CN105984879A - MWW-structure molecular sieve and preparation method thereof - Google Patents

MWW-structure molecular sieve and preparation method thereof Download PDF

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CN105984879A
CN105984879A CN 201510046936 CN201510046936A CN105984879A CN 105984879 A CN105984879 A CN 105984879A CN 201510046936 CN201510046936 CN 201510046936 CN 201510046936 A CN201510046936 A CN 201510046936A CN 105984879 A CN105984879 A CN 105984879A
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molecular
sieve
adsorption
desorption
nitrogen
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CN 201510046936
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邢恩会
石艳春
谢文华
张凤美
慕旭宏
刘强
王卫东
秦凤明
舒兴田
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中国石油化工股份有限公司
中国石油化工股份有限公司石油化工科学研究院
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Abstract

The invention discloses a MWW-structure molecular sieve, wherein a BJH curve of nitrogen adsorption-desorption of the molecular sieve shows that nitrogen desorption quantity at 3.8 +/- 0.5 nm is 0.01-0.10 cm<3>/g; in addition, the molecular sieve is not less than 35 [mu]mol/g in adsorption quantity of 2,4,6-trimethylpyridine after adsorption at 20 DEG C and desorption at 200 DEG C.

Description

一种MWW结构分子筛及其制备方法 One kind of zeolite MWW structure and preparation method

技术领域 FIELD

[0001] 本发明是关于一种分子筛及其制备方法,更具体地说是关于一种Mffff结构分子筛及其制备方法。 [0001] The present invention relates to a method for preparing molecular sieves and, more particularly relates to a method for preparing molecular sieves and Mffff structure.

背景技术 Background technique

[0002] Mffff 结构分子筛包括MCM-22、MCM-49、MCM-36、MCM-56、SSZ-25、ITQ-1、ITQ-2 和UZM-8等分子筛。 [0002] Mffff structure molecular sieves include MCM-22, MCM-49, MCM-36, MCM-56, SSZ-25, ITQ-1, ITQ-2, and the like UZM-8 zeolite. 1990年,Mobil公司首次以六亚甲基亚胺为模板剂水热合成MCM-22分子筛(US,4954325,1990),并于1994年首次解析出其结构,并以此命名为MWW结构分子筛,因此具有Mffff拓扑结构的层状分子筛又称为MCM-22族分子筛。 1990, the first time to Mobil hexamethyleneimine hydrothermal synthesis template zeolite MCM-22 (US, 4954325,1990), and in 1994 for the first time by parsing the structure, and is so named zeolite MWW structure, Thus Mffff layered molecular sieve has the topology of MCM-22 family, also known as molecular sieves.

[0003] Mffff结构分子筛具有两套互不交叉的独立孔道:层内孔径为0.40X0.59nm的椭圆形1MR 二维正弦孔道;层间为0.71X0.71X1.82nm的12MR超笼,且以0.40X0.54nm的1MR开口与外界相通;另外在其表面还分布一些12MR孔穴,是超笼的一半,深度约为0.91nm(Science, 1994,264:1910)。 [0003] Mffff zeolite structure having two separate channels do not cross: the pore size of the inner layer of the elliptical 0.40X0.59nm 1MR dimensional sinusoidal channels; 0.71X0.71X1.82nm interlayer of the supercages 12MR, and 0.40 1MR opening communicating with the outside X0.54nm; additionally also be distributed on the surface thereof a number of apertures 12MR, super cage half a depth of about 0.91nm (Science, 1994,264: 1910). MWW结构分子筛因其独特的孔道结构和物化性质在烷基化(US,5600048, 1997)、芳构化(催化学报,2002,23:24)、催化裂化(J.Catal.,1997,167:438)和异构化(J.Catal.,1996,158:561)等反应中具有广阔的应用前景。 Zeolite MWW structure because of its unique pore structure and physicochemical properties of the alkylation (US, 5600048, 1997), aromatization (Journal of Catalysis, 2002, 23: 24), cracking (J.Catal, 1997,167.: 438) and isomerization (J.Catal, 1996,158:. 561) and other reactions have broad application prospects.

[0004] MWW结构分子筛虽然具有较高的微孔比表面积,但是由于十元环孔径的限制,超笼内的酸性位很难得到利用。 [0004] MWW zeolite structure while having a high specific surface area of ​​micropores, but due to the limitations of 10-membered ring pore, supercages acid sites is difficult to be utilized. 为了使超笼内的酸性位得到充分利用,很多研究致力于在MffW分子筛内引入介孔或使层内十元环正弦孔道和层间超笼相通,从而改善内部扩散。 In order to supercages acid sites are fully utilized, many researches are devoted introduced in the mesoporous molecular sieve or MffW communication between the ultrafine cage 10-membered ring channels sine inner layer and the layer, thereby improving internal diffusion.

[0005] 与三维分子筛相比,Mffff等层状分子筛因为层间结合不紧密而表现出结构的多样性和可塑性,并且在合成之后仍可进一步进行结构修饰。 [0005] Compared with three-dimensional molecular sieve, Mffff like layered zeolite as binding does not close the interlayer exhibits plasticity and diversity of structures and still further structural modification after synthesis. 比如对MCM-22P进行层间溶胀,剥离(部分剥离或完全剥离),以及插层、扩孔及柱撑等后处理,可以得到既保持MWW基本层结构单元,又具有大孔径和高比表面积的催化材料,如MCM-56同系物,MCM-36,ITQ-2和IEZ系列分子筛。 Example of MCM-22P for interlayer swelling, peeling (partially peeled or totally peeled off), and after the intercalation, reaming and pillared other treatment, can be obtained while maintaining the MWW base layer structural units, but also has a catalytic large pore size and high specific surface area materials, such as MCM-56 homolog, MCM-36, ITQ-2 zeolite and IEZ series.

[0006] 利用NaOH处理分子筛生成大量介孔的文献及其综述非常之多,它们通过利用NaOH的碱性来实现可控的溶硅,从而在分子筛晶体内部或晶体间生成大量的介孔,从而达到提高扩散性能的目的。 Document [0006] with NaOH treated zeolite and a large amount of mesopores review very much, which is achieved by the silicon controlled with NaOH solution alkaline, thereby generating a large number of mesopores within and between the molecular sieve crystals or crystals, as to improve the diffusion properties. 吴鹏等以焙烧后的MCM-22分子筛为原料,采用有机胺保护高硅Mffff结构分子筛的骨架选择性溶硅,成功的制备了介孔的MCM-22分子筛。 Wu Peng the like to calcined MCM-22 zeolite as raw material, organic solvent selective silicon backbone amine protecting high-silica molecular sieve structure Mffff successful preparation of mesoporous MCM-22 molecular sieve. 与单独用NaOH溶硅会造成骨架坍塌相比,该方法在三维结构与二维层状结构转化的同时引入了孔径在20nm左右的晶内介孔,分子筛结晶度也保持完好,分子筛的硅铝比由原料的60脱硅到20〜30。 NaOH solution and the resulting silicon alone will collapse the skeleton compared to the three-dimensional structure and method, while a two-dimensional layered structure intragranular transformation is introduced via-hole diameter of about 20nm, zeolite crystallinity remains intact, silicoaluminophosphate molecular sieves off ratio of from 60 to 20 to 30 starting material silicon. 徐龙伢等仅利用NaOH对焙烧前后的MCM-22分子筛进行处理,同样也可以显著增加MCM-22分子筛的介孔。 Xu Longya only with NaOH and the like before and after the firing process MCM-22 molecular sieves, can also significantly increase the mesoporous MCM-22 molecular sieves.

[0007] Mffff结构分子筛的后处理多集中于无机碱NaOH处理,由于NaOH的强碱性,因而脱硅可控程度较差。 After [0007] Mffff treated zeolite structure more concentrated NaOH and inorganic bases due to the strong alkaline NaOH and thus poor off silicon controlled extent. 虽然可以通过引入有机胺选择性地保护分子筛骨架,但是NaOH对分子筛骨架的破坏仍是不可避免。 While the molecular sieve framework may be protected by selective introduction of an organic amine, but damage to the molecular sieve framework NaOH is still unavoidable.

发明内容 SUMMARY

[0008] 本发明的目的之一是提供一种有别于现有技术、具有特殊物化性质的MWW结构分子筛。 [0008] One object of the present invention is to provide a different from the prior art, MWW structure having specific physicochemical properties of the molecular sieve.

[0009] 本发明的目的之二是提供一种制备上述有别于现有技术的MWW结构分子筛的方法。 [0009] Second object of the present invention is to provide a method different from the above-described prior art zeolite MWW structure prepared.

[0010] 发明人在大量试验的基础上意外发现,Mffff结构分子筛在经历有别于现有技术的碱性物质处理过程之后得到的分子筛样品,其形貌由原“花朵状”紧密堆积转变为片状松散堆积,混乱程度显著增加,分子筛晶粒越分散,比表面积和孔体积有所增加,同时具有更低的Na+含量,表现为具有不同于常规MWW结构分子筛的特定的氮气吸附-脱附的BJH曲线3.8±0.5nm处的氮气脱附量以及特定的2,4,6-三甲基吡啶的吸附量。 [0010] The inventors have surprisingly found that in a large number of tests on the sample Mffff zeolite molecular sieve structure after undergoing a basic substance is different from the prior art process obtained, the morphology original "flower-shaped" tightly packed into a sheet loosely packed, a significant increase in the degree of confusion, the zeolite crystal dispersion, increased surface area and pore volume, while having a lower content of Na +, appear to have the nitrogen adsorption specific MWW structure different from the conventional molecular sieve - desorption 3.8 ± desorption curves of nitrogen and the amount of 0.5nm BJH adsorption amount at the specific 2,4,6-trimethyl pyridine. 基于此,形成本发明。 Based on this, the present invention is formed.

[0011] 为了实现目的之一,本发明提供的MWW结构分子筛,其特征在于该分子筛的氮气吸附-脱附的BJH曲线显示在3.8±0.5nm处的氮气脱附量为0.01〜0.10cm3/g,且其20°C吸附、200°C脱附后的2,4,6-三甲基吡啶的吸附量为彡35 ymol/g。 [0011] In order to achieve one of the objects, MWW zeolite structure of the present invention provides, wherein the molecular sieve nitrogen adsorption - desorption curve shows the BJH nitrogen desorption amount is at 3.8 ± 0.5nm 0.01~0.10cm3 / g , which is 20 ° C and adsorption, adsorption and desorption after 200 ° C for 2,4,6-trimethylpyridine San 35 ymol / g.

[0012] 为了实现目的之二,本发明还提供了一种制备方法,其特征在于将原料MWW结构分子筛、含氮有机碱RU有机胺R2、去离子水混合均匀得到摩尔比为H20/Si02= 5〜100、Rl/Si02= 0.01〜5、R2/Si02= O〜I的混合物,并将该混合物在100〜180°C下晶化5〜72h并回收,其中,所说的含氮有机碱Rl,选自四甲基氢氧化铵、四乙基氢氧化铵、四丙基氢氧化铵、二甲基二乙基氢氧化铵、一甲基三乙基氢氧化铵、一甲基三丙基氢氧化铵、二甲基二丙基氢氧化铵、二乙基二丙基氢氧化铵和一乙基三丙基氢氧化铵中的至少一种,所说的有机胺R2,选自五亚甲基亚胺、六亚甲基亚胺、七亚甲基亚胺、1,4-二氮环庚烷、环庚烷胺、环己烷胺、环戊胺、苯胺、哌啶和哌嗪中的至少一种。 [0012] In order to achieve the two purposes, the present invention also provides a method for preparing, characterized in that the raw material zeolite MWW structure, a nitrogen-containing organic bases RU organic amine R2, deionized water were mixed uniformly to obtain a molar ratio of H20 / Si02 = 5~100, Rl / Si02 = 0.01~5, R2 / Si02 = O~I mixture, and the mixture was stirred at 100~180 ° C and recovering the crystallized 5~72h, wherein said nitrogen-containing organic bases Rl, is selected from tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, dimethyl diethyl ammonium hydroxide, monomethyl-triethyl ammonium hydroxide, methyl tripropylene a ammonium hydroxide, dimethyl dipropyl ammonium hydroxide, diethyl-dipropyl ammonium hydroxide, and a three-propyl ethyl ammonium hydroxide at least one of said organic amine R2, is selected from five methylene imine, hexamethylene imine, heptamethylene imine, 1,4-N cycloheptane, cycloheptane amine, cyclohexane amine, cyclopentylamine, aniline, piperidine and of at least one piperazine.

[0013] 本发明提供的MWW结构分子筛,形貌为片状松散堆积,混乱程度显著增加,分子筛晶粒更分散。 [0013] MWW structure of the present invention provides a molecular sieve, a sheet loosely packed morphology, a significant increase in the degree of disorder, and more dispersed grain sieve. 所提供的制备方法,是在维持MWW结构分子筛高结晶度的前提下,实现其形貌改变,形貌由原“花朵状”聚集转变为片状松散堆积;同时处理后的分子筛样品的比表面积和孔体积均提高,该技术效果完全不同于现有技术以牺牲结晶度而实现分子筛的扩孔的处理方式。 The method of preparation is provided, is a molecular sieve under the premise of maintaining a high degree of crystallinity MWW structure, to achieve the morphology changes, the original topography "flower-shaped" loosely packed aggregates into a sheet; specific surface area of ​​the molecular sieve sample after treatment at the same time and pore volume were increased, the technical effect is completely different from the prior art is achieved at the expense of the degree of crystallinity of the molecular sieve treatment counterbore.

附图说明 BRIEF DESCRIPTION

[0014] 图1为对比例I和实施例1所得的D-1、A-1-1和A_l_2样品的SEM图。 [0014] FIG. 1 is a SEM image of the D-1, A-1-1, and Comparative Examples I and A_l_2 samples obtained in Example 1 of.

[0015] 图2为对比例2和实施例2所得的D-2、A_2_l和A-2-2样品的SEM图。 [0015] FIG. 2 is a Comparative Example 2, and D-2, A_2_l and SEM samples A-2-2 obtained in Example 2 FIG.

