Study of Mn incorporation into SAPO framework: Synthesis, characterization and catalysis in chloromethane conversion to light olefins

MnAPSO-34 molecular sieve has been synthesized with triethylamine as the template, characterized with XRD, XRF, ³¹P, ²⁷Al and ²⁹Si NMR and FT-IR techniques and compared with SAPO-34. The template decomposition and removal have been investigated with TG–DTG–DSC coupled with mass spectrometer. Mn incorporation generates a negligible difference on the chemical shift in ³¹P and ²⁷Al MAS NMR, while an effect on the intensity of resonance peaks is revealed. ²⁹Si MAS NMR study has demonstrated that Mn incorporation favors the Si island formation, which may give rise to the stronger acidic sites. The thermal analysis (TG–DSC) on template removal in a diluted oxygen atmosphere, leading to the formation of CO₂, NO and H₂O, showed, besides a low temperature endothermic weight loss due to the desorption of water, two weight losses (200–400 and 400–600 °C) for SAPO-34 and MnAPSO-34, suggesting two different chemical location environments of template molecules in these two molecular sieves. The quantity of template removed at higher temperature range is much higher in MnAPSO-34, indicating stronger template–framework interaction and stronger acidity after calcination. The acid difference caused by Mn incorporation has also been evidenced by ammonia adsorption evaluated by FT-IR. Chloromethane transformation was carried out over MnAPSO-34 and SAPO-34 and the catalytic performance showed that both molecular sieves are very active and selective catalyst for light olefins production. MnAPSO-34 demonstrated higher activity and light olefins selectivity.     

硅溶胶粒径大小对SAPO-34合成及甲醇制烯烃催化性能的影响

在合成SAPO-34的过程中加入不同粒径的硅溶胶来考察其对分子筛酸性和甲醇制烯烃（MTO）性能的影响。采用XRD、SEM、FTIR、NH₃-TPD和²⁹Si MAS NMR等表征手段对合成的分子筛进行表征,并通过固定床反应器对制备的SAPO-34分子筛进行MTO催化性能评价。实验结果表明,不同粒径的硅溶胶对合成的分子筛酸性有很大影响,通过NH₃-TPD表征结果可以看出,随着硅溶胶粒径的增大,分子筛的强酸量、弱酸量均降低。由分子筛的NMR表征结果发现,大颗粒硅溶胶合成的SAPO-34分子筛中存在硅岛。从MTO性能评价结果可以发现,适宜的硅溶胶粒径更有利于提高催化剂的双烯选择性和催化寿命。     

硅含量对氯甲烷制取低碳烯烃的SAPO-34分子筛酸性的影响

以三乙胺-四乙基氢氧化铵为复合模板剂,合成了不同硅含量的SAPO-34分子筛,并采用XRD、NH₃-TPD、以及²⁹Si MASNMR等方法对其进行了表征,最后考察了不同硅含量SAPO-34分子筛催化转化氯甲烷制取乙烯、丙烯的反应性能。结果表明:硅铝比在0.10~0.80时,均能合成规整的SAPO-34立方晶粒;硅铝比低于0.05或高于1.00时,易伴随形成片状和无定形晶相。当硅铝比为0.6时,SAPO-34的结晶度最大,微孔比表面积为588m²/g,微孔体积为0.267cm³/g。硅铝比从0.05到0.60逐渐增大时,SAPO-34酸强度和酸数目明显增多,继续增大硅铝比,酸强度增强,弱酸数目减少。在T=425℃、氯甲烷WHSV=2.73h^-1时,对所合成SAPO-34分子筛催化氯甲烷的反应性能进行了评价,随硅铝比增大,SAPO-34的酸性增强,氯甲烷的初始转化率逐渐升高,然而二次反应加剧致使乙烯丙烯选择性略有下降。     

Catalytic performance of CeAPSO-34 molecular sieve with various cerium content for methanol conversion to olefin

