WO2024098501A1 - Mww-structured molecular sieve, preparation method therefor and use thereof - Google Patents

Mww-structured molecular sieve, preparation method therefor and use thereof Download PDF

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WO2024098501A1
WO2024098501A1 PCT/CN2022/138658 CN2022138658W WO2024098501A1 WO 2024098501 A1 WO2024098501 A1 WO 2024098501A1 CN 2022138658 W CN2022138658 W CN 2022138658W WO 2024098501 A1 WO2024098501 A1 WO 2024098501A1
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molecular sieve
mww
preparation
template
source
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Chinese (zh)
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崔岩
邢世勇
韩明汉
王晓化
郭成玉
谢音
于宏悦
乔亮
迟克彬
张上
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中国石油天然气股份有限公司
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  • the invention relates to the technical field of molecular sieve material synthesis, and in particular to an MWW structure molecular sieve and a preparation method and application thereof.
  • the MWW molecular sieve has a very typical two-dimensional sheet morphology. Its sheet structure is composed of several basic monolayers stacked together, and also forms a unique pore structure, mainly including two-dimensional sinusoidal ten-membered ring channels in the ab axis plane and twelve-membered ring supercage structures and half-supercage structures along the c axis.
  • the opening size of its ten-membered ring channel is 0.41nm ⁇ 0.51nm, distributed outside the supercage structure; the twelve-membered ring supercage has a size of 0.71nm ⁇ 0.71nm ⁇ 1.82nm, and is connected to the six identical supercages in the surrounding ab axis plane through the ten-membered ring; the half-supercage distributed on the surface of the sheet has a size of 0.71nm ⁇ 0.71nm ⁇ 0.8nm, and its open twelve-membered opening is very conducive to the diffusion of reactants. It has excellent catalytic reaction performance for macromolecular reactions and has been widely used in alkylation and other reaction processes.
  • MWW molecular sieves can be divided into several varieties according to the different stacking methods of the basic single layers, including MCM-22 molecular sieves, MCM-49 molecular sieves with oxygen bridge bonds between single layers, MCM-36 molecular sieves with pillared structures between layers, MCM-56 molecular sieves with disordered stacking between layers, and ITQ-2 molecular sieves with single-layer structures.
  • the MCM-22 molecular sieve is obtained by calcining the interlayer silanol dehydration to form oxygen bridge bonds.
  • the crystal structure of the calcined MCM-22 molecular sieve is the same as that of the MCM-49 molecular sieve.
  • Templates for direct induction synthesis of MWW structured molecular sieves generally include hexamethyleneimine, piperidine, and homopiperazine.
  • hexamethyleneimine is the most widely used, but it has the disadvantages of being volatile, flammable, and highly toxic.
  • Piperidine is difficult to obtain commercially.
  • Homopiperazine is expensive and difficult to use. Therefore, it is very important to develop a cheap, green method for synthesizing MWW structured molecular sieves.
  • the purpose of the present invention is to provide a MWW structure molecular sieve and its preparation method and application.
  • the present invention can directly synthesize the MWW structure molecular sieve without using hexamethyleneimine, piperidine and homopiperazine by using a method of coordinated crystallization with seed crystals and two template agents.
  • the present invention provides a preparation method of an MWW structure molecular sieve, which comprises: mixing an aluminum source, water, an alkali source, a first template, a second template, a silicon source and a seed to form a gel, and crystallizing the gel to obtain the MWW structure molecular sieve; wherein the first template comprises cyclohexylamine, and the second template comprises diisopropylamine (molecular formula C 6 H 15 N), di-n-butylamine (molecular formula C 8 H 19 N), diisobutylamine (molecular formula C 8 H 19 N), 1,4-diazabicyclo[2.2.2]octane (molecular formula C 6 H 12 N 2 ), 1,6-hexanediamine (molecular formula C 6 H 16 N 2 ), N,N,N,N-tetramethyl-1,6-hexanediamine (CAS No. 111-18-2, molecular formula C 10
  • the first template and the second template both use low-toxic, cheap organic amines.
  • the first template as the main template, can be coordinated with the seed to realize the construction of the molecular sieve base layer structure.
  • the second template is used as a secondary template and the second template uses a fatty amine with a carbon number of 6-10 and a N atom of sp 3 hybridization. It can rely on the idle orbital holes in the sp 3 hybrid orbit of the nitrogen atom to form interlayer hydrogen bonds with the silicon hydroxyl groups on the surface of the monolayer structure, and the process of forming hydrogen bonds will not affect the overall crystallization effect of the molecular sieve. Therefore, in some embodiments, the MWW structure molecular sieve obtained by the above-mentioned preparation method has an interlayer hydrogen bond formed by silicon hydroxyl groups and the second template.
  • the present invention has been found that the use of the above-mentioned first template, the second template or a single one of the seed crystals cannot obtain an MWW structure molecular sieve with interlayer hydrogen bonds.
  • the second template when the second template is omitted, only the first template and the seed crystals can obtain the MCM-49 molecular sieve, which has oxygen bridge bonds rather than hydrogen bonds between the layers of the molecular sieve.
  • the above-mentioned preparation method provided by the present invention can synthesize a molecular sieve with an MWW structure having interlayer hydrogen bonds by omitting hexamethyleneimine, piperidine, and homopiperazine through the synergistic effect between the first template, the second template, and the seed crystals.
  • the molar ratio of the first template to the second template is generally controlled to be 0.5-20: 1, for example, it can be controlled to be 0.5-1.5: 1.
  • the crystallization temperature is generally controlled to be 120-170°C, such as 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, 165°C, 170°C, etc.
  • the crystallization time is generally controlled to be 12-120h, such as 12h, 20h, 30h, 40h, 50h, 60h, 70h, 72h, 80h, 90h, 100h, 110h, 120h, etc.
  • the silicon source may include silicon dioxide, silicate, silicate, etc.
  • the silicon source may include one or a combination of two or more of silica sol, solid silica gel, white carbon black, water glass, ethyl orthosilicate, etc.
  • the aluminum source may include one or a combination of two or more of aluminate (such as sodium aluminate), aluminum sulfate, aluminum oxide, pseudo-boehmite, etc.
  • aluminate such as sodium aluminate
  • aluminum sulfate aluminum oxide
  • pseudo-boehmite etc.
  • the seed generally adopts a molecular sieve having an MWW topological structure, for example, commercially available MCM-22 molecular sieves, MCM-49 molecular sieves, etc. can be used.
  • the seed can also adopt a molecular sieve having an MWW topological structure obtained by the preparation method of the present invention.
  • the seed is preferably an MCM-22 molecular sieve without a template, which has interlayer hydrogen bonds.
  • the application of the seed in the above preparation process is conducive to obtaining an MWW structure molecular sieve having interlayer hydrogen bonds and a structure similar to that of the MCM-22 molecular sieve.
  • the alkali source may include sodium hydroxide and/or potassium hydroxide, etc.
  • the above-mentioned preparation method may specifically include: mixing an aluminum source, water, an alkali source, a first template, and a second template to obtain an intermediate solution, adding a silicon source and a seed crystal to the intermediate solution, mixing to form a gel, and crystallizing the gel to obtain the MWW structure molecular sieve.
  • the first template and the second template are added after the aluminum source, which helps the aluminum source to be completely dissolved and evenly dispersed in the solution.
  • the silicon source can be added slowly, and the seed crystal can be added after the silicon source, which can improve the uniformity and stability of the reaction system, and avoid the problem of forming a colloid with the aluminum source after the silicon source is quickly added, resulting in uneven dispersion of the reaction system.
  • the present invention also provides an MWW structured molecular sieve obtained by the above-mentioned preparation method.
  • the MWW structured molecular sieve provided by the present invention has an MWW topological structure and has interlayer hydrogen bonds.
  • the XRD spectrum of the above-mentioned MWW structured molecular sieve has relatively obvious characteristic peaks at about 6.5-7.15° (such as 7.09°) and 7.18°.
  • the MWW structured molecular sieve of the present invention has interlayer hydrogen bonds and is similar to the structure of the MCM-22 molecular sieve when it is not calcined (also without removing the template agent), so it can be regarded as a precursor of the MCM-22 molecular sieve (which can be recorded as MCM-22 (P) molecular sieve).
  • the MWW structured molecular sieve of the present invention has good modification potential. For example, it can be prepared into MCM-36 molecular sieve after swelling and pillaring, and it can be prepared into ITQ-2 molecular sieve after swelling and peeling.
  • the present invention has found that the MCM-49 molecular sieve does not have interlayer hydrogen bonds and cannot swell and peel; the MCM-22 molecular sieve made with a conventional template agent (hexamethyleneimine) and the MWW structured molecular sieve provided by the present invention have interlayer hydrogen bonds, so both molecular sieves have the ability to swell and peel.
  • the MWW structure molecular sieve provided by the present invention has lower difficulty in stripping, which can be specifically reflected in that the pH of the alkaline environment required for stripping is closer to neutral, indicating that the interlayer hydrogen bond strength of the MWW structure molecular sieve provided by the present invention is more moderate than that of the MCM-22 molecular sieve.
  • the molecular sieve is pillared or stripped, it is more conducive to retaining the integrity of the molecular sieve flaky crystal structure, improving the stability of the molecular sieve, and reducing the loss of catalytic active sites. Therefore, it is beneficial to improve the catalytic activity and stability of the molecular sieve when it is used in reactions such as alkylation, isomerization or cracking.
  • the MWW structured molecular sieve has a relatively high specific surface area, which can reach above 500 m 2 ⁇ g.
  • the micropore specific surface area of the MWW structured molecular sieve can reach 350 m 2 ⁇ g or more, and the mesopore specific surface area of the MWW structured molecular sieve can reach 140 m 2 ⁇ g or more.
  • the pore volume of the MWW structured molecular sieve can reach above 0.60 cm 3 ⁇ g.
  • the micropore volume of the MWW molecular sieve can reach above 0.16 cm 3 ⁇ g.
  • the present invention also provides the use of the above-mentioned MWW structure molecular sieve in alkylation reaction, isomerization reaction or cracking reaction catalysis.
  • the catalytic effect of the above-mentioned molecular sieve provided by the present invention is no less than that of the commercially available MCM-22 molecular sieve.
  • the invented MWW structure molecular sieve is applied to the alkylation reaction, and the olefin conversion rate can reach more than 99.97%, the selectivity can reach more than 42%, and further can reach more than 96%.
  • the present invention relies on seed crystals and a first template to realize the construction of a base layer structure, and relies on a second template to realize the construction of interlayer hydrogen bonds. Without using traditional templates such as hexamethyleneimine, piperidine, and homopiperazine, the product can still have properties similar to those of MCM-22 molecular sieves and exhibit higher catalytic ability.
  • the first template and the second template used in the present invention are both low-toxic, easily available organic amines with low cost, which can greatly improve the operability of the production of MWW structured molecular sieves and have strong practical application significance.
  • Figure 1 is the XRD spectrum of the seed crystal.
  • Figure 2 is a SEM image of the seed crystal.
  • FIG. 3 is an XRD spectrum of the molecular sieve synthesized in Example 1.
  • FIG. 4 is a SEM image of the molecular sieve synthesized in Example 1.
  • FIG5 is an XRD spectrum of the molecular sieve synthesized in Example 2.
  • FIG. 6 is a SEM image of the molecular sieve synthesized in Example 2.
  • FIG. 7 is an XRD spectrum of the molecular sieve synthesized in Comparative Example 1.
  • FIG8 is a SEM image of the molecular sieve synthesized in Comparative Example 1.
  • FIG. 9 is an XRD spectrum of the molecular sieve synthesized in Comparative Example 2.
  • FIG10 is a SEM image of the molecular sieve synthesized in Comparative Example 2.
  • FIG. 11 is an XRD spectrum of the molecular sieve synthesized in Comparative Example 3.
  • FIG12 is a SEM image of the molecular sieve synthesized in Comparative Example 3.
  • FIG13 is a TEM image of the molecular sieve synthesized in Comparative Example 1.
  • FIG. 14 is a TEM image of the molecular sieve synthesized in Example 1.
