CN106853972A - Stable synthetic method for TON zeolite - Google Patents

Stable synthetic method for TON zeolite Download PDF

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CN106853972A
CN106853972A CN 201510900661 CN201510900661A CN106853972A CN 106853972 A CN106853972 A CN 106853972A CN 201510900661 CN201510900661 CN 201510900661 CN 201510900661 A CN201510900661 A CN 201510900661A CN 106853972 A CN106853972 A CN 106853972A
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ton
zeolite
source
gel
mother liquor
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CN 201510900661
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Chinese (zh)
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谢彬
王新苗
翟绪丽
高善彬
杨晓东
张志华
胡胜
王延飞
付凯妹
余颖龙
张雅琳
张瑀健
庄梦琪
刘彦峰
郭金涛
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中国石油天然气股份有限公司
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Abstract

The invention relates to a stable synthetic method for TON zeolite. According to the method, zeolite crystallization mother liquor with a TON structure is used as an inductive agent for synthesis of zeolite with the TON structure. The method comprises the following steps: adding the TON zeolite crystallization mother liquor into initial gel in proportion and carrying out a hydro-thermal reaction under sealing conditions so as to obtain a TON zeolite product with a crystallization degree of more than 97%. According to the method, mother liquor produced in primary crystallization of TON zeolite is recovered and utilized; the TON zeolite product with high purity can be obtained in a short period of time under the condition of standing or nonviolent stirring; so the success rate of synthesis of the zeolite is increased, and growth of crystal phases like ZSM-5 and cristobalite is prevented.

Description

一种TON沸石的稳定合成方法 A method for stabilizing synthetic zeolites TON

技术领域 FIELD

[0001] 本发明涉及一种TON沸石的合成方法。 [0001] The present invention relates to a method for synthesizing zeolites TON.

背景技术 Background technique

[0002] TON沸石分子筛于1985年由Mobil公司专利报道US4556477,由于其具有一维10 圆环的椭圆形中孔结构,孔径约为〇. 46X0. 57nm。 [0002] TON Zeolite Mobil in 1985 reported by the patent US4556477, since the circular ring 10 having an elliptical shape in one-dimensional pore structure, pore size of about square. 46X0. 57nm. 由于其在烯烃选择性转化过程中表现出优异的选择性,因此被作为一种重要的烃类异构催化剂载体,而被广泛地应用在重质油脱异构蜡反应之中。 Since it exhibits excellent selectivity in olefin selectivity of the conversion process, therefore as an important hydrocarbon isomerization catalyst carrier, are widely used in heavy oil off into a wax isomerization reaction.

[0003] 通常TON 沸石的合成是将Si02、Al203、K20 或Na20、H2N-(CH2)n-NH2(n = 2-12)等有机模板剂与水混合,在高压反应釜中于90〜200°C水热处理3〜7天制得。 [0003] Synthetic zeolites are generally TON will Si02, Al203, K20 or Na20, H2N- (CH2) n-NH2 (n = 2-12) and the like organic templating agent is mixed with water, in an autoclave at 90~200 ° C water heat prepared 3~7 days. 但是,这一反应必须通过高速搅拌(300〜400rpm)以换取TON分子筛的纯度,如US4481177、US4902406、 US4900528,否则很容易合成失败,而得到ZSM-5或白硅石等杂晶。 However, this reaction must be a high speed stirring (300~400rpm) in exchange for purity TON molecular sieves, such as US4481177, US4902406, US4900528, or readily synthesized failure to obtain ZSM-5 or silica, etc. heteroaryl white crystals.