A series of CeAPSO-34s with various cerium contents was synthesized and characterized by multiple techniques such as XRD, SEM, BET, ²⁹Si MAS NMR, NH₃-TPD and CO₂-TPD. NH₃-TPD spectra showed that a number of acid sites, especially those of strong acidity, is reduced with the increasing of Ce incorporation. Incorporation of metal ions gave rise to more silica-islands in the CeAPSO-34 framework. CO₂-TPD showed that basic sites on the surface of modified samples are due to the presence of Ce-containing species incorporation into the framework of CeAPSO-34 molecular sieves. The performance of the catalysts was studied in methanol to olefin reactions at 425 °C under the atmospheric pressure. The results showed that the incorporation of cerium ions had great effects on the structure and acidity of the molecular sieves. All SAPO-34 and MeAPSO-34 molecular sieves were the very active and selective catalyst for light olefins production. Cerium incorporation improved the catalyst lifetime and favored the ethylene and propylene generation. However, an excess Ce content resulted in an inferior catalytic performance and stability. Therefore, there existed optimal cerium content for a specific SAPO-34.     

Synthesis of dimethyl carbonate by transesterification with various MgO–CeO2 mixed oxide catalysts

Abstact SAPO-34s with low and high Si content were synthesized and characterized by XRD, XRF, NMR, FTIR and TG-DSC. Different Si content generated no apparent difference in XRD patterns and ³¹P and ²⁷Al MAS NMR spectra. The Si coordination states studied by ²⁹Si MAS NMR predicted the acidity difference caused by Si incorporation. The absorbance of bridge hydroxyls in FTIR spectra also showed the amount of active sites differed with Si content. Both of the two samples were employed as catalysts in the transformation of chloromethane to light olefins and proved to be very selective catalysts for light olefins production. The influences of Si content on chloromethane conversion and product selectivity were investigated in details. Coke amount and coke species were determined by TG-DSC and FTIR. Coke formation was related to the Si content of SAPO-34 and corresponded to the catalytic performance.     

Chloromethane Conversion to Higher Hydrocarbons over Zeolites and SAPOs

Chloromethane transformations were carried out over zeolites and SAPOs and the conversion and product distribution differed from the porous structure and acidity of the catalysts. Chloromethane was mainly transferred to higher hydrocarbons in gasoline range over most of zeolite catalysts, while SAPOs molecular sieves, SAPO-34 and SAPO-5, showed high selectivity for light olefins production, such as ethylene, propylene and butenes. TG analysis was used to study the coke formation during the transformation and the acid difference of the catalysts was evidenced by Temperature programmed desorption of ammonia. HZSM-5, with high activity and less coke formation, was proved to be a potential catalyst for hydrocarbons production from chloromethane conversion. It is of particular interest that SAPO-34 gave an excellent performance in light olefins production from chloromethane transformation, which may be attributed to the shape selectivity and medium strong acidity of SAPO-34.     

SAPO-34分子筛催化剂制备及发展现状

乙烯和丙烯作为重要的化工原料,在经济发展中的需求量越来越大。在石油资源越来越匮乏的今天,甲醇制烯烃作为一种可以代替常规石油路线生产低碳烯烃的新工艺受到广泛关注。SAPO-34分子筛因为高甲醇转化率和优良烯烃选择性成为当前甲醇制烯烃工艺催化剂的研究重点。合成SAPO-34分子筛的影响因素有模板剂、合成原料和反应条件等。通过调节分子筛粒径尺寸、酸性、金属改性可以实现分子筛的性能优化。介绍了SAPO-34分子筛催化剂常用的制备方法和一些分子筛催化剂改进的专利。使用一定时间后催化剂由于积炭而失活,再生工艺目前主要采用烧焦再生。2011年,神华煤制烯烃示范工程进入工业化运行,近年陆续有多套甲醇制烯烃装置投产和在建,煤制烯烃正在改变中国聚烯烃市场格局。     

