技术领域technical field
本发明涉及一种分子筛的合成方法，具体涉及一种Nu-6(1)分子筛的合成方法。The invention relates to a method for synthesizing molecular sieves, in particular to a method for synthesizing Nu-6(1) molecular sieves.
背景技术Background technique
分子筛是具有规则微孔结构的硅铝酸盐晶体材料，可以在催化、吸附分离等领域有广泛的应用。Molecular sieves are aluminosilicate crystal materials with regular microporous structures, which can be widely used in the fields of catalysis, adsorption and separation.
Nu-6(1)是具有层状结构的分子筛，由[SiO4]和[SiO3OH]四面体构成各层，结构导向剂4,4'-联吡啶分子位于夹层中间。煅烧去除4,4'-联吡啶后，Nu-6(1)转变成具有NSI型骨架结构的Nu-6(2)分子筛。Nu-6(2)分子筛可作为歧化、异构化反应的催化剂，并且由于其具有较小的孔径和片状生长性质，Nu-6(2)杂化膜，用于H2的选择性渗透。Nu-6(1) is a molecular sieve with a layered structure, each layer is composed of [SiO4 ] and [SiO3 OH] tetrahedra, and the structure-directing agent 4,4'-bipyridine molecule is located in the middle of the interlayer. After calcination to remove 4,4'-bipyridine, Nu-6(1) was transformed into Nu-6(2) molecular sieve with NSI-type framework structure. Nu-6(2) molecular sieves can be used as catalysts for disproportionation, isomerization reactions, and due to their smaller pore size and sheet-like growth properties, Nu-6(2) hybrid membranes for selective permeation ofH2 .
Corma等通过动态晶化的方式得到了Nu-6(1)分子筛，并通过撑开剥离Nu-6(1)得到了层状的ITQ-18，其比表面积达到588m2/g，远大于剥离前Nu-6(2)(焙烧Nu-6(1)后得到)的35m2/g的BET比表面积[Chem.Commun.(2001)2642–2643]。Patricia等在弱碱性(PH约为9)和室温条件下，成功将Nu-6(1)剥离；BET比表面积与剥离前的Nu-6(2)相比，由50m2/g提高到300m2/g[Micropo Mesopo Mat.142(2011)122–129]。Galve等探究了Nu-6(1)分子筛中的Al分布对其结构的影响，主要通过XRD、SEM、TEM、NMR等分析手段，分别探究了Si/Al＝24，45，90，∞条件下(原子比由XRF确定)Al原子的分布，结果表明，由模拟生成能的角度看，在六个可能的T位置中，Al原子更倾向于处于其中的两个位置，即层状分子筛晶格空间中的末端位置，此位置靠近带正电荷的胺模板剂分子[Micropo Mesopo Mat.145(2011)211–216]。Patricia等利用剥离后的Nu-6(2)，制备出了具有不同4MPD/DABA摩尔比的6FDA-4MPD/6FDA-DABA共聚酰亚胺膜，此杂化膜对于H2/CH4及O2/N2混合气均具有较好的分离特性。当4MPD/DABA的摩尔比为4时，膜中分子筛含量为5.3wt％，可以得到的H2/CH4最高选择性为37.9(H2的渗透率为500Barrer)；分子筛含量为9.7wt％，可以得到的最大的O2渗透率为147Barrer(O2/N2的选择性为4)[J.Membrane.Sci.411(2012)146–152]。Corma et al. obtained Nu-6(1) molecular sieve through dynamic crystallization, and obtained layered ITQ-18 by stretching and exfoliating Nu-6(1), with a specific surface area of 588m2 /g, much larger than the exfoliated BET specific surface area of 35 m2 /g for pre-Nu-6(2) (obtained after calcination of Nu-6(1)) [Chem. Commun. (2001) 2642-2643]. Patricia et al. successfully stripped Nu-6(1) under weak alkaline (PH about 9) and room temperature conditions; compared with Nu-6(2) before stripping, the BET specific surface area increased from 50m2 /g to 300 m2 /g [Micropo Mesopo Mat. 142 (2011) 122–129]. Galve et al. explored the influence of Al distribution in Nu-6(1) molecular sieves on its structure, mainly through XRD, SEM, TEM, NMR and other analysis methods, respectively explored the conditions of Si/Al=24, 45, 90, ∞ (Atomic ratio determined by XRF) distribution of Al atoms, the results show that from the perspective of simulated generation energy, among the six possible T positions, Al atoms tend to be in two of them, namely the layered molecular sieve lattice The terminal position in space, which is close to the positively charged amine template molecule [Micropo Mesopo Mat. 145(2011) 211–216]. Patricia et al. used the stripped Nu-6(2) to prepare 6FDA-4MPD/6FDA-DABA copolyimide membranes with different 4MPD/DABA molar ratios. This hybrid membrane is suitable for H2 /CH4 and O2 /N2 mixtures have good separation characteristics. When the molar ratio of 4MPD/DABA was 4, the molecular sieve content in the membrane was 5.3wt%, and the availableH2 /CHThe highest selectivity was 37.9 (the permeability ofH2 was 500Barrer); the molecular sieve content was 9.7wt%, The maximum O2 permeability that can be obtained is 147 Barrer (O2 /N2 selectivity of 4) [J.Membrane.Sci.411 (2012) 146–152].
因此，纯相、均一的Nu-6(1)分子筛的制备对于后续剥离或焙烧制备Nu-6(2)分子筛，及其在催化或气体分离中的应用是十分重要的。而传统的Nu-6(1)合成方法，由于原料中水含量和模板剂含量较高，造成其合成成本高、原料浪费多、污染较大；且由于采用动态合成的方式，工艺繁琐。Therefore, the preparation of pure phase and uniform Nu-6(1) molecular sieve is very important for subsequent exfoliation or calcination to prepare Nu-6(2) molecular sieve and its application in catalysis or gas separation. However, in the traditional Nu-6(1) synthesis method, due to the high water content and template content in the raw materials, the synthesis cost is high, the waste of raw materials is large, and the pollution is relatively large; and due to the dynamic synthesis method, the process is cumbersome.