[0016] 图3为对比例3和实施例3所得的D-3、A_3_l和A-3-2样品的SEM图。 [0016] FIG. 3 is a comparative embodiment 3 and obtained in Example 3 D-3, A_3_l and SEM samples A-3-2 in FIG.

[0017] 图4为对比例3和实施例4所得的D-3、A_4_l和A_4_2样品的SEM图。 [0017] FIG. 4 is a Comparative Example 3 and 4 obtained D-3, A_4_l and SEM samples A_4_2 FIG.

[0018] 图5为对比例3和实施例5所得的D-3、A_5_l和A-5-2样品的SEM图。 [0018] FIG 5 is a SEM image of Example 5 and Comparative Example 3 obtained in Example D-3, A_5_l A-5-2 and sample.

[0019] 图6为对比例3和实施例6所得的D-3、A_6_l和A-6-2样品的SEM图。 [0019] FIG. 6 is a SEM image of Example 6 and Comparative Example 3 obtained D-3, A_6_l A-6-2 and sample.

[0020] 图7为对比例3和实施例7所得的D-3、A_7_l和A-7-2样品的SEM图。 [0020] FIG. 7 is a comparative embodiment 3 and 7 obtained in Example D-3, A_7_l and SEM samples A-7-2 in FIG.

[0021 ] 图8为对比例3和实施例8所得的D-3、A_8_l和A-8-2样品的SEM图。 [0021] FIG. 8 is a Comparative Example 3 and Example 8 obtained D-3, A_8_l and SEM samples A-8-2 in FIG.

[0022] 图9为对比例3和实施例9所得的D-3、A_9_l和A_9_2样品的SEM图。 [0022] FIG. 9 is a Comparative Example 3 and Example 9 is obtained D-3, A_9_l and SEM samples A_9_2 FIG.

[0023] 图10为对比例3和实施例10所得的D-3、A-10-1和A-10-2样品的SEM图。 [0023] FIG 10 is a SEM image of Example 10 and Comparative Example 3 obtained in Example D-3, A-10-1 and A-10-2 sample.

[0024] 图11为对比例4和实施例11所得的D-4、A-11 -1和A-11 -2样品的SEM图。 [0024] Figure 11 is a SEM image of Example 11 and Comparative Example 4 obtained in Example D-4, A-11 A-11 -2 and -1 of the sample.

[0025] 图12为对比例4和实施例12所得的D_4、A-12-1和A-12-2样品的SEM图。 [0025] FIG. 12 is obtained in Example 12 D_4, A-12-1 and A-12-2 SEM sample 4 and comparative embodiment of FIG.

[0026] 图13为对比例3、对比例5和对比例6所得的D_3、D_5和D_6样品的SEM图。 [0026] FIG. 13 is a Comparative Example 3, Comparative Examples 5 and 6 Comparative SEM images of the resulting D_3, D_5 and D_6 sample.

具体实施方式 detailed description

[0027] —种MWW结构分子筛,其特征在于该分子筛的氮气吸附-脱附的BJH曲线显示在3.8±0.5nm处的氮气脱附量为0.01〜0.10cm3/g,且其20°C吸附、200°C脱附后的2,4,6-三甲基吡啶的吸附量为彡35 ymol/g。 [0027] - molecular sieves MWW structure types, wherein the molecular sieve nitrogen adsorption - desorption curve is shown in the BJH nitrogen desorption amount is at 3.8 ± 0.5nm 0.01~0.10cm3 / g, which is 20 ° C and adsorption, 2,4,6-collidine adsorption of 200 ° C after the desorption of San 35 ymol / g.

[0028] 本发明的MWW结构分子筛,具有特定的氮气吸附-脱附参数特征,其氮气吸附-脱附的BJH曲线显示在3.8±0.5nm处的氮气脱附量为0.01〜0.10cm3/g,而现有技术常规水热合成的MWW分子筛的氮气吸附-脱附的BJH曲线显示在3.Snm处的氮气脱附量多0.20cm3/g。 [0028] MWW structure of the present invention, molecular sieves having a specific nitrogen adsorption - desorption characteristic parameters, which nitrogen adsorption - desorption curve shows BJH nitrogen desorption amount is at 3.8 ± 0.5nm 0.01~0.10cm3 / g, whereas conventional prior art MWW zeolite hydrothermal synthesis nitrogen adsorption - BJH desorption curve is shown in the desorption amount of nitrogen at a plurality 3.Snm 0.20cm3 / g. 氮气脱附量量越少,则说明分子筛晶粒越分散。 The less the amount of nitrogen desorbed, then more dispersed grain sieve. BJH曲线显示在3.Snm处的氮气脱附量的测试方法是在静态氮吸附仪上进行,测量得到净化样品在不同比压P/PC条件下对氮气的吸附量。 BJH curve is displayed on a static nitrogen Sorption of nitrogen in the desorption amount of the test method at 3.Snm, measured by adsorption of nitrogen gas purge samples at different pressure ratio P / PC conditions.

[0029] 本发明的MWW结构分子筛,除了具有氮气吸附-脱附的BJH曲线显示在 [0029] MWW zeolite structure of the present invention, in addition to having a nitrogen adsorption - BJH desorption curve is shown in

3.8±0.5nm处的氮气脱附量为0.01〜0.10cm3/g这一特定的技术特征外,还具有特定的2,4,6-三甲基吡啶吸附量,其吸附量彡35 ymol/g。 The amount of nitrogen desorbed at 3.8 ± 0.5nm is 0.01~0.10cm3 / g in this specific technical features, but also has a specific adsorption 2,4,6-picoline, San adsorption capacity 35 ymol / g . 2,4,6-三甲基吡啶吸附量越多,则表明分子筛活性中心的可接近性越好。 More 2,4,6-collidine adsorption amount indicates the better accessibility of the active sites of the molecular sieve. 传统水热合成的MWW结构分子筛,其吸附量均小于35 μmol/go 2,4,6-三甲基吡啶的吸附量特性参数是将分子筛样品压成10至20mg的自撑片,置于原位池中,于20°C吸附2,4,6-三甲基吡啶,并于200°C脱除物理吸附的2,4,6-三甲基吡啶,由傅里叶变换红外光谱测得的。 Conventional hydrothermal synthesis of MWW structure molecular sieve adsorption capacity of less than 35 μmol / adsorption characteristic parameter go 2,4,6- trimethylpyridine molecular sieve is 10 to 20mg sample is pressed into self-supporting sheet, placed on the original bit cell, at 20 ° C 2,4,6-collidine adsorption, and at 200 ° C to remove physically adsorbed 2,4,6-collidine by Fourier transform infrared Spectroscopy was measured of.

[0030] 本发明的MWW结构分子筛,氮气吸附-脱附的BJH曲线显示在3.8±0.5nm处的氮气脱附量优选为0.01〜0.08cm3/g,且其20°C吸附、200°C脱附后的2,4,6-三甲基吡啶的吸附量为40〜60ymol/g。 [0030] MWW zeolite structure of the present invention, the nitrogen adsorption - BJH desorption curve is shown in the desorption amount of nitrogen is preferably at 3.8 ± 0.5nm is 0.01~0.08cm3 / g, which is 20 ° C and adsorption, 200 ° C de adsorption after attachment of 2,4,6-collidine 40~60ymol / g. 更优选的,氮气吸附-脱附的BJH曲线显示在3.8±0.5nm处的氮气脱附量为0.01〜0.05cm3/g,且其20°C吸附、200°C脱附后的2,4,6-三甲基吡啶的吸附量为40〜50 ymol/g。 More preferably, the nitrogen adsorption - BJH desorption curve is shown in the desorption amount of nitrogen is at 3.8 ± 0.5nm 0.01~0.05cm3 / g, which is 20 ° C and adsorption, 2,4 desorbed after 200 ° C, 6- trimethylpyridine adsorption amount of 40~50 ymol / g.

[0031] 通过SEM电镜照片可以看出,本发明的分子筛与现有技术常规水热合成的分子筛的堆积形貌有很大的不同。 [0031] As can be seen by SEM electron micrographs, stacking morphology of the zeolite molecular sieves according to the present invention and the prior art conventional hydrothermal synthesis are very different. 本发明中的分子筛形貌呈现片状松散堆积,而现有技术常规水热合成的MWW分子筛的堆积形貌,为较为规则的“花朵”状和“莲座”状为主、堆积程度较为规整。 Zeolite morphology of the sheet in the present invention exhibits a loosely packed, whereas the conventional prior art MWW zeolite hydrothermal synthesis stacking morphology, the "flower" shape more regular and "rosette" shape-based, the degree of accumulation is more regular.

[0032] 本发明还进一步提供了上述本发明的MWW结构分子筛的制备方法,其特征在于将原料MWW结构分子筛、含氮有机碱R1、有机胺R2、去离子水混合均匀得到摩尔比为H20/Si02=5〜100、R1/Si02= 0.01〜5、R2/Si02= O〜I的混合物,并将该混合物在100〜180°C下晶化5〜72h并回收,其中,所说的含氮有机碱R1,选自四甲基氢氧化铵、四乙基氢氧化铵、四丙基氢氧化铵、二甲基二乙基氢氧化铵、一甲基三乙基氢氧化铵、一甲基三丙基氢氧化铵、二甲基二丙基氢氧化铵、一乙基三甲基氢氧化铵、二乙基二丙基氢氧化铵、一乙基三丙基氢氧化铵、一丙基三甲基氢氧化铵和一丙基三乙基氢氧化铵中的至少一种,所说的有机胺R2,选自五亚甲基亚胺、六亚甲基亚胺、七亚甲基亚胺、1,4-二氮环庚烷、环庚烷胺、环己烷胺、环戊胺、苯胺、哌啶和哌嗪中的至少一种。 [0032] The present invention further provides a method for preparing an MWW structure of the molecular sieves of the present invention is characterized in that the raw material zeolite MWW structure, a nitrogen-containing organic bases R1, organic amine R2, deionized water were mixed uniformly to obtain a molar ratio of H20 / 5~100, R1 / Si02 = 0.01~5, R2 / Si02 = Si02 = O~I mixture, and the mixture was stirred at 100~180 ° C and recovering the crystallized 5~72h, wherein said nitrogen-containing organic bases R1, is selected from tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, dimethyl diethyl ammonium hydroxide, monomethyl-triethyl ammonium hydroxide, monomethyl tripropyl ammonium hydroxide, dimethyl dipropyl ammonium hydroxide, an ethyl trimethyl ammonium hydroxide, diethyl-dipropyl ammonium hydroxide, an ammonium hydroxide, tripropyl ethyl, a propyl trimethyl ammonium hydroxide and at least one of a propyl-triethyl ammonium hydroxide, said organic amine R2, imines selected pentamethylene, hexamethylene imine, heptamethyleneimino amine, 1,4-cycloheptane nitrogen, at least one amine cycloheptane, cyclohexane amine, cyclopentylamine, aniline, piperidine and piperazine in.

[0033] 所说的混合物,优选的摩尔比为H20/Si02= 5〜50、Rl/Si02= 0.05〜0.5、R2/S12= O 〜0.5,更优选的摩尔比为H20/Si02= 10 〜25、Rl/Si02= 0.05 〜0.2、R2/Si02=0.1〜0.3 ;所说的晶化是优选在为140〜160°C下进行8〜36h,更优选是在150°C晶化时间8〜24h。 [0033] said mixture, the preferred molar ratio of H20 / Si02 = 5~50, Rl / Si02 = 0.05~0.5, R2 / S12 = O ~0.5, more preferably a molar ratio of H20 / Si02 = 10 ~25 , Rl / Si02 = 0.05 ~0.2, R2 / Si02 = 0.1~0.3; said crystallization is preferably carried out at 8~36h of 140~160 ° C, more preferably at 150 ° C the crystallization time 8~24h .

[0034] 所说的含氮有机碱R1,选自四甲基氢氧化铵、四乙基氢氧化铵、四丙基氢氧化铵、二甲基二乙基氢氧化铵、一甲基三乙基氢氧化铵、一甲基三丙基氢氧化铵、二甲基二丙基氢氧化铵、一乙基三甲基氢氧化铵、二乙基二丙基氢氧化铵、一乙基三丙基氢氧化铵、一丙基三甲基氢氧化铵和一丙基三乙基氢氧化铵等季铵碱中的至少一种,优选的含氮有机碱Rl为四乙基氢氧化铵、二甲基二乙基氢氧化铵的至少一种。 [0034] The nitrogen-containing organic bases of said R1, is selected from tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, dimethyl diethyl ammonium hydroxide, a triethyl methyl ammonium hydroxide, a methyl tripropyl ammonium hydroxide, dimethyl dipropyl ammonium hydroxide, an ethyl trimethyl ammonium hydroxide, diethyl-dipropyl ammonium hydroxide, an ethyl tripropoxy ammonium hydroxide, an ammonium hydroxide, trimethylammonium and triethylammonium a propyl ammonium hydroxide of at least one, preferably a nitrogen-containing organic base is a quaternary ammonium hydroxide Rl tetraethyl ammonium hydroxide, bis methyl diethyl ammonium hydroxide of at least one. 所说的有机胺R2,选自五亚甲基亚胺、六亚甲基亚胺、七亚甲基亚胺、1,4-二氮环庚烷、环庚烷胺、环己烷胺、环戊胺、苯胺、哌啶、哌嗪中的至少一种,优选的有机胺R2为六亚甲基亚胺、苯胺、哌啶、哌嗪中的至少一种。 Said organic amine R2, imines selected pentamethylene, hexamethylene imine, heptamethylene imine, 1,4-N cycloheptane, cycloheptane amines, amine cyclohexane, cyclopentylamine, aniline, piperidine, piperazine, at least one, preferably R2 is an organic amine hexamethyleneimine, aniline, piperidine, piperazine is at least one. 在更优选的情况下,所说的含氮有机碱Rl为四乙基氢氧化铵和/或二甲基二乙基氢氧化铵,同时有机胺R2为六亚甲基亚胺和/或哌啶。 In the more preferred case, nitrogen-containing organic bases of said Rl is tetraethyl ammonium hydroxide and / or dimethyl diethyl ammonium hydroxide, and organic amines R2 is hexamethyleneimine and / or piperazine pyridine.