复合模板剂制备片状SAPO-34分子筛及催化MTO反应

采用三乙胺为主模板剂、双端氨基聚乙二醇800为辅助模板剂制备出片状SAPO-34分子筛,使用XRD、SEM、BET及NH₃-TPD对样品进行表征;并考察在甲醇制烯烃反应中的催化性能。结果表明,所合成的片状SAPO-34分子筛具有较大的比表面积(720 m²/g)和适中的酸性。在催化甲醇制烯烃反应中表现出较长的寿命,甲醇转化率达到99%以上,乙烯和丙烯(双烯)选择性达到80%以上。     

Synthesis, characterization and catalytic properties of SAPO-34 synthesized using diethylamine as a template

SAPO-34 molecular sieve was successfully synthesized using diethylamine (DEA) as a template. The influence of template concentration and silica concentration on the synthesis were investigated. Pure SAPO-34 could be obtained when n(DEA)/n(Al₂O₃)  1.5 and n(SiO₂)/n(Al₂O₃) > 0.1 in the synthesis gel. Further increase of DEA concentration in the starting gel [n(DEA)/n(Al₂O₃) > 3] has a negative effect on both crystallinity and crystal yield. The products were characterized by XRD, XRF, SEM, NMR, FT-IR, TG-DTA and nitrogen adsorption techniques. It was found that SAPO-34 synthesized with DEA as a template has the characteristic of high silicon incorporation and exhibits good thermal and hydrothermal stability. The catalytic performance of SAPO-34 was tested by methanol-to-olefin (MTO) reaction and high olefins (C₂H₄ + C₃H₆) selectivity was obtained.     

Characterization of AlPO4-based molecular sieves and methanol conversion to light olefins

Of the AlPO₄-based molecular sieves, A1PO₄, SAPOs, and MeAPOs of different pore sizes were prepared at 100-200°C by a hydrothermal crystallization method. This study was purposed to maximize the yield of light olefins through methanol conversion. Crystal structure was confirmed by means of XRD and SEM, and acidity was examined by TPD and IR of adsorbed ammonia on the catalysts. It was found that SAPO-34 exhibited more than 90% selectivity for light olefins such as ethylene, propylene, and butylene due to shape selectivity through small pores, although it had a strong acidity. MeAPO-34 exhibited slightly lower selectivity for light olefins than SAPO-34 and different product distribution, depending on the electronegativity of the metal in its framework. SAPO17 and SAPO-44, which have the same pore size with SAPO-34 but different pore structure from SAPO-34, showed less selectivity for light olefins than SAPO-34.     

Characterization of SAPO-11 and SAPO-31 synthesized from aqueous and non-aqueous media

Medium-pore SAPO-11 and SAPO-31 molecular sieves were synthesized from aqueous and non-aqueous (ethylene glycol) media. All the samples were characterized by XRD, SEM, N₂ adsorption (BET analysis), TGA-DTA, pyridine-TPD, ²⁷Al MAS-NMR, and ²⁹Si MAS-NMR. The samples synthesized from non-aqueous medium possess higher acidity due to higher substitution of Si⁴⁺ at P⁵⁺ sites and less silica island formation, as evidenced from ²⁹Si MAS-NMR spectra. It is possible to incorporate more silicon in the samples by synthesis in ethylene glycol medium. The SAPOs synthesized from non-aqueous medium show higher activity for the isomerization of m-xylene.     

SAPO-34分子筛的合成

以吗啉和四乙基氢氧化铵为模板剂,合成SAPO-34分子筛,研究不同温度和物料比对SAPO-34分子筛合成的影响。结果表明,在180℃和n(吗啉)∶n(SiO_2)∶n(Al_2O_3)∶n(P_2O_5)∶n(H_2O)=2∶1∶1∶1∶30条件下,SAPO-34分子筛的相对结晶度达100%。     

SAPO分子筛上氯甲烷催化转化制氯乙烯单体

采用水热合成法制备了SAPO分子筛,考察磷与铝物质的量比对SAPO分子筛催化转化氯甲烷制氯乙烯单体反应催化性能的影响.结果表明,SAPO-34在氯甲烷催化转化制备氯乙烯单体反应中,表现出较好的催化性能及稳定性.     