  • Silicon source silica sol (SiO 2 content 40%, content is mass content, the same below), solid silica gel (SiO 2 content 95%), white carbon black (SiO 2 content 93%), tetraethyl orthosilicate (SiO 2 content 98% in terms of silicon element);
  • Aluminum source sodium aluminate (calculated by aluminum content, Al 2 O 3 content 41%), aluminum sulfate (calculated by aluminum content, Al 2 O 3 content 15%), alumina (calculated by aluminum content, alumina content 95%), pseudo-boehmite (calculated by aluminum content, Al 2 O 3 content 70%);
  • Alkali source sodium hydroxide (99%), potassium hydroxide (99%);
  • Second template agent diisopropylamine (99%), di-n-butylamine (99%), diisobutylamine (99%), 1,4-diazabicyclo[2.2.2]octane (99%), 1,6-hexanediamine (99%), N,N,N,N-tetramethyl-1,6-hexanediamine (99%);
  • Seed MCM-22 molecular sieve produced by Mobil Corporation, which has not been calcined to remove the template agent;
  • the molecular sieve products of the examples and comparative examples used for characterization were first calcined in an air atmosphere at 540° C. and then subjected to BET characterization.
  • This embodiment provides a MWW structure molecule, and the preparation method thereof includes:
  • the content of the silicon source is calculated as SiO 2
  • the amount of the aluminum source is calculated as Al 2 O 3
  • This embodiment provides a MWW structure molecule, and the preparation method thereof includes:
  • the content of the silicon source is calculated as SiO 2
  • the amount of the aluminum source is calculated as Al 2 O 3
  • This embodiment provides a MWW structure molecule, and the preparation method thereof includes:
  • the content of the silicon source is calculated as SiO 2
  • the amount of the aluminum source is calculated as Al 2 O 3
  • This embodiment provides a MWW structure molecule, and the preparation method thereof includes:
  • the content of the silicon source is calculated as SiO 2
  • the amount of the aluminum source is calculated as Al 2 O 3
  • This embodiment provides a MWW structure molecule, and the preparation method thereof includes:
  • the content of the silicon source is calculated as SiO 2
  • the amount of the aluminum source is calculated as Al 2 O 3
  • This comparative example provides a molecular sieve, and its preparation method comprises:
  • This comparative example provides a molecular sieve, and its preparation method comprises:
  • the method uses hexamethyleneimine, which is a typical template for preparing MCM-22 molecular sieves.
  • hexamethyleneimine which is a typical template for preparing MCM-22 molecular sieves.
  • the comparative example can obtain pure phase MCM-22 molecular sieves, the amount of template hexamethyleneimine used is relatively large, and the template is expensive and highly toxic.
  • This comparative example provides a molecular sieve, and its preparation method comprises:
  • This test example is used to characterize the structures of the above-mentioned embodiments and comparative examples.
  • FIG. 1 and FIG. 2 are respectively the XRD spectra and SEM photos of the seed crystals (MCM-22 molecular sieve sold by Mobil Corporation) used in the above-mentioned embodiments and comparative examples.
  • Figures 3 and 4 are respectively the XRD spectra and SEM photos of the molecular sieve product of Example 1.
  • the molecular sieve product prepared in Example 1 has typical MWW structural characteristic peaks, and the morphology of the molecular sieve product presents a flower cluster shape of nanosheet stacking.
  • Figures 5 and 6 are respectively the XRD spectra and SEM photos of the molecular sieve product of Example 2.
  • the molecular sieve product prepared in Example 2 has typical MWW structural characteristic peaks, and the morphology of the molecular sieve product presents a flower cluster shape of nanosheet stacking.
  • Example 3 XRD and SEM characterizations were performed on the molecular sieve products of Example 3, Example 4, and Example 5, and it can also be seen that the above samples have typical MWW structural characteristic peaks, and the morphology of the molecular sieve products presents a flower cluster shape of stacked nanosheets.
  • Figures 7 and 8 are respectively the XRD spectra and SEM photos of the molecular sieve product of Comparative Example 1.
  • the molecular sieve product prepared in Comparative Example 1 has a typical MWW structural characteristic peak and can be subdivided into MCM-49 molecular sieve.
  • the morphology of the molecular sieve product presents orderly stacked nanosheets.
  • Figures 9 and 10 are respectively the XRD spectrum and SEM photo of the molecular sieve product of Comparative Example 2. It can be seen that the molecular sieve product prepared in Comparative Example 2 has typical MWW structural characteristic peaks and can be subdivided into MCM-22 molecular sieves, and the molecular sieve morphology is nanosheets.
  • Figures 11 and 12 are respectively the XRD spectrum and SEM photograph of the molecular sieve product of Comparative Example 3. It can be seen that the molecular sieve product prepared in Comparative Example 3 has a typical MWW structural characteristic peak, the molecular sieve product is a mixture of MCM-22 and MCM-49 molecular sieves, and the molecular sieve morphology is in the form of stacked nanosheets.
  • the hexamethyleneimine used in Comparative Example 2 is a typical template for preparing MCM-22 molecular sieves, and the molecular sieve obtained in Comparative Example 2 is a pure phase MCM-22 molecular sieve. Comparing the XRD results of the molecular sieve products of Examples 1 to 5 with the XRD results of Comparative Example 2, it can be seen that the molecular sieves of Examples 1 to 5 have a structure similar to that of the MCM-22 molecular sieve, further confirming that the molecular sieves of the present application have interlayer hydrogen bonds with MCM-22.
  • the reason why the composite template of hexamethyleneimine and cyclohexylamine cannot obtain a pure-phase molecular sieve is that when a certain proportion of hexamethyleneimine is replaced by cyclohexylamine, cyclohexylamine does not have the ability to build interlayer hydrogen bonds, and the concentration of hexamethyleneimine is low and cannot build sufficient hydrogen bonds, so only a mixture of two molecular sieves can be obtained, and a single pure-phase molecular sieve cannot be obtained.
  • Figure 13 is a TEM image of the molecular sieve product prepared in Comparative Example 1
  • Figure 14 is a TEM image of the molecular sieve product prepared in Example 1.
  • This test example provides the specific surface area and pore volume results of the molecular sieve products of Examples 1 to 5 and Comparative Example 1 measured by BET, and the specific results are shown in Table 1.
  • S BET is the specific surface area
  • S mic is the micropore surface area
  • S ext is the mesopore surface area
  • V pore is the pore volume
  • V mic is the micropore volume.
  • the micropore specific surface area, mesopore specific surface area, total specific surface area and total pore volume of the molecular sieves prepared in Examples 1 to 5 of the present invention are greater than those of the molecular sieve products prepared in Comparative Examples 1 to 3, and the micropore volume of the molecular sieves prepared in Examples 1 to 5 is not less than that of the molecular sieve products prepared in Comparative Examples 1 to 3.
  • the preparation method provided by the present invention can form hydrogen bonds with hydrogen in the second template using the orbital holes of N atoms sp 3 in the second template, and the molecular sieve thus obtained not only has MWW topological structure, but also has interlayer hydrogen bonds similar to MCM-22 molecular sieves, and has the characteristics of MCM-22 molecular sieves, and the total specific surface area and total pore volume of the molecular sieve of the present invention are also significantly increased.
  • the molecular sieve product prepared by the present invention has a lower stacking number and a smaller sheet thickness, and the stacking morphology of the molecular sieve is changed compared to the MCM-49 molecular sieve.
  • Comparative Example 1 can directly synthesize a MWW structure molecular sieve with high crystallinity and pure phase when using cyclohexylamine as a template, and can be subdivided into MCM-49 molecular sieve, but because cyclohexylamine cannot construct interlayer hydrogen bonds, cyclohexylamine is only suitable for synthesizing MCM-49 molecular sieves as a template, and other types of MWW structure molecular sieves cannot be synthesized.
  • Comparative Example 3 uses cyclohexylamine to replace part of hexamethyleneimine as a composite template, and it is also impossible to construct sufficient interlayer hydrogen bonds, so only a mixture of MCM-22 molecular sieves and MCM-49 molecular sieves can be prepared, and a pure phase molecular sieve with MCM-22 structure cannot be obtained.
  • This example provides the use of the molecular sieve product of Example 1 in a catalytic alkylation reaction.
  • the molecular sieve product of Example 1 was calcined at 540°C for 5 h in air atmosphere to remove the template, then ammonium exchanged in 1 mol/L ammonium nitrate solution at 80°C for 2 h, and calcined again at 540°C for 4 h in air atmosphere to obtain an H-type molecular sieve.
  • reaction conditions are: benzene-ethylene ratio 5, reaction temperature 330°C, reaction pressure 1.4MPa, mass space velocity 2.0h -1 .
  • reaction results are as follows: after 500 hours of reaction, the olefin conversion rate is 99.99% and the ethylbenzene selectivity is 96.21%.
  • This example provides the use of the molecular sieve product of Example 2 in a catalytic alkylation reaction.
  • the molecular sieve product of Example 2 was calcined at 540°C for 5 h in air atmosphere to remove the template, then ammonium exchanged in 1 mol/L ammonium nitrate solution at 80°C for 2 h, and calcined again at 540°C for 4 h in air atmosphere to obtain H-type molecular sieve.
  • reaction conditions are: benzene to propylene ratio 4, reaction temperature 150°C, reaction pressure 2.5MPa, mass space velocity 3.0h -1 .
  • reaction results are as follows: after 300 hours of reaction, the olefin conversion rate is 99.97% and the isopropylbenzene selectivity is 99.20%.
  • This example provides the use of the molecular sieve product of Example 3 in a catalytic alkylation reaction.
  • the molecular sieve product of Example 3 was calcined at 540°C for 5 h in air atmosphere to remove the template, then ammonium exchanged in 1 mol/L ammonium nitrate solution at 80°C for 2 h, and calcined again at 540°C for 4 h in air atmosphere to obtain an H-type molecular sieve.
  • reaction conditions are: benzene to olefin ratio 15, reaction temperature 150°C, reaction pressure 3.0MPa, mass space velocity 2.0h -1 .
  • reaction results are as follows: after 300 hours of reaction, the olefin conversion rate is 99.97% and the 2-alkylbenzene selectivity is 42.01%.
  • This comparative example provides the use of the molecular sieve product of comparative example 1 in a catalytic alkylation reaction.
  • the molecular sieve of comparative example 1 was calcined at 540°C for 5 hours in air atmosphere to remove the template, then ammonium exchanged in 1 mol/L ammonium nitrate solution at 80°C for 2 hours, and calcined again at 540°C for 4 hours in air atmosphere to obtain H-type molecular sieve.
  • reaction conditions are: benzene to olefin ratio 15, reaction temperature 150°C, reaction pressure 3.0MPa, mass space velocity 2.0h -1 .
  • reaction results are as follows: after 100 hours of reaction, the olefin conversion rate is 76.32%, and the 2-alkylbenzene selectivity is 45.03%.
  • the thickness of the molecular sieve sheet prepared in Examples 1 to 3 is less than that of the MCM-49 molecular sieve in Comparative Example 1, and the number of surface catalytic active sites exposed by the catalyst per unit mass is more, not only the catalytic activity is higher, but also the deactivation problem caused by blockage in the reaction can be avoided, and the catalyst life is longer.
  • the preparation method provided by the present invention can synthesize an MWW structured molecular sieve with interlayer hydrogen bonds while omitting traditional template agents such as hexamethyleneimine, piperidine, and homopiperazine.
  • the molecular sieve has properties similar to those of the MCM-22 molecular sieve and has higher catalytic activity.

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Abstract

An MWW-structured molecular sieve, a preparation method therefor and a use thereof. The method comprises mixing an aluminum source, water, an alkali source, a first template agent, a second template agent, a silicon source, and a seed crystal, and crystallizing the mixture to obtain the MWW-structured molecular sieve, wherein the first template agent comprises cyclohexylamine, and the second template agent comprises diisopropylamine, dibutylamine, diisobutylamine, 1,4-azabicyclo[2.2.2]octane, 1,6-hexamethylenediamine, and N,N,N,N-tetramethyl-1,6-hexamethylenediamine.

Description

MWW结构分子筛及其制备方法与应用MWW structure molecular sieve and its preparation method and application 技术领域Technical Field
本发明涉及分子筛材料合成技术领域，尤其涉及一种MWW结构分子筛及其制备方法与应用。The invention relates to the technical field of molecular sieve material synthesis, and in particular to an MWW structure molecular sieve and a preparation method and application thereof.