[0035] 本发明制备方法中,所说的原料MWW结构分子筛选自未经焙烧脱除模板剂和/或经过焙烧脱除模板剂的MWW结构分子筛,其中优选的是未经焙烧脱除模板剂的。 [0035] The production method of the present invention, said molecular sieve material is selected from the unfired structure of MWW remove the templating agent, and / or calcined zeolite MWW structure to remove the templating agent, preferably wherein the removal of the templating agent is unfired of. 所说的原料MWW 结构分子筛可以是MCM-22 (US4954325, Mobil/CN103771435A, RIPP)、MCM-49(US5236575, Mobil)、MCM-56(US5362697, Mobil)、SSZ-25(US5202014, Chevron)和UZM-8 (US 6756030B1, UOP)等各种直接水热合成的MWW结构硅铝分子筛,也可以是ITQ-2和MCM-36等对MCM-22P进行处理而得到的Mffff结构分子筛。 MWW structure of said molecular sieve material may be a MCM-22 (US4954325, Mobil / CN103771435A, RIPP), MCM-49 (US5236575, Mobil), MCM-56 (US5362697, Mobil), SSZ-25 (US5202014, Chevron) and UZM -8 (US 6756030B1, UOP) and other direct hydrothermal synthesis of MWW structure silicoaluminophosphate molecular sieve, the molecular sieve structure may be Mffff ITQ-2 and MCM-36 MCM-22P, etc. for processing obtained. 尽管对ITQ-2和MCM-36分子筛也可以进行本发明提供的处理过程,但从工艺简单的角度来考虑,所说的原料MWW结构分子筛以直接处理水热合成的MWW结构分子筛可以获得更好的效果且工艺简单。 Although ITQ-2 and MCM-36 molecular sieve can be provided by the process of the invention, but the simple process point of view, the structure of said molecular sieve material to directly process MWW hydrothermal synthesis zeolite MWW structure can be better effects and simple process.

[0036] 本发明提供的制备方法,所说的混合物中Rl/Si02= 0.05〜0.5、R2/Si0 2= O〜0.5,即R2/Si02的范围端点值为零的情况下,表示可以单独采用含氮有机碱R1。 [0036] The present invention provides a method of preparing said mixture Rl / Si02 = 0.05~0.5, R2 / Si0 2 = O~0.5, the scope endpoints i.e. R2 / Si02 is zero, may be employed alone represents nitrogen-containing organic base R1. 单独采用含氮有机碱Rl的方式尤其适用于原料MWW分子筛结晶完整的情况,例如一般要求原料MffW结构分子筛的相对结晶度为多100%。 Nitrogen-containing organic bases alone Rl manner particularly suitable for complete crystallization MWW zeolite material, for example a relative crystallinity MffW general requirements of the raw material zeolite structure than 100%. 该方式可以在结晶度略有下降的前提下实现MWW结构分子筛产物样品的比表面积、孔体积及2,4,6-三甲基吡啶吸附量均显著增加。 This embodiment can achieve a specific surface area sample of the product zeolite MWW structure under the premise of a slight decrease of the crystallinity, pore volume and 2,4,6-collidine adsorption capacity is significantly increased.

[0037] 本发明提供的制备方法中,采用含氮有机碱Rl与有机胺R2同时处理的方式尤其适用于结晶不完整或结晶度有损失的MWW结构分子筛,例如相对结晶度低于90%的MWW结构分子筛。 [0037] The production method according to the present invention, provided, by way of nitrogen-containing organic bases with organic amines Rl R2 is particularly suitable for simultaneously processing an incomplete crystallization or crystallinity of zeolite MWW structure has a loss, for example, the relative crystallinity is less than 90% MWW molecular sieve structure. 该方式可以促进二次晶化,显著提高结晶度至少5%以上。 The second embodiment can facilitate crystallization, significantly increase the degree of crystallinity of at least 5% or more. 所说的相对结晶度小于90%的MWW结构分子筛,可以包括因晶化时间不够或模板剂用量过低引起的结晶不完整的MWW分子筛,也可以是结晶完全的MWW结构分子筛在损失了结晶度之后的MWW结构分子筛。 The relative crystallinity of said molecular sieve is less than 90% of the MWW structure may include a lack of time or due to crystallization caused by low amount of template incomplete crystalline MWW zeolite may be fully crystalline zeolite MWW structure loss in crystallinity MWW structure of the molecular sieve after. 米用含氮有机碱Rl与有机胺R2同时处理的方式下,Mffff结构分子筛产物样品在结晶度明显提高的前提下实现比表面积、孔体积及2,4,6-三甲基吡啶吸附量均显著增加。 M with the nitrogen-containing organic base mode with organic amines Rl R2 processed simultaneously, Mffff structure of the molecular sieve sample of the product to achieve a specific surface area, pore volume, and 2,4,6-collidine adsorption capacity at markedly improved crystallinity premise A significant increase. 另外,离子交换程度会更加明显,Na+降至0.05重%以下,产物样品可不经过铵交换过程,可直接焙烧为H-型分子筛使用为酸性催化剂活性组分用于烷基化、芳构化、裂化、异构化等反应。 Further, the degree of ion exchange will become more apparent, Na + to 0.05 weight% or less, the product sample without going through ammonium exchange process, roasting is H- directly using acidic molecular sieve catalytically active component used for the alkylation, aromatization, cracking, isomerization reactions.

[0038] 所述的回收产物,其过程为本领域技术人员所熟悉,包括固液分离、洗涤、干燥和焙烧,在此不再繁述。 Recovering the product of [0038] which process is familiar to the skilled person, including solid-liquid separation, washing, drying and calcining, the fan will not be described. 本发明可实施但并不限于此的一个具体回收产物的过程是在水热晶化完成后,将反应体系温度降至室温,晶化产物经固体与母液分离,其中固体经去离子水洗涤至PH值接近7,再于100°C烘干后,以2°C /min的升温速率升温至550°C焙烧1h脱除模板剂,得到焙烧后的MWW结构分子筛。 The present invention is not limited to one particular embodiment of the process, but this product is recovered after completion of the hydrothermal crystallization, the reaction system was lowered to room temperature, the solid was crystallized product is separated from the mother liquor, wherein the solid washed with deionized water to PH value close to 7, and then after drying at 100 ° C, at a heating rate of 2 ° C / min heating to 550 ° C calcined to remove the template agent 1h, zeolite MWW structure obtained after firing.

[0039] 下面通过实施例对本发明作进行进一步说明,但并不因此而限制本发明的内容。 [0039] Hereinafter, the present invention will be further described by way of examples, but is not so limit the present invention.

[0040] 实施例和对比例中,样品的X-射线衍射(XRD)晶相图在Siemens D5005型X-射线衍射仪上进行测定。 [0040] Examples and Comparative Examples, sample X- ray diffraction (XRD) crystal phase diagram was measured in Siemens D5005 X- ray diffraction pattern. 以样品与基准样品在2 Θ为22.5°〜25.0°之间衍射特征峰的衍射强度(峰高)之和的比值来表示样品相对于基准样品的结晶度,即相对结晶度(以对比例I样品为基准样品,其结晶度计为100% )。 In the reference sample and the sample 2 Θ diffraction peaks of 22.5 ° ~25.0 ° between the diffraction intensity (peak height) ratio of the sum of the sample expressed relative to the crystallinity of the reference sample, i.e., the relative degree of crystallinity (in Comparative Example I the reference sample is a sample which crystallized meter 100%).

[0041] 实施例和对比例中,BJH曲线显示在3.8nm处的氮气脱附量的测试采用Quantachrome仪器公司生产的AS-3静态氮吸附仪在测试条件:将样品置于样品处理系统,在300°C下抽真空至1.33X 10 2Pa,保温保压4h,净化样品;测试过程:在液氮温度_196°C下,测量净化样品在不同比压P/P(]条件下对氮气的吸附量。 [0041] Examples and Comparative Examples, using the BJH curve shows Quantachrome Instruments AS-3 produced by a static nitrogen Sorption test conditions in the desorption amount of nitrogen at 3.8nm test: The sample was placed in the sample processing system, pumping at 300 ° C in vacuo to 1.33X 10 2Pa, pressure and temperature for 4h, sample purification; test: at a liquid nitrogen temperature _196 ° C, measured at different sample purge pressure ratio P / P (] nitrogen conditions Adsorption capacity.

[0042] 实施例和对比例中,2,4,6-三甲基吡啶的吸附量特性参数是将分子筛样品压成10至20mg的自撑片,置于原位池中,于20°C吸附2,4,6-三甲基吡啶,并于200°C脱除物理吸附的2,4,6-三甲基吡啶,由傅里叶变换红外光谱测得的。 [0042] Examples and Comparative Examples, the amount of adsorption characteristic parameters of 2,4,6-trimethylpyridine is a molecular sieve 10 to 20mg sample is pressed into a self-supporting sheet, was placed in situ in the pool, at 20 ° C 2,4,6-trimethyl pyridine adsorption, and at 200 ° C to remove physically adsorbed 2,4,6-collidine by Fourier transform infrared spectroscopy measured.

[0043] 对比例I [0043] Comparative Example I

[0044] 本对比例说明按照US 4954325的方法制备的MCM-22分子筛。 [0044] This comparative example illustrates the preparation of MCM-22 zeolite according to the method of US 4954325.

[0045] 将偏铝酸钠(国药集团,分析纯)与氢氧化钠(北京试剂公司,分析纯)溶于去离子水中,搅拌至完全溶解,将固体硅胶(青岛海洋化工厂,干基97% )加入上述溶液,再加入六亚甲基亚胺(HMI),搅拌均匀后,所得混合物胶体摩尔配比为:0.1SNaOH:Si02:0.033A1203:0.30HM1:15H20。 [0045] Sodium aluminate (Sinopharm, analytical grade) and sodium hydroxide (Beijing Reagent Company, analytically pure) dissolved in deionized water, stirring until completely dissolved, and the solid on silica gel (Qingdao Ocean Chemical Plant, dry basis 97 %) added to the solution, was added hexamethyleneimine (the HMI), after mixing, the resulting mixture molar ratio of colloid: 0.1SNaOH: Si02: 0.033A1203: 0.30HM1: 15H20. 然后将所得混合物转移至密闭晶化釜中,晶化温度为145°C,动态晶化72h,冷却后取出产物,经过滤、洗涤、干燥和焙烧后,得到样品。 The resulting mixture was transferred to a closed crystallization vessel, the crystallization temperature was 145 ° C, 72h dynamic crystallization, the product was removed after cooling, filtering, washing, drying and calcination, the sample was obtained.

[0046] 测试样品的XRD衍射图,2 Θ角5至35 °,产物为MCM-22分子筛,标记为D-1,以此D-1样品的结晶度设为100%,此后的实施例样品的相对结晶度数据以此为基准。 [0046] XRD diffraction pattern of the test sample, 2 Θ angle of 5 to 35 °, the product is zeolite MCM-22, labeled D-1, D-1 thus crystallinity of the sample is 100%, thereafter the sample embodiment embodiment the relative crystallinity of data as a reference.

[0047] 通过扫描电镜测试,形貌为“花朵状”聚集,分子筛晶粒大小约为3.0〜4.0 μ m。 [0047] By scanning electron microscopy, morphology of the "flower-shaped" aggregate, zeolite crystal size is about 3.0~4.0 μ m.

[0048] 测试样品的BET分析其比表面积和孔体积,比表面积和孔体积分别为451m2/g和0.55cm3/go [0048] BET test sample for analyte specific surface area and pore volume, surface area and pore volume of 451m2 / g and 0.55cm3 / go, respectively

[0049] XRF 分析其Na2O 含量为0.65wt.%。 [0049] XRF analysis which Na2O content of 0.65wt.%.

[0050] 氮气吸附-脱附的BJH曲线显示在3.8±0.5nm处的氮气脱附量为0.22cm3/g,且其20°C吸附、200°C脱附后的2,4,6-三甲基吡啶的吸附量为22 ymol/g。 [0050] The nitrogen adsorption - BJH desorption curves show the amount of nitrogen desorbed at 3.8 ± 0.5nm is 0.22cm3 / g, which is 20 ° C and adsorption, 2,4,6 desorbed after 200 ° C adsorption methylpyridine 22 ymol / g.

[0051] 实施例1 [0051] Example 1

[0052] 本实施例说明本发明提供的分子筛和制备方法。 [0052] This example illustrates the method of preparation and molecular sieve provided by the invention.

[0053] 上述对比例I中,未经焙烧、含有六亚甲基亚胺的MCM-22样品为MCM-22P分子筛,经过焙烧、已经脱除六亚甲基亚胺的MCM-22样品为MCM-22C分子筛。 [0053] Comparative Example I above, the unfired, MCM-22 sample containing hexamethyleneimine molecular sieve is MCM-22P, calcined, MCM-22 samples has been removed hexamethyleneimine was MCM -22C molecular sieve.

[0054] 将四乙基氢氧化铵溶液(TEAOH,25wt.% )加入去离子水中,然后将MCM-22P或MCM-22C分子筛加入上述溶液中,继续搅拌均匀,所得混合物胶体摩尔配比为S12:0.1TEA0H:15H20。 [0054] Tetraethyl ammonium hydroxide solution (TEAOH, 25wt.%) Of deionized water was added, and then the MCM-22P or zeolite MCM-22C was added to the solution, and stirring was continued for a uniform, the resulting mixture was colloid molar ratio of S12 : 0.1TEA0H: 15H20. 将所得混合物胶体转移至密闭晶化釜中,在晶化温度为150°C下动态晶化16h,冷却后取出产物,经过滤、洗涤、干燥和焙烧后,得到处理后分子筛原粉,MCM-22P对应的处理后样品的编号为A-1-1 ;MCM-22C对应的处理后样品的编号为A-1-2。 The resulting mixture was transferred to a closed crystallization colloidal kettle, molecular sieve powder after crystallization temperature of 150 ° C under dynamic crystallization for 16 h, cooled product was removed by filtration, washed, dried and calcined, the processed, MCM- 22P corresponding to the number of samples after the processing a-1-1; MCM-22C after treatment number of the samples corresponding to a-1-2.