发明内容Contents of the invention
鉴于以上所述现有技术的缺点，本发明的目的在于提供一种Nu-6(1)分子筛的合成方法，以克服现有技术中人工量大，制作周期长的缺陷。In view of the above-mentioned shortcoming of prior art, the object of the present invention is to provide a kind of synthetic method of Nu-6(1) molecular sieve, to overcome the defects of large amount of manpower and long production period in prior art.
为了实现上述目的或者其他目的，本发明是通过以下技术方案实现的。In order to achieve the above objects or other objects, the present invention is achieved through the following technical solutions.
一种合成分子筛Nu-6(1)的方法，包括如下步骤：A method for synthesizing molecular sieve Nu-6(1), comprising the steps:
1)制备母液：模板剂和乙醇混合得到A溶液；硅源、碱源和水混合得到B溶液；铝源、水和有调节pH值作用的酸混合得到C溶液；向A溶液中滴加B溶液，再向A和B混合溶液中滴加C溶液，老化，加入晶种获得母液；1) Prepare mother liquor: mix template agent and ethanol to obtain solution A; mix silicon source, alkali source and water to obtain solution B; mix aluminum source, water and an acid that can adjust the pH value to obtain solution C; add solution B dropwise to solution A solution, and then dropwise add solution C to the mixed solution of A and B, age, add seed crystals to obtain mother liquor;
2)将步骤1)的母液烘干，并研磨成粉末；2) drying the mother liquor of step 1), and grinding it into powder;
3)粉末与水混合，晶化合成Nu-6(1)分子筛。3) The powder is mixed with water and crystallized to synthesize Nu-6(1) molecular sieve.
优选地，步骤1)中所述模板剂为4,4’-联吡啶。Preferably, the templating agent in step 1) is 4,4'-bipyridine.
优选地，步骤1)中，将硅源换算成SiO2，将铝源换算成Al2O3，将碱源换算成碱源的氧化物计，金属氧化物、SiO2、Al2O3、模板剂的摩尔比为(0.01～1):1:(0.01～0.1):(0.01～0.001)。Preferably, in step 1), the silicon source is converted into SiO2 , the aluminum source is converted into Al2 O3 , and the alkali source is converted into the oxide of the alkali source, metal oxide, SiO2 , Al2 O3 , The molar ratio of the templating agent is (0.01-1):1:(0.01-0.1):(0.01-0.001).
优选地，所述硅源为硅酸钠溶液，硅溶胶，白炭黑白炭黑，正硅酸四乙酯等中的一种或多种。Preferably, the silicon source is one or more of sodium silicate solution, silica sol, white carbon black and white carbon black, tetraethyl orthosilicate and the like.
优选地，所述铝源为硫酸铝，偏铝酸钠，氢氧化铝，硝酸铝等中的一种或多种。Preferably, the aluminum source is one or more of aluminum sulfate, sodium metaaluminate, aluminum hydroxide, aluminum nitrate and the like.
优选地，所述碱源为氢氧化钠，硅酸钠溶液等中的一种或多种。Preferably, the alkali source is one or more of sodium hydroxide, sodium silicate solution and the like.
更优选地，所述碱源的氧化物为Na2O。More preferably, the oxide of the alkali source is Na2 O.
优选地，所述调节pH用的酸为浓硫酸和浓硝酸中的一种或多种。Preferably, the acid used for pH adjustment is one or more of concentrated sulfuric acid and concentrated nitric acid.
优选地，步骤1)中使用酸调节母液pH值至9～11。Preferably, acid is used in step 1) to adjust the pH value of the mother liquor to 9-11.
优选地，步骤1)中老化的温度为25～80℃。Preferably, the aging temperature in step 1) is 25-80°C.
优选地，步骤1)中老化的时间为1h～72h。Preferably, the aging time in step 1) is 1h-72h.
优选地，步骤1)中晶种为Nu-6(1)晶种。Preferably, the seed crystal in step 1) is a Nu-6(1) seed crystal.
更为优选地，分别将模板剂4,4’-联吡啶和无水乙醇混合得到A溶液，硅酸钠溶液和去离子水混合得到B溶液，硫酸铝，去离子水和浓硫酸混合得到C溶液；向A溶液中滴加B溶液，再向A、B混合溶液中滴加C溶液，老化后，加入Nu-6(1)晶种。More preferably, the template agent 4,4'-bipyridyl and absolute ethanol are mixed to obtain A solution, sodium silicate solution and deionized water are mixed to obtain B solution, aluminum sulfate, deionized water and concentrated sulfuric acid are mixed to obtain C solution; add solution B dropwise to solution A, then add solution C dropwise to the mixed solution A and B, after aging, add Nu-6(1) seed crystals.
优选地，以所述硅源按照硅原子的摩尔数换算成SiO2后的质量为基准计，步骤1)中晶种的添加量为1～10wt％。Preferably, based on the mass of the silicon source converted into SiO2 according to the number of moles of silicon atoms, the amount of seed crystals added in step 1) is 1-10 wt%.
优选地，步骤2)中烘干温度为25～90℃。Preferably, the drying temperature in step 2) is 25-90°C.
优选地，步骤3)水的摩尔数为粉末中硅原子摩尔数的0.01～100倍。Preferably, the number of moles of water in step 3) is 0.01 to 100 times the number of moles of silicon atoms in the powder.