[0004] 为解决这一技术问题,US5783168专利报道了一种TON沸石的改进合成技术。 [0004] In order to solve this technical problem, US5783168 patent reports an improved synthesis technique TON zeolite. 其主要特征是在通常的合成体系下,引入TON沸石作为晶种,加入量占凝胶质量的在500-3000ppm,即使在搅拌不充分的条件下,经过水热反应,依然可以获得纯度很高的TON 沸石结构,降低了反应的苛刻性。 Its main feature is in the usual synthesis system, incorporated TON zeolite as a seed crystal, high quality gel was added in an amount of 500-3000 ppm, even under conditions of insufficient stirring, after the hydrothermal reaction, the purity can be obtained still the zeolites TON structure, reducing the severity of the reaction. CN101941718报道了一种采用导向剂合成TON沸石的方法。 CN101941718 reported a method of using TON zeolite synthesis directing agent. 其主要特征是首先合成出TON沸石的结构导向剂,然后在通常的合成体系中加入其凝胶质量的5〜20%的结构导向剂,经水热反应,即可以得到具有纯度较高的TON沸石产品。 Its main feature is the first synthetic zeolite TON structure directing agent, and then added 5~20% by mass of gel structure directing agent in a conventional synthetic system, the hydrothermal reaction, which can be obtained with higher purity TON zeolite products. CN103274428A中报道了将TON分子筛晶化母液循环使用,在微波辅助下合成纳米TON分子筛的方法,有利于母液回收并减少污染。 CN103274428A TON molecular sieves reported in the crystallization mother liquor recycled, in a method for synthesizing nano microwave assisted TON molecular sieves, and recycled mother liquor is beneficial to reduce pollution. 由于微波技术的引入,有利于物质受热均匀,加速分子筛的晶化速率,但其合成过程均是在动态搅拌条件下辅助实现。 Since the introduction of microwave technology, to facilitate uniform heating material, accelerate the rate of crystallization of the molecular sieve, but its synthesis are achieved at a dynamic auxiliary stirring. 而且并未对搅拌速率提出具体要求。 But did not make specific demands on the stirring rate. 众所周知,剧烈搅拌可以提高物料返混程度,实现反应釜内物料的均匀,有利于合成相对结晶度较高的TON沸石分子筛。 It is well known materials with vigorous stirring may enhance the degree of backmixing, to achieve uniformity in the reaction vessel material, facilitate the synthesis of relatively high crystallinity TON zeolitic molecular sieve. 但这也对反应釜的搅拌材质提出了过高的要求,不利于实际工业生产的进行。 But it also stirred reactor material put forward excessive demands, not conducive to the actual industrial production.

发明内容 SUMMARY

[0005] 本发明目的是提供一种稳定合成TON沸石的方法,该方法回收TON沸石一次晶化母液来制备TON沸石,制得的TON沸石相对结晶度高,并且降低了反应的苛刻程度。 [0005] The object of the present invention to provide a method for stabilizing synthetic zeolites TON, the primary process for recovering zeolite crystals prepared TON TON zeolite mother liquor, the resulting zeolite TON relatively high crystallinity, and reduces the severity of the reaction.

[0006] 为达到上述目的,本发明提供一种TON沸石的稳定合成方法,向反应凝胶中加入TON沸石一次晶化母液,TON沸石一次晶化母液的质量为反应凝胶质量的11〜35%,在静止的条件下,经水热反应,得到相对结晶度高于97%的TON沸石产品。 [0006] To achieve the above object, the present invention provides a method of stabilizing TON zeolite synthesis, the zeolite is added to the reaction TON gel primary crystallization mother liquor, once TON zeolite crystallization mother liquor of the reaction mass of the gel mass 11~35 %, under stationary conditions, the hydrothermal reaction, TON zeolite product to give a relative crystallinity of greater than 97%.

[0007] 本发明所述的TON沸石的稳定合成方法,其中,所述TON沸石一次晶化母液的质量优选为反应凝胶质量的11〜30%。 TON stable zeolite synthesis method of [0007] the present invention, wherein the zeolite is a crystalline quality TON mother liquor is preferably 11~30% by mass of the reaction gel.

[0008] 本发明所述的TON沸石的稳定合成方法,其中,所述TON沸石一次晶化母液的质量优选为反应凝胶质量的15〜25%。 [0008] TON stable zeolite synthesis method of the present invention, wherein the zeolite is a crystalline quality TON mother liquor is preferably 15~25% by mass of the reaction gel.

[0009] 本发明所述的TON沸石的稳定合成方法,其中,所述反应凝胶是由以下组分混合搅拌制成的: [0009] TON stable zeolite synthesis method of the present invention, wherein the gel is a reaction mixture of the following components was stirred to make:

[0010] (1)硅源或锗源; [0010] (1) a silicon source and germanium source;

[0011] ⑵铝源; [0011] ⑵ aluminum source;

[0012] (3)碱金属源; [0012] (3) an alkali metal source;

[0013] (4)有机模板剂; [0013] (4) an organic templating agent;

[0014] (5)去离子水。 [0014] (5) of deionized water.

[0015] 其中,所述硅源为含有氧化硅成分的硅溶胶、白炭黑或正硅酸乙酯;所述锗源、铝源、硼源、镓源、铁源、钒源、铬源为含有对应金属的氧化物;所述碱金属源为NaOH和/或K0H,简称MeOH ;有机模板剂为1,6-己二胺和/或乙胺,简称R ;各组分的摩尔比例为:Si〇2/ A1203= 30 〜300,MeOH/Al 203= 0. 2 〜0. 8, R/Si02= 0. 2 〜0• 7, H20/Si02= 1〇〜60。 [0015] wherein the silicon source is silica sol containing silicon oxide component, silica or tetraethoxysilane; a germanium source, an aluminum source, a boron source, a gallium source, an iron source, a vanadium source, a chromium source containing an oxide of the corresponding metal; the alkali metal source is NaOH and / or K0H, referred MeOH; organic templating agent is hexamethylenediamine and / or ethylamine, referred to as R & lt; molar ratio of the components is : Si〇2 / A1203 = 30 ~300, MeOH / Al 203 = 0. 2 ~0 8, R / Si02 = 0. 2 ~0 • 7, H20 / Si02 = 1〇~60. [0016] 本发明所述的TON沸石的稳定合成方法,其中,优选的是,所述TON沸石产品中,白硅石和/或ZSM-5的含量小于TON沸石产品质量的3%。 TON stable zeolite synthesis method of [0016] the present invention, wherein, preferably, the TON zeolite product, and / or cristobalite content of ZSM-5 is less than 3% TON zeolite product quality.