背景技术Background technique
MWW结构分子筛具有非常典型的二维片状形貌，其片状结构由若干基础单层堆叠而成，也形成了独特的孔道结构，主要包括ab轴平面的二维正弦十元环孔道和沿c轴方向的十二元环超笼结构和半超笼结构。其十元环孔道开口尺寸为0.41nm×0.51nm，分布于超笼结构之外；十二元环超笼尺寸为0.71nm×0.71nm×1.82nm，通过十元环与周围的ab轴平面的六个相同超笼相通；分布于片层表面的半超笼尺寸为0.71nm×0.71nm×0.8nm，其开放的十二元开口十分有利于反应物的扩散，针对大分子反应具有优异的催化反应性能，已被广泛应用于烷基化等反应过程中。The MWW molecular sieve has a very typical two-dimensional sheet morphology. Its sheet structure is composed of several basic monolayers stacked together, and also forms a unique pore structure, mainly including two-dimensional sinusoidal ten-membered ring channels in the ab axis plane and twelve-membered ring supercage structures and half-supercage structures along the c axis. The opening size of its ten-membered ring channel is 0.41nm×0.51nm, distributed outside the supercage structure; the twelve-membered ring supercage has a size of 0.71nm×0.71nm×1.82nm, and is connected to the six identical supercages in the surrounding ab axis plane through the ten-membered ring; the half-supercage distributed on the surface of the sheet has a size of 0.71nm×0.71nm×0.8nm, and its open twelve-membered opening is very conducive to the diffusion of reactants. It has excellent catalytic reaction performance for macromolecular reactions and has been widely used in alkylation and other reaction processes.
MWW结构分子筛按照基础单层的堆叠方式的不同又可细分为多个品种，其中主要包括MCM-22分子筛，单层间为氧桥键的MCM-49分子筛，层间形成柱撑结构的MCM-36分子筛，层间无序堆叠的MCM-56分子筛，单层结构的ITQ-2分子筛等。其中的MCM-22分子筛是经过焙烧层间硅羟基脱水形成氧桥键后得到的，经过焙烧的MCM-22分子筛的晶体结构与MCM-49分子筛相同。MWW molecular sieves can be divided into several varieties according to the different stacking methods of the basic single layers, including MCM-22 molecular sieves, MCM-49 molecular sieves with oxygen bridge bonds between single layers, MCM-36 molecular sieves with pillared structures between layers, MCM-56 molecular sieves with disordered stacking between layers, and ITQ-2 molecular sieves with single-layer structures. The MCM-22 molecular sieve is obtained by calcining the interlayer silanol dehydration to form oxygen bridge bonds. The crystal structure of the calcined MCM-22 molecular sieve is the same as that of the MCM-49 molecular sieve.
用于直接诱导合成MWW结构分子筛的模板剂一般包括六亚甲基亚胺、哌啶、高哌嗪。其中六亚甲基亚胺应用最多，但是存在易挥发易燃和高毒性的缺点。哌啶难以商购获得。高哌嗪售价昂贵，难以应用。因此开发一种廉价的、绿色的MWW结构分子筛合成方法是非常重要的。Templates for direct induction synthesis of MWW structured molecular sieves generally include hexamethyleneimine, piperidine, and homopiperazine. Among them, hexamethyleneimine is the most widely used, but it has the disadvantages of being volatile, flammable, and highly toxic. Piperidine is difficult to obtain commercially. Homopiperazine is expensive and difficult to use. Therefore, it is very important to develop a cheap, green method for synthesizing MWW structured molecular sieves.
现有的MWW结构分子筛的合成通常采用六亚甲基亚胺与另一种有机胺配合实现MCM-22等分子筛的合成。The synthesis of existing MWW structure molecular sieves usually adopts hexamethyleneimine and another organic amine to achieve the synthesis of molecular sieves such as MCM-22.
从现有技术可以发现，由于MWW结构分子筛的特殊性，直接用晶种是无法实现合成的，通过在加入晶种的基础上加入有机胺可以构建出完整的MCM-49分子筛。目前为止，不使用六亚甲基亚胺、哌啶、高哌嗪的情况下合成MCM-22分子筛的先例尚未存在，因此亟需开发一种可操作性强的、绿色、廉价的MCM-22分子筛等MWW分子筛的制备方法。It can be found from the prior art that due to the particularity of the MWW structure molecular sieve, it is impossible to synthesize it directly with seed crystals. A complete MCM-49 molecular sieve can be constructed by adding organic amines on the basis of adding seed crystals. So far, there is no precedent for synthesizing MCM-22 molecular sieves without using hexamethyleneimine, piperidine, and homopiperazine. Therefore, it is urgent to develop a method for preparing MWW molecular sieves such as MCM-22 molecular sieves that is highly operable, green, and inexpensive.
发明内容Summary of the invention
为了解决上述问题，本发明的目的在于提供一种MWW结构分子筛及其制备方法与应用。本发明通过以晶种与两种模板剂协同辅助晶化的方法，可以在不使用六亚甲基亚胺、哌啶、高哌嗪的情况下直接合成MWW结构分子筛。In order to solve the above problems, the purpose of the present invention is to provide a MWW structure molecular sieve and its preparation method and application. The present invention can directly synthesize the MWW structure molecular sieve without using hexamethyleneimine, piperidine and homopiperazine by using a method of coordinated crystallization with seed crystals and two template agents.
为了达到上述目的，本发明提供了一种MWW结构分子筛的制备方法，该制备方法包括：将铝源、水、碱源、第一模板剂、第二模板剂、硅源和晶种混合形成凝胶，使凝胶晶化，得到所述MWW结构分子筛；其中，所述第一模板剂包括环己胺，所述第二模板剂可以包括二异丙胺(分子式为C 6H 15N)、二正丁胺(分子式为C 8H 19N)、二异丁胺(分子式为C 8H 19N)、1,4-二氮杂二环[2.2.2]辛烷(分子式C 6H 12N 2)、1,6-己二胺(分子式为C 6H 16N 2)、N,N,N,N-四甲基-1,6-己二胺(CAS号为111-18-2，分子式为C 10H 24N 2)中的一种或两种以上的组合。 In order to achieve the above-mentioned object, the present invention provides a preparation method of an MWW structure molecular sieve, which comprises: mixing an aluminum source, water, an alkali source, a first template, a second template, a silicon source and a seed to form a gel, and crystallizing the gel to obtain the MWW structure molecular sieve; wherein the first template comprises cyclohexylamine, and the second template comprises diisopropylamine (molecular formula C 6 H 15 N), di-n-butylamine (molecular formula C 8 H 19 N), diisobutylamine (molecular formula C 8 H 19 N), 1,4-diazabicyclo[2.2.2]octane (molecular formula C 6 H 12 N 2 ), 1,6-hexanediamine (molecular formula C 6 H 16 N 2 ), N,N,N,N-tetramethyl-1,6-hexanediamine (CAS No. 111-18-2, molecular formula C 10 H 24 N 2 ) or a combination of two or more thereof.
在上述制备方法中，第一模板剂和第二模板剂均采用低毒、价廉的有机胺。其中，第一模板剂作为主模板剂，可与晶种配合以实现对分子筛基础层结构的构建。第二模板剂作为副模板剂、并且第二模板剂采用碳数为6-10、N原子为sp 3杂化的脂肪胺，可以依靠氮原子sp 3杂化轨道中空闲的轨道空穴与单层结构表面的硅羟基形成层间氢键，并且形成氢键的过程不会影响分子筛的整体晶化效果。因此，在一些实施方案中，上述制备方法得到的MWW结构分子筛具有硅羟基与第二模板剂形成的层间氢键。 In the above-mentioned preparation method, the first template and the second template both use low-toxic, cheap organic amines. Wherein, the first template, as the main template, can be coordinated with the seed to realize the construction of the molecular sieve base layer structure. The second template is used as a secondary template and the second template uses a fatty amine with a carbon number of 6-10 and a N atom of sp 3 hybridization. It can rely on the idle orbital holes in the sp 3 hybrid orbit of the nitrogen atom to form interlayer hydrogen bonds with the silicon hydroxyl groups on the surface of the monolayer structure, and the process of forming hydrogen bonds will not affect the overall crystallization effect of the molecular sieve. Therefore, in some embodiments, the MWW structure molecular sieve obtained by the above-mentioned preparation method has an interlayer hydrogen bond formed by silicon hydroxyl groups and the second template.
本发明研究发现，利用上述第一模板剂、第二模板剂或晶种中的单独一种无法得到具有层间氢键的MWW结构分子筛。例如在省略第二模板剂的情况下，仅利用第一模板剂和晶种只能获得MCM-49分子筛，该分子筛层间为氧桥键而非氢键。本发明提供的上述制备方法通过第一模板剂、第二模板剂、晶种之间的协同作用，可以在省略六亚甲基亚胺、哌啶、高哌嗪的情况下合成具有层间氢键的MWW结构的分子筛。在一些具体实施方案中，所述第一模板剂与第二模板剂的摩尔比一般控制为0.5-20:1，例如可以控制为0.5-1.5:1。The present invention has been found that the use of the above-mentioned first template, the second template or a single one of the seed crystals cannot obtain an MWW structure molecular sieve with interlayer hydrogen bonds. For example, when the second template is omitted, only the first template and the seed crystals can obtain the MCM-49 molecular sieve, which has oxygen bridge bonds rather than hydrogen bonds between the layers of the molecular sieve. The above-mentioned preparation method provided by the present invention can synthesize a molecular sieve with an MWW structure having interlayer hydrogen bonds by omitting hexamethyleneimine, piperidine, and homopiperazine through the synergistic effect between the first template, the second template, and the seed crystals. In some specific embodiments, the molar ratio of the first template to the second template is generally controlled to be 0.5-20: 1, for example, it can be controlled to be 0.5-1.5: 1.
在本发明的具体实施方案中，将所述碱源记为MOH(M为碱源中形成阳离子的原子，M的价态一般为一价，例如碱源为NaOH、则M为Na)，硅源以SiO 2计，铝源以Al 2O 3计，碱源以M 2O计，第一模板剂与第二模板剂之和记为T，所述凝胶的化学组成一般满足以下摩尔比范围：Al 2O 3/SiO 2＝0.005-0.05，M 2O/SiO 2＝0.03-0.50，T/SiO 2＝0.10-0.75，H 2O/SiO 2＝8-120；晶种以干基质量计，晶种与硅源的质量比一般满足：晶种/SiO 2＝0.01-0.25。 In a specific embodiment of the present invention, the alkali source is denoted as MOH (M is an atom forming a cation in the alkali source, and the valence state of M is generally monovalent, for example, if the alkali source is NaOH, then M is Na), the silicon source is calculated as SiO2 , the aluminum source is calculated as Al2O3 , the alkali source is calculated as M2O , the sum of the first template and the second template is denoted as T, and the chemical composition of the gel generally satisfies the following molar ratio range: Al2O3 / SiO2 =0.005-0.05, M2O / SiO2 =0.03-0.50, T/ SiO2 =0.10-0.75, H2O / SiO2 =8-120; the seed crystals are calculated on a dry basis, and the mass ratio of the seed crystals to the silicon source generally satisfies: seed crystals/ SiO2 =0.01-0.25.
在一些具体实施方案中，所述硅源和铝源可以满足以下摩尔比： Al 2O 3/SiO 2＝0.01-0.05、进一步可满足Al 2O 3/SiO 2＝0.01-0.02。 In some specific embodiments, the silicon source and the aluminum source may satisfy the following molar ratio: Al 2 O 3 /SiO 2 =0.01-0.05, and may further satisfy Al 2 O 3 /SiO 2 =0.01-0.02.
在一些具体实施方案中，所述硅源与水可满足以下摩尔比：H 2O/SiO 2＝15-120，或者可满足H 2O/SiO 2＝8-13。 In some specific embodiments, the silicon source and water may satisfy the following molar ratio: H 2 O/SiO 2 =15-120, or may satisfy H 2 O/SiO 2 =8-13.
在本发明的具体实施方案中，所述晶化的温度一般控制为120-170℃，例如120℃、125℃、130℃、135℃、140℃、145℃、150℃、155℃、160℃、165℃、170℃等。所述晶化的时间一般控制为12-120h，例如12h、20h、30h、40h、50h、60h、70h、72h、80h、90h、100h、110h、120h等。In a specific embodiment of the present invention, the crystallization temperature is generally controlled to be 120-170°C, such as 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, 165°C, 170°C, etc. The crystallization time is generally controlled to be 12-120h, such as 12h, 20h, 30h, 40h, 50h, 60h, 70h, 72h, 80h, 90h, 100h, 110h, 120h, etc.