优选地，步骤3)中合成方式为静态合成。Preferably, the synthesis method in step 3) is static synthesis.
优选地，步骤3)中合成温度为100～200℃。Preferably, the synthesis temperature in step 3) is 100-200°C.
优选地，步骤3)中合成时间为3h～240h。Preferably, the synthesis time in step 3) is 3h-240h.
一种分子筛Nu-6(1)，所述分子筛Nu-6(1)由上述所述的方法制备获得。A molecular sieve Nu-6(1), the molecular sieve Nu-6(1) is prepared by the method described above.
优选地，上述无溶剂、低模板剂方法中获得的Nu-6(1)分子筛的尺寸为1微米左右。Preferably, the size of the Nu-6(1) molecular sieve obtained in the solvent-free, low-template method is about 1 micron.
本发明所述方法在无溶剂和低模板剂条件下，以较短的时间静态合成出高结晶度的Nu-6(1)分子筛。其极大的降低了原料中水和模板剂的含量，从而极大的减少了原料成本和环境污染，符合绿色化学的要求。且制得的Nu-6(1)分子筛晶体尺度均一，粒径在1μm左右，产率接近100％，在分离以及催化领域具有极大的应用潜力。The method of the invention statically synthesizes the Nu-6(1) molecular sieve with high crystallinity in a short time under the condition of no solvent and low template agent. It greatly reduces the content of water and templating agent in raw materials, thereby greatly reducing raw material costs and environmental pollution, and meets the requirements of green chemistry. Moreover, the prepared Nu-6(1) molecular sieve has a uniform crystal size, a particle size of about 1 μm, and a yield close to 100%, which has great application potential in the fields of separation and catalysis.
附图说明Description of drawings
图1是由配方0.278Na2O:1SiO2:0.02Al2O3:0.13 4,4’-联吡啶:x H2O(x＝30～0.5)合成的Nu-6(1)分子筛的扫描电镜照片；Figure 1 is the scan of Nu-6(1) molecular sieve synthesized from the formula 0.278Na2 O:1SiO2 :0.02Al2 O3 :0.13 4,4'-bipyridyl:x H2 O (x=30～0.5) Electron microscope photo;
图2是由配方0.278Na2O:1SiO2:0.02Al2O3:0.13 4,4’-联吡啶:x H2O(x＝30～0.5)合成的Nu-6(1)分子筛的XRD图谱；Figure 2 is the XRD of Nu-6(1) molecular sieve synthesized from the formula 0.278Na2 O:1SiO2 :0.02Al2 O3 :0.13 4,4'-bipyridyl:x H2 O (x=30～0.5) Atlas;
图3是实施例1中由配方0.278Na2O:1SiO2:0.02Al2O3:0.13 4,4’-联吡啶:0.5H2O合成的Nu-6(1)分子筛的扫描电镜照片；Fig. 3 is a scanning electron micrograph of Nu-6(1) molecular sieve synthesized from the formula 0.278Na2O:1SiO2 :0.02Al2O3 :0.13 4,4'- bipyridine:0.5H2O in Example1 ;
图4是实施例1中由配方0.278Na2O:1SiO2:0.02Al2O3:0.13 4,4’-联吡啶:0.5H2O合成的Nu-6(1)分子筛的XRD图谱；Fig. 4 is the XRD spectrum of Nu-6(1) molecular sieve synthesized from the formula 0.278Na2 O: 1SiO2 : 0.02Al2 O3 : 0.13 4,4'-bipyridine: 0.5H2 O in Example 1;
图5，图6分别是实施例1中由配方0.278Na2O:1SiO2:0.02Al2O3:0.13 4,4’-联吡啶:0.5H2O合成的Nu-6(1)分子筛的29Si，27Al固体核磁图谱；Fig. 5 and Fig. 6 are respectively the Nu-6(1) molecular sieve synthesized by the formula 0.278Na2 O: 1SiO2 : 0.02Al2 O3 : 0.13 4,4'-bipyridine: 0.5H2 O in Example 129 Si,27 Al solid NMR spectra;
图7是实施例2中由配方0.278Na2O:1SiO2:0.02Al2O3:0.065 4,4’-联吡啶:0.5H2O合成的Nu-6(1)分子筛的扫描电镜照片；Fig. 7 is a scanning electron micrograph of Nu-6(1) molecular sieve synthesized from the formula 0.278Na2 O: 1SiO2 : 0.02Al2 O3 : 0.065 4,4'-bipyridine: 0.5H2 O in Example 2;
图8是实施例2中由配方0.278Na2O:1SiO2:0.02Al2O3:0.065 4,4’-联吡啶:0.5H2O合成的Nu-6(1)分子筛的XRD图谱；Fig. 8 is the XRD pattern of Nu-6(1) molecular sieve synthesized from the formula 0.278Na2 O: 1SiO2 : 0.02Al2 O3 : 0.065 4,4'-bipyridine: 0.5H2 O in Example 2;
图9是实施例3中由配方0.278Na2O:1SiO2:0.02Al2O3:0.065 4,4’-联吡啶:3H2O合成的Nu-6(1)分子筛的扫描电镜照片；Fig. 9 is a scanning electron micrograph of Nu-6(1) molecular sieve synthesized from the formula 0.278Na2 O: 1SiO2 : 0.02Al2 O3 : 0.065 4,4'-bipyridine: 3H2 O in Example 3;
图10是实施例3中由配方0.278Na2O:1SiO2:0.02Al2O3:0.065 4,4’-联吡啶:3H2O合成的Nu-6(1)分子筛的XRD图谱；Figure 10 is the XRD pattern of Nu-6(1) molecular sieve synthesized from the formula 0.278Na2 O:1SiO2 :0.02Al2 O3 :0.065 4,4'-bipyridyl:3H2 O in Example 3;
图11是实施例4中由配方0.278Na2O:1SiO2:0.02Al2O3:0.01634,4’-联吡啶:3H2O合成的Nu-6(1)分子筛的扫描电镜照片；Figure 11 is a scanning electron micrograph of Nu-6(1) molecular sieve synthesized from the formula 0.278Na2 O:1SiO2 :0.02Al2 O3 :0.01634,4'-bipyridyl:3H2 O in Example 4;
图12是实施例4中由配方0.278Na2O:1SiO2:0.02Al2O3:0.0163 4,4’-联吡啶:3H2O合成的Nu-6(1)分子筛的XRD图谱。Fig. 12 is the XRD spectrum of Nu-6(1) molecular sieve synthesized from the formula 0.278Na2 O: 1SiO2 : 0.02Al2 O3 : 0.0163 4,4'-bipyridine: 3H2 O in Example 4.