[0017] 本发明所述的TON沸石的稳定合成方法,其中,优选的是,所述TON沸石产品中,白硅石和/或ZSM-5的含量小于TON沸石产品质量的3%。 [0017] TON stable zeolite synthesis method of the present invention, wherein, preferably, the TON zeolite product, and / or cristobalite content of ZSM-5 is less than 3% TON zeolite product quality.

[0018] 本发明所述的TON沸石的稳定合成方法,其中,所述水热反应时间最好少于等于44小时。 [0018] TON stable zeolite synthesis method of the present invention, wherein the hydrothermal reaction time is preferably less than or equal 44 hours.

[0019] 本发明所述的TON沸石的稳定合成方法,其中,所述水热反应时间最好少于等于44小时。 [0019] TON stable zeolite synthesis method of the present invention, wherein the hydrothermal reaction time is preferably less than or equal 44 hours.

[0020] 众所周知,沸石分子筛的晶化母液中,含有大量有机模板剂,排废压力较大,处理费用较高。 [0020] It is well known Zeolite Crystallization of the mother liquor, it contains a large amount of organic templating agent, waste discharge pressure, higher treatment costs. 另外,由于沸石晶化母液中含有大量可以组成该沸石的次级结构或复合态的结构单元,因此可以将其回收利用,并作为结构诱导剂提高该沸石的合成效率。 Further, since the zeolite crystallization mother liquor may constitute a structural unit containing a large amount of secondary structure, or a composite state of the zeolite, so it can be recycled and increase the efficiency of the synthesis of the zeolite as a structure-inducing agent.

[0021] 本发明的有益效果为:将一次合成过程所产生的母液进行回收,在二次合成过程中,只需向其中加入一定量一次合成所产生的母液,在常规可合成出TON沸石的配比条件下进行晶化,即使在体系静止或搅拌不剧烈的情况下,仍可得到高纯度TON沸石分子筛。 [0021] Advantageous effects of the present invention is: a synthetic mother liquor produced by the process for recycling in the secondary synthesis process, to which only a certain amount of mother liquor generated synthesis, can be synthesized in a conventional zeolites TON ratios crystallization conditions, even in a system not vigorously stirred or static conditions, may still obtain high purity TON zeolitic molecular sieves. 解决了工业放大过程中由于搅拌不充分,合成易失败,而转变为ZSM-5晶相或伴生出白硅石等晶相污染的问题,进而提高TON沸石的合成成功率,从原料和生产工艺两方面共同降低了生产成本。 Solve industrial scale process due to insufficient stirring, the synthesis is easy fails converted into ZSM-5 crystal phase or accompanying the crystal phase contamination problem of white silica and the like, thereby improving the successful synthesis of TON zeolites from raw materials and production processes two aspects common to reduce production costs.

[0022] 与常规技术所需高速搅拌或含有白硅石污染物相比,本反应静止条件下得到相对结晶度高的TON沸石分子筛降低了反应苛刻度,提高了合成成功率。 [0022] Compared with the conventional technique required a high-speed stirring or white silica containing contaminants present reaction TON relatively high crystallinity of zeolite molecular sieves under static conditions reduces the reaction severity, improve the success rate of synthesis.

附图说明: BRIEF DESCRIPTION OF:

[0023] 图1是本发明实施例1合成的TON沸石分子筛X光衍射(以下简称:XRD)谱图。 [0023] FIG. 1 is a zeolitic molecular sieve TON X-ray diffraction (hereinafter referred to as: XRD) Synthesis Example 1 of the present invention spectra.

[0024] 图2是本发明实施例1合成的TON沸石分子筛扫描电镜图片(下简称SEM)。 [0024] FIG. 2 is a zeolitic molecular sieve TON SEM image (hereinafter referred to as SEM) Synthesis Example 1 of the present invention.

[0025] 图3是本发明实施例2合成的纯品的TON沸石分子XRD谱图。 [0025] FIG. 3 is a zeolite molecular TON XRD spectrum of Example 2 Synthesis of pure embodiments of the present invention.

[0026] 图4是本发明实施例2的对比例1合成的ZSM-5分子筛XRD谱图。 [0026] FIG. 4 is synthesized in Comparative Example 1. XRD pattern of zeolite ZSM-5 of Example 2 of the present invention.