CuO-ZnO/(SAPO-34)-高岭土催化CO2加氢合成低碳烯烃

以廉价的高岭土为原料,三乙胺为模板剂,采用水热法制备了负载型催化剂(SAPO-34)-高岭土。通过将CuO-ZnO负载于(SAPO-34)-高岭土表面制备了双功能催化剂CuO-ZnO/(SAPO-34)-高岭土,用XRD、SEM、EDS、BET、H_2-TPR及NH_3-TPD对合成的催化剂进行了表征,将其用于催化CO_2加氢制备低碳烯烃,在反应温度为673 K、反应压力为3 MPa、空速为1 800 m L/(g_(cat)·h)、V(CO_2)∶V(H_2)=1∶3的条件下,CO_2单程转化率为43.5%,低碳烯烃的选择性和产率分别为63.8%和27.8%。在连续8 h的催化性能测试中,低碳烯烃的产率最低为18.7%。     

Hydroisomerization of Long-Chain Alkane Over Pt/SAPO-11 Catalysts Synthesized from Nonaqueous Media

SAPO-11 molecular sieves were synthesized from nonaqueous media. The effects of Si and Al sources as well as solvents on the catalytic performance of SAPO-11 were investigated by the hydroisomerization reaction of n-dodecane. The samples were characterized by XRD, XRF, N₂-adsorption, SEM, NH₃-TPD, IR-NH₃ and ²⁹Si CP MAS NMR. The SAPO-11 samples synthesized with tetraethoxysilane as the Si source showed higher Si incorporation contents than the SAPO molecular sieves prepared with polymeric Si sources (fumed silica and Si colloidal gel). The reaction results showed that Pt/SAPO-11 catalysts synthesized from ethylene glycol and glycerol media with the monomeric Si and Al sources (tetraethoxysilane, aluminum isopropoxide) exhibited higher catalytic activities than those catalysts with the polymeric Si or Al (pseudo-boehmite) sources, due to the larger external surface area and higher acidity of the former ones. Especially, the catalyst synthesized in an ethylene glycol medium possessed the highest catalytic activity. Over this catalyst, 88% conversion of n-dodecane was achieved at a low temperature of 250 °C.     

Use of different templates on SAPO-34 synthesis: Effect on the acidity and catalytic activity in the MTO reaction

SAPO-34 molecular sieves have been synthesized with different structure directing agents. Although materials with the same framework structure (CHA type) are obtained in all cases, they possess different physicochemical properties, especially textural parameters and crystal size. These catalysts have been tested in the MTO process. All the samples exhibited high activity and selectivity to short chain olefins at the initial stages of the reaction, but they deactivate rapidly with time on stream, especially at high space velocity. It has been observed an important influence of the external surface, crystal size and acidity on the activity, selectivity and lifetime of the different samples. Thus, the sample synthesized with tetraethylammonium hydroxide as structure directing agent rendered the best catalytic performance owing to its higher external surface, smaller crystal size and higher acidity.     

Comparison study of Na poisoning effect on copper-based chabazite micropore catalysts for NH3-SCR reaction

Using wet impregnation method to mimic alkali metal poison of ammonia-selective catalytic reduction (NH₃-SCR) catalysts, Cu-based micropore zeolites Cu/SSZ-13 and Cu/SAPO-34 with different Na contents(mass fraction) were prepared, and the Na poisoning mechanism on them was studied. The results show that the externally introduced Na ions can severely affect the NH₃-SCR catalytic activity of the two catalysts, resulting in the collapse of the crystal structure of the catalyst, the decrease of acidity and the reduction of active species. In detail, when Na content was less than 1.82%, Cu/SAPO-34 has higher resistance of Na ions than Cu/SZZ-13; while when Na> 3.48%, Cu/SAPO-34 catalysts almost deactivated thoroughly. By structural characterization (BET, XRD and SEM) and acidity characterization (DRIFTS, NH₃-TPD and H₂-TPR), it was found that with Na poisoning deeper and deeper, Cu/SSZ-13 took a gradual style of the structural destruction, but Cu/SAPO-34 adopted a sudden way. Studies on the mechanism of Na poisoning show that the decrease of acid sites is the main reason for the decrease of SCR activity of Cu/SSZ-13, and the structural collapse is the main reason for the decrease of SCR activity of Cu/SAPO-34.     

