Moreover, the locations of CHAs, host–guest interaction and the Bronsted acid sites were explored by Rietveld refinement against powder X-ray diffraction data of as-made SAPO-17-8.0%. The refinement results showed that two CHAs exist within one eri cage and that the protonated CHA forms a hydrogen bond with O4, which indicates that the proton bonding with O4 will form the Bronsted acid site after the calcination.

Preparation and Property of Ni/TiO₂-SAPO-11 Catalyst for N-Heptane Isomerization

For enhancing the activity of Ni/TiO2-SAPO-11 catalyst, SAPO-11, the precursor was prepared by hydrothermal crystallization, and TiO2-SAPO-11 complex carrier was prepared by sol-gel method, then Ni/TiO2-SAPO-11 was produced by the final product. The catalytic performance of Ni/TiO2-SAPO-11 was studied in n-heptane isomerization, and the impact of catalyst preparation conditions on n-heptane isomerization was discussed in detail. The results showed that, with 20% of TiO2 composition, 2% of Ni capacity percentage and calcined temperature at 500°C, conversion of n-heptane and isomerization selectivity was up to 40.94% and 88.97% respectively.

Z-18催化分子筛抗焦活化剂在乍得炼厂的应用

介绍Z-18催化分子筛抗焦活化剂在乍得恩贾梅纳炼油有限公司催化裂化装置上的应用,应用结果表明,该剂通过调节催化剂酸性中心为主的机理下使催化剂反应活性得以有效维持,从而减小了催化剂表面结焦,改善了产品分布。