[0027] 图5是本发明实施例3合成的纯品的TON沸石分子筛XRD谱图。 [0027] FIG. 5 is a TON of pure zeolite synthesized in Example 3 XRD pattern of zeolite embodiment of the present invention.

[0028] 图6是本发明实施例4合成的含有少于1% ZSM-5的TON沸石分子筛XRD谱图。 [0028] FIG. 6 is an embodiment of the present invention synthesized in Example 4 containing less than 1% ZSM-5 zeolitic molecular sieves of TON XRD spectrum.

[0029] 图7是本发明对比例2合成的含有大量ZSM-5、无定型与TON沸石分子筛XI®谱图。 [0029] FIG. 7 contains a large amount of the present invention is ZSM-5 synthesized in Comparative Example 2, amorphous zeolite molecular sieve with TON XI® spectrum.

[0030] 图8是本发明对比例3合成的相对结晶度小于90%的TON沸石分子筛XRD谱图。 [0030] FIG. 8 is a relative crystallinity of the present invention synthesized in Example 3 less than 90% of the zeolitic molecular sieve TON XRD spectrum.

[0031] 图9是本发明实施例5合成的TON沸石分子筛XRD谱图。 [0031] FIG. 9 is an XRD pattern of zeolite molecular sieve TON Example 5 Synthesis embodiment of the present invention.

[0032] 图10是本发明实施例5合成的TON沸石分子筛SEM图片。 [0032] FIG. 10 is a TON zeolite synthesis of Example 5 of the present invention, the molecular sieve SEM image.

[0033] 图11是本发明对比例4合成的ZSM-5分子筛XRD谱图。 [0033] Example 4 FIG. 11 is a synthetic zeolite ZSM-5 XRD pattern of the present invention.

具体实施方式 detailed description

[0034] 以下通过实施例进一步详细描述本发明,但这些实施例不应认为是对本发明的限制。 [0034] The present invention is described in further detail by way of examples, but these examples should not be construed as limiting the present invention.

[0035] 实施例1 [0035] Example 1

[0036] TON沸石一次晶化母液的获得 [0036] TON a zeolite crystallization mother liquor obtained

[0037] 参照US5783168专利的合成方法制备TON沸石分子筛,并将其一次过滤母液回收。 [0037] Referring synthetic process patent US5783168 TON zeolite molecular sieves, filtered and the mother liquor recovered once.

[0038] 具体操作如下:在搅拌条件下,将〇• 3¾ A12(S04)3 • 1洲20溶解于30g水中,然后加入0. 9g K0H,充分搅拌后形成澄清溶液A ;称取2. 5g 1,6-己二胺(DAH),加入溶液A中, 待溶解后,再向溶液A中加入l〇g硅溶胶(含Si02质量3〇% ),经搅拌后,形成一均匀凝胶B ;其具体组成为(摩尔比)Si02:l. 00A1 203:14_ 00K20 :38. 60DAH :3610H20 = 88. 00 :1. 00 : 14. 00 :38. 60 :3610〇 [0038] Specific operation is as follows: Under stirring, square • 3¾ A12 (S04) 3 • 1 was dissolved in 20 Chau 30g water and then adding 0. 9g K0H, A clear solution is formed. After stirring; Weigh 2. 5g 1,6-diamine (the DAH), solution a was added, to be dissolved, the solution a was added again l〇g silica sol (Si02 containing 3〇% by mass), was stirred to form a homogeneous gel B ; specific composition (molar ratio) Si02: l 00A1 203: 14_ 00K20: 38 60DAH: 3610H20 = 88. 00: 1 00: 14. 00: 38 60: 3610〇....

[0039] 将凝胶B转入到具有聚四氟乙烯衬里的100mL不锈钢反应釜中,在160°C条件下, 搅拌速率400rpm,水热反应4Sh。 [0039] The gel was transferred to a B having a 100mL teflon-lined stainless steel reactor, under conditions of 160 ° C, agitation rate of 400 rpm, a hydrothermal reaction 4Sh. 待冷却后,将产物室温过滤,得到2. 6g产品,41g —次过滤母液。 After cooling, the product was filtered at room temperature to give product 2. 6g, 41g - secondary mother liquor by filtration. 经XRD表征得知,产品为相对结晶度为97 %的TON沸石分子筛。 Characterized by XRD that the product is a relative crystallinity of 97% TON zeolitic molecular sieve. 图1、图2所示。 FIG 1 and FIG 2.