基于NH3-SCR反应铜基小孔分子筛催化剂Na中毒对比研究

以浸渍法模拟碱金属中毒NH₃-SCR催化剂过程,制备不同Na含量（质量分数）的铜基小孔分子筛Cu/SSZ-13和Cu/SAPO-34,对比研究了二者的碱金属中毒机理。结果表明,外引Na离子均可严重影响两种催化剂的NH₃-SCR催化活性,造成催化剂的晶相结构坍塌,酸性量减少,活性物种减少。不同的是,Na引入量较低（<1.82%）时,Cu/SAPO-34比Cu/SSZ-13具有更强的Na离子耐受性,而当Na含量高于3.48%时,Cu/SAPO-34几乎完全丧失NH₃-SCR催化活性。通过催化剂的结构表征（BET、XRD和SEM）和酸性位表征（DRIFTS、NH₃-TPD和H₂-TPR）,研究表明随着Na中毒程度的加深,Cu/SSZ-13的结构破坏是渐变式的,而Cu/SAPO-34的结构破坏是突变式的;Na中毒的机理研究表明,酸性位的减少是Cu/SSZ-13的SCR活性下降的主导原因,结构坍塌是Cu/SAPO-34的SCR活性下降的主导原因。     

用于催化甲醇制烯烃的SAPO-34分子筛合成的研究进展

介绍了用于催化甲醇制烯烃的SAPO-34分子筛合成的研究近况。SAPO-34分子筛的合成过程是影响其晶粒尺寸、酸性强弱等物化性能的重要因素, 因而是影响其催化性能的关键因素。本文详细叙述了原料配比及其种类、模板剂、F^-等合成因素对SAPO-34分子筛物化性能及其MTO反应催化性能的影响。针对SAPO-34合成及其催化性能优化的新技术, 综述了SAPO-34分子筛的金属改性及其超声波、微波辅助合成的特点和效果, 指出通过研发新的模板剂及其助剂、改性或制备新工艺进而改善分子筛的酸性、提高其烯烃选择性、延长催化反应寿命、降低合成成本是SAPO-34今后研发的重要方向。     

双模板剂法SAPO-34分子筛的合成及其MTO催化性能调变

以四乙基氢氧化铵（TEAOH）和二乙铵（DEA）为混合模板剂，在低投料硅铝比[n (SiO₂) ∶n (Al₂O₃)=0.2]及低模板剂用量[n (模板剂) ∶n (Al₂O₃)=1.9]下，考察了两种模板剂比例的调变对合成的SAPO-34分子筛物化性能及其催化甲醇制烯烃反应（MTO）催化性能的影响。研究发现，通过改变两种模板剂比例，可以明显调变SAPO-34分子筛晶粒尺寸、硅分布（晶粒表面和体相的硅分布）、硅原子的配位环境，从而影响其MTO催化反应的效果。在低模板剂用量制备的SAPO-34产品中，晶粒尺寸是影响其催化寿命的最主要因素，小晶粒分子筛因其扩散路径短有利于延长催化寿命。此外，硅分布也是影响催化寿命的因素之一，表面富硅的分子筛导致外表面积炭程度大于晶内积炭，积炭趋势由外向内发展，加速分子筛“假性”失活。硅分布还影响MTO反应产物分布，表面富硅分子筛外表面更易发生非择形催化，显著提高C₄～C₆等产物的选择性，不利于目标产物双烯（乙烯+丙烯）选择性的提高。