具体实施方式detailed description
以下由特定的具体实施例说明本发明的实施方式，熟悉此技术的人士可由本说明书所揭露的内容轻易地了解本发明的其他优点及功效。The implementation of the present invention will be illustrated by specific specific examples below, and those skilled in the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification.
在进一步描述本发明具体实施方式之前，应理解，本发明的保护范围不局限于下述特定的具体实施方案；还应当理解，本发明实施例中使用的术语是为了描述特定的具体实施方案，而不是为了限制本发明的保护范围。下列实施例中未注明具体条件的试验方法，通常按照常规条件，或者按照各制造商所建议的条件。Before further describing the specific embodiments of the present invention, it should be understood that the protection scope of the present invention is not limited to the following specific specific embodiments; it should also be understood that the terms used in the examples of the present invention are to describe specific specific embodiments, It is not intended to limit the protection scope of the present invention. The test methods for which specific conditions are not indicated in the following examples are usually in accordance with conventional conditions, or in accordance with the conditions suggested by each manufacturer.
当实施例给出数值范围时，应理解，除非本发明另有说明，每个数值范围的两个端点以及两个端点之间任何一个数值均可选用。除非另外定义，本发明中使用的所有技术和科学术语与本技术领域技术人员通常理解的意义相同。除实施例中使用的具体方法、设备、材料外，根据本技术领域的技术人员对现有技术的掌握及本发明的记载，还可以使用与本发明实施例中所述的方法、设备、材料相似或等同的现有技术的任何方法、设备和材料来实现本发明。When the examples give numerical ranges, it should be understood that unless otherwise specified in the present invention, the two endpoints of each numerical range and any value between the two endpoints can be selected. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition to the specific methods, equipment, and materials used in the embodiments, according to those skilled in the art's grasp of the prior art and the description of the present invention, the methods, equipment, and materials described in the embodiments of the present invention can also be used Any methods, devices and materials of the prior art similar or equivalent to the practice of the present invention.
实施例1Example 1
合成Nu-6(1)的摩尔配比为：0.278Na2O:1SiO2:0.02Al2O3:0.13 4,4’-联吡啶:0.5H2O，加入1wt％晶种，静态晶化，135℃下反应72小时，制备Nu-6(1)分子筛。The molar ratio for synthesizing Nu-6(1) is: 0.278Na2 O: 1SiO2 : 0.02Al2 O3 : 0.13 4,4'-bipyridyl: 0.5H2 O, adding 1wt% seed crystal, static crystallization , reacted at 135° C. for 72 hours to prepare Nu-6(1) molecular sieve.
1)分别将0.912克4,4’-联吡啶和5.040克无水乙醇混合得到A溶液，10.158克硅酸钠溶液和5.960克去离子水混合得到B溶液，0.310克硫酸铝，12.110克去离子水和0.760克浓硫酸混合得到C溶液，分别搅拌2小时；1) Mix 0.912 grams of 4,4'-bipyridine and 5.040 grams of absolute ethanol to obtain solution A, 10.158 grams of sodium silicate solution and 5.960 grams of deionized water to obtain solution B, 0.310 grams of aluminum sulfate, and 12.110 grams of deionized Water and 0.760 gram of concentrated sulfuric acid were mixed to obtain C solution, which was stirred for 2 hours respectively;
2)向步骤1)中制备的A溶液中滴加B溶液，搅拌1小时，再向A、B混合溶液中滴加C溶液，室温下老化24小时后，加入27毫克Nu-6(1)晶种。2) Add solution B dropwise to solution A prepared in step 1), stir for 1 hour, then add solution C dropwise to the mixed solution of A and B, and after aging for 24 hours at room temperature, add 27 mg of Nu-6(1) Seed.
将步骤2)中的母液，80℃下烘干24小时，并研磨成粉末；Dry the mother liquor in step 2) at 80°C for 24 hours, and grind it into powder;
3)将粉末倒入聚四氟乙烯反应釜中，加入0.522克去离子水，搅拌均匀，然后在135℃反应72小时。获得的产物经洗涤、烘干得到Nu-6(1)分子筛晶体。3) Pour the powder into a polytetrafluoroethylene reactor, add 0.522 g of deionized water, stir evenly, and react at 135° C. for 72 hours. The obtained product is washed and dried to obtain Nu-6(1) molecular sieve crystals.
图3为本实施例中获得的Nu-6(1)分子筛的扫描电镜照片，Nu-6(1)分子筛晶体为约1微米的片状晶体，晶体大小较均匀。同传统硅铝Nu-6(1)合成方法相比，水硅比由30降到0.5，水热合成的条件由动态晶化，反应96小时，改进为，静态晶化，反应72小时。Fig. 3 is a scanning electron micrograph of the Nu-6(1) molecular sieve obtained in this example, the crystal of the Nu-6(1) molecular sieve is a sheet crystal of about 1 micron, and the crystal size is relatively uniform. Compared with the traditional silicon-aluminum Nu-6(1) synthesis method, the water-silicon ratio is reduced from 30 to 0.5, and the hydrothermal synthesis conditions are improved from dynamic crystallization and 96-hour reaction to static crystallization and 72-hour reaction.