[0040] 实施例2 [0040] Example 2

[0041] 160°C、反应42小时,15%母液使用量,静止合成TON分子筛 [0041] 160 ° C, reaction was 42 hours, 15% of the amount of mother liquor, still synthetic zeolite TON

[0042] 按照实施例1中所述,制备凝胶B。 [0042] In the embodiment according to Example 1, B. Preparation of Gel 其具体组成为(摩尔比)Si02:1.00Al 203: 14. OOK20 :38. 60DAH :3610H20 = 88. 00 :1. 00 :14. 00 :38. 60 :3610。 The specific composition (molar ratio) Si02: 1.00Al 203: 14. OOK20:. 38 60DAH: 3610H20 = 88. 00:. 1 00:. 14 00:. 38 60: 3610. 然后向其中加入凝胶B 总质量15%的TON沸石一次过滤母液。 It was then added the total mass of the gel TON B 15% of a zeolite mother liquor by filtration. 经搅拌,形成均匀凝胶C。 Stirred, homogeneous gel is formed C. 将凝胶C转入到具有聚四氟乙烯衬里的lOOmL不锈钢反应釜中,在160°C,静止条件下,水热反应42h。 The gel was transferred to a lOOmL C with a teflon-lined stainless steel autoclave at 160 ° C, static conditions, the hydrothermal reaction was 42h. 待冷却后, 将产物室温过滤,得到2.6g产品。 After cooling, the product was filtered at room temperature to give 2.6g product. 经XRD表征得知,产品为纯净TON沸石分子筛。 Characterized by XRD that the product is pure TON zeolite. 图3所不。 FIG 3 is not.

[0043] 对比例1 [0043] Comparative Example 1

[0044] 按照实施例1中所述,制备凝胶B。 [0044] In the embodiment according to Example 1, B. Preparation of Gel 其具体组成为(摩尔比)Si02:l. 00A1 203: 14. 00K20 : 38. 60DAH :3610H20 = 88. 00 :1. 00 :14. 00 :38. 60 :3610。 The specific composition (molar ratio) Si02: l 00A1 203:. 14. 00K20: 38. 60DAH: 3610H20 = 88. 00:. 1 00:. 14 00:. 38 60: 3610. 将凝胶B 转入到具有聚四氟乙烯衬里的lOOmL不锈钢反应釜中,在16(TC,静止条件下,水热反应44h。待冷却后, 将产物室温过滤,得到2. 6g产品。经XRD表征得知,产品为纯净ZSM-5沸石分子筛。图4 所示。 The gel was transferred to a B lOOmL stainless steel autoclave lined with polytetrafluoroethylene, at 16 (TC, quiescent conditions, the hydrothermal reaction was 44h. After cooling to room temperature the product was filtered to give product 2. 6g. By XRD results that the product is pure ZSM-5 zeolite molecular sieve. 4 shown in FIG.

[0045] 由图3和图4进行对比可知,采用晶化母液诱导合成,在静止条件下可以得到TON 为主晶相的广品;反之则只能得到ZSM-5沸石分子筛。 [0045] by comparison of FIGS. 3 and 4 shows that induce the synthesis using crystallization mother liquor, obtained main crystalline phase is wide TON product under stationary conditions; otherwise only obtained ZSM-5 zeolite molecular sieve.

[0046] 实施例3 [0046] Example 3

[0047] 160°C、反应似小时,2〇%母液使用量,静止合成TON分子筛 [0047] 160 ° C, the reaction seems hours, the amount of liquor 2〇%, still synthetic zeolite TON

[0048] 按照实施例1中所述,制备凝胶B,其中硅源为白炭黑、铝源为拟薄水铝石。 [0048] 1 according to the prepared gel B, where the silicon source is silica embodiment, the aluminum source is quasi boehmite. 其具体组成为(摩尔比)Si02:l. 00A1 203:14. 00K20 :38. 60DAH :3610H20 = 88. 00 :1_ 〇〇:14_ 00 : 38. 60 :3610。 The specific composition (molar ratio) Si02: l 00A1 203:.. 14 00K20:. 38 60DAH: 3610H20 = 88. 00: 1_ thousand and: 14_ 00: 38.60: 3610. 然后向其中加入凝胶B总质量20%的TON沸石一次过滤母液。 It was then added the total mass of the gel B 20% of a zeolite TON filtered mother liquor. 经搅拌,形成均匀凝胶C。 Stirred, homogeneous gel is formed C. 将凝胶C转入到具有聚四氟乙烯衬里的lOOmL不锈钢反应釜中,在16(TC,静止条件下,水热反应42h。待冷却后,将产物室温过滤,得到2. 6g产品。经XRD表征得知,产品为纯净TON沸石分子筛。图5所示。 The gel was transferred to a lOOmL C stainless steel autoclave lined with polytetrafluoroethylene, in 16 (TC, under static conditions, the hydrothermal reaction was 42h. After cooling to room temperature the product was filtered to give product 2. 6g. By XRD results that the product is pure zeolite TON. 5 shown in FIG.