[0055] 测试样品得到XRD衍射图,A-1-1为MCM-22分子筛,而A-1-2为MCM-49分子筛,相对结晶度分别为105%和96%。 [0055] The XRD patterns of the test sample was obtained, A-1-1 is a molecular sieve MCM-22, and A-1-2 is a molecular sieve MCM-49, the relative degree of crystallinity of 96% and 105%, respectively.

[0056] SEM显示A-1-1样品和A_l_2形貌均由样品D_1的“花朵状”聚集转变为片状松散堆积。 [0056] SEM display A_l_2 A-1-1 and sample by sample morphology D_1 the "flower-shaped" loosely packed aggregates into a sheet.

[0057] BET分子筛显不:A_1_1分子筛的比表面积和孔体积分别为481m2/g和0.65cm3/g ;而A-1-2分子筛的比表面积和孔体积分别为476m2/g和0.63cm3/g。 [0057] BET without significant molecular sieves: the specific surface area and pore volume of the molecular sieves were A_1_1 481m2 / g and 0.65cm3 / g; A-1-2 and the specific surface area and pore volume of the molecular sieve are 476m2 / g and 0.63cm3 / g .

[0058] XRF 分析A-1-1 和A-1-2 的Na2O 含量分别为0.25wt.%和0.23wt.%。 [0058] XRF analysis of A-1-1 and A-1-2 Na2O content of 0.25wt.% And 0.23wt.%, Respectively.

[0059] 氮气吸附-脱附的BJH曲线显示在3.8±0.5nm处的氮气脱附量为0.1OcmVg和0.lOcmVg,且其20°C吸附、200°C脱附后的2,4,6-三甲基吡啶的吸附量为38.2 ymol/g和 [0059] The nitrogen adsorption - BJH desorption curve is shown in the desorption amount of nitrogen is at 3.8 ± 0.5nm and 0.1OcmVg 0.lOcmVg, 20 ° C and its adsorption, 2,4,6 200 ° C after desorption - trimethyl pyridine adsorption amount was 38.2 ymol / g and

36.7 μmol/go 36.7 μmol / go

[0060] 对比例2 [0060] Comparative Example 2

[0061 ] 本对比例说明按照US 5326575的方法制备MCM-49分子筛的过程。 [0061] This comparative example illustrates the process according to US 5326575 a method for preparing MCM-49 molecular sieve.

[0062] 将偏铝酸钠(国药集团,分析纯)与氢氧化钠(北京试剂公司,分析纯)溶于去离子水中,搅拌至完全溶解,将固体硅胶(青岛海洋化工厂,干基97% )加入上述溶液,再加入六亚甲基亚胺,搅拌均匀后,所得混合物胶体摩尔配比为:0.18Na0H:Si02:0.040A1 203:0.30HM1:15H20。 [0062] Sodium aluminate (Sinopharm, analytical grade) and sodium hydroxide (Beijing Reagent Company, analytically pure) dissolved in deionized water, stirring until completely dissolved, and the solid on silica gel (Qingdao Ocean Chemical Plant, dry basis 97 %) added to the solution, hexamethyleneimine was added, stirred uniformly, and the resulting mixture molar ratio of colloid: 0.18Na0H: Si02: 0.040A1 203: 0.30HM1: 15H20. 然后将所得混合物转移至密闭晶化釜中,晶化温度为145°C,动态晶化72h,冷却后取出产物,经过滤、洗涤、干燥和焙烧后,得到样品。 The resulting mixture was transferred to a closed crystallization vessel, the crystallization temperature was 145 ° C, 72h dynamic crystallization, the product was removed after cooling, filtering, washing, drying and calcination, the sample was obtained.

[0063] 测试样品得到的XRD衍射图,2 Θ角5至35 °,产物为MCM-49分子筛,标记为D-2。 [0063] XRD diffraction pattern of the obtained test sample, 2 Θ angle of 5 to 35 °, the product is zeolite MCM-49, labeled D-2.

[0064] 相对结晶度为100 %;晶粒大小约为3.0〜4.0 μ m ;BET分析比表面积和孔体积分别为462m2/g 和0.56cm3/g。 [0064] The relative crystallinity of 100%; grain size of about 3.0~4.0 μ m; BET specific surface area and pore volume analyzes were 462m2 / g and 0.56cm3 / g.

[0065] XRF 分析其Na2O 含量为0.58wt.%。 [0065] XRF analysis which Na2O content of 0.58wt.%.

[0066] 氮气吸附-脱附的BJH曲线显示在3.8±0.5nm处的氮气脱附量为0.20cm3/g,且其20°C吸附、200°C脱附后的2,4,6-三甲基吡啶的吸附量为26 ymol/g。 [0066] The nitrogen adsorption - BJH desorption curves show the amount of nitrogen desorbed at 3.8 ± 0.5nm is 0.20cm3 / g, which is 20 ° C and adsorption, 2,4,6 desorbed after 200 ° C adsorption methylpyridine 26 ymol / g.

[0067] 实施例2 [0067] Example 2

[0068] 本实施例说明本发明提供的分子筛和制备方法。 [0068] This example illustrates the method of preparation and molecular sieve provided by the invention.

[0069] 将四乙基氢氧化铵溶液(25wt.% )加入去离子水中,然后将对比例2中未经焙烧、含有六亚甲基亚胺的MCM-49加入上述溶液中,继续搅拌均匀。 [0069] Tetraethyl ammonium hydroxide solution (25wt.%) Of deionized water was added, and Comparative Example 2 will be in the unfired, hexamethyleneimine containing MCM-49 is added to the solution, continue to stir . 所得混合物胶体摩尔配比为S12=0.1TEA0H:15H20。 The resulting mixture was a colloidal molar ratio of S12 = 0.1TEA0H: 15H20. 然后,将所得混合物转移至密闭晶化釜中,晶化温度为150°C,动态晶化16h,冷却后取出产物,经过滤、洗涤、干燥和焙烧后,得到改性后分子筛原粉,样品编号为A-2-lo Then, the resulting mixture was transferred to a closed crystallization vessel, the crystallization temperature was 150 ° C, a dynamic crystallization for 16 h, cooled product was removed by filtration, washed, dried and calcined after the molecular sieve powder to obtain a modified samples No. A-2-lo

[0070] 同上,区别在于将对比例2未经焙烧、含有六亚甲基亚胺的MCM-49替换为对比例2经过焙烧、已经脱除六亚甲基亚胺的MCM-49。 [0070] Ibid., Comparative Example 2 except that will unfired, hexamethyleneimine containing MCM-49 is replaced with a calcined Comparative Example 2, has been removed hexamethyleneimine of MCM-49. 得到改性后分子筛原粉,样品编号为A-2-2。 After the modified molecular sieve raw powder obtained, Sample No. A-2-2.

[0071] 测试得到XRD衍射图,A-2-1和A_2_2均为MCM-49分子筛,相对结晶度分别为103%和96%o [0071] The XRD patterns obtained test, A-2-1, and A_2_2 molecular sieve are MCM-49, respectively, the relative crystallinity of 103% and 96% o

[0072] SEM测试显示样品A-2-1和A_2_2的形貌均由D_2的“花朵状”聚集转变为片状松散堆积。 [0072] SEM tests showed that the morphology Samples of A-2-1 and A_2_2 D_2 by the "flower-shaped" loosely packed aggregates into a sheet.

[0073] BET分子筛显不:A_2_1分子筛的比表面积和孔体积分别为475m2/g和0.67cm3/g ;而A-2-2分子筛的比表面积和孔体积分别为471m2/g和0.62cm3/g。 [0073] BET without significant molecular sieves: the specific surface area and pore volume of the molecular sieves were A_2_1 475m2 / g and 0.67cm3 / g; A-2-2 and the specific surface area and pore volume of the molecular sieve are 471m2 / g and 0.62cm3 / g .

[0074] XRF 分析其Na2O 含量分别为0.2 Iwt.%和0.18wt.%。 [0074] XRF analysis which Na2O content of 0.2 Iwt.% And 0.18wt.%, Respectively.

[0075] 氮气吸附-脱附的BJH曲线显示在3.8±0.5nm处的氮气脱附量为0.09cm3/g和0.lOcmVg,且其20°C吸附、200°C脱附后的2,4,6-三甲基吡啶的吸附量为40.3 ymol/g和38.7 μmol/go [0075] The nitrogen adsorption - BJH desorption curves show the amount of nitrogen desorbed at 3.8 ± 0.5nm is 0.09cm3 / g and 0.lOcmVg, 20 ° C and its adsorption, 2,4 desorbed after 200 ° C , 6- trimethyl pyridine adsorption amount was 40.3 ymol / g and 38.7 μmol / go

[0076] 对比例3 [0076] Comparative Example 3

[0077] 本对比例说明按照CN103771435A中实施例1的方法以六亚甲基亚胺和苯胺为模板剂合成MCM-22分子筛的过程。 [0077] This comparative example illustrates embodiments in accordance with the method of Example 1 CN103771435A to hexamethyleneimine and aniline as a process template synthesized MCM-22 molecular sieve.

[0078] 将偏铝酸钠(国药集团,分析纯)与氢氧化钠(北京试剂公司,分析纯)溶于去离子水中,搅拌至完全溶解,将海陵硅胶(青岛海洋化工厂,S12含量为97%)加入上述溶液,再加入六亚甲基亚胺(日本TCI公司,分析纯)、苯胺(北京化工厂,分析纯)。 [0078] Sodium aluminate (Sinopharm, analytical grade) and sodium hydroxide (Beijing Reagent Company, analytically pure) dissolved in deionized water, stirring until completely dissolved, hailing silica gel (Qingdao Ocean Chemical Plant, S12 content 97%) was added to the solution, then added hexamethyleneimine (TCI, Japan, analytical grade), aniline (Beijing chemical Plant, analytical grade). 混合物胶体摩尔配比为0.18Na0H:Si02:0.033A1 203:0.10HM1:0.20AN:15H 20,晶化温度145°C,自生压力下,以每分钟300转得搅拌速度晶化72小时,冷却后取出产物,经过滤、洗涤和干燥和焙烧后,得到样品。 After 15H 20, the crystallization temperature of 145 ° C, under autogenous pressure, to give 300 revolutions per minute stirring speed crystallization for 72 hours was cooled: the molar ratio of the mixture of colloidal 0.18Na0H: Si02: 0.033A1 203: 0.10HM1: 0.20AN remove the product was filtered, washed and dried and calcined to obtain a sample.

[0079] 测试得到样品的XRD衍射图,2 Θ角为5至35°,样品为MCM-22分子筛,编号为为D-3,相对结晶度为101% ; [0079] XRD diffraction patterns obtained test sample, 2 Θ angle 5 to 35 °, the sample of zeolite MCM-22, No. of D-3, the relative degree of crystallization of 101%;

[0080] SEM测试,D-3样品的晶粒大小约为3.0〜4.0 μ m ; [0080] SEM test, samples D-3 grain size of about 3.0~4.0 μ m;

[0081] BET分析其比表面积和孔体积分别为450m2/g和0.55cm3/g ; [0081] BET specific surface area analysis and the pore volume are 450m2 / g and 0.55cm3 / g;

[0082] XRF 分析Na2O 含量为0.55wt.%。 [0082] XRF analysis Na2O content of 0.55wt.%.

[0083] 氮气吸附-脱附的BJH曲线显示在3.8±0.5nm处的氮气脱附量为0.20cm3/g,且其20°C吸附、200°C脱附后的2,4,6-三甲基吡啶的吸附量为28.7 ymol/g。 [0083] The nitrogen adsorption - BJH desorption curves show the amount of nitrogen desorbed at 3.8 ± 0.5nm is 0.20cm3 / g, which is 20 ° C and adsorption, 2,4,6 desorbed after 200 ° C adsorption methylpyridine 28.7 ymol / g.

[0084] 实施例3 [0084] Example 3

[0085] 本实施例说明本发明提供的分子筛和制备方法。 [0085] This example illustrates the method of preparation and molecular sieve provided by the invention.

[0086] 将四甲基氢氧化铵溶液(25wt.% )加入去离子水中,然后将对比例3中未经焙烧、含有六亚甲基亚胺和苯胺的MCM-22加入上述溶液中,继续搅拌均匀。 [0086] The tetramethylammonium hydroxide solution (25wt.%) To deionized water, and then firing of Comparative Example 3 without containing hexamethyleneimine, aniline and MCM-22 was added to the solution, continue stir. 所得混合物胶体摩尔配比为Si02:0.1TMA0H:15Η20ο然后,将所得混合物转移至密闭晶化釜中,晶化温度为150°C,动态晶化16h,冷却后取出产物,经过滤、洗涤、干燥和焙烧后,得到改性后分子筛原粉,样品编号为A-3-1。 The resulting mixture was a colloidal molar ratio of Si02: 0.1TMA0H: 15Η20ο Then, the resulting mixture was transferred to a closed crystallization vessel, the crystallization temperature was 150 ° C, a dynamic crystallization for 16 h, cooled product was removed by filtration, washed, and dried and after calcination, the modified molecular sieve to obtain raw powder sample No. A-3-1.