图4为本实施例中获得的Nu-6(1)分子筛以及焙烧后得到的Nu-6(2)分子筛的XRD图谱，分别与标准图谱一致。Figure 4 shows the XRD patterns of the Nu-6(1) molecular sieve obtained in this example and the Nu-6(2) molecular sieve obtained after calcination, which are consistent with the standard patterns respectively.
图5为本实施例中获得的Nu-6(2)分子筛晶体的29Si固体核磁图谱。由图可知，在-116，-113，-110，-108ppm的共振峰属于Si(4Si,0Al)，-104ppm的共振峰属于Q3(Si(3Si,OH))共振，-106ppm的共振峰归因于Si(3Si,1Al)。Fig. 5 is the29 Si solid nuclear magnetic spectrum of the Nu-6(2) molecular sieve crystal obtained in this example. It can be seen from the figure that the resonance peaks at -116, -113, -110, and -108ppm belong to Si (4Si, 0Al), the resonance peak at -104ppm belongs to Q3 (Si(3Si, OH)) resonance, and the resonance peak at -106ppm belongs to Due to Si (3Si, 1Al).
图6为本实施例中获得的Nu-6(2)分子筛晶体的27Al固体核磁图谱。由图可知，对于此配方所得的Nu-6(2)，仅存在四配位的Al。Fig. 6 is the27 Al solid NMR spectrum of the Nu-6(2) molecular sieve crystal obtained in this example. It can be seen from the figure that for the Nu-6(2) obtained from this formula, only four-coordinated Al exists.
实施例2Example 2
合成Nu-6(1)的摩尔配比为：0.278Na2O:1SiO2:0.02Al2O3:0.065 4,4’-联吡啶:0.5H2O，加入5wt％晶种，静态晶化，135℃下反应72小时，制备Nu-6(1)分子筛。The molar ratio for synthesizing Nu-6(1) is: 0.278Na2 O: 1SiO2 : 0.02Al2 O3 : 0.065 4,4'-bipyridine: 0.5H2 O, adding 5wt% seed crystals, and static crystallization , reacted at 135° C. for 72 hours to prepare Nu-6(1) molecular sieve.
与实施例1的不同之处在于，步骤1)中A溶液里加入0.458克4,4’-联吡啶；步骤2)中加入135毫克Nu-6(1)晶种；步骤4)中加入0.478克去离子水，加入酸调节pH值为1.0。其余步骤及参数与实施例1相同。The difference from Example 1 is that 0.458 g of 4,4'-bipyridyl was added to the A solution in step 1); 135 mg of Nu-6(1) seed crystals were added in step 2); 0.478 g deionized water, add acid to adjust the pH to 1.0. All the other steps and parameters are the same as in Example 1.
图7为Nu-6(1)分子筛的扫描电镜照片，Nu-6(1)分子筛晶体为约1微米的片状晶体，晶体大小较均匀。同传统Nu-6(1)合成方法相比，水硅比由30降到0.5的同时，硅和模板剂的比由0.13降到0.065，水热合成的条件由动态晶化，反应96小时，改进为，静态晶化，反应72小时。Fig. 7 is a scanning electron micrograph of Nu-6(1) molecular sieve, the crystal of Nu-6(1) molecular sieve is about 1 micron flake crystal, and the crystal size is relatively uniform. Compared with the traditional Nu-6(1) synthesis method, the ratio of water to silicon is reduced from 30 to 0.5, and the ratio of silicon to template is reduced from 0.13 to 0.065. The conditions of hydrothermal synthesis are dynamic crystallization and reaction for 96 hours. The improvement is static crystallization and reaction for 72 hours.
图8为Nu-6(1)分子筛以及焙烧后得到的Nu-6(2)分子筛的XRD图谱，分别与标准图谱一致。Figure 8 shows the XRD patterns of Nu-6(1) molecular sieve and Nu-6(2) molecular sieve obtained after calcination, which are consistent with the standard patterns respectively.
实施例3Example 3
合成Nu-6(1)的摩尔配比为：0.278Na2O:1SiO2:0.02Al2O3:0.065 4,4’-联吡啶:3H2O，加入1wt％晶种，静态晶化，135℃下反应72小时，制备Nu-6(1)分子筛。The molar ratio for synthesizing Nu-6(1) is: 0.278Na2 O: 1SiO2 : 0.02Al2 O3 : 0.065 4,4'-bipyridine: 3H2 O, adding 1wt% seed crystals, static crystallization, React at 135°C for 72 hours to prepare Nu-6(1) molecular sieve.
与实施例1的不同之处在于，步骤1)中A溶液里加入0.458克4,4’-联吡啶；步骤4)中加入1.632克去离子水，加入酸调节pH值为11.0。其余步骤及参数与实施例1相同。The difference from Example 1 is that 0.458 g of 4,4'-bipyridine was added to the solution A in step 1); 1.632 g of deionized water was added in step 4), and acid was added to adjust the pH to 11.0. All the other steps and parameters are the same as in Example 1.