在本发明的具体实施方案中，所述硅源的成分可以包括二氧化硅、硅酸盐、硅酸酯等。具体地，所述硅源可以包括硅溶胶、固体硅胶、白炭黑、水玻璃、正硅酸乙酯等中的一种或两种以上的组合。In a specific embodiment of the present invention, the silicon source may include silicon dioxide, silicate, silicate, etc. Specifically, the silicon source may include one or a combination of two or more of silica sol, solid silica gel, white carbon black, water glass, ethyl orthosilicate, etc.
在本发明的具体实施方案中，所述铝源可以包括偏铝酸盐(如偏铝酸钠)、硫酸铝、氧化铝、拟薄水铝石等中的一种或两种以上的组合。In a specific embodiment of the present invention, the aluminum source may include one or a combination of two or more of aluminate (such as sodium aluminate), aluminum sulfate, aluminum oxide, pseudo-boehmite, etc.
在本发明的具体实施方案中，所述晶种一般采用具有MWW拓扑结构的分子筛，例如可以采用商购的MCM-22分子筛、MCM-49分子筛等。在一些具体实施方案中，所述晶种也可以采用通过本发明的制备方法得到的具有MWW拓扑结构的分子筛。所述晶种优选未脱模板剂的MCM-22分子筛，该分子筛中具有层间氢键，作为晶种应用于上述制备过程有利于获得具有层间氢键、与MCM-22分子筛结构相似的MWW结构分子筛。In a specific embodiment of the present invention, the seed generally adopts a molecular sieve having an MWW topological structure, for example, commercially available MCM-22 molecular sieves, MCM-49 molecular sieves, etc. can be used. In some specific embodiments, the seed can also adopt a molecular sieve having an MWW topological structure obtained by the preparation method of the present invention. The seed is preferably an MCM-22 molecular sieve without a template, which has interlayer hydrogen bonds. The application of the seed in the above preparation process is conducive to obtaining an MWW structure molecular sieve having interlayer hydrogen bonds and a structure similar to that of the MCM-22 molecular sieve.
在本发明的具体实施方案中，所述碱源可以包括氢氧化钠和/或氢氧化钾等。In a specific embodiment of the present invention, the alkali source may include sodium hydroxide and/or potassium hydroxide, etc.
在本发明的具体实施方案中，上述制备方法具体可以包括：将铝源、水、碱源、第一模板剂、第二模板剂混合得到中间溶液，向所述中间溶液中加入硅源和晶种，混合形成凝胶，使凝胶晶化，得到所述MWW结构分子筛。通过采用上述顺序合成，有利于各原料均匀分散、促进晶化反应。在一些具体实施方案中，第一模板剂和第二模板剂在铝源之后添加，有助于铝源在溶液中完全溶解并分散均匀。加入硅源的方式可以是缓慢加入，且晶种可以在硅源之后添加，可以提高反应体系的均匀性和稳定性，避免快速加入硅源后与铝源形成胶体、导致反应体系分散不均的问题。In a specific embodiment of the present invention, the above-mentioned preparation method may specifically include: mixing an aluminum source, water, an alkali source, a first template, and a second template to obtain an intermediate solution, adding a silicon source and a seed crystal to the intermediate solution, mixing to form a gel, and crystallizing the gel to obtain the MWW structure molecular sieve. By adopting the above-mentioned sequential synthesis, it is beneficial to uniformly disperse the raw materials and promote the crystallization reaction. In some specific embodiments, the first template and the second template are added after the aluminum source, which helps the aluminum source to be completely dissolved and evenly dispersed in the solution. The silicon source can be added slowly, and the seed crystal can be added after the silicon source, which can improve the uniformity and stability of the reaction system, and avoid the problem of forming a colloid with the aluminum source after the silicon source is quickly added, resulting in uneven dispersion of the reaction system.
本发明还提供了由上述制备方法得到的MWW结构分子筛。本发明提供的MWW结构分子筛具有MWW拓扑结构、并且具有层间氢键。在一些具体实施方案中，上述MWW结构分子筛的XRD谱图中，在6.5-7.15°(如7.09°)和7.18°左右分别具有较为明显的特征峰。The present invention also provides an MWW structured molecular sieve obtained by the above-mentioned preparation method. The MWW structured molecular sieve provided by the present invention has an MWW topological structure and has interlayer hydrogen bonds. In some specific embodiments, the XRD spectrum of the above-mentioned MWW structured molecular sieve has relatively obvious characteristic peaks at about 6.5-7.15° (such as 7.09°) and 7.18°.
本发明的MWW结构分子筛具有层间氢键、与MCM-22分子筛未经焙烧(也是未 脱除模板剂)时的结构相似，因此可以看作是MCM-22分子筛的前驱体(可记为MCM-22(P)分子筛)。本发明的MWW结构分子筛具有良好的改性潜力，例如经过溶胀柱撑可以制备成MCM-36分子筛，经过溶胀剥层可以制备成ITQ-2分子筛。本发明研究发现，MCM-49分子筛不具有层间氢键、无法溶胀剥层；采用常规模板剂(六亚甲基亚胺)制成的MCM-22分子筛、以及本发明提供的MWW结构分子筛由于都具有层间氢键，因此这两种分子筛都具有溶胀剥层的能力。相对于常规模板剂(六亚甲基亚胺)制成的MCM-22分子筛，本发明提供的MWW结构分子筛的剥层难度更小、具体可以体现在剥层所需的碱性环境的pH更接近中性，说明本发明提供的MWW结构分子筛的层间氢键强度比MCM-22分子筛的层间氢键强度更加适中，对分子筛进行柱撑或者剥层改性时更有利于分子筛片状晶体结构完整性的保留，提高分子筛稳定性，减少催化活性位点的损失，因此有利于提高分子筛应用于烷基化反应、异构化反应或裂化反应等反应时的催化活性和稳定性。The MWW structured molecular sieve of the present invention has interlayer hydrogen bonds and is similar to the structure of the MCM-22 molecular sieve when it is not calcined (also without removing the template agent), so it can be regarded as a precursor of the MCM-22 molecular sieve (which can be recorded as MCM-22 (P) molecular sieve). The MWW structured molecular sieve of the present invention has good modification potential. For example, it can be prepared into MCM-36 molecular sieve after swelling and pillaring, and it can be prepared into ITQ-2 molecular sieve after swelling and peeling. The present invention has found that the MCM-49 molecular sieve does not have interlayer hydrogen bonds and cannot swell and peel; the MCM-22 molecular sieve made with a conventional template agent (hexamethyleneimine) and the MWW structured molecular sieve provided by the present invention have interlayer hydrogen bonds, so both molecular sieves have the ability to swell and peel. Compared with the MCM-22 molecular sieve made of conventional template (hexamethyleneimine), the MWW structure molecular sieve provided by the present invention has lower difficulty in stripping, which can be specifically reflected in that the pH of the alkaline environment required for stripping is closer to neutral, indicating that the interlayer hydrogen bond strength of the MWW structure molecular sieve provided by the present invention is more moderate than that of the MCM-22 molecular sieve. When the molecular sieve is pillared or stripped, it is more conducive to retaining the integrity of the molecular sieve flaky crystal structure, improving the stability of the molecular sieve, and reducing the loss of catalytic active sites. Therefore, it is beneficial to improve the catalytic activity and stability of the molecular sieve when it is used in reactions such as alkylation, isomerization or cracking.
在本发明的具体实施方案中，所述MWW结构分子筛的比表面积较高、可以达到500m 2·g以上。 In a specific embodiment of the present invention, the MWW structured molecular sieve has a relatively high specific surface area, which can reach above 500 m 2 ·g.
在本发明的具体实施方案中，所述MWW结构分子筛的微孔比表面积可以达到350m 2·g以上，所述MWW结构分子筛的介孔比表面积可以达到140m 2·g以上。 In a specific embodiment of the present invention, the micropore specific surface area of the MWW structured molecular sieve can reach 350 m 2 ·g or more, and the mesopore specific surface area of the MWW structured molecular sieve can reach 140 m 2 ·g or more.
在本发明的具体实施方案中，所述MWW结构分子筛的孔体积可以达到0.60cm 3·g以上。 In a specific embodiment of the present invention, the pore volume of the MWW structured molecular sieve can reach above 0.60 cm 3 ·g.
在本发明的具体实施方案中，所述MWW分子筛的微孔孔体积可以达到0.16cm 3·g以上。 In a specific embodiment of the present invention, the micropore volume of the MWW molecular sieve can reach above 0.16 cm 3 ·g.
本发明还提供了上述MWW结构分子筛在烷基化反应、异构化反应或裂化反应催化中的应用。本发明提供的上述分子筛的催化效果不亚于商售MCM-22分子筛。在一些具体实施方案中，发明的MWW结构分子筛应用于烷基化反应，烯烃转化率可以达到99.97％以上，选择性可以达到42％以上、进一步可达到96％以上。The present invention also provides the use of the above-mentioned MWW structure molecular sieve in alkylation reaction, isomerization reaction or cracking reaction catalysis. The catalytic effect of the above-mentioned molecular sieve provided by the present invention is no less than that of the commercially available MCM-22 molecular sieve. In some specific embodiments, the invented MWW structure molecular sieve is applied to the alkylation reaction, and the olefin conversion rate can reach more than 99.97%, the selectivity can reach more than 42%, and further can reach more than 96%.
本发明的有益效果包括：The beneficial effects of the present invention include:
1、本发明依靠晶种和第一模板剂实现基础层结构的构建，依靠第二模板剂来实现层间氢键的构建，在不使用六亚甲基亚胺、哌啶、高哌嗪等传统模板剂的情况下，仍然可以使产品具有类似MCM-22分子筛的特性，表现出较高的催化能力。1. The present invention relies on seed crystals and a first template to realize the construction of a base layer structure, and relies on a second template to realize the construction of interlayer hydrogen bonds. Without using traditional templates such as hexamethyleneimine, piperidine, and homopiperazine, the product can still have properties similar to those of MCM-22 molecular sieves and exhibit higher catalytic ability.
2、本发明采用的第一模板剂和第二模板剂均为低毒、易获取的有机胺，且成本低廉，可以极大提高MWW结构分子筛生产的可操作性，具有较强实际应用意义。2. The first template and the second template used in the present invention are both low-toxic, easily available organic amines with low cost, which can greatly improve the operability of the production of MWW structured molecular sieves and have strong practical application significance.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为晶种的XRD谱图。Figure 1 is the XRD spectrum of the seed crystal.
图2为晶种的SEM图。Figure 2 is a SEM image of the seed crystal.
图3为实施例1合成的分子筛的XRD谱图。FIG. 3 is an XRD spectrum of the molecular sieve synthesized in Example 1.
图4为实施例1合成的分子筛的SEM图。FIG. 4 is a SEM image of the molecular sieve synthesized in Example 1.
图5为实施例2合成的分子筛的XRD谱图。FIG5 is an XRD spectrum of the molecular sieve synthesized in Example 2.
图6为实施例2合成的分子筛的SEM图。FIG. 6 is a SEM image of the molecular sieve synthesized in Example 2.
图7为对比例1合成的分子筛的XRD谱图。FIG. 7 is an XRD spectrum of the molecular sieve synthesized in Comparative Example 1.
图8为对比例1合成的分子筛的SEM图。FIG8 is a SEM image of the molecular sieve synthesized in Comparative Example 1.
图9为对比例2合成的分子筛的XRD谱图。FIG. 9 is an XRD spectrum of the molecular sieve synthesized in Comparative Example 2.
图10为对比例2合成的分子筛的SEM图。FIG10 is a SEM image of the molecular sieve synthesized in Comparative Example 2.
图11为对比例3合成的分子筛的XRD谱图。FIG. 11 is an XRD spectrum of the molecular sieve synthesized in Comparative Example 3.
图12为对比例3合成的分子筛的SEM图。FIG12 is a SEM image of the molecular sieve synthesized in Comparative Example 3.
图13为对比例1合成的分子筛的TEM图。FIG13 is a TEM image of the molecular sieve synthesized in Comparative Example 1.
图14为实施例1合成的分子筛的TEM图。FIG. 14 is a TEM image of the molecular sieve synthesized in Example 1.
具体实施方式Detailed ways
为了对本发明的技术特征、目的和有益效果有更加清楚的理解，现对本发明的技术方案进行以下详细说明，但不能理解为对本发明的可实施范围的限定。In order to have a clearer understanding of the technical features, purposes and beneficial effects of the present invention, the technical solution of the present invention is now described in detail below, but it should not be construed as limiting the applicable scope of the present invention.