[0087] 同上,区别在于将对比例3的未经焙烧、含有六亚甲基亚胺和苯胺的MCM-49替换为对比例3已经焙烧、不含六亚甲基亚胺和苯胺的MCM-22 (焙烧后的MCM-22C分子筛,其与MCM-49分子筛XRD衍射峰相同)。 [0087] Ibid., Except that the calcination of Comparative Example 3 without containing hexamethyleneimine, aniline and MCM-49 is replaced been calcined MCM- Comparative Example 3, free of hexamethyleneimine and aniline 22 (MCM-22C calcined molecular sieve MCM-49 zeolite the same as the XRD peaks). 得到改性后分子筛原粉,样品编号为A-3-2。 After the modified molecular sieve raw powder obtained, Sample No. A-3-2.

[0088] 测试得到XRD衍射图,A-3-1为MCM-22分子筛,A-3-2为MCM-49分子筛,相对结晶度分别为94%和92%。 [0088] The XRD patterns obtained test, A-3-1 is zeolite MCM-22, A-3-2 as MCM-49 zeolite, the relative crystallinity of 94% and 92%, respectively.

[0089] 形貌均由“花朵状”聚集转变为片状松散堆积。 [0089] morphology by "flower-shaped" loosely packed aggregates into a sheet.

[0090] BET分析显不,A_3_1样品的的比表面积和孔体积分别为502m2/g和0.60cm3/g ;而A-3-2样品的比表面积和孔体积分别为491m2/g和0.62cm3/g。 [0090] BET analysis is not significant, the specific surface area and pore volume of the sample were A_3_1 502m2 / g and 0.60cm3 / g; pore volume and the specific surface area A-3-2 were samples 491m2 / g and 0.62cm3 / g.

[0091] XRF 分析其Na2O 含量分别为0.1Owt.%和0.1lwt.%。 [0091] XRF analysis which Na2O content 0.1Owt.% And 0.1lwt.%, Respectively.

[0092] 氮气吸附-脱附的BJH曲线显示在3.8±0.5nm处的氮气脱附量为0.08cm3/g和0.07cm3/g,且其20°C吸附、200°C脱附后的2,4,6-三甲基吡啶的吸附量为42.1 ymol/g和 [0092] The nitrogen adsorption - BJH desorption curves show the amount of nitrogen desorbed at 3.8 ± 0.5nm is 0.08cm3 / g and 0.07cm3 / g, which is 20 ° C and adsorption, desorption of 200 ° C after 2, 4,6-trimethyl pyridine adsorption amount was 42.1 ymol / g and

40.3 μmol/go 40.3 μmol / go

[0093] 实施例4 [0093] Example 4

[0094] 本实施例说明本发明提供的分子筛和制备方法。 [0094] This example illustrates the method of preparation and molecular sieve provided by the invention.

[0095] 将四甲基氢氧化铵溶液(25wt.% )和哌啶(PI)加入去离子水中,然后将对比例3中未经焙烧、含有六亚甲基亚胺和苯胺的MCM-22加入上述溶液中,继续搅拌均匀。 [0095] The tetramethylammonium hydroxide solution (25wt.%) And piperidine (PI) of deionized water was added, and Comparative Example 3 will unfired, containing hexamethyleneimine, aniline and MCM-22 added to the solution, continue to stir. 所得混合物胶体摩尔配比为:Si02:0.1TMAOH:0.3PI:15H 20o然后,将所得混合物转移至密闭晶化釜中,晶化温度为150 °C,动态晶化16h,冷却后取出产物,经过滤、洗涤、干燥和焙烧后,得到改性后分子筛原粉,样品编号为A-4-1。 The resulting mixture molar ratio of colloid: Si02: 0.1TMAOH: 0.3PI: 15H 20o Then, the resulting mixture was transferred to a closed crystallization vessel, the crystallization temperature was 150 ° C, a dynamic crystallization for 16 h, the product was removed after cooling, the filtered, washed, dried and calcined, to obtain the modified molecular sieve raw powder sample No. A-4-1.

[0096] 同上,区别在于将对比例3未经焙烧、含有六亚甲基亚胺和苯胺的MCM-22替换为对比例3已经焙烧、不含六亚甲基亚胺和苯胺的MCM-22。 [0096] Ibid., Comparative Example 3 except that will unfired, MCM-22 containing hexamethyleneimine, aniline and Comparative Example 3 has been replaced by firing free of hexamethyleneimine, aniline and MCM-22 . 得到改性后分子筛原粉,样品编号为A-4-2。 After the modified molecular sieve raw powder obtained, Sample No. A-4-2.

[0097] 测试得到XRD衍射图,A-4-1和A_4_2为MCM-22分子筛,相对结晶度分别为113%和108% ; [0097] The XRD patterns obtained test, A-4-1, and MCM-22 zeolite as A_4_2, the relative degree of crystallinity of 113% and 108%, respectively;

[0098] SEM测试,样品形貌均由D-3的“花朵状”聚集转变为片状松散堆积; [0098] SEM test sample D-3 by the morphology of the "flower-shaped" loosely packed aggregates into a sheet;

[0099] BET分析显不:A_8_1分子筛的比表面积和孔体积分别为483m2/g和0.64cm3/g ;而A-8-2分子筛的比表面积和孔体积分别为492m2/g和0.63cm3/g ; [0099] BET analysis revealed no: A_8_1 zeolite surface area and pore volume are 483m2 / g and 0.64cm3 / g; specific surface area and the pore volume of the zeolite A-8-2 were 492m2 / g and 0.63cm3 / g ;

[0100] XRF 分析其Na2O 含量分别为0.0 Iwt.% 和0.02wt.%。 [0100] XRF analysis which Na2O content of 0.0 Iwt.% And 0.02wt.%, Respectively.

[0101] 氮气吸附-脱附的BJH曲线显示在3.8±0.5nm处的氮气脱附量为0.08cm3/g和 [0101] nitrogen adsorption - BJH desorption curves show the amount of nitrogen desorbed at 3.8 ± 0.5nm is 0.08cm3 / g and

0.07cm3/g,且其20°C吸附、200°C脱附后的2,4,6-三甲基吡啶的吸附量为42.1 ymol/g和40.2 μmol/go 0.07cm3 / g, which is 20 ° C and adsorption, adsorption and desorption after the 200 ° C 2,4,6-trimethylpyridine was 42.1 ymol / g and 40.2 μmol / go

[0102] 实施例5 [0102] Example 5

[0103] 本实施例说明本发明提供的分子筛和制备方法。 [0103] This example illustrates the method of preparation and molecular sieve provided by the invention.

[0104] 将四乙基氢氧化铵溶液(25wt.% )加入去离子水中,然后将对比例3中未经焙烧、含有六亚甲基亚胺和苯胺的MCM-22加入上述溶液中,继续搅拌均匀。 [0104] Tetraethyl ammonium hydroxide solution (25wt.%) To deionized water, and then firing of Comparative Example 3 without containing hexamethyleneimine, aniline and MCM-22 was added to the solution, continue stir. 所得混合物胶体摩尔配比为Si02:0.1TEA0H:15H20。 The resulting mixture was a colloidal molar ratio of Si02: 0.1TEA0H: 15H20. 然后,将所得混合物转移至密闭晶化釜中,晶化温度为150°C,动态晶化16h,冷却后取出产物,经过滤、洗涤、干燥和焙烧后,得到改性后分子筛原粉,样品编号为A-5-1。 Then, the resulting mixture was transferred to a closed crystallization vessel, the crystallization temperature was 150 ° C, a dynamic crystallization for 16 h, cooled product was removed by filtration, washed, dried and calcined after the molecular sieve powder to obtain a modified samples No. A-5-1.

[0105] 同上,区别在于将对比例3的未经焙烧、含有六亚甲基亚胺和苯胺的MCM-22替换为对比例3已经焙烧、不含六亚甲基亚胺和苯胺的MCM-22。 [0105] Ibid., Except that of Comparative unfired 3, MCM-22 containing hexamethyleneimine, aniline and Comparative Example 3 has been replaced by firing free of hexamethyleneimine and MCM- aniline twenty two. 得到改性后分子筛原粉,样品编号为A-5-2。 After the modified molecular sieve raw powder obtained, Sample No. A-5-2.

[0106] 测试得到XRD衍射图,A-5-1为MCM-22分子筛,A-5-2为MCM-49分子筛,相对结晶度分别为100%和96%。 [0106] The XRD patterns obtained test, A-5-1 is zeolite MCM-22, A-5-2 as MCM-49 zeolite, the relative crystallinity of 100% and 96%, respectively.

[0107] 形貌均由“花朵状”聚集转变为片状松散堆积。 [0107] morphology by "flower-shaped" loosely packed aggregates into a sheet.

[0108] BET分析显不,A-5-1样品的的比表面积和孔体积分别为500m2/g和0.67cm3/g ;而A-5-2样品的比表面积和孔体积分别为495m2/g和0.65cm3/g。 [0108] BET analysis is not significant, the specific surface area A-5-1 and the pore volume of the sample were 500m2 / g and 0.67cm3 / g; specific surface area of ​​the sample A-5-2 and the pore volume are 495m2 / g and 0.65cm3 / g.

[0109] XRF 分析其Na2O 含量分别为0.20wt.%和0.15wt.%。 [0109] XRF analysis which Na2O content of 0.20wt.% And 0.15wt.%, Respectively.

[0110] 氮气吸附-脱附的BJH曲线显示在3.8±0.5nm处的氮气脱附量为0.05cm3/g和 [0110] nitrogen adsorption - BJH desorption curves show the amount of nitrogen desorbed at 3.8 ± 0.5nm is 0.05cm3 / g and

0.05cm3/g,且其20°C吸附、200°C脱附后的2,4,6-三甲基吡啶的吸附量为46.1 ymol/g和 0.05cm3 / g, which is 20 ° C and adsorption, adsorption and desorption after the 200 ° C 2,4,6-trimethylpyridine was 46.1 ymol / g and

43.4 μmol/go 43.4 μmol / go

[0111] 实施例6 [0111] Example 6

[0112] 本实施例说明本发明提供的分子筛和制备方法。 [0112] This example illustrates the method of preparation and molecular sieve provided by the invention.

[0113] 将四乙基氢氧化铵溶液(25wt.% )和哌啶(PI)加入去离子水中,然后将对比例3中未经焙烧、含有六亚甲基亚胺和苯胺的MCM-22加入上述溶液中,继续搅拌均匀。 [0113] Tetraethyl ammonium hydroxide solution (25wt.%) And piperidine (PI) of deionized water was added, and Comparative Example 3 will unfired, containing hexamethyleneimine, aniline and MCM-22 added to the solution, continue to stir. 所得混合物胶体摩尔配比为:Si02:0.1TEAOH:0.3PI:15H 20o然后,将所得混合物转移至密闭晶化釜中,晶化温度为150 °C,动态晶化16h,冷却后取出产物,经过滤、洗涤、干燥和焙烧后,得到改性后分子筛原粉,样品编号为A-6-1。 The resulting mixture molar ratio of colloid: Si02: 0.1TEAOH: 0.3PI: 15H 20o Then, the resulting mixture was transferred to a closed crystallization vessel, the crystallization temperature was 150 ° C, a dynamic crystallization for 16 h, the product was removed after cooling, the filtered, washed, dried and calcined, to obtain the modified molecular sieve raw powder sample No. A-6-1.

[0114] 同上,区别在于将对比例3未经焙烧、含有六亚甲基亚胺和苯胺的MCM-22替换为对比例3已经焙烧、不含六亚甲基亚胺和苯胺的MCM-22。 [0114] Ibid., Comparative Example 3 except that will unfired, MCM-22 containing hexamethyleneimine, aniline and Comparative Example 3 has been replaced by firing free of hexamethyleneimine, aniline and MCM-22 . 得到改性后分子筛原粉,样品编号为A-6-2. After the modified molecular sieve raw powder obtained, Sample No. A-6-2.

[0115] 测试得到XRD衍射图,A-6-1和A_6_2为MCM-22分子筛,相对结晶度分别为112%和110% ; [0115] The XRD patterns obtained test, A-6-1, and MCM-22 zeolite as A_6_2, the relative degree of crystallinity of 112% and 110%, respectively;

[0116] SEM测试,样品形貌均由D-3的“花朵状”聚集转变为片状松散堆积; [0116] SEM test sample D-3 by the morphology of the "flower-shaped" loosely packed aggregates into a sheet;

[0117] BET分析显不:A-6_1分子筛的比表面积和孔体积分别为485m2/g和0.72cm3/g ;而A-6-2分子筛的比表面积和孔体积分别为494m2/g和0.63cm3/g ; [0117] BET analysis revealed no: specific surface area and pore volume of the zeolite A-6_1 were 485m2 / g and 0.72cm3 / g; specific surface area and the pore volume of the zeolite A-6-2 were 494m2 / g and 0.63cm3 / g;

[0118] XRF 分析其Na2O 含量分别为0.03wt.% 和0.02wt.%。 [0118] XRF analysis which Na2O content of 0.03wt.% And 0.02wt.%, Respectively.

[0119] 氮气吸附-脱附的BJH曲线显示在3.8±0.5nm处的氮气脱附量为0.08cm3/g和 [0119] nitrogen adsorption - BJH desorption curves show the amount of nitrogen desorbed at 3.8 ± 0.5nm is 0.08cm3 / g and

0.07cm3/g,且其20°C吸附、200°C脱附后的2,4,6-三甲基吡啶的吸附量为43.1 ymol/g和 0.07cm3 / g, which is 20 ° C and adsorption, adsorption and desorption after the 200 ° C 2,4,6-trimethylpyridine was 43.1 ymol / g and

41.5 μmol/g0 41.5 μmol / g0

[0120] 实施例7 [0120] Example 7

[0121] 本实施例说明本发明提供的分子筛和制备方法。 [0121] This example illustrates the method of preparation and molecular sieve provided by the invention.