图9为Nu-6(1)分子筛的扫描电镜照片，Nu-6(1)分子筛晶体为约1微米的片状晶体，晶体大小较均匀。同传统Nu-6(1)合成方法相比，水硅比由30降到3的同时，硅和模板剂的比由0.13降到0.065，水热合成的条件由动态晶化，反应96小时，改进为，静态晶化，反应72小时。Fig. 9 is a scanning electron micrograph of Nu-6(1) molecular sieve, the crystal of Nu-6(1) molecular sieve is about 1 micron flaky crystal, and the crystal size is relatively uniform. Compared with the traditional Nu-6(1) synthesis method, while the ratio of water to silicon is reduced from 30 to 3, the ratio of silicon to template is reduced from 0.13 to 0.065. The conditions of hydrothermal synthesis are dynamic crystallization and reaction for 96 hours. The improvement is static crystallization and reaction for 72 hours.
图10为Nu-6(1)分子筛以及焙烧后得到的Nu-6(2)分子筛的XRD图谱，分别与标准图谱一致。Figure 10 shows the XRD patterns of Nu-6(1) molecular sieve and Nu-6(2) molecular sieve obtained after calcination, which are consistent with the standard patterns respectively.
实施例4Example 4
合成Nu-6(1)的摩尔配比为：0.278Na2O:1SiO2:0.02Al2O3:0.0163 4,4’-联吡啶:3H2O，加入5wt％晶种，静态晶化，135℃下反应72小时，制备Nu-6(1)分子筛。The molar ratio for synthesizing Nu-6(1) is: 0.278Na2 O: 1SiO2 : 0.02Al2 O3 : 0.0163 4,4'-bipyridine: 3H2 O, adding 5wt% seed crystals, static crystallization, React at 135°C for 72 hours to prepare Nu-6(1) molecular sieve.
与实施例1的不同之处在于，步骤1)中A溶液里加入0.056克4,4’-联吡啶；步骤2)中加入135毫克Nu-6(1)晶种；步骤4)中加入1.669克去离子水；加入酸调节pH值为10.0。其余步骤及参数与实施例1相同。The difference from Example 1 is that 0.056 g of 4,4'-bipyridine was added to solution A in step 1); 135 mg of Nu-6(1) seed crystals were added in step 2); 1.669 g of Nu-6(1) was added in step 4). g deionized water; add acid to adjust pH to 10.0. All the other steps and parameters are the same as in Example 1.
图11为Nu-6(1)分子筛的扫描电镜照片，Nu-6(1)分子筛晶体为约1微米的片状晶体，晶体大小较均匀。同传统Nu-6(1)合成方法相比，水硅比由30降到3的同时，硅和模板剂的比由0.13降到0.0163，水热合成的条件由动态晶化，反应96小时，改进为，静态晶化，反应72小时。Fig. 11 is a scanning electron micrograph of Nu-6(1) molecular sieve, the crystal of Nu-6(1) molecular sieve is about 1 micron flake crystal, and the crystal size is relatively uniform. Compared with the traditional Nu-6(1) synthesis method, while the ratio of water to silicon is reduced from 30 to 3, the ratio of silicon to template is reduced from 0.13 to 0.0163. The conditions of hydrothermal synthesis are dynamic crystallization and reaction for 96 hours. The improvement is static crystallization and reaction for 72 hours.
图12为Nu-6(1)分子筛以及焙烧后得到的Nu-6(2)分子筛的XRD图谱，分别与标准图谱一致。Figure 12 shows the XRD patterns of Nu-6(1) molecular sieve and Nu-6(2) molecular sieve obtained after calcination, which are consistent with the standard patterns respectively.
实施例5Example 5
合成Nu-6(1)的摩尔配比为：0.278Na2O:1SiO2:0.02Al2O3:0.008 4,4’-联吡啶:3H2O，加入5wt％晶种，静态晶化，135℃下反应72小时，制备Nu-6(1)分子筛。The molar ratio for synthesizing Nu-6(1) is: 0.278Na2 O: 1SiO2 : 0.02Al2 O3 : 0.008 4,4'-bipyridine: 3H2 O, adding 5wt% seed crystals, static crystallization, React at 135°C for 72 hours to prepare Nu-6(1) molecular sieve.
与实施例1的不同之处在于，步骤1)中A溶液里加入0.028克4,4’-联吡啶；步骤2)中加入135毫克Nu-6(1)晶种；步骤4)中加入1.582克去离子水；加入酸调节pH值为10.0。其余步骤及参数与实施例1相同。The difference from Example 1 is that 0.028 g of 4,4'-bipyridyl was added to solution A in step 1); 135 mg of Nu-6(1) seed crystals were added in step 2); 1.582 g deionized water; add acid to adjust pH to 10.0. All the other steps and parameters are the same as in Example 1.
实施例6Example 6
合成Nu-6(1)的摩尔配比为：0.278Na2O:1SiO2:0.02Al2O3:0.0163 4,4’-联吡啶:0.5H2O，加入5wt％晶种，静态晶化，135℃下反应72小时，制备Nu-6(1)分子筛。The molar ratio for synthesizing Nu-6(1) is: 0.278Na2 O: 1SiO2 : 0.02Al2 O3 : 0.0163 4,4'-bipyridyl: 0.5H2 O, adding 5wt% seed crystals, static crystallization , reacted at 135° C. for 72 hours to prepare Nu-6(1) molecular sieve.
与实施例1的不同之处在于，步骤1)中A溶液里加入0.056克4,4’-联吡啶；步骤2)中加入135毫克Nu-6(1)晶种；步骤4)中加入0.609克去离子水。其余步骤及参数与实施例1相同。The difference from Example 1 is that 0.056 g of 4,4'-bipyridine was added to solution A in step 1); 135 mg of Nu-6(1) seed crystals were added in step 2); 0.609 grams of deionized water. All the other steps and parameters are the same as in Example 1.