以下对本发明的实施例作详细说明：本实施例在以本发明技术方案为前提下进行实施，给出了详细的实施方式和过程，但本发明的保护范围不限于下述的实施例，下列实施例中未注明具体条件的实验方法，通常按照常规条件。The following is a detailed description of the embodiments of the present invention: This embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation method and process are given, but the protection scope of the present invention is not limited to the following embodiments. The experimental methods in the following embodiments without specifying specific conditions are usually carried out under conventional conditions.
以下实施例和对比例中采用的原料为：The raw materials used in the following examples and comparative examples are:
硅源：硅溶胶(SiO 2含量40％，含量为质量含量，下同)、固体硅胶(SiO 2含量95％)、白碳黑(SiO 2含量93％)、正硅酸乙酯(以硅元素计，SiO 2含量98％)； Silicon source: silica sol (SiO 2 content 40%, content is mass content, the same below), solid silica gel (SiO 2 content 95%), white carbon black (SiO 2 content 93%), tetraethyl orthosilicate (SiO 2 content 98% in terms of silicon element);
铝源：偏铝酸钠(以铝元素含量计，Al 2O 3含量41％)、硫酸铝(以铝元素含量计，Al 2O 3含量15％)、氧化铝(以铝元素含量计，氧化铝含量95％)、拟薄水铝石(以铝元素含量计，Al 2O 3含量70％)； Aluminum source: sodium aluminate (calculated by aluminum content, Al 2 O 3 content 41%), aluminum sulfate (calculated by aluminum content, Al 2 O 3 content 15%), alumina (calculated by aluminum content, alumina content 95%), pseudo-boehmite (calculated by aluminum content, Al 2 O 3 content 70%);
碱源：氢氧化钠(99％)、氢氧化钾(99％)；Alkali source: sodium hydroxide (99%), potassium hydroxide (99%);
第一模板剂：环己胺(99％)；First template agent: cyclohexylamine (99%);
第二模板剂：二异丙胺(99％)、二正丁胺(99％)、二异丁胺(99％)、1,4-二氮 杂二环[2.2.2]辛烷(99％)、1,6-己二胺(99％)、N,N,N,N-四甲基-1,6-己二胺(99％)；Second template agent: diisopropylamine (99%), di-n-butylamine (99%), diisobutylamine (99%), 1,4-diazabicyclo[2.2.2]octane (99%), 1,6-hexanediamine (99%), N,N,N,N-tetramethyl-1,6-hexanediamine (99%);
晶种：Mobil公司生产的MCM-22分子筛，该分子筛未经焙烧脱除模板剂的过程；Seed: MCM-22 molecular sieve produced by Mobil Corporation, which has not been calcined to remove the template agent;
水：去离子水。Water: deionized water.
用于表征的实施例和对比例的分子筛产物，先经过540℃空气氛围焙烧的处理，然后再进行BET表征。The molecular sieve products of the examples and comparative examples used for characterization were first calcined in an air atmosphere at 540° C. and then subjected to BET characterization.
实施例1Example 1
本实施例提供了一种MWW结构分子，其制备方法包括：This embodiment provides a MWW structure molecule, and the preparation method thereof includes:
1、将1.87g氢氧化钠加入120g去离子水中，搅拌溶解；再加入2.15g偏铝酸钠，持续强烈搅拌1h使其溶解；再缓慢加入9.50g环己胺，持续强烈搅拌0.5h；然后缓慢加入6.50g二异丙胺，持续强烈搅拌0.5h，得到中间溶液。1. Add 1.87g of sodium hydroxide to 120g of deionized water and stir to dissolve; then add 2.15g of sodium aluminate and continue to stir vigorously for 1h to dissolve it; then slowly add 9.50g of cyclohexylamine and continue to stir vigorously for 0.5h; then slowly add 6.50g of diisopropylamine and continue to stir vigorously for 0.5h to obtain an intermediate solution.
2、向中间溶液中缓慢加入80g硅溶胶，持续强烈搅拌3h；再加入晶种、晶种的质量为硅溶胶中二氧化硅含量的3％，持续强烈搅拌1h，制得凝胶。将凝胶在140℃晶化60h，晶化结束，降温至常温。将晶化产物以去离子水洗涤过滤，120℃烘干4h，得到分子筛产物。2. Slowly add 80g of silica sol to the intermediate solution and continue to stir vigorously for 3h; then add seed crystals with a mass of 3% of the silica content in the silica sol and continue to stir vigorously for 1h to obtain a gel. Crystallize the gel at 140℃ for 60h, and cool to room temperature after crystallization. Wash and filter the crystallized product with deionized water and dry it at 120℃ for 4h to obtain a molecular sieve product.
上述实验中，硅源的含量以SiO 2计、铝源的用量以Al 2O 3计算，硅源与铝源的摩尔比为：SiO 2/Al 2O 3＝62。 In the above experiment, the content of the silicon source is calculated as SiO 2 , the amount of the aluminum source is calculated as Al 2 O 3 , and the molar ratio of the silicon source to the aluminum source is: SiO 2 /Al 2 O 3 =62.
实施例2Example 2
本实施例提供了一种MWW结构分子，其制备方法包括：This embodiment provides a MWW structure molecule, and the preparation method thereof includes:
1、将1.87g氢氧化钠加入120g去离子水中搅拌溶解；加入2.50g偏铝酸钠，持续强烈搅拌1h使其溶解；缓慢加入9.00g环己胺，持续强烈搅拌0.5h；缓慢加入8.00g 1,6-己二胺，持续强烈搅拌0.5h，得到中间溶液。1. Add 1.87g of sodium hydroxide to 120g of deionized water and stir to dissolve; add 2.50g of sodium aluminate and continue to stir vigorously for 1h to dissolve it; slowly add 9.00g of cyclohexylamine and continue to stir vigorously for 0.5h; slowly add 8.00g of 1,6-hexanediamine and continue to stir vigorously for 0.5h to obtain an intermediate solution.
2、向中间溶液缓慢加入80g硅溶胶，持续强烈搅拌3h；再加入晶种、晶种的质量为硅溶胶中二氧化硅含量的5％，持续强烈搅拌1h，制得凝胶。将凝胶在145℃晶化72h。晶化结束，降温至常温。将晶化产物以去离子水洗涤过滤，120℃烘干4h，得到分子筛产物。2. Slowly add 80g silica sol to the intermediate solution and continue to stir vigorously for 3h; then add seed crystals with a mass of 5% of the silica content in the silica sol, continue to stir vigorously for 1h to obtain a gel. Crystallize the gel at 145℃ for 72h. After crystallization, cool to room temperature. Wash and filter the crystallized product with deionized water, and dry at 120℃ for 4h to obtain a molecular sieve product.
上述实验中，硅源的含量以SiO 2计、铝源的用量以Al 2O 3计算，硅源与铝源的摩尔比为：SiO 2/Al 2O 3＝53.3。 In the above experiment, the content of the silicon source is calculated as SiO 2 , the amount of the aluminum source is calculated as Al 2 O 3 , and the molar ratio of the silicon source to the aluminum source is: SiO 2 /Al 2 O 3 =53.3.
实施例3Example 3
本实施例提供了一种MWW结构分子，其制备方法包括：This embodiment provides a MWW structure molecule, and the preparation method thereof includes:
1、将1.95g氢氧化钠加入130g去离子水中，搅拌溶解；加入2.33g偏铝酸钠，持 续强烈搅拌1h；缓慢加入9.00g环己胺，持续强烈搅拌0.5h；缓慢加入9.00g 1,4-二氮杂二环[2.2.2]辛烷，持续强烈搅拌0.5h，得到中间溶液。1. Add 1.95g of sodium hydroxide to 130g of deionized water, stir to dissolve; add 2.33g of sodium aluminate, continue to stir vigorously for 1h; slowly add 9.00g of cyclohexylamine, continue to stir vigorously for 0.5h; slowly add 9.00g of 1,4-diazabicyclo[2.2.2]octane, continue to stir vigorously for 0.5h to obtain an intermediate solution.
2、向中间溶液缓慢加入80g硅溶胶，持续强烈搅拌3h；再加入晶种、晶种的质量为硅溶胶中二氧化硅含量的5％，持续强烈搅拌1h，制得凝胶。将凝胶在140℃晶化72h。晶化结束，降温至常温。将晶化产物以去离子水洗涤过滤，自然阴干48h，得到分子筛产物。2. Slowly add 80g silica sol to the intermediate solution and continue to stir vigorously for 3h; then add seed crystals with a mass of 5% of the silica content in the silica sol and continue to stir vigorously for 1h to obtain a gel. Crystallize the gel at 140℃ for 72h. After crystallization, cool to room temperature. Wash and filter the crystallized product with deionized water and dry it naturally in the shade for 48h to obtain a molecular sieve product.
上述实验中，硅源的含量以SiO 2计、铝源的用量以Al 2O 3计算，硅源与铝源的摩尔比为：SiO 2/Al 2O 3＝57.2。 In the above experiment, the content of the silicon source is calculated as SiO 2 , the amount of the aluminum source is calculated as Al 2 O 3 , and the molar ratio of the silicon source to the aluminum source is: SiO 2 /Al 2 O 3 =57.2.
实施例4Example 4
本实施例提供了一种MWW结构分子，其制备方法包括：This embodiment provides a MWW structure molecule, and the preparation method thereof includes:
1、将1.93g氢氧化钠加入150g去离子水中，搅拌溶解；加入1.50g偏铝酸钠，持续强烈搅拌1h；缓慢加入12.25g环己胺，持续强烈搅拌0.5h；缓慢加入8.50gN,N,N,N-四甲基-1,6-己二胺，持续强烈搅拌0.5h，得到中间溶液。1. Add 1.93 g of sodium hydroxide to 150 g of deionized water, stir to dissolve; add 1.50 g of sodium aluminate, continue to stir vigorously for 1 hour; slowly add 12.25 g of cyclohexylamine, continue to stir vigorously for 0.5 hour; slowly add 8.50 g of N,N,N,N-tetramethyl-1,6-hexanediamine, continue to stir vigorously for 0.5 hour to obtain an intermediate solution.
2、向中间溶液缓慢加入80g硅溶胶，持续强烈搅拌3h；再加入10％晶种，持续强烈搅拌1h，制得凝胶。将凝胶在140℃晶化100h。晶化结束，降温至常温。产物以去离子水洗涤过滤，120℃烘干4h，得到分子筛产物。2. Slowly add 80g silica sol to the intermediate solution and continue to stir vigorously for 3h; then add 10% seed crystals and continue to stir vigorously for 1h to obtain gel. Crystallize the gel at 140℃ for 100h. After crystallization, cool to room temperature. Wash and filter the product with deionized water, and dry it at 120℃ for 4h to obtain a molecular sieve product.
上述实验中，硅源的含量以SiO 2计、铝源的用量以Al 2O 3计算，硅源与铝源的摩尔比为：SiO 2/Al 2O 3＝88.9。 In the above experiment, the content of the silicon source is calculated as SiO 2 , the amount of the aluminum source is calculated as Al 2 O 3 , and the molar ratio of the silicon source to the aluminum source is: SiO 2 /Al 2 O 3 = 88.9.
实施例5Example 5
本实施例提供了一种MWW结构分子，其制备方法包括：This embodiment provides a MWW structure molecule, and the preparation method thereof includes:
1、将2.21g氢氧化钠加入175g去离子水中，搅拌溶解；加入1.25g偏铝酸钠，持续强烈搅拌1h；缓慢加入7.55g环己胺，持续强烈搅拌0.5h；缓慢加入10.50g二异丁胺，持续强烈搅拌0.5h，得到中间溶液。1. Add 2.21g of sodium hydroxide to 175g of deionized water, stir to dissolve; add 1.25g of sodium aluminate, continue to stir vigorously for 1h; slowly add 7.55g of cyclohexylamine, continue to stir vigorously for 0.5h; slowly add 10.50g of diisobutylamine, continue to stir vigorously for 0.5h to obtain an intermediate solution.