[0122] 将四丙基氢氧化铵溶液(25wt.% )加入去离子水中,然后将对比例3中未经焙烧、含有六亚甲基亚胺和苯胺的MCM-22加入上述溶液中,继续搅拌均匀。 [0122] tetra-propyl ammonium hydroxide solution (25wt.%) To deionized water, and then firing of Comparative Example 3 without containing hexamethyleneimine, aniline and MCM-22 was added to the solution, continue stir. 所得混合物胶体摩尔配比为Si02:0.1TPA0H:15H20。 The resulting mixture was a colloidal molar ratio of Si02: 0.1TPA0H: 15H20. 然后,将所得混合物转移至密闭晶化釜中,晶化温度为150°C,动态晶化16h,冷却后取出产物,经过滤、洗涤、干燥和焙烧后,得到改性后分子筛原粉,样品编号为A-7-1。 Then, the resulting mixture was transferred to a closed crystallization vessel, the crystallization temperature was 150 ° C, a dynamic crystallization for 16 h, cooled product was removed by filtration, washed, dried and calcined after the molecular sieve powder to obtain a modified samples No. A-7-1.

[0123] 同上,区别在于将对比例3的未经焙烧、含有六亚甲基亚胺和苯胺的MCM-22替换为对比例3已经焙烧、不含六亚甲基亚胺和苯胺的MCM-22。 [0123] Ibid., Except that of Comparative unfired 3, MCM-22 containing hexamethyleneimine, aniline and Comparative Example 3 has been replaced by firing free of hexamethyleneimine and MCM- aniline twenty two. 得到改性后分子筛原粉,样品编号为A-7-2。 After the modified molecular sieve raw powder obtained, Sample No. A-7-2.

[0124] 测试得到XRD衍射图,A-7-1为MCM-22分子筛,A-7-2为MCM-49分子筛,相对结晶度分别为95%和93%。 [0124] The XRD patterns obtained test, A-7-1 is zeolite MCM-22, A-7-2 as MCM-49 zeolite, the relative crystallinity of 95% and 93%, respectively.

[0125] 形貌均由“花朵状”聚集转变为片状松散堆积。 [0125] morphology by "flower-shaped" loosely packed aggregates into a sheet.

[0126] BET分析显不,A-7-1样品的的比表面积和孔体积分别为488m2/g和0.68cm3/g ;而A-7-2样品的比表面积和孔体积分别为502m2/g和0.62cm3/g。 [0126] BET analysis is not significant, the specific surface area A-7-1 and the pore volume of the sample were 488m2 / g and 0.68cm3 / g; specific surface area of ​​the sample A-7-2 and the pore volume are 502m2 / g and 0.62cm3 / g.

[0127] XRF 分析其Na2O 含量分别为0.38wt.% 和0.39wt.%。 [0127] XRF analysis which Na2O content of 0.38wt.% And 0.39wt.%, Respectively.

[0128] 氮气吸附-脱附的BJH曲线显示在3.8±0.5nm处的氮气脱附量为0.1OcmVg和 [0128] nitrogen adsorption - BJH desorption curve is shown in the desorption amount of nitrogen is at 3.8 ± 0.5nm and 0.1OcmVg

0.09cm3/g,且其20°C吸附、200°C脱附后的2,4,6-三甲基吡啶的吸附量为40.3 ymol/g和 0.09cm3 / g, which is 20 ° C and adsorption, adsorption and desorption after the 200 ° C 2,4,6-trimethylpyridine was 40.3 ymol / g and

39.5 μmol/go 39.5 μmol / go

[0129] 实施例8 [0129] Example 8

[0130] 本实施例说明本发明提供的分子筛和制备方法。 [0130] This example illustrates the method of preparation and molecular sieve provided by the invention.

[0131] 将四丙基氢氧化铵溶液(25wt.% )和哌啶(PI)加入去离子水中,然后将对比例3中未经焙烧、含有六亚甲基亚胺和苯胺的MCM-22加入上述溶液中,继续搅拌均匀。 [0131] tetra-propyl ammonium hydroxide solution (25wt.%) And piperidine (PI) of deionized water was added, and Comparative Example 3 will unfired, containing hexamethyleneimine, aniline and MCM-22 added to the solution, continue to stir. 所得混合物胶体摩尔配比为:Si02:0.1TPA0H:0.3PI:15H 20o然后,将所得混合物转移至密闭晶化釜中,晶化温度为150 °C,动态晶化16h,冷却后取出产物,经过滤、洗涤、干燥和焙烧后,得到改性后分子筛原粉,样品编号为A-8-1。 The resulting mixture molar ratio of colloid: Si02: 0.1TPA0H: 0.3PI: 15H 20o Then, the resulting mixture was transferred to a closed crystallization vessel, the crystallization temperature was 150 ° C, a dynamic crystallization for 16 h, the product was removed after cooling, the filtered, washed, dried and calcined, to obtain the modified molecular sieve raw powder sample No. A-8-1.

[0132] 同上,区别在于将对比例3未经焙烧、含有六亚甲基亚胺和苯胺的MCM-22替换为对比例3已经焙烧、不含六亚甲基亚胺和苯胺的MCM-22。 [0132] Ibid., Comparative Example 3 except that will unfired, MCM-22 containing hexamethyleneimine, aniline and Comparative Example 3 has been replaced by firing free of hexamethyleneimine, aniline and MCM-22 . 得到改性后分子筛原粉,样品编号为A-8-2. After the modified molecular sieve raw powder obtained, Sample No. A-8-2.

[0133] 测试得到XRD衍射图,A-8-1和A_8_2为MCM-22分子筛,相对结晶度分别为110 %和103% ; [0133] The XRD patterns obtained test, A-8-1, and MCM-22 zeolite as A_8_2, the relative degree of crystallinity of 110% and 103%, respectively;

[0134] SEM测试,样品形貌均由D-3的“花朵状”聚集转变为片状松散堆积; [0134] SEM test sample D-3 by the morphology of the "flower-shaped" loosely packed aggregates into a sheet;

[0135] BET分析显不:A_8_1分子筛的比表面积和孔体积分别为488m2/g和0.65cm3/g ;而A-8-2分子筛的比表面积和孔体积分别为497m2/g和0.65cm3/g ; [0135] BET analysis revealed no: A_8_1 zeolite surface area and pore volume are 488m2 / g and 0.65cm3 / g; specific surface area and the pore volume of the zeolite A-8-2 were 497m2 / g and 0.65cm3 / g ;

[0136] XRF 分析其Na2O 含量分别为0.07wt.% 和0.06wt.%。 [0136] XRF analysis which Na2O content of 0.07wt.% And 0.06wt.%, Respectively.

[0137] 氮气吸附-脱附的BJH曲线显示在3.8±0.5nm处的氮气脱附量为0.08cm3/g和 [0137] nitrogen adsorption - BJH desorption curves show the amount of nitrogen desorbed at 3.8 ± 0.5nm is 0.08cm3 / g and

0.07cm3/g,且其20°C吸附、200°C脱附后的2,4,6-三甲基吡啶的吸附量为40.4 ymol/g和 0.07cm3 / g, which is 20 ° C and adsorption, adsorption and desorption after the 200 ° C 2,4,6-trimethylpyridine was 40.4 ymol / g and

38.6 μmol/go 38.6 μmol / go

[0138] 实施例9 [0138] Example 9

[0139] 本实施例说明本发明提供的分子筛和制备方法。 [0139] This example illustrates the method of preparation and molecular sieve provided by the invention.

[0140] 将二甲基二乙基氢氧化铵溶液(DEDMAOH,25wt.% )加入去离子水中,然后将对比例3中未经焙烧、含有六亚甲基亚胺和苯胺的MCM-22分子筛加入上述溶液中,继续搅拌均匀。 [0140] The dimethyl diethyl ammonium hydroxide solution (DEDMAOH, 25wt.%) To deionized water, and then firing of Comparative Example 3 without containing hexamethyleneimine, aniline and MCM-22 zeolite added to the solution, continue to stir. 所得混合物胶体摩尔配比为Si02:0.1DEDMA0H:15H20o将所得混合物转移至密闭晶化釜中,晶化温度为150 °C,动态晶化16h,冷却后取出产物,经过滤、洗涤、干燥和焙烧后,得到改性后分子筛原粉,产品编号A-9-1。 The resulting mixture was a colloidal molar ratio of Si02: 0.1DEDMA0H: 15H20o The resulting mixture was transferred to a closed crystallization vessel, the crystallization temperature was 150 ° C, a dynamic crystallization for 16 h, cooled product was removed by filtration, washed, dried and calcined after the modified molecular sieve to obtain raw powder, product No. A-9-1.

[0141] 同上,区别在于将对比例3未经焙烧、含有六亚甲基亚胺和苯胺的MCM-22分子筛替换为对比例3已经焙烧、不含六亚甲基亚胺和苯胺的MCM-22分子筛。 [0141] Ibid., Except that the calcination of Comparative Example 3 without containing hexamethyleneimine, aniline and zeolite MCM-22 Comparative Example 3 has been replaced by firing free of hexamethyleneimine and MCM- aniline 22 molecular sieve. 得到改性后分子筛原粉,广品编号A-9-2。 After the modified molecular sieve raw powder obtained, wide sample No. A-9-2.

[0142] 测试得到XRD衍射图,A-9-1为MCM-22分子筛,A-9-2为MCM-49分子筛,相对结晶度分别为98%和98% ; [0142] The XRD patterns obtained test, A-9-1 is zeolite MCM-22, A-9-2 is a molecular sieve MCM-49, the relative degree of crystallinity of 98% and 98%, respectively;

[0143] SEM测试显示A-9-1和A_9_2的形貌均由D_3的“花朵状”聚集转变为片状松散堆积; [0143] SEM tests showed A-9-1, and morphology by A_9_2 D_3 the "flower-shaped" loosely packed aggregates into a sheet;

[0144] BET分析显不:A_9_1分子筛的比表面积和孔体积分别为499m2/g和0.59cm3/g ;而A-9-2分子筛的比表面积和孔体积分别为499m2/g和0.60cm3/g ; [0144] BET analysis revealed no: specific surface area and pore volume of the molecular sieves were A_9_1 499m2 / g and 0.59cm3 / g; A-9-2 and the specific surface area and pore volume of the molecular sieve are 499m2 / g and 0.60cm3 / g ;

[0145] XRF 分析其Na2O 含量分别为0.40wt.% 和0.44wt.%。 [0145] XRF analysis which Na2O content of 0.40wt.% And 0.44wt.%, Respectively.

[0146] 氮气吸附-脱附的BJH曲线显示在3.8±0.5nm处的氮气脱附量为0.06cm3/g和 [0146] nitrogen adsorption - BJH desorption curves show the amount of nitrogen desorbed at 3.8 ± 0.5nm is 0.06cm3 / g and

0.06cm3/g,且其20°C吸附、200°C脱附后的2,4,6-三甲基吡啶的吸附量为44.3 ymol/g和42.1 μmol/g0 0.06cm3 / g, which is 20 ° C and adsorption, adsorption and desorption after the 200 ° C 2,4,6-trimethylpyridine was 44.3 ymol / g and 42.1 μmol / g0

[0147] 实施例10 [0147] Example 10

[0148] 本实施例说明本发明提供的分子筛和制备方法。 [0148] This example illustrates the method of preparation and molecular sieve provided by the invention. .

[0149] 将二甲基二乙基氢氧化铵溶液(25wt.% )和哌啶(PI)加入去离子水中,然后将对比例3中未经焙烧、含有六亚甲基亚胺和苯胺的MCM-22分子筛加入上述溶液中,继续搅拌均匀。 [0149] The dimethyl diethyl ammonium hydroxide solution (25wt.%) And piperidine (PI) of deionized water was added, and Comparative Example 3 will unfired, containing hexamethyleneimine, aniline and MCM-22 molecular sieve was added to the solution, and stirring was continued uniformly. 所得混合物胶体摩尔配比为Si02:0.1DEDMA0H:0.3PI:15H 20o然后,将所得混合物转移至密闭晶化釜中,晶化温度为150°C,动态晶化16h,冷却后取出产物,经过滤、洗涤、干燥和焙烧后,得到改性后分子筛原粉,产品编号A-10-1。 The resulting mixture was a colloidal molar ratio of Si02: 0.1DEDMA0H: 0.3PI: 15H 20o Then, the resulting mixture was transferred to a closed crystallization vessel, the crystallization temperature was 150 ° C, a dynamic crystallization for 16 h, cooled product was removed by filtration after washing, drying and calcining, to obtain the modified molecular sieve powder, product No. A-10-1.

[0150] 同上,区别在于将对比例3未经焙烧、含有六亚甲基亚胺和苯胺的MCM-22分子筛替换为对比例3中已经焙烧、不含六亚甲基亚胺和苯胺的MCM-22分子筛。 [0150] Ibid., Except that the calcination of Comparative Example 3 without containing hexamethyleneimine, aniline and zeolite MCM-22 is replaced in Comparative Example 3 has been fired, free of hexamethyleneimine and MCM aniline -22 molecular sieve. 得到改性后分子筛原粉,广品编号A-10-2。 After the modified molecular sieve raw powder obtained, wide sample No. A-10-2.

[0151] 测试得到XRD衍射图,A-10-1和A-10-2为MCM-22分子筛,相对结晶度分别为110%和110% ; [0151] The XRD patterns obtained test, A-10-1 and A-10-2 as MCM-22 zeolite, the relative crystallinity of 110% and 110%, respectively;

[0152] SEM测试显示,A-10-1和A_10_2形貌均D_3的“花朵状”聚集转变为片状松散堆积; [0152] SEM tests showed, A-10-1 and morphology are A_10_2 D_3 the "flower-shaped" loosely packed aggregates into a sheet;

[0153] BET分析显不:Α_10_1分子筛的比表面积和孔体积分别为499m2/g和0.65cm3/g ;而A-10-2分子筛的比表面积和孔体积分别为506m2/g和0.60cm3/g。 [0153] BET analysis revealed no: Α_10_1 zeolite surface area and pore volume are 499m2 / g and 0.65cm3 / g; and A-10-2 specific surface area and pore volume of the molecular sieve are 506m2 / g and 0.60cm3 / g .

[0154] XRF 分析其Na2O 含量分别为0.05wt.% 和0.1 Iwt.%。 [0154] XRF analysis which Na2O content of 0.05 wt.% And 0.1 Iwt.%, Respectively.