[0049] 实施例4 [0049] Example 4

[0050] 160°C、反应48小时,25%母液使用量,静止合成TON分子筛 [0050] 160 ° C, 48 hours, 25% of the amount of mother liquor, still synthetic zeolite TON

[0051] 按照实施例1中所述,制备凝胶B,其中硅源为硅胶、铝源为氯化铝。 [0051] Example 1 according to the prepared gel B, where the silicon is a silica source, an aluminum source is aluminum chloride. 其具体组成为(摩尔比)Si02:l. 00A1 203:14. 00K20 :38. 60DAH :3610H20 = 88. 00 :1. 00 :14. 00 : 38_ 60 : 3610。 The specific composition (molar ratio) Si02: l 00A1 203:.. 14 00K20:. 38 60DAH: 3610H20 = 88. 00:. 1 00:. 14 00: 38_ 60: 3610. 然后向其中加入凝胶B总质量25%的TON沸石一次过滤母液。 Then added to the total mass of the B 25% gel once TON zeolite mother liquor by filtration. 经搅拌,形成均匀凝胶C。 Stirred, homogeneous gel is formed C. 将凝胶C转入到具有聚四氟乙烯衬里的100mL不锈钢反应釜中,在160°C,静止条件下,水热反应44h。 The gel was transferred to a 100mL stainless steel having a C teflon-lined autoclave at 160 ° C, static conditions, the hydrothermal reaction was 44h. 待冷却后,将产物室温过滤,得到2. 6g产品。 After cooling, the product was filtered at room temperature to yield 2. 6g products. 经XRD表征得知,产品为含有少于1 % ZSM-5的TON沸石分子筛。 Characterized by XRD that the product containing Zeolite TON 1% ZSM-5 is less than the. 图6所示。 6 shown in FIG.

[0052] 对比例2 [0052] Comparative Example 2

[0053] 160°C、反应48小时,5%母液使用量静止合成TON分子筛 [0053] 160 ° C, 48 hours, 5% of the amount of the mother liquor still synthetic zeolite TON

[0054] 按照实施例1中所述,制备凝胶B。 [0054] In the embodiment according to Example 1, B. Preparation of Gel 其具体组成为(摩尔比)Si02:1.00Al 203: 14. 00K2O :38. 60DAH :3610H20 = 88. 00 :1. 00 :14. 00 : 38. 60 : 3610。 The specific composition (molar ratio) Si02: 1.00Al 203: 14. 00K2O:. 38 60DAH: 3610H20 = 88. 00:. 1 00:. 14 00: 38. 60: 3610. 然后向其中加入凝胶B 总质量5%的TON沸石一次过滤母液。 Gel was then added to the total mass of TON zeolite B 5% mother liquor was filtered again. 经搅拌,形成均匀凝胶C。 Stirred, homogeneous gel is formed C. 将凝胶C转入到具有聚四氟乙烯衬里的100mL不锈钢反应釜中,在160°C条件下,静止水热反应48h。 C The gel was transferred to a 100mL stainless steel autoclave having a Teflon-liner, under conditions of 160 ° C, hydrothermal reaction stationary 48h. 待冷却后,将产物室温过滤,得到2. 6g产品。 After cooling, the product was filtered at room temperature to yield 2. 6g products. 经XRD表征得知,产品为大量ZSM-5杂晶、无定型与TON沸石分子筛。 Characterized by XRD that, a large number of ZSM-5 is the product of miscellaneous crystals, amorphous zeolite molecular sieve and TON. 图7所示。 Figure 7. 当母液使用量少于5%时,无法获得结晶度相对较高的TON沸石分子筛。 When using the mother liquor is less than 5% can not be obtained a relatively high degree of crystallinity TON zeolitic molecular sieve.

[0055] 对比例3 [0055] Comparative Example 3

[0056] 160°C、反应48小时,10%母液使用量,静止合成TON分子筛 [0056] 160 ° C, 48 hours, 10% of the amount of liquor, still synthetic zeolite TON

[0057] 按照实施例1中所述,制备凝胶B。 [0057] In the embodiment according to Example 1, B. Preparation of Gel 其具体组成为(摩尔比)Si02:l.〇〇Al 203: 14. 00K20 : 38. 60DAH :3610H20 = 88. 00 :1. 00 :14. 00 :38. 60 :3610。 The specific composition (molar ratio) Si02: l.〇〇Al 203: 14. 00K20: 38. 60DAH: 3610H20 = 88. 00:. 1 00:. 14 00:. 38 60: 3610. 然后向其中加入凝胶B 总质量10%的TON沸石一次过滤母液。 It was then added the total mass of the gel TON B 10% of a zeolite mother liquor by filtration. 经搅拌,形成均匀凝胶C。 Stirred, homogeneous gel is formed C. 将凝胶C转入到具有聚四氟乙烯衬里的100mL不锈钢反应釜中,在16(TC,静止条件下,水热反应48h。待冷却后, 将产物室温过滤,得到2. 6g产品。经XRD表征得知,产品为含有10% ZSM-5的TON沸石分子筛。图8所示。当母液使用量少于10%时,无法获得相对结晶度高于97%的TON沸石分子筛。 C The gel was transferred to a 100mL stainless steel autoclave lined with polytetrafluoroethylene, in 16 (TC, under static conditions, the hydrothermal reaction was 48h. After cooling to room temperature the product was filtered to give product 2. 6g. By XRD analysis that, TON product containing 10% ZSM-5 zeolite molecular sieves. Figure 8. when using the mother liquor is less than 10%, the relative degree of crystallinity can not be obtained than 97% of the zeolitic molecular sieve TON.