2、向中间溶液缓慢加入80g硅溶胶，持续强烈搅拌3h；加入晶种、晶种的质量为硅溶胶中二氧化硅含量的15％，持续强烈搅拌1h，制得凝胶。将凝胶在140℃晶化120h。晶化结束，降温至常温。产物以去离子水洗涤过滤，自然阴干48h，得到分子筛产物。2. Slowly add 80g silica sol to the intermediate solution and continue to stir vigorously for 3h; add seed crystals with a mass of 15% of the silica content in the silica sol and continue to stir vigorously for 1h to obtain gel. Crystallize the gel at 140℃ for 120h. After crystallization, cool to room temperature. Wash and filter the product with deionized water and dry it naturally in the shade for 48h to obtain a molecular sieve product.
上述实验中，硅源的含量以SiO 2计、铝源的用量以Al 2O 3计算，硅源与铝源的摩尔比为：SiO 2/Al 2O 3＝106.6。 In the above experiment, the content of the silicon source is calculated as SiO 2 , the amount of the aluminum source is calculated as Al 2 O 3 , and the molar ratio of the silicon source to the aluminum source is: SiO 2 /Al 2 O 3 =106.6.
对比例1Comparative Example 1
本对比例提供了一种分子筛，其制备方法包括：This comparative example provides a molecular sieve, and its preparation method comprises:
1、将1.95g氢氧化钠加入130g去离子水，搅拌溶解；加入2.33g偏铝酸钠，持续强烈搅拌1h；缓慢加入9.00g环己胺，持续强烈搅拌0.5h，得到中间溶液。1. Add 1.95g of sodium hydroxide to 130g of deionized water and stir to dissolve; add 2.33g of sodium aluminate and continue to stir vigorously for 1h; slowly add 9.00g of cyclohexylamine and continue to stir vigorously for 0.5h to obtain an intermediate solution.
2、向中间溶液缓慢加入80g硅溶胶，持续强烈搅拌3h；加入晶种、晶种的质量为硅溶胶中二氧化硅含量的5％，持续强烈搅拌1h，制得凝胶。将凝胶在140℃晶化72h。晶化结束，降温至常温。产物以去离子水洗涤过滤，自然阴干48h，得到分子筛产物。2. Slowly add 80g silica sol to the intermediate solution and continue to stir vigorously for 3h; add seed crystals with a mass of 5% of the silica content in the silica sol and continue to stir vigorously for 1h to obtain gel. Crystallize the gel at 140℃ for 72h. After crystallization, cool to room temperature. Wash and filter the product with deionized water and dry it naturally in the shade for 48h to obtain a molecular sieve product.
对比例2Comparative Example 2
本对比例提供了一种分子筛，其制备方法包括：This comparative example provides a molecular sieve, and its preparation method comprises:
1、将1.87g氢氧化钠加入120g去离子水中，搅拌溶解；加入2.15g偏铝酸钠，搅拌溶解。持续强烈搅拌1h。缓慢加入19.0g六亚甲基亚胺(模板剂与硅源的摩尔比为0.35：1)，持续强烈搅拌0.5h，得到中间溶液；1. Add 1.87g sodium hydroxide to 120g deionized water, stir to dissolve; add 2.15g sodium aluminate, stir to dissolve. Continue to stir vigorously for 1h. Slowly add 19.0g hexamethyleneimine (the molar ratio of template to silicon source is 0.35:1), continue to stir vigorously for 0.5h, and obtain an intermediate solution;
2、向中间溶液缓慢加入80g硅溶胶，持续强烈搅拌3h，制得晶化凝胶。将晶化凝胶在155℃晶化60h。晶化结束，降温至常温。产物以去离子水洗涤过滤，120℃烘干4h，得到分子筛产物。2. Slowly add 80g silica sol to the intermediate solution and continue to stir vigorously for 3 hours to obtain a crystallized gel. Crystallize the crystallized gel at 155℃ for 60 hours. After the crystallization is completed, cool to room temperature. Wash and filter the product with deionized water, and dry it at 120℃ for 4 hours to obtain a molecular sieve product.
该方法是采用的六亚甲基亚胺是制备MCM-22分子筛的典型模板剂，本对比例虽然可以得到纯相的MCM-22分子筛，但模板剂六亚甲基亚胺用量较大，且模板剂价格高昂、毒性大。The method uses hexamethyleneimine, which is a typical template for preparing MCM-22 molecular sieves. Although the comparative example can obtain pure phase MCM-22 molecular sieves, the amount of template hexamethyleneimine used is relatively large, and the template is expensive and highly toxic.
对比例3Comparative Example 3
本对比例提供了一种分子筛，其制备方法包括：This comparative example provides a molecular sieve, and its preparation method comprises:
1、将1.87g氢氧化钠加入120g去离子水中，搅拌溶解。加入2.15g偏铝酸钠，搅拌溶解。持续强烈搅拌1h。缓慢加入9.50g环己胺，9.50g六亚甲基亚胺，持续强烈搅拌0.5h，得到中间溶液。1. Add 1.87g sodium hydroxide to 120g deionized water and stir to dissolve. Add 2.15g sodium aluminate and stir to dissolve. Continue to stir vigorously for 1h. Slowly add 9.50g cyclohexylamine and 9.50g hexamethyleneimine and continue to stir vigorously for 0.5h to obtain an intermediate solution.
2、向中间溶液缓慢加入80g硅溶胶，持续强烈搅拌3h，制得晶化凝胶。将晶化凝胶在155℃晶化60h。晶化结束，降温至常温。产物以去离子水洗涤过滤，120℃烘干4h，得到分子筛产物。2. Slowly add 80g silica sol to the intermediate solution and continue to stir vigorously for 3 hours to obtain a crystallized gel. Crystallize the crystallized gel at 155℃ for 60 hours. After the crystallization is completed, cool to room temperature. Wash and filter the product with deionized water, and dry it at 120℃ for 4 hours to obtain a molecular sieve product.
测试例1Test Example 1
本测试例对上述实施例和对比例进行结构表征。This test example is used to characterize the structures of the above-mentioned embodiments and comparative examples.
图1、图2分别为上述实施例和对比例所用的晶种(mobil公司销售的MCM-22分子筛)的XRD谱图和SEM照片。FIG. 1 and FIG. 2 are respectively the XRD spectra and SEM photos of the seed crystals (MCM-22 molecular sieve sold by Mobil Corporation) used in the above-mentioned embodiments and comparative examples.
图3、图4分别为实施例1的分子筛产物的XRD谱图和SEM照片。从图3、图4可以看出，实施例1制备的分子筛产物具有典型的MWW结构特征峰，且分子筛产物形 貌呈现纳米片堆积的花簇状。Figures 3 and 4 are respectively the XRD spectra and SEM photos of the molecular sieve product of Example 1. As can be seen from Figures 3 and 4, the molecular sieve product prepared in Example 1 has typical MWW structural characteristic peaks, and the morphology of the molecular sieve product presents a flower cluster shape of nanosheet stacking.
图5、图6分别为实施例2的分子筛产物的XRD谱图和SEM照片。从图5、图6可以看出，实施例2制备的分子筛产物具有典型的MWW结构特征峰，且分子筛产物形貌呈现纳米片堆积的花簇状。Figures 5 and 6 are respectively the XRD spectra and SEM photos of the molecular sieve product of Example 2. As can be seen from Figures 5 and 6, the molecular sieve product prepared in Example 2 has typical MWW structural characteristic peaks, and the morphology of the molecular sieve product presents a flower cluster shape of nanosheet stacking.
对实施例3、实施例4、实施例5的分子筛产物进行XRD和SEM表征，也可以看出上述样品具有典型的MWW结构特征峰，且分子筛产物形貌呈现纳米片堆积的花簇状。XRD and SEM characterizations were performed on the molecular sieve products of Example 3, Example 4, and Example 5, and it can also be seen that the above samples have typical MWW structural characteristic peaks, and the morphology of the molecular sieve products presents a flower cluster shape of stacked nanosheets.
图7、图8分别为对比例1的分子筛产物的XRD谱图和SEM照片。从图7、图8可以看出，对比例1制备的分子筛产物具有典型的MWW结构特征峰、可细分为MCM-49分子筛。并且，该分子筛产物形貌呈现有序堆积的纳米片。Figures 7 and 8 are respectively the XRD spectra and SEM photos of the molecular sieve product of Comparative Example 1. As can be seen from Figures 7 and 8, the molecular sieve product prepared in Comparative Example 1 has a typical MWW structural characteristic peak and can be subdivided into MCM-49 molecular sieve. In addition, the morphology of the molecular sieve product presents orderly stacked nanosheets.
图9、图10分别为对比例2的分子筛产物的XRD谱图和SEM照片。可以看出，对比例2制备的分子筛产物具有典型MWW结构特征峰，且可细分为MCM-22分子筛，分子筛形貌呈纳米片。Figures 9 and 10 are respectively the XRD spectrum and SEM photo of the molecular sieve product of Comparative Example 2. It can be seen that the molecular sieve product prepared in Comparative Example 2 has typical MWW structural characteristic peaks and can be subdivided into MCM-22 molecular sieves, and the molecular sieve morphology is nanosheets.
图11、图12分别为对比例3的分子筛产物的XRD谱图和SEM照片。可以看出，对比例3制备的分子筛产物具有典型MWW结构特征峰，分子筛产物为MCM-22和MCM-49分子筛的混合物，分子筛形貌呈纳米片堆叠状。Figures 11 and 12 are respectively the XRD spectrum and SEM photograph of the molecular sieve product of Comparative Example 3. It can be seen that the molecular sieve product prepared in Comparative Example 3 has a typical MWW structural characteristic peak, the molecular sieve product is a mixture of MCM-22 and MCM-49 molecular sieves, and the molecular sieve morphology is in the form of stacked nanosheets.
将实施例1至实施例5的分子筛产物的XRD结果与对比例1的XRD结果进行比较可以看出：实施例1至实施例5的分子筛产物在7.09°(对应002晶面)和7.18°分别具有独立的特征峰，这两个特征峰的代表该分子筛产物中002晶面之间具有明显的层间距，这是由于第二模板剂在相邻的002晶面之间构筑层间氢键并产生一定位阻，从而使相邻晶面之间具有明显的距离。而对比例1产物的XRD图中只在7.18°具有明显的特征峰、7.09°处不具有明显的特征峰，这是因为对比例1产物中002晶面相互堆叠、不具有明显的层间距，对比例1的产物中层间为缩合的氧桥键。Comparing the XRD results of the molecular sieve products of Examples 1 to 5 with the XRD results of Comparative Example 1, it can be seen that the molecular sieve products of Examples 1 to 5 have independent characteristic peaks at 7.09° (corresponding to the 002 crystal plane) and 7.18°, respectively. These two characteristic peaks represent that there is a clear interlayer distance between the 002 crystal planes in the molecular sieve products. This is because the second template constructs interlayer hydrogen bonds between adjacent 002 crystal planes and produces a certain steric resistance, thereby making the adjacent crystal planes have a clear distance. The XRD diagram of the product of Comparative Example 1 only has a clear characteristic peak at 7.18° and no clear characteristic peak at 7.09°. This is because the 002 crystal planes in the product of Comparative Example 1 are stacked on each other and do not have a clear interlayer distance. The interlayers in the product of Comparative Example 1 are condensed oxygen bridge bonds.
对比例2所用的六亚甲基亚胺是制备MCM-22分子筛的典型模板剂，对比例2得到的分子筛为纯相的MCM-22分子筛。将实施例1至实施例5的分子筛产物的XRD结果与对比例2的XRD结果进行比较可以看出，实施例1至实施例5的分子筛具有与MCM-22分子筛相似的结构，进一步证实本申请的分子筛同MCM-22都具有层间氢键。The hexamethyleneimine used in Comparative Example 2 is a typical template for preparing MCM-22 molecular sieves, and the molecular sieve obtained in Comparative Example 2 is a pure phase MCM-22 molecular sieve. Comparing the XRD results of the molecular sieve products of Examples 1 to 5 with the XRD results of Comparative Example 2, it can be seen that the molecular sieves of Examples 1 to 5 have a structure similar to that of the MCM-22 molecular sieve, further confirming that the molecular sieves of the present application have interlayer hydrogen bonds with MCM-22.
上述比较结果可以证明：单独采用环己胺作为模板剂，获得的产物为MCM-49分子筛；而采用环己胺与第二模板剂作为模板剂，可以制备得到MWW结构分子筛，该分子筛具有层间氢键、并且分子筛具有与mobil公司生产的MCM-22分子筛相似的结构。The above comparison results can prove that when cyclohexylamine is used alone as a template, the product obtained is MCM-49 molecular sieve; while when cyclohexylamine and a second template are used as templates, an MWW structured molecular sieve can be prepared, which has interlayer hydrogen bonds and a structure similar to the MCM-22 molecular sieve produced by Mobil.