实施例7Example 7
合成Nu-6(1)的摩尔配比为：0.278Na2O:1SiO2:0.02Al2O3:0.008 4,4’-联吡啶:0.5H2O，加入5wt％晶种，静态晶化，135℃下反应72小时，制备Nu-6(1)分子筛。The molar ratio for synthesizing Nu-6(1) is: 0.278Na2 O: 1SiO2 : 0.02Al2 O3 : 0.008 4,4'-bipyridyl: 0.5H2 O, adding 5wt% seed crystals, static crystallization , reacted at 135° C. for 72 hours to prepare Nu-6(1) molecular sieve.
与实施例1的不同之处在于，步骤1)中A溶液里加入0.028克4,4’-联吡啶；步骤2)中加入135毫克Nu-6(1)晶种；步骤4)中加入0.579克去离子水。其余步骤及参数与实施例1相同。The difference from Example 1 is that 0.028 g of 4,4'-bipyridine was added to solution A in step 1); 135 mg of Nu-6(1) seed crystals were added in step 2); 0.579 grams of deionized water. All the other steps and parameters are the same as in Example 1.
实施例8Example 8
合成Nu-6(1)的摩尔配比为：0.278Na2O:1SiO2:0.02Al2O3:0.13 4,4’-联吡啶:80H2O，加入1wt％晶种，静态晶化，135℃下反应200小时，制备Nu-6(1)分子筛。The molar ratio for synthesizing Nu-6(1) is: 0.278Na2 O: 1SiO2 : 0.02Al2 O3 : 0.13 4,4'-bipyridine: 80H2 O, adding 1wt% seed crystals, static crystallization, React at 135°C for 200 hours to prepare Nu-6(1) molecular sieve.
与实施例1的不同之处在于，步骤1)中B溶液里加入去离子水46.581克；省去步骤3)；步骤4)中无需加入去离子水。其余步骤及参数与实施例1相同。The difference from Example 1 is that 46.581 grams of deionized water is added to the B solution in step 1); step 3) is omitted; and deionized water does not need to be added in step 4). All the other steps and parameters are the same as in Example 1.
实施例9Example 9
合成Nu-6(1)的摩尔配比为：0.278Na2O:1SiO2:0.02Al2O3:0.5 4,4’-联吡啶:30H2O，加入1wt％晶种，静态晶化，135℃下反应72小时，制备Nu-6(1)分子筛。The molar ratio for synthesizing Nu-6(1) is: 0.278Na2 O: 1SiO2 : 0.02Al2 O3 : 0.5 4,4'-bipyridine: 30H2 O, adding 1wt% seed crystals, static crystallization, React at 135°C for 72 hours to prepare Nu-6(1) molecular sieve.
与实施例1的不同之处在于，步骤1)中A溶液里加入3.525克模板剂4,4’-联吡啶；省去步骤3)；步骤4)中无需加入去离子水。其余步骤及参数与实施例1相同。The difference from Example 1 is that 3.525 grams of template agent 4,4'-bipyridine is added to the solution A in step 1); step 3) is omitted; deionized water does not need to be added in step 4). All the other steps and parameters are the same as in Example 1.
实施例10Example 10
合成Nu-6(1)的摩尔配比为：0.278Na2O:1SiO2:0.06Al2O3:0.13 4,4’-联吡啶:30H2O，加入1wt％晶种，静态晶化，135℃下反应72小时，制备Nu-6(1)分子筛。The molar ratio for synthesizing Nu-6(1) is: 0.278Na2 O: 1SiO2 : 0.06Al2 O3 : 0.13 4,4'-bipyridine: 30H2 O, adding 1wt% seed crystals, static crystallization, React at 135°C for 72 hours to prepare Nu-6(1) molecular sieve.
与实施例1的不同之处在于，步骤1)中C溶液里加入0.926克硫酸铝；省去步骤3)；步骤4)中无需加入去离子水。其余步骤及参数与实施例1相同。The difference from Example 1 is that 0.926 g of aluminum sulfate is added to the C solution in step 1); step 3) is omitted; deionized water does not need to be added in step 4). All the other steps and parameters are the same as in Example 1.
实施例11Example 11
合成Nu-6(1)的摩尔配比为：0.278Na2O:1SiO2:0.1Al2O3:0.13 4,4’-联吡啶:30H2O，加入1wt％晶种，静态晶化，135℃下反应72小时，制备Nu-6(1)分子筛。The molar ratio for synthesizing Nu-6(1) is: 0.278Na2 O: 1SiO2 : 0.1Al2 O3 : 0.13 4,4'-bipyridine: 30H2 O, adding 1wt% seed crystals, static crystallization, React at 135°C for 72 hours to prepare Nu-6(1) molecular sieve.
与实施例1的不同之处在于，步骤1)中C溶液里加入1.544克硫酸铝；省去步骤3)；步骤4)中无需加入去离子水。其余步骤及参数与实施例1相同。The difference from Example 1 is that 1.544 grams of aluminum sulfate is added to the C solution in step 1); step 3) is omitted; deionized water does not need to be added in step 4). All the other steps and parameters are the same as in Example 1.
实施例12Example 12
合成Nu-6(1)的摩尔配比为：0.5Na2O:1SiO2:0.02Al2O3:0.13 4,4’-联吡啶:30H2O，加入1wt％晶种，静态晶化，135℃下反应72小时，制备Nu-6(1)分子筛。The molar ratio for synthesizing Nu-6(1) is: 0.5Na2 O: 1SiO2 : 0.02Al2 O3 : 0.13 4,4'-bipyridine: 30H2 O, adding 1wt% seed crystals, static crystallization, React at 135°C for 72 hours to prepare Nu-6(1) molecular sieve.