[0058] 实施例5 [0058] Example 5

[0059] l6〇°C、反应42小时,15%母液使用量,30rpm合成TON分子筛 [0059] l6〇 ° C, reaction was 42 hours, 15% of the amount of liquor, 30 rpm synthetic zeolite TON

[0060] 按照实施例1中所述,制备凝胶B。 [0060] In the embodiment according to Example 1, B. Preparation of Gel 其具体组成为(摩尔比)Si02:l_〇〇Al 203: 14. 00K2O :38. 60DAH :3610H20 = 88. 00 :1. 00 :14. 00 : 38. 60 : 3610。 The specific composition (molar ratio) Si02: l_〇〇Al 203: 14. 00K2O:. 38 60DAH: 3610H20 = 88. 00:. 1 00:. 14 00: 38. 60: 3610. 然后向其中加入凝胶B 总质量15%的TON沸石一次过滤母液。 It was then added the total mass of the gel TON B 15% of a zeolite mother liquor by filtration. 经搅拌,形成均匀凝胶C。 Stirred, homogeneous gel is formed C. 将凝胶C转入到具有聚四氟乙烯衬里的100mL不锈钢反应釜中,在16CTC,搅拌速率3〇rpm条件下,水热反应42h。 C The gel was transferred to a 100mL stainless steel autoclave having a Teflon-liner, under 16CTC, stirring rate 3〇rpm conditions, the hydrothermal reaction was 42h. 待冷却后,将产物室温过滤,得到2. 6g产品。 After cooling, the product was filtered at room temperature to yield 2. 6g products. 经XRD表征得知,产品为含有纯品TON沸石分子筛。 Characterized by XRD that, TON pure product containing zeolitic molecular sieve. 图9、10所示。 9 and 10 shown in FIG.

[0061] 对比例4 [0061] Comparative Example 4

[0062] 按照实施例1中所述,制备凝胶B。 [0062] In the embodiment according to Example 1, B. Preparation of Gel 其具体组成为(摩尔比)Si02:l.〇〇Al 203: 14. 00K20 :38. 60DAH :3610H20 = 88. 00 :1. 00 :14. 00 :38. 60 :3610。 The specific composition (molar ratio) Si02: l.〇〇Al 203: 14. 00K20:. 38 60DAH: 3610H20 = 88. 00:. 1 00:. 14 00:. 38 60: 3610. 将凝胶B 转入到具有聚四氟乙烯衬里的100mL不锈钢反应釜中,在16(TC,搅拌速率30rpm条件下,水热反应42h。 待冷却后,将产物室温过滤,得到2. 6g产品。经XRD表征得知,产品为ZSM-5沸石分子筛, 图11所示。说明不使用一次晶化母液为诱导剂,低速搅拌条件下,无法获得TON分子筛。 [0063]当然,本发明还可有其它多种实施例,在不背离本发明精神及其实质的情况下,熟悉本领域的技术人员可根据本发明作出各种相应的改变和变形,但这些相应的改变和变形都应属于本发明的保护范围。 The gel was transferred to a B 100mL stainless steel autoclave lined with polytetrafluoroethylene, in 16 (TC, 30rpm agitation speed conditions, the hydrothermal reaction was 42h. After cooling to room temperature the product was filtered to give product 2. 6g . by XRD analysis that the product was ZSM-5 zeolite molecular sieve, as shown in FIG. 11. Description is not used as a crystallization inducer mother liquor, under low speed agitation conditions, TON molecular sieves can not be obtained. [0063] of course, the present invention may also other various embodiments, without departing from the spirit and essence of the invention, those skilled in the art may make various corresponding modifications and variations according to the present invention, these corresponding modifications and variations shall fall within the present the scope of the invention.