[0155] 氮气吸附-脱附的BJH曲线显示在3.8±0.5nm处的氮气脱附量为0.06cm3/g和 [0155] nitrogen adsorption - BJH desorption curves show the amount of nitrogen desorbed at 3.8 ± 0.5nm is 0.06cm3 / g and

0.06cm3/g,且其20°C吸附、200°C脱附后的2,4,6-三甲基吡啶的吸附量为40.4 ymol/g和 0.06cm3 / g, which is 20 ° C and adsorption, adsorption and desorption after the 200 ° C 2,4,6-trimethylpyridine was 40.4 ymol / g and

38.6 μmol/go 38.6 μmol / go

[0156] 对比例4 [0156] Comparative Example 4

[0157] 本对比例是按照CN103771435A中的方法以六亚甲基亚胺和苯胺为模板剂合成MCM-22分子筛。 [0157] This comparative example is the method according to CN103771435A hexamethyleneimine as the template the synthesis of aniline and MCM-22 molecular sieve.

[0158] —定量的偏铝酸钠(国药集团,分析纯)与氢氧化钠(北京试剂公司,分析纯)溶于去离子水中,搅拌至完全溶解,将海陵硅胶(青岛海洋化工厂,S12含量为97% )加入上述溶液,再加入六亚甲基亚胺(日本TCI公司,分析纯)、苯胺(北京化工厂,分析纯)。 [0158] - amount of sodium aluminate (Sinopharm, analytical grade) and sodium hydroxide (Beijing Reagent Company, analytically pure) dissolved in deionized water, stirring until completely dissolved, hailing silica gel (Qingdao Ocean Chemical Plant, S12 content of 97%) was added to the solution, then added hexamethyleneimine (TCI, Japan, analytical grade), aniline (Beijing chemical Plant, analytical grade). 混合物胶体摩尔配比为:0.18Na0H:Si02:0.033A1 203:0.05ΗΜΙ:0.25AN:15H 20,晶化温度145°C,自生压力下,以每分钟300转得搅拌速度晶化72小时,冷却后取出产物,经过滤、洗涤和干燥和焙烧后,得到样品。 The mixture molar ratio of colloid: 0.18Na0H: Si02: 0.033A1 203: 0.05ΗΜΙ: 0.25AN: 15H 20, the crystallization temperature of 145 ° C, under autogenous pressure, to give 300 revolutions per minute stirring speed crystallization for 72 hours cooled after the product was removed by filtration, washing and drying and after firing, to obtain a sample.

[0159] 测试得到XRD衍射图,2 Θ角5至35°。 [0159] XRD diffraction patterns obtained test, 2 Θ angle of 5 to 35 °. 产物为MCM-22分子筛,标记为D-4,相对结晶度为83% ; The product is zeolite MCM-22, labeled D-4, the relative degree of crystallinity of 83%;

[0160] SEM测试显示晶粒大小约为2.0〜4.0 μ m ; [0160] SEM tests showed that the grain size of about 2.0~4.0 μ m;

[0161] BET分析其比表面积和孔体积分别为375m2/g和0.44cm3/g ; [0161] BET specific surface area analysis and the pore volume are 375m2 / g and 0.44cm3 / g;

[0162] XRF 分析Na2O 含量为1.36wt.%。 [0162] XRF analysis Na2O content of 1.36wt.%.

[0163] 氮气吸附-脱附的BJH曲线显示在3.8±0.5nm处的氮气脱附量为0.18cm3/g,且其20°C吸附、200°C脱附后的2,4,6-三甲基吡啶的吸附量为18 ymol/g。 [0163] nitrogen adsorption - BJH desorption curves show the amount of nitrogen desorbed at 3.8 ± 0.5nm is 0.18cm3 / g, which is 20 ° C and adsorption, 2,4,6 desorbed after 200 ° C adsorption methylpyridine 18 ymol / g.

[0164] 实施例11 [0164] Example 11

[0165] 本实施例说明本发明提供的分子筛和制备方法。 [0165] This example illustrates the method of preparation and molecular sieve provided by the invention.

[0166] 将四乙基氢氧化铵溶液(25wt.% )和哌啶(PI)加入去离子水中,然后将对比例4中未经焙烧、含有六亚甲基亚胺和苯胺的MCM-22分子筛加入上述溶液中,继续搅拌均匀。 [0166] Tetraethyl ammonium hydroxide solution (25wt.%) And piperidine (PI) of deionized water was added, and in Comparative Example 4 will unfired, containing hexamethyleneimine, aniline and MCM-22 molecular sieves added to the solution, stirring was continued uniformly. 所得混合物胶体摩尔配比为Si02:0.1TEA0H:0.3P1:15H20。 The resulting mixture was a colloidal molar ratio of Si02: 0.1TEA0H: 0.3P1: 15H20. 然后,将所得混合物转移至密闭晶化釜中,晶化温度为150°C,动态晶化16h,冷却后取出产物,经过滤、洗涤、干燥和焙烧后,得到改性后分子筛原粉,产品编号为A-7-1。 Then, the resulting mixture was transferred to a closed crystallization vessel, the crystallization temperature was 150 ° C, a dynamic crystallization for 16 h, cooled product was removed by filtration, washed, dried and calcined after the molecular sieve powder to obtain a modified product No. A-7-1.

[0167] 同上,区别在于将对比例4中未经焙烧、含有六亚甲基亚胺和苯胺的MCM-22分子筛替换为对比例4中已经焙烧、不含六亚甲基亚胺和苯胺的MCM-22分子筛。 [0167] Ibid., Except that in Comparative Example 4 will unfired, MCM-22 containing hexamethyleneimine, aniline and replaced with molecular sieve in Comparative Example 4 has been fired, free of hexamethyleneimine and aniline MCM-22 molecular sieve. 得到改性后分子筛原粉,广品编号为A-7-2。 After the modified molecular sieve raw powder obtained, wide product No. A-7-2.

[0168] 测试得到XRD衍射图,A-11-1和A_ll_2为MCM-22分子筛,相对结晶度分别为110%和101% ; [0168] The XRD patterns obtained test, A-11-1 and A_ll_2 as MCM-22 zeolite, the relative crystallinity of 110% and 101%, respectively;

[0169] SEM测试显示,A-11-1和A_ll_2形貌均由D_4的“花朵状”聚集转变为片状松散堆积。 [0169] SEM tests showed, A-11-1 and morphology by A_ll_2 D_4 the "flower-shaped" loosely packed aggregates into a sheet.

[0170] BET分析显不分子筛的比表面积和孔体积分别为471m2/g和0.62cm3/g ;而A-11-2分子筛的比表面积和孔体积分别为485m2/g和0.60cm3/g。 [0170] BET specific surface area and pore volume analysis without significant molecular sieves were 471m2 / g and 0.62cm3 / g; and A-11-2 specific surface area and pore volume of the molecular sieve are 485m2 / g and 0.60cm3 / g.

[0171] XRF 分析其Na2O 含量分别为0.1lwt.%和0.25wt.%。 [0171] XRF analysis which Na2O content 0.1lwt.% And 0.25wt.%, Respectively.

[0172] 氮气吸附-脱附的BJH曲线显示在3.8±0.5nm处的氮气脱附量为0.05cm3/g和 [0172] nitrogen adsorption - BJH desorption curves show the amount of nitrogen desorbed at 3.8 ± 0.5nm is 0.05cm3 / g and

0.05cm3/g,且其20°C吸附、200°C脱附后的2,4,6-三甲基吡啶的吸附量为46.2 ymol/g和 0.05cm3 / g, which is 20 ° C and adsorption, adsorption and desorption after the 200 ° C 2,4,6-trimethylpyridine was 46.2 ymol / g and

46.1 μmol/g0 46.1 μmol / g0

[0173] 实施例12 [0173] Example 12

[0174] 本实施例说明本发明提供的分子筛和制备方法。 [0174] This example illustrates the method of preparation and molecular sieve provided by the invention.

[0175] 将二甲基二乙基氢氧化铵溶液(25wt.% )和哌啶(PI)加入去离子水中,然后将对比例4中未经焙烧,含有六亚甲基亚胺和苯胺的MCM-22分子筛加入上述溶液中,继续搅拌均匀。 [0175] The dimethyl diethyl ammonium hydroxide solution (25wt.%) And piperidine (PI) of deionized water was added, and in Comparative Example 4 will unfired, containing hexamethyleneimine, aniline and MCM-22 molecular sieve was added to the solution, and stirring was continued uniformly. 所得混合物胶体摩尔配比为:Si02:0.1DEDMA0H:0.3P1:15H20。 The resulting mixture molar ratio of colloid: Si02: 0.1DEDMA0H: 0.3P1: 15H20. 然后,将所得混合物转移至密闭晶化釜中,晶化温度为150°C,动态晶化16h,冷却后取出产物,经过滤、洗涤、干燥和焙烧后,得到处理后分子筛原粉,产品编号A-12-1。 Then, the resulting mixture was transferred to a closed crystallization vessel, the crystallization temperature was 150 ° C, a dynamic crystallization for 16 h, the product was removed after cooling, filtering, washing, drying and calcination was obtained after workup molecular sieve powder, Product No. A-12-1.

[0176] 同上,区别在于将对比例4中未经焙烧,含有六亚甲基亚胺和苯胺的MCM-22分子筛替换为对比例4的已经焙烧、不含有六亚甲基亚胺和苯胺的MCM-22分子筛。 [0176] Ibid., Except that in Comparative Example 4 will unfired, MCM-22 containing hexamethyleneimine, aniline and molecular sieves has been fired for the replacement of Comparative Example 4, not containing hexamethyleneimine, aniline and MCM-22 molecular sieve. 处理后分子筛原粉,广品编号A_12_2。 Post-processing molecular sieve powder, wide product number A_12_2.

[0177] 测试得到XRD衍射图,A-12-1和A_12_2为MCM-22分子筛,相对结晶度分别为104%和100% ; [0177] The XRD patterns obtained test, A-12-1 and A_12_2 as MCM-22 zeolite, the relative crystallinity of 104% and 100%, respectively;

[0178] SEM测试显示,A-12-1和A-12-2形貌均由D-4 “花朵状”聚集转变为片状松散堆积; [0178] SEM tests showed, A-12-1 A-12-2, and morphology by D-4 "flower-shaped" loosely packed aggregates into a sheet;

[0179] BET分子筛显不:A_12_1分子筛的比表面积和孔体积分别为450m2/g和0.57cm3/g ;而A-12-2分子筛的比表面积和孔体积分别为493m2/g和0.54cm3/g。 [0179] BET without significant molecular sieves: the specific surface area and pore volume of the molecular sieves were A_12_1 450m2 / g and 0.57cm3 / g; and A-12-2 specific surface area and pore volume of the molecular sieve are 493m2 / g and 0.54cm3 / g .

[0180] XRF 分析其Na2O 含量分别为0.29wt.% 和0.20wt.%。 [0180] XRF analysis which Na2O content of 0.29wt.% And 0.20wt.%, Respectively.

[0181] 氮气吸附-脱附的BJH曲线显示在3.8±0.5nm处的氮气脱附量为0.07cm3/g和 [0181] nitrogen adsorption - BJH desorption curves show the amount of nitrogen desorbed at 3.8 ± 0.5nm is 0.07cm3 / g and

0.06cm3/g,且其20°C吸附、200°C脱附后的2,4,6-三甲基吡啶的吸附量为42.0ymol/g和40.6 μmol/go 0.06cm3 / g, which is 20 ° C and adsorption, adsorption and desorption after 200 ° C for 2,4,6-trimethylpyridine 42.0ymol / g and 40.6 μmol / go

[0182] 对比例5 [0182] Comparative Example 5

[0183] 本对比例说明单独以无机碱处理原料MWW结构分子筛的过程和产物。 [0183] This comparative example illustrates the process of an inorganic base to separate material MWW structure and the molecular sieve product.

[0184] 本对比例中,原料MWW结构分子筛为上述对比例3中,未经焙烧、含有六亚甲基亚胺的MCM-22分子筛。 [0184] MCM-22 of the present comparative example, the raw material zeolite MWW structure as the above-described Comparative Example 3, unfired, hexamethyleneimine containing molecular sieves.

[0185] 将氢氧化钠(NaOH,96wt.% )加入去离子水中,然后将MCM-22分子筛加入上述溶液中,继续搅拌均匀,所得混合物胶体摩尔配比为Si02:0.1NaOH:15H20。 [0185] Sodium hydroxide (. NaOH, 96wt%) in deionized water was added, and then the MCM-22 molecular sieve was added to the solution, and stirring was continued for a uniform, the resulting mixture was colloid molar ratio of Si02: 0.1NaOH: 15H20. 将所得混合物胶体转移至密闭晶化釜中,在晶化温度为150°C下动态晶化16h,冷却后取出产物,经过滤、洗涤、干燥和焙烧后,得到处理后分子筛原粉,对应的处理后样品的编号为D-5-1。 The resulting mixture was colloid was transferred to a closed crystallization vessel, molecular sieve powder after crystallization temperature of 150 ° C under dynamic crystallization for 16 h, the product was removed after cooling, filtering, washing, drying and calcining after processed, the corresponding No treatment after the sample was D-5-1.

[0186] 同上,区别在于将对比例3的未经焙烧、含有六亚甲基亚胺和苯胺的MCM-22替换为对比例3已经焙烧、不含六亚甲基亚胺和苯胺的MCM-22。 [0186] Ibid., Except that of Comparative unfired 3, MCM-22 containing hexamethyleneimine, aniline and Comparative Example 3 has been replaced by firing free of hexamethyleneimine and MCM- aniline twenty two. 得到改性后分子筛原粉,对应的处理后样品的编号为D-5-2。 After the modified molecular sieve raw powder obtained, after the processing corresponding to the number of samples D-5-2.