将对比例3与实施例1的产物组成对比可以看出，使用六亚甲基亚胺和环己胺作为复合模板剂虽然可以合成出纯相的MWW结构分子筛，但是对比例3的产物为MCM-22和MCM-49分子筛的混合物，而无法获得纯相的MCM-22结构的分子筛。而六亚甲基亚胺和环己胺的复合模板剂无法获得纯相分子筛的原因在于：以环己胺替代一定比例的六亚甲基亚胺，环己胺不具有构筑层间氢键的能力，六亚甲基亚胺浓度较低、无法构筑足够的氢键，因此只能获得两种分子筛的混合物、而不能获得单独的纯相分子筛。Comparing the product compositions of Comparative Example 3 and Example 1, it can be seen that although pure-phase MWW structure molecular sieves can be synthesized by using hexamethyleneimine and cyclohexylamine as composite templates, the product of Comparative Example 3 is a mixture of MCM-22 and MCM-49 molecular sieves, and a pure-phase MCM-22 structure molecular sieve cannot be obtained. The reason why the composite template of hexamethyleneimine and cyclohexylamine cannot obtain a pure-phase molecular sieve is that when a certain proportion of hexamethyleneimine is replaced by cyclohexylamine, cyclohexylamine does not have the ability to build interlayer hydrogen bonds, and the concentration of hexamethyleneimine is low and cannot build sufficient hydrogen bonds, so only a mixture of two molecular sieves can be obtained, and a single pure-phase molecular sieve cannot be obtained.
图13为对比例1制备的分子筛产物的TEM图，图14为实施例1制备的分子筛产物的TEM图。对比图13、图14可以看出，对比例1的分子筛的基础层具有明显堆叠，片层厚度约为20nm；相比之下，实施例1的分子筛的基础层堆叠数降低，分子筛片层厚度约为10nm、片层厚度相比于对比例1有明显减小。Figure 13 is a TEM image of the molecular sieve product prepared in Comparative Example 1, and Figure 14 is a TEM image of the molecular sieve product prepared in Example 1. By comparing Figures 13 and 14, it can be seen that the base layer of the molecular sieve of Comparative Example 1 has obvious stacking, and the sheet thickness is about 20nm; in contrast, the number of stacking of the base layer of the molecular sieve of Example 1 is reduced, the molecular sieve sheet thickness is about 10nm, and the sheet thickness is significantly reduced compared with Comparative Example 1.
测试例2Test Example 2
本测试例提供了BET测得的实施例1至实施例5和对比例1的分子筛产物的比表面积和孔体积结果，具体结果如表1所示。其中，S BET为比表面积，S mic为微孔表面积，S ext为介孔表面积，V pore为孔体积，V mic为微孔体积。 This test example provides the specific surface area and pore volume results of the molecular sieve products of Examples 1 to 5 and Comparative Example 1 measured by BET, and the specific results are shown in Table 1. Wherein, S BET is the specific surface area, S mic is the micropore surface area, S ext is the mesopore surface area, V pore is the pore volume, and V mic is the micropore volume.
表1Table 1
Figure PCTCN2022138658-appb-000001
Figure PCTCN2022138658-appb-000001
从表1可以看出，本发明实施例1至实施例5制备的分子筛的微孔比表面积、介孔比表面积、总比表面积和总孔体积均大于对比例1至对比例3制备的分子筛产物，并且实施例1至5制备的分子筛的微孔体积不低于对比例1至3制备的分子筛产物。It can be seen from Table 1 that the micropore specific surface area, mesopore specific surface area, total specific surface area and total pore volume of the molecular sieves prepared in Examples 1 to 5 of the present invention are greater than those of the molecular sieve products prepared in Comparative Examples 1 to 3, and the micropore volume of the molecular sieves prepared in Examples 1 to 5 is not less than that of the molecular sieve products prepared in Comparative Examples 1 to 3.
将表1数据与图13、图14结果结合可知，本发明提供的制备方法通过添加第二模板剂，可以利用第二模板剂中N原子sp 3的轨道空穴与硅羟基中的氢形成氢键，由此获得的分子筛不仅具有MWW拓扑结构，并且分子筛的结构与MCM-22分子筛相似、都具有层间氢键，从而具有MCM-22分子筛的特性，并且本发明分子筛的总比表面积和总孔体积也明显增加。此外，本发明制备的分子筛产物具有较低的堆叠数和较小的片层厚 度，分子筛的堆叠形貌相比于MCM-49分子筛发生改变。 Combining the data of Table 1 with the results of Figures 13 and 14, it can be seen that the preparation method provided by the present invention can form hydrogen bonds with hydrogen in the second template using the orbital holes of N atoms sp 3 in the second template, and the molecular sieve thus obtained not only has MWW topological structure, but also has interlayer hydrogen bonds similar to MCM-22 molecular sieves, and has the characteristics of MCM-22 molecular sieves, and the total specific surface area and total pore volume of the molecular sieve of the present invention are also significantly increased. In addition, the molecular sieve product prepared by the present invention has a lower stacking number and a smaller sheet thickness, and the stacking morphology of the molecular sieve is changed compared to the MCM-49 molecular sieve.
结合测试例1与测试例2的结果可以看出，对比例1在使用环己胺作为模板剂的情况下可以直接合成出结晶度较高、纯相的MWW结构分子筛，且可细分为MCM-49分子筛，但由于环己胺是无法构筑层间氢键的，因此环己胺作为模板剂只适用于合成MCM-49分子筛，无法合成其他种类MWW结构分子筛。对比例3用环己胺代替一部分六亚甲基亚胺作为复合模板剂也无法构筑足够的层间氢键，因此只能制备得到MCM-22分子筛和MCM-49分子筛的混合物，无法得到纯相的具有MCM-22结构的分子筛。Combining the results of Test Example 1 and Test Example 2, it can be seen that Comparative Example 1 can directly synthesize a MWW structure molecular sieve with high crystallinity and pure phase when using cyclohexylamine as a template, and can be subdivided into MCM-49 molecular sieve, but because cyclohexylamine cannot construct interlayer hydrogen bonds, cyclohexylamine is only suitable for synthesizing MCM-49 molecular sieves as a template, and other types of MWW structure molecular sieves cannot be synthesized. Comparative Example 3 uses cyclohexylamine to replace part of hexamethyleneimine as a composite template, and it is also impossible to construct sufficient interlayer hydrogen bonds, so only a mixture of MCM-22 molecular sieves and MCM-49 molecular sieves can be prepared, and a pure phase molecular sieve with MCM-22 structure cannot be obtained.
实施例6Example 6
本实施例提供了实施例1的分子筛产物在催化烷基化反应中的应用。This example provides the use of the molecular sieve product of Example 1 in a catalytic alkylation reaction.
取实施例1分子筛产品，空气氛围下540℃焙烧5h脱除模板剂。然后在1mol/L硝酸铵溶液80℃铵交换2h，再次在空气氛围下540℃焙烧4h，获得H型分子筛。The molecular sieve product of Example 1 was calcined at 540°C for 5 h in air atmosphere to remove the template, then ammonium exchanged in 1 mol/L ammonium nitrate solution at 80°C for 2 h, and calcined again at 540°C for 4 h in air atmosphere to obtain an H-type molecular sieve.
将90g上述H型分子筛与15g拟薄水铝石混合均匀，边混捏边逐渐加入55g硝酸溶液，挤条成型为φ2.0mm圆柱型催化剂，截断为长度2.5mm圆柱形催化剂。对催化剂进行常温阴干24h，然后在550℃焙烧6h，得到催化剂成品。90g of the above H-type molecular sieve and 15g of pseudo-boehmite were mixed evenly, and 55g of nitric acid solution was gradually added while kneading, and extruded into a φ2.0mm cylindrical catalyst, which was cut into a 2.5mm long cylindrical catalyst. The catalyst was dried in the shade at room temperature for 24h, and then calcined at 550℃ for 6h to obtain a finished catalyst.
取上述催化剂成品2g，装入固定床反应器中，通入苯与乙烯混合物。反应条件为：苯烯比5，反应温度330℃，反应压力1.4MPa，质量空速2.0h -1。 Take 2g of the finished catalyst and load it into a fixed bed reactor, and introduce a mixture of benzene and ethylene. The reaction conditions are: benzene-ethylene ratio 5, reaction temperature 330°C, reaction pressure 1.4MPa, mass space velocity 2.0h -1 .
反应结果为：反应500h后，烯转化率为99.99％，乙苯选择性96.21％。The reaction results are as follows: after 500 hours of reaction, the olefin conversion rate is 99.99% and the ethylbenzene selectivity is 96.21%.
实施例7Example 7
本实施例提供了实施例2的分子筛产物在催化烷基化反应中的应用。This example provides the use of the molecular sieve product of Example 2 in a catalytic alkylation reaction.
取实施例2分子筛产品，空气氛围下540℃焙烧5h脱除模板剂。然后在1mol/L硝酸铵溶液80℃铵交换2h，再次在空气氛围下540℃焙烧4h，获得H型分子筛。The molecular sieve product of Example 2 was calcined at 540°C for 5 h in air atmosphere to remove the template, then ammonium exchanged in 1 mol/L ammonium nitrate solution at 80°C for 2 h, and calcined again at 540°C for 4 h in air atmosphere to obtain H-type molecular sieve.
将90g上述H型分子筛与15g拟薄水铝石混合均匀，边混捏边逐渐加入55g硝酸溶液，挤条成型为φ2.0mm圆柱型催化剂，截断为长度2.5mm圆柱形催化剂。对催化剂进行常温阴干24h，然后在550℃焙烧6h，得到催化剂成品。90g of the above H-type molecular sieve and 15g of pseudo-boehmite were mixed evenly, and 55g of nitric acid solution was gradually added while kneading, and extruded into a φ2.0mm cylindrical catalyst, which was cut into a 2.5mm long cylindrical catalyst. The catalyst was dried in the shade at room temperature for 24h, and then calcined at 550℃ for 6h to obtain a finished catalyst.
取上述催化剂成品2g，装入固定床反应器中，通入苯与丙烯混合物。反应条件为：苯烯比4，反应温度150℃，反应压力2.5MPa，质量空速3.0h -1。 Take 2g of the finished catalyst and load it into a fixed bed reactor, and introduce a mixture of benzene and propylene. The reaction conditions are: benzene to propylene ratio 4, reaction temperature 150°C, reaction pressure 2.5MPa, mass space velocity 3.0h -1 .
反应结果为：反应300h后，烯转化率为99.97％，异丙苯选择性99.20％。The reaction results are as follows: after 300 hours of reaction, the olefin conversion rate is 99.97% and the isopropylbenzene selectivity is 99.20%.
实施例8Example 8
本实施例提供了实施例3的分子筛产物在催化烷基化反应中的应用。This example provides the use of the molecular sieve product of Example 3 in a catalytic alkylation reaction.
取实施例3分子筛产品，空气氛围下540℃焙烧5h脱除模板剂。然后在1mol/L硝酸铵溶液80℃铵交换2h，再次在空气氛围下540℃焙烧4h，获得H型分子筛。The molecular sieve product of Example 3 was calcined at 540°C for 5 h in air atmosphere to remove the template, then ammonium exchanged in 1 mol/L ammonium nitrate solution at 80°C for 2 h, and calcined again at 540°C for 4 h in air atmosphere to obtain an H-type molecular sieve.
将90g上述H型分子筛与15g拟薄水铝石混合均匀，边混捏边逐渐加入55g硝酸溶液，挤条成型为φ2.0mm圆柱型催化剂，截断为长度2.5mm圆柱形催化剂。对催化剂进行常温阴干24h，然后在550℃焙烧6h，得到催化剂成品。90g of the above H-type molecular sieve and 15g of pseudo-boehmite were mixed evenly, and 55g of nitric acid solution was gradually added while kneading, and extruded into a φ2.0mm cylindrical catalyst, which was cut into a 2.5mm long cylindrical catalyst. The catalyst was dried in the shade at room temperature for 24h, and then calcined at 550℃ for 6h to obtain a finished catalyst.
取上述催化剂成品2g，装入固定床反应器中，通入苯与正十二烯混合物。反应条件为：苯烯比15，反应温度150℃，反应压力3.0MPa，质量空速2.0h -1。 Take 2g of the finished catalyst and load it into a fixed bed reactor, and introduce a mixture of benzene and n-dodecene. The reaction conditions are: benzene to olefin ratio 15, reaction temperature 150°C, reaction pressure 3.0MPa, mass space velocity 2.0h -1 .