Claims (8)

  1. 1.一种TON沸石的稳定合成方法,其特征在于,向反应凝胶中加入TON沸石一次晶化母液,TON沸石一次晶化母液的质量为反应凝胶质量的11〜35%,在静止的条件下,经水热反应,得到相对结晶度高于97%的TON沸石产品。 A stable synthetic zeolite TON, characterized in that the gel was added to the reaction TON zeolite crystallization mother liquor once, a TON zeolite crystallization mother liquor of the reaction mass of the gel is 11~35 mass%, in still under the conditions, the hydrothermal reaction, TON zeolite product to give a relative crystallinity of greater than 97%.
  2. 2. 根据权利要求1所述的TON沸石的稳定合成方法,其特征在于,所述TON沸石一次晶化母液的质量为反应凝胶质量的11〜30%。 2. Stable synthetic zeolite of the TON method according to claim 1, wherein said zeolite is a crystalline quality TON mother liquor is 11~30% by mass of the reaction gel.
  3. 3. 根据权利要求2所述的TON沸石的稳定合成方法,其特征在于,所述TON沸石一次晶化母液的质量为反应凝胶质量的15〜25%。 3. The stable synthetic zeolite of the TON method according to claim 2, wherein said zeolite is a crystalline quality TON mother liquor is 15~25% by mass of the reaction gel.
  4. 4. 根据权利要求1-3任一项所述的TON沸石的稳定合成方法,其特征在于,所述反应凝胶是由以下组分混合搅拌制成的: (1) 硅源或锗源; (2) 铝源; (3) 碱金属源; (4) 有机模板剂; (5) 去离子水。 4. The method of any of claims 1-3 stabilizing a synthetic zeolite of the TON claim, characterized in that the reaction is a gel by mixing the following components with stirring made: (1) a silicon source and germanium source; (2) an aluminum source; (3) an alkali metal source; (4) an organic templating agent; (5) deionized water. 其中,所述硅源为含有氧化硅成分的硅溶胶、白炭黑或正硅酸乙酯;所述锗源、铝源、硼源、镓源、铁源、钒源、铬源为含有对应金属的氧化物;所述碱金属源为NaOH和/或K0H,简称MeOH ;有机模板剂为1,6-己二胺和/或乙胺,简称R ;各组分的摩尔比例为:Si02/Al203 =30 〜300, Me0H/Al203= 0. 2 〜0• 8, R/SiO 2= 0• 2 〜0. 7, H 20/Si02= 10 〜60。 Wherein said silicon source is silica sol containing silicon oxide component, silica or tetraethoxysilane; a germanium source, an aluminum source, a boron source, a gallium source, an iron source, a vanadium source, a chromium source containing the corresponding metal oxides; NaOH as the alkali metal source and / or K0H, referred MeOH; organic templating agent is hexamethylenediamine and / or ethylamine, referred to as R & lt; molar ratio of each component is: Si02 / Al203 = 30 ~300, Me0H / Al203 = 0. 2 ~0 • 8, R / SiO 2 = 0 • 2 ~0. 7, H 20 / Si02 = 10 ~60.
  5. 5. 根据权利要求1-3任一项所述的TON沸石的稳定合成方法,其特征在于,所述TON沸石产品中,白硅石和/或ZSM-5的含量小于TON沸石产品质量的3%。 The stable synthetic method of any one of claims 1-3 TON zeolite as claimed in claim, wherein the zeolite product TON, and / or cristobalite content of ZSM-5 is less than 3% TON zeolite product quality .
  6. 6.根据权利要求4所述的TON沸石的稳定合成方法,其特征在于,所述TON沸石产品中,白硅石和/或ZSM-5的含量小于TON沸石产品质量的3%。 6. The stable synthetic zeolite TON method according to claim 4, wherein the zeolite product TON, and / or cristobalite content of ZSM-5 is less than 3% TON zeolite product quality.
  7. 7.根据权利要求1-3和6任一项所述的TON沸石的稳定合成方法,其特征在于,所述水热反应时间少于等于44小时。 7. The method of any of 1-3, and the stable synthesis is one of the 6 TON zeolite according to claim, characterized in that the hydrothermal reaction time is less than equal to 44 hours.
  8. 8.根据权利要求5所述的TON沸石的稳定合成方法,其特征在于,所述水热反应时间少于等于44小时。 The stable synthetic zeolite of the TON according to claim 5, characterized in that the hydrothermal reaction time is less than equal to 44 hours.
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US4556477A (en) * 1984-03-07 1985-12-03 Mobil Oil Corporation Highly siliceous porous crystalline material ZSM-22 and its use in catalytic dewaxing of petroleum stocks
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CN101941718A (en) * 2009-07-09 2011-01-12 中国石油化工股份有限公司抚顺石油化工研究院 Synthesis method of molecular sieve of TON structure
CN103274428A (en) * 2013-07-01 2013-09-04 中国海洋石油总公司 Method of synthesizing nano Nu-10 molecular sieve by recycling mother solution

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US4481177A (en) * 1982-12-09 1984-11-06 Mobil Oil Corporation Synthesis of zeolite ZSM-22 with a heterocyclic organic compound
US4556477A (en) * 1984-03-07 1985-12-03 Mobil Oil Corporation Highly siliceous porous crystalline material ZSM-22 and its use in catalytic dewaxing of petroleum stocks
CN101941718A (en) * 2009-07-09 2011-01-12 中国石油化工股份有限公司抚顺石油化工研究院 Synthesis method of molecular sieve of TON structure
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