[0187] 测试样品得到XRD衍射图,D-5-1为MCM-22分子筛,而D_5_2为MCM-49分子筛,相对结晶度分别为88%和80%。 [0187] The XRD patterns of the test sample was obtained, D-5-1 is a molecular sieve MCM-22, and MCM-49 molecular sieve is D_5_2, the relative degree of crystallinity of 88% and 80%, respectively.

[0188] SEM显示D-5-1和D_5_2样品形貌均由样品D-1的“花朵状”聚集转变为片状松散堆积。 [0188] SEM display D-5-1 and sample morphology D_5_2 by the sample D-1 "flower-shaped" into a sheet of loosely packed aggregates.

[0189] BET分子筛显不:D_5_1分子筛的比表面积和孔体积分别为461m2/g和0.71cm3/g ;而D-5-2分子筛的比表面积和孔体积分别为446m2/g和0.67cm3/g。 [0189] BET without significant molecular sieves: the specific surface area and pore volume of the molecular sieves were D_5_1 461m2 / g and 0.71cm3 / g; specific surface area and pore volume of the D-5-2 molecular sieves were 446m2 / g and 0.67cm3 / g .

[0190] XRF 分析D-5-1 和D-5-2 的Na2O 含量分别为3.29wt.%和3.48wt.%。 [0190] XRF analysis of D-5-1 and D-5-2 Na2O content of 3.29wt.% And 3.48wt.%, Respectively.

[0191] 氮气吸附-脱附的BJH曲线显示在3.8±0.5nm处的氮气脱附量为0.13cm3/g,且其20°C吸附、200°C脱附后的2,4,6-三甲基吡啶的吸附量为28 ymol/g。 [0191] nitrogen adsorption - BJH desorption curves show the amount of nitrogen desorbed at 3.8 ± 0.5nm is 0.13cm3 / g, which is 20 ° C and adsorption, 2,4,6 desorbed after 200 ° C adsorption methylpyridine 28 ymol / g.

[0192] 对比例6 [0192] Comparative Example 6

[0193] 本对比例说明以无机碱和有机胺处理原料MWW结构分子筛的过程和产物。 [0193] This comparative example illustrates an inorganic base and an organic amine, zeolite MWW structure of the raw material and the process product.

[0194] 将氢氧化钠(96wt.% )和哌啶(PI)加入去离子水中,然后将对比例3中未经焙烧、含有六亚甲基亚胺和苯胺的MCM-22加入上述溶液中,继续搅拌均匀。 [0194] Sodium hydroxide (96wt.%) And piperidine (PI) of deionized water was added, and Comparative Example 3 will unfired, containing hexamethyleneimine, aniline and MCM-22 was added to the solution stirring was continued for uniform. 所得混合物胶体摩尔配比为:Si02:0.1NaOH:0.3P1:15H20。 The resulting mixture molar ratio of colloid: Si02: 0.1NaOH: 0.3P1: 15H20. 然后,将所得混合物转移至密闭晶化釜中,晶化温度为150°C,动态晶化16h,冷却后取出产物,经过滤、洗涤、干燥和焙烧后,得到改性后分子筛原粉,样品编号为D-6-1。 Then, the resulting mixture was transferred to a closed crystallization vessel, the crystallization temperature was 150 ° C, a dynamic crystallization for 16 h, cooled product was removed by filtration, washed, dried and calcined after the molecular sieve powder to obtain a modified samples No. D-6-1.

[0195] 同上,区别在于将对比例3未经焙烧、含有六亚甲基亚胺和苯胺的MCM-22替换为对比例3已经焙烧、不含六亚甲基亚胺和苯胺的MCM-22。 [0195] Ibid., Comparative Example 3 except that will unfired, MCM-22 containing hexamethyleneimine, aniline and Comparative Example 3 has been replaced by firing free of hexamethyleneimine, aniline and MCM-22 . 得到改性后分子筛原粉,样品编号为D-6-2. Modified molecular sieve raw powder obtained after the sample No. D-6-2.

[0196] 测试得到XRD衍射图,D-6-1和D_6_2为MCM-22分子筛,相对结晶度分别为93 %和90% ; [0196] The XRD patterns of test result, D-6-1 D_6_2 as MCM-22 and zeolite, the relative crystallinity of 93% and 90%, respectively;

[0197] SEM测试,样品形貌均由D-3的“花朵状”聚集转变为片状松散堆积; [0197] SEM test sample D-3 by the morphology of the "flower-shaped" loosely packed aggregates into a sheet;

[0198] BET分析显不:D_6_1分子筛的比表面积和孔体积分别为481m2/g和0.74cm3/g ;而D-6-2分子筛的比表面积和孔体积分别为470m2/g和0.65cm3/g ; [0198] BET analysis revealed no: specific surface area and pore volume of the molecular sieves were D_6_1 481m2 / g and 0.74cm3 / g; specific surface area and pore volume of the D-6-2 molecular sieves were 470m2 / g and 0.65cm3 / g ;

[0199] XRF 分析其Na2O 含量分别为3.63wt.%和3.26wt.%。 [0199] XRF analysis which Na2O content of 3.63wt.% And 3.26wt.%, Respectively.

[0200] 氮气吸附-脱附的BJH曲线显示在3.8±0.5nm处的氮气脱附量为0.12cm3/g和 [0200] nitrogen adsorption - BJH desorption curves show the amount of nitrogen desorbed at 3.8 ± 0.5nm is 0.12cm3 / g and

0.lOcmVg,且其20°C吸附、200°C脱附后的2,4,6-三甲基吡啶的吸附量为33.lymol/g和 0.lOcmVg, and which is 20 ° C, and the adsorption amount after 200 ° C desorption of 2,4,6-trimethylpyridine 33.lymol / g and

30.1 μmol/go 30.1 μmol / go

Claims (14)

  1. 1.一种MWW结构分子筛,其特征在于该分子筛的氮气吸附-脱附的BJH曲线显示在3.8±0.5nm处的氮气脱附量为0.0l〜0.10cm3/g,且其20°C吸附、200°C脱附后的2,4,6-三甲基吡啶的吸附量为彡35 ymol/go A zeolite MWW structure, wherein the molecular sieve adsorption of nitrogen - BJH desorption curve is shown in the desorption amount of nitrogen is at 3.8 ± 0.5nm 0.0l~0.10cm3 / g, which is 20 ° C and adsorption, adsorption and desorption after 200 ° C for 2,4,6-trimethylpyridine San 35 ymol / go
  2. 2.按照权利要求1的分子筛,其中,所述的该分子筛的氮气吸附-脱附的BJH曲线显示在3.8±0.5nm处的氮气脱附量0.01〜0.08cm3/g,且其20 °C吸附、200 °C脱附后的2,4,6-三甲基吡啶的吸附量为40〜60 ymol/g。 2. The molecular sieve according to claim 1, wherein the nitrogen adsorption of the molecular sieve - BJH desorption curves show the amount of nitrogen desorbed at 3.8 ± 0.5nm 0.01~0.08cm3 / g, which is 20 ° C and adsorption , adsorption and desorption after 200 ° C for 2,4,6-trimethylpyridine 40~60 ymol / g.
  3. 3.按照权利要求1的分子筛,其中,所述的该分子筛的氮气吸附-脱附的BJH曲线显示在3.8 ± 0.5nm处的氮气脱附量为0.0I〜0.05cm3/g,且其20 °C吸附、200 °C脱附后的2,4,6-三甲基吡啶的吸附量为40〜50 ymol/g。 3. The molecular sieve according to claim 1, wherein the nitrogen adsorption of the molecular sieve - BJH desorption curve is shown in the desorption amount of nitrogen is at 3.8 ± 0.5nm 0.0I~0.05cm3 / g, and its 20 ° C, and the adsorption amount after 200 ° C desorption of 2,4,6-trimethylpyridine 40~50 ymol / g.
  4. 4.按照权利要求1的分子筛,其特征在于分子筛形貌呈现片状松散堆积。 4. The molecular sieve according to claim 1, characterized in that the zeolite exhibits a sheet-like morphology loosely packed.
  5. 5.权利要求1-4的MWW结构分子筛的制备方法,其特征在于将原料MWW结构分子筛、含氮有机碱RU有机胺R2、去离子水混合均匀得到摩尔比为H20/Si02= 5〜100、Rl/S1 2=0.01〜5、R2/Si02= O〜I的混合物,并将该混合物在100〜180°C下晶化处理5〜72h并回收,其中,所说的含氮有机碱Rl,选自四甲基氢氧化铵、四乙基氢氧化铵、四丙基氢氧化铵、二甲基二乙基氢氧化铵、一甲基三乙基氢氧化铵、一甲基三丙基氢氧化铵、二甲基二丙基氢氧化铵、一乙基三甲基氢氧化铵、二乙基二丙基氢氧化铵、一乙基三丙基氢氧化铵、一丙基三甲基氢氧化铵和一丙基三乙基氢氧化铵中的至少一种,所说的有机胺R2,选自五亚甲基亚胺、六亚甲基亚胺、七亚甲基亚胺、1,4-二氮环庚烷、环庚烷胺、环己烷胺、环戊胺、苯胺、哌啶和哌嗪中的至少一种。 Zeolite MWW structure prepared according to claim 1-4, characterized in that the raw material zeolite MWW structure, a nitrogen-containing organic bases RU organic amine R2, deionized water were mixed uniformly to obtain a molar ratio of H20 / Si02 = 5~100, Rl / S1 2 = 0.01~5, R2 / Si02 = O~I the mixture, and the mixture was 5~72h crystallization treatment at 100~180 ° C and recovering, wherein said nitrogen-containing organic bases Rl, is selected from tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, dimethyl diethyl ammonium hydroxide, monomethyl-triethyl ammonium hydroxide, tripropyl-methyl hydrogen ammonium hydroxide, dimethyl dipropyl ammonium hydroxide, an ethyl trimethyl ammonium hydroxide, diethyl-dipropyl ammonium hydroxide, an ammonium hydroxide, tripropyl ethyl, a propyl trimethylhydroquinone ammonium oxide and a triethyl propyl ammonium hydroxide, at least one of said organic amine R2, imines selected pentamethylene, hexamethylene imine, heptamethylene imine, 1, 4-N cycloheptane, cycloheptane at least one amine, cyclohexane amine, cyclopentylamine, aniline, piperidine and piperazine in.
  6. 6.按照权利要求5的方法,其中,所述的原料MWW结构分子筛为未经焙烧脱除模板剂的Mffff结构分子筛。 6. The method according to claim 5, wherein said material is a zeolite MWW structure Mffff unfired structure of the molecular sieve to remove the templating agent.
  7. 7.按照权利要求5或6的方法,其中,所述的原料MWW结构分子筛选自MCM-22、MCM-49、MCM-56、SSZ-25和UZM-8中的一种或多种分子筛。 7. A method according to claim 5 or 6, wherein said material is selected from zeolite MWW structure MCM-22, MCM-49, MCM-56, one or more molecular sieve SSZ-25 and 8 UZM-.
  8. 8.按照权利要求5的方法,其中,所述的原料MWW结构分子筛的相对结晶度小于90%。 8. The method according to claim 5, wherein said zeolite MWW structure relative crystallinity of less than 90% of the starting material.
  9. 9.按照权利要求5的方法,其中,所述的混合物的摩尔比为H20/Si02= 5〜50、R1/Si02=0.05 〜0.5、R2/Si02= O 〜0.5。 9. The method according to claim 5, wherein the molar ratio of said mixture of H20 / Si02 = 5~50, R1 / Si02 = 0.05 ~0.5, R2 / Si02 = O ~0.5.
  10. 10.按照权利要求5的方法,其中,所述的混合物的摩尔比为H20/Si02= 10〜25、Rl/S12= 0.05 〜0.2、R2/Si0 2= 0.1 〜0.3。 10. The method according to claim 5, wherein the molar ratio of said mixture of H20 / Si02 = 10~25, Rl / S12 = 0.05 ~0.2, R2 / Si0 2 = 0.1 ~0.3.
  11. 11.按照权利要求5的方法,其中,所述的含氮有机碱Rl为四乙基氢氧化铵和/或二甲基二乙基氢氧化铵。 11. The method according to claim 5, wherein said nitrogen-containing organic bases Rl is tetraethyl ammonium hydroxide and / or dimethyl diethyl ammonium hydroxide.
  12. 12.按照权利要求5的方法,其中,所述的有机胺R2为六亚甲基亚胺、苯胺、哌啶和哌嗪中的至少一种。 12. The method according to claim 5, wherein said R2 is at least one organic amine hexamethyleneimine, aniline, piperidine and piperazine in.
  13. 13.按照权利要求5的方法,其中,所述的含氮有机碱Rl为四乙基氢氧化铵和/或二甲基二乙基氢氧化铵,同时有机胺R2为六亚甲基亚胺和/或哌啶。 13. The method according to claim 5, wherein said nitrogen-containing organic bases Rl is tetraethyl ammonium hydroxide and / or dimethyl diethyl ammonium hydroxide, and organic amines R2 is hexamethylene imine and / or piperidine.
  14. 14.按照权利要求5的方法,其中,所说的混合物在140〜160°C晶化时间8〜36h。 14. The method according to claim 5, wherein said mixture at 140~160 ° C the crystallization time 8~36h.
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CN102309980A (en) * 2010-06-30 2012-01-11 中国石油化工股份有限公司 Steam modifying method of titanium-silicon molecular sieve
CN102850197A (en) * 2011-06-30 2013-01-02 中国石油化工股份有限公司 Method for preparing cyclohexanone

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Publication number Priority date Publication date Assignee Title
US5340563A (en) * 1992-06-30 1994-08-23 Chevron Research And Technology Company Preparation of zeolites using low silica/alumina zeolites as a source of aluminum
CN101850986A (en) * 2009-03-31 2010-10-06 中国石油化工股份有限公司;中国石油化工股份有限公司石油化工科学研究院 Method for modifying titanium-silicalite
CN102309980A (en) * 2010-06-30 2012-01-11 中国石油化工股份有限公司 Steam modifying method of titanium-silicon molecular sieve
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