反应结果为：反应300h后，烯转化率为99.97％，2-烷基苯选择性42.01％。The reaction results are as follows: after 300 hours of reaction, the olefin conversion rate is 99.97% and the 2-alkylbenzene selectivity is 42.01%.
对比例4Comparative Example 4
本对比例提供了对比例1的分子筛产物在催化烷基化反应中的应用。This comparative example provides the use of the molecular sieve product of comparative example 1 in a catalytic alkylation reaction.
将对比例1的分子筛在空气氛围下540℃焙烧5h脱除模板剂。然后在1mol/L硝酸铵溶液80℃铵交换2h，再次在空气氛围下540℃焙烧4h，获得H型分子筛。The molecular sieve of comparative example 1 was calcined at 540°C for 5 hours in air atmosphere to remove the template, then ammonium exchanged in 1 mol/L ammonium nitrate solution at 80°C for 2 hours, and calcined again at 540°C for 4 hours in air atmosphere to obtain H-type molecular sieve.
将90g上述H型分子筛与15g拟薄水铝石混合均匀，边混捏边逐渐加入55g硝酸溶液，挤条成型为φ2.0mm圆柱型催化剂，截断为长度2.5mm圆柱形催化剂。对催化剂进行常温阴干24h，然后在550℃焙烧6h，得到催化剂成品。90g of the above H-type molecular sieve and 15g of pseudo-boehmite were mixed evenly, and 55g of nitric acid solution was gradually added while kneading, and extruded into a φ2.0mm cylindrical catalyst, which was cut into a 2.5mm long cylindrical catalyst. The catalyst was dried in the shade at room temperature for 24h, and then calcined at 550℃ for 6h to obtain a finished catalyst.
取上述催化剂成品2g，装入固定床反应器中，通入苯与正十二烯混合物。反应条件为：苯烯比15，反应温度150℃，反应压力3.0MPa，质量空速2.0h -1。 Take 2g of the finished catalyst and load it into a fixed bed reactor, and introduce a mixture of benzene and n-dodecene. The reaction conditions are: benzene to olefin ratio 15, reaction temperature 150°C, reaction pressure 3.0MPa, mass space velocity 2.0h -1 .
反应结果为：反应100h后，烯转化率为76.32％，2-烷基苯选择性45.03％。The reaction results are as follows: after 100 hours of reaction, the olefin conversion rate is 76.32%, and the 2-alkylbenzene selectivity is 45.03%.
将对比例4与实施例6至8的结果对比可以看出，实施例6至8中的催化剂具有更高的烯转化率和异丙苯选择性。原因在于：对比例1制备的MCM-49分子筛层间不具有氢键、各单层趋向于相互堆叠、形成缩合的氧桥键、层叠程度高；而各实施例制备的分子筛存在层间氢键，氢键以及用于构筑氢键的模板剂在层间具有位阻效应，可以避免分子筛各层之间的堆叠，则各实施例的分子筛中层叠程度低。由于实施例分子筛的层叠程度低于对比例1分子筛的层叠程度，因此实施例1至实施例3制备的分子筛片层厚度小于对比例1的MCM-49分子筛的片层厚度，单位质量催化剂暴露出的表面催化活性位点数量更多，不仅催化活性更高，并且也可避免在反应中因堵塞导致的失活问题、催化剂寿命更长。Comparing the results of Comparative Example 4 with those of Examples 6 to 8, it can be seen that the catalysts in Examples 6 to 8 have higher olefin conversion and isopropylbenzene selectivity. The reason is that the MCM-49 molecular sieve prepared in Comparative Example 1 does not have hydrogen bonds between layers, each monolayer tends to stack with each other, forms condensed oxygen bridge bonds, and has a high degree of stacking; while the molecular sieves prepared in each embodiment have interlayer hydrogen bonds, hydrogen bonds, and templates for building hydrogen bonds have steric effects between layers, which can avoid stacking between layers of the molecular sieves, and the molecular sieves in each embodiment have a low degree of stacking. Since the stacking degree of the embodiment molecular sieve is lower than that of the molecular sieve in Comparative Example 1, the thickness of the molecular sieve sheet prepared in Examples 1 to 3 is less than that of the MCM-49 molecular sieve in Comparative Example 1, and the number of surface catalytic active sites exposed by the catalyst per unit mass is more, not only the catalytic activity is higher, but also the deactivation problem caused by blockage in the reaction can be avoided, and the catalyst life is longer.
由上可知，本发明提供的制备方法可以在省略六亚甲基亚胺、哌啶、高哌嗪等传统模板剂的情况下，合成出具有层间氢键的MWW结构分子筛，该分子筛具有类似MCM-22分子筛的特性，并具有较高的催化活性。It can be seen from the above that the preparation method provided by the present invention can synthesize an MWW structured molecular sieve with interlayer hydrogen bonds while omitting traditional template agents such as hexamethyleneimine, piperidine, and homopiperazine. The molecular sieve has properties similar to those of the MCM-22 molecular sieve and has higher catalytic activity.

Claims (18)

  1. 一种MWW结构分子筛的制备方法，其中，该制备方法包括：A method for preparing a MWW structured molecular sieve, wherein the preparation method comprises:
    将铝源、水、碱源、第一模板剂、第二模板剂、硅源和晶种混合形成凝胶，使凝胶晶化，得到所述MWW结构分子筛；Mixing an aluminum source, water, an alkali source, a first template, a second template, a silicon source and a seed to form a gel, and crystallizing the gel to obtain the MWW structure molecular sieve;
    其中，所述第一模板剂包括环己胺，所述第二模板剂包括二异丙胺、二正丁胺、二异丁胺、1,4-二氮杂二环[2.2.2]辛烷、1,6-己二胺、N,N,N,N-四甲基-1,6-己二胺中的一种或两种以上的组合。The first template agent includes cyclohexylamine, and the second template agent includes one or a combination of two or more of diisopropylamine, di-n-butylamine, diisobutylamine, 1,4-diazabicyclo[2.2.2]octane, 1,6-hexanediamine, and N,N,N,N-tetramethyl-1,6-hexanediamine.
  2. 根据权利要求1所述的制备方法，其中，所述第一模板剂与第二模板剂的摩尔比为0.5-20:1。The preparation method according to claim 1, wherein the molar ratio of the first template to the second template is 0.5-20:1.
  3. 根据权利要求1所述的制备方法，其中，碱源记为MOH，硅源以SiO 2计，铝源以Al 2O 3计，碱源以M 2O计，第一模板剂与第二模板剂之和记为T，所述凝胶的化学组成满足以下摩尔比范围： The preparation method according to claim 1, wherein the alkali source is recorded as MOH, the silicon source is calculated as SiO 2 , the aluminum source is calculated as Al 2 O 3 , the alkali source is calculated as M 2 O, the sum of the first template and the second template is recorded as T, and the chemical composition of the gel satisfies the following molar ratio range:
    Al 2O 3/SiO 2＝0.005-0.05，M 2O/SiO 2＝0.03-0.50，T/SiO 2＝0.10-0.75，H 2O/SiO 2＝8-120； Al 2 O 3 /SiO 2 =0.005-0.05, M 2 O/SiO 2 =0.03-0.50, T/SiO 2 =0.10-0.75, H 2 O/SiO 2 =8-120;
    晶种以干基质量计，晶种与硅源的质量比满足：晶种/SiO 2＝0.01-0.25。 The seed crystals are calculated on a dry basis, and the mass ratio of the seed crystals to the silicon source satisfies: seed crystals/SiO 2 = 0.01-0.25.
  4. 根据权利要求3所述的制备方法，其中，所述凝胶的化学组成满足以下摩尔比范围：H 2O/SiO 2＝15-120。 The preparation method according to claim 3, wherein the chemical composition of the gel satisfies the following molar ratio range: H 2 O/SiO 2 = 15-120.
  5. 根据权利要求1所述的制备方法，其中，所述晶化的温度为120-170℃，所述晶化的时间为12-120h。The preparation method according to claim 1, wherein the crystallization temperature is 120-170°C and the crystallization time is 12-120h.
  6. 根据权利要求1所述的制备方法，其中，所述硅源包括二氧化硅、硅酸盐、硅酸酯中的一种或两种以上的组合。The preparation method according to claim 1, wherein the silicon source comprises one or a combination of two or more of silicon dioxide, silicate, and silicate ester.
  7. 根据权利要求1或6所述的制备方法，其中，所述硅源包括硅溶胶、固体硅胶、白炭黑、水玻璃、正硅酸乙酯中的一种或两种以上的组合。The preparation method according to claim 1 or 6, wherein the silicon source comprises one or a combination of two or more of silica sol, solid silica gel, white carbon black, water glass, and tetraethyl orthosilicate.
  8. 根据权利要求1所述的制备方法，其中，所述铝源包括偏铝酸盐、硫酸铝、氧化铝、拟薄水铝石中的一种或两种以上的组合。The preparation method according to claim 1, wherein the aluminum source comprises one or a combination of two or more of aluminate, aluminum sulfate, alumina, and pseudo-boehmite.
  9. 根据权利要求1所述的制备方法，其中，所述晶种为具有MWW拓扑结构的分子筛。The preparation method according to claim 1, wherein the seed crystal is a molecular sieve having an MWW topological structure.
  10. 根据权利要求1所述的制备方法，其中，所述晶种包括MCM-22分子筛和/或MCM-49分子筛。The preparation method according to claim 1, wherein the seed crystal comprises MCM-22 molecular sieve and/or MCM-49 molecular sieve.
  11. 根据权利要求1所述的制备方法，其中，所述碱源包括氢氧化钠和/或氢氧化钾。The preparation method according to claim 1, wherein the alkali source comprises sodium hydroxide and/or potassium hydroxide.
  12. 根据权利要求1-11任一项所述的制备方法，其中，该制备方法包括：The preparation method according to any one of claims 1 to 11, wherein the preparation method comprises:
    将铝源、水、碱源、第一模板剂、第二模板剂混合得到中间溶液，向所述中间溶液中加入硅源和晶种，混合形成凝胶，使凝胶晶化，得到所述MWW结构分子筛。An aluminum source, water, an alkali source, a first template agent, and a second template agent are mixed to obtain an intermediate solution, a silicon source and a seed crystal are added to the intermediate solution, the mixture is mixed to form a gel, and the gel is crystallized to obtain the MWW structure molecular sieve.
  13. 一种MWW结构分子筛，其是由权利要求1-12任一项所述的制备方法得到的。A MWW structured molecular sieve obtained by the preparation method according to any one of claims 1 to 12.
  14. 根据权利要求13所述的MWW结构分子筛，其中，所述MWW结构分子筛的比表面积为500m 2·g以上。 The MWW structured molecular sieve according to claim 13, wherein the specific surface area of the MWW structured molecular sieve is greater than 500 m 2 ·g.
  15. 根据权利要求13所述的MWW结构分子筛，其中，所述MWW结构分子筛的微孔比表面积为350m 2·g以上，所述MWW结构分子筛的介孔比表面积为140m 2·g以上。 The MWW structured molecular sieve according to claim 13, wherein the micropore specific surface area of the MWW structured molecular sieve is greater than 350 m 2 ·g, and the mesopore specific surface area of the MWW structured molecular sieve is greater than 140 m 2 ·g.
  16. 根据权利要求13所述的MWW结构分子筛，其中，所述MWW结构分子筛的孔体积为0.60cm 3·g以上。 The MWW structured molecular sieve according to claim 13, wherein the pore volume of the MWW structured molecular sieve is greater than 0.60 cm 3 ·g.
  17. 根据权利要求13所述的MWW结构分子筛，其中所述MWW结构分子筛的微孔孔体积为0.16cm 3·g以上。 The MWW structured molecular sieve according to claim 13, wherein the micropore volume of the MWW structured molecular sieve is greater than 0.16 cm 3 ·g.
  18. 权利要求13-17任一项所述的MWW结构分子筛在烷基化反应、异构化反应或裂化反应催化中的应用。Use of the MWW structured molecular sieve according to any one of claims 13 to 17 in catalysis of alkylation reactions, isomerization reactions or cracking reactions.
PCT/CN2022/138658 2022-11-08 2022-12-13 Mww-structured molecular sieve, preparation method therefor and use thereof WO2024098501A1 (en)

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