与实施例1的不同之处在于，步骤1)中硅源为白炭黑，铝源为氢氧化铝，使用浓硝酸调节PH。即B溶液里加入2.708克白炭黑，1.805克氢氧化钠以及12.181克去离子水。C溶液里加入0.174克氢氧化铝，12.11克去离子水，以及0.978克浓硝酸；省去步骤3)；步骤4)中无需加入去离子水。其余步骤及参数与实施例1相同。The difference from Example 1 is that in step 1), the silicon source is white carbon black, the aluminum source is aluminum hydroxide, and concentrated nitric acid is used to adjust the pH. That is, 2.708 grams of white carbon black, 1.805 grams of sodium hydroxide and 12.181 grams of deionized water were added to solution B. Add 0.174 grams of aluminum hydroxide, 12.11 grams of deionized water, and 0.978 grams of concentrated nitric acid into solution C; omit step 3); no need to add deionized water in step 4). All the other steps and parameters are the same as in Example 1.
实施例13Example 13
合成Nu-6(1)的摩尔配比为：0.8Na2O:1SiO2:0.02Al2O3:0.13 4,4’-联吡啶:30H2O，加入1wt％晶种，静态晶化，135℃下反应72小时，制备Nu-6(1)分子筛。The molar ratio for synthesizing Nu-6(1) is: 0.8Na2 O: 1SiO2 : 0.02Al2 O3 : 0.13 4,4'-bipyridine: 30H2 O, adding 1wt% seed crystals, static crystallization, React at 135°C for 72 hours to prepare Nu-6(1) molecular sieve.
与实施例1的不同之处在于，步骤1)中硅源为白炭黑，铝源为氢氧化铝。即B溶液里加入2.708克白炭黑，2.792克氢氧化钠以及12.181克去离子水。C溶液里加入0.174克偏铝酸钠；省去步骤3)；步骤4)中无需加入去离子水。其余步骤及参数与实施例1相同。The difference from Example 1 is that the silicon source in step 1) is white carbon black, and the aluminum source is aluminum hydroxide. That is, 2.708 grams of white carbon black, 2.792 grams of sodium hydroxide and 12.181 grams of deionized water were added to solution B. Add 0.174 g of sodium metaaluminate to solution C; omit step 3); step 4) does not need to add deionized water. All the other steps and parameters are the same as in Example 1.
实施例14Example 14
合成Nu-6(1)的摩尔配比为：0.278Na2O:1SiO2:0.02Al2O3:0.13 4,4’-联吡啶:30H2O，加入1wt％晶种，静态晶化，158℃下反应6小时，制备Nu-6(1)分子筛。The molar ratio for synthesizing Nu-6(1) is: 0.278Na2 O: 1SiO2 : 0.02Al2 O3 : 0.13 4,4'-bipyridine: 30H2 O, adding 1wt% seed crystals, static crystallization, React at 158°C for 6 hours to prepare Nu-6(1) molecular sieve.
与实施例1的不同之处在于，步骤1)中硅源改为硅溶胶(SiO2的质量为40wt％)，即B溶液里加入的是1.077克氢氧化钠，6.248g硅溶胶，以及9.667g去离子水；省去步骤3)；步骤4)中无需加入去离子水。其余步骤及参数与实施例1相同。The difference with Example 1 is that in step 1) the silicon source is changed to silica sol (SiOThe quality is 40wt%), that is, 1.077 grams of sodium hydroxide, 6.248g of silica sol, and 9.667 grams of sodium hydroxide were added in the B solution. g deionized water; omit step 3); step 4) without adding deionized water. All the other steps and parameters are the same as in Example 1.
实施例15Example 15
合成Nu-6(1)的摩尔配比为：0.01Na2O:1SiO2:0.01Al2O3:1 4,4’-联吡啶:20H2O，加入10wt％晶种，静态晶化，200℃下反应6小时，制备Nu-6(1)分子筛。其余步骤及参数与实施例1相同。The molar ratio for synthesizing Nu-6(1) is: 0.01Na2 O: 1SiO2 : 0.01Al2 O3 : 1 4,4'-bipyridine: 20H2 O, adding 10wt% seed crystals, static crystallization, React at 200°C for 6 hours to prepare Nu-6(1) molecular sieve. All the other steps and parameters are the same as in Example 1.
实施例16Example 16
合成Nu-6(1)的摩尔配比为：1Na2O:1SiO2:0.06Al2O3:0.01 4,4’-联吡啶:100H2O，加入8wt％晶种，静态晶化，100℃下反应6小时，制备Nu-6(1)分子筛。其余步骤及参数与实施例1相同。The molar ratio for synthesizing Nu-6(1) is: 1Na2 O: 1SiO2 : 0.06Al2 O3 : 0.01 4,4'-bipyridine: 100H2 O, adding 8wt% seeds, static crystallization, 100 React at ℃ for 6 hours to prepare Nu-6(1) molecular sieve. All the other steps and parameters are the same as in Example 1.
上述实施例仅例示性说明本发明的原理及其功效，而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下，对上述实施例进行修饰或改变。因此，举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变，仍应由本发明的权利要求所涵盖。The above-mentioned embodiments only illustrate the principles and effects of the present invention, but are not intended to limit the present invention. Anyone skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or changes made by those skilled in the art without departing from the spirit and technical ideas disclosed in the present invention shall still be covered by the claims of the present invention.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4397825A (en)* | 1980-12-11 | 1983-08-09 | Imperial Chemical Industries Plc | Zeolites Nu-6(1) and Nu-6(2) |
| CN104724720A (en)* | 2015-03-18 | 2015-06-24 | 宁夏大学 | Synthesis method of HZSM-5 molecular sieve |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4397825A (en)* | 1980-12-11 | 1983-08-09 | Imperial Chemical Industries Plc | Zeolites Nu-6(1) and Nu-6(2) |
| CN104724720A (en)* | 2015-03-18 | 2015-06-24 | 宁夏大学 | Synthesis method of HZSM-5 molecular sieve |
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