WO2015161630A1 - 一种FeZSM-5分子筛及其合成方法 - Google Patents

一种FeZSM-5分子筛及其合成方法 Download PDF

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WO2015161630A1
WO2015161630A1 PCT/CN2014/089007 CN2014089007W WO2015161630A1 WO 2015161630 A1 WO2015161630 A1 WO 2015161630A1 CN 2014089007 W CN2014089007 W CN 2014089007W WO 2015161630 A1 WO2015161630 A1 WO 2015161630A1
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molecular sieve
silicon
mineral
fezsm
aluminum
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PCT/CN2014/089007
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English (en)
French (fr)
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鲍晓军
岳源源
刘海燕
袁珮
石冈
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中国石油大学(北京)
北京中石大格林催化科技有限公司
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C01B39/38—Type ZSM-5
    • C01B39/40—Type ZSM-5 using at least one organic template directing agent

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  • the invention belongs to the field of molecular sieve synthesis, and relates to a FeZSM-5 molecular sieve and a synthetic method thereof, which provide all silicon source, aluminum source and iron source required for synthesizing FeZSM-5 molecular sieve by using natural mineral as raw material.
  • the Si or Al in the molecular sieve skeleton is substituted with other elements such as Fe, B, Ti, Ga or the like to obtain a hetero atom molecular sieve.
  • the use of heteroatoms to replace the framework elements in molecular sieves is one of the important methods for molecular sieve modification. This method can change the activity, stability and selectivity of molecular sieves by modifying the acidity and pore structure of molecular sieves.
  • FeZSM-5 molecular sieve modified with transition metal Fe has become a research hotspot. FeZSM-5 with its excellent catalytic performance attracted widespread interest, directly decompose N 2 O, N 2 O selective catalytic reduction of N 2 O and the oxidation reaction of benzene to phenol, exhibited excellent catalytic properties.
  • the direct synthesis method is to add Fe species to the FeZSM-5 molecular sieve during the synthesis process.
  • the post-modification method is to treat the existing ZSM-5 molecular sieve by some special methods, including: liquid ion exchange method, solid ion exchange Method, isomorphous substitution method and chemical vapor phase method.
  • CN1256243 discloses a preparation method of small-grain FeZSM-5 molecular sieve, which comprises a silicon-containing substance, an inorganic iron salt, an inorganic sodium salt, an organic amine, an inorganic acid and deionized water as a raw material, and is hydrothermally synthesized and stirred.
  • the crystallization was completed at a rate of 400-500 rpm, from room temperature to 100-140 ° C at a rate of 2 ° C/min, and at a constant temperature of 130 h.
  • the method must be completed under stirring conditions, and the equipment requirements are high.
  • the FeZSM-5 molecular sieve can not be obtained under the static condition by the method; and the crystallization time is too long, up to 130 h.
  • CN103183359 A discloses a nano-scale FeZSM-5 molecular sieve and a preparation method and application thereof.
  • the preparation method comprises the following steps: dissolving a templating agent and an aluminum source in deionized water, stirring at 25-40 ° C until clarification, and then adding a silicon source.
  • Kaolin is a 1:1 type dioctahedral layered aluminosilicate clay mineral. Its basic structure consists of a layer of aluminum oxide octahedron and a layer of silicon oxytetrahedron periodically arranged in the c-axis direction.
  • the typical chemical composition is Al 2 O 3 ⁇ 2SiO 2 ⁇ 2H 2 O, so it can be used as a silicon source and an aluminum source for synthesizing molecular sieves; at the same time, natural kaolin minerals are accompanied by iron impurities, which can be synthetic hetero-containing atoms.
  • the FeZSM-5 molecular sieve provides an iron source.
  • the basic structural unit of the rector soil is a silicon oxytetrahedron and an aluminoxy octahedron.
  • the siloxane tetrahedron is connected to the three adjacent tetrahedrons by a co-angled oxygen to form a layer. a unitary layer of a silicate mineral.
  • the combination of the tetrahedral sheet and the octahedral sheet may be 1:1 type or 2:1 type, and the unit cell has a chemical formula of Al 4 [Si 8 O 20 ](OH) 4 , and thus may also As a source of silicon and aluminum for the synthesis of molecular sieves; at the same time, natural rector soil minerals are also accompanied by iron impurities, which can provide iron source for the synthesis of heteroatom-containing FeZSM-5 molecular sieves.
  • Diatomaceous earth is a kind of biological sedimentary rock preserved by diatoms in the form of diatom remains by diatoms under the physical and chemical conditions such as light, temperature and nutrients.
  • the general theoretical formula of diatomaceous earth is Mg 8 [Si 12 O 30 ](OH) 4 (OH 2 ) 4 ⁇ 8H 2 O, which is a 2:1 chain layer structure.
  • the chemical composition of diatomaceous earth is mainly amorphous SiO 2 , and also contains a small amount of Al 2 O 3 and Fe 2 O 3 , which can be used as a silicon source, an aluminum source and an iron source for synthesizing molecular sieves.
  • Diatomaceous earth is mainly used in the industry as a filter aid, a filler and a catalyst carrier, and the synthesis of zeolite using diatomaceous earth as a raw material is mainly concentrated on LTA, SOD and MOR zeolites having a low silicon to aluminum ratio, and has not been used for synthesis. A molecular sieve of heteroatom Fe is reported.
  • An object of the present invention is to provide a FeZSM-5 molecular sieve; the FeZSM-5 molecular sieve of the present invention provides all the silicon source, aluminum source and iron source required for synthesis by natural minerals, and obtains FeZSM-5 type by hydrothermal crystallization. Molecular sieves.
  • Another object of the present invention is to provide a method for synthesizing the FeZSM-5 molecular sieve.
  • the present invention provides a method for synthesizing a FeZSM-5 molecular sieve, the method comprising the steps of:
  • Activation of minerals low silica-alumina is activated separately from minerals and/or high-silicon-aluminum minerals; the activation of low-silicon-aluminum-specific minerals is uniformly mixed with sodium hydroxide solution, and then dried; The activation of the mineral is a roasting treatment;
  • the low silicon aluminum ratio mineral and the high silicon aluminum ratio mineral described in the step (1) are terms commonly used by those skilled in the art, and those skilled in the art clearly know the meaning thereof;
  • the low silicon aluminum to mineral has a silicon to aluminum molar ratio of 10 or less
  • the high silicon aluminum to mineral has a silicon to aluminum ratio of 30 or more;
  • the low silicon aluminum ratio mineral of the step (1) is kaolin and/or a rector;
  • the high silicon aluminum specific mineral is diatomaceous earth and/or white carbon black.
  • the invention provides all the silicon source, the aluminum source and the iron source required for synthesizing the molecular sieve from the natural mineral raw material, and does not need to add other forms of chemical silicon source, aluminum source and iron source, and broadens the application field of the natural mineral and the raw material of the synthetic molecular sieve. source.
  • the ratio of the low silicon aluminum to mineral and the high silicon aluminum specific mineral of the present invention is required to satisfy the molar ratio of 1 SiO 2 : 0.02-0.5Al 2 O 3 ; under the above molar ratio, the low silicon aluminum can be selected according to the selected
  • the ratio of the ratio of the minerals to the minerals and the high silica-alumina ratio of the minerals is calculated, which may be a suitable blend of low silica-alumina minerals and high silica-alumina minerals, or even one of them.
  • the step (2) can also preferably control the amount of the feed so that the molar ratio satisfies: 0.15 to 0.35 Na 2 O: 1 SiO 2 : 0.02 - 0.06 Al 2 O 3 : 0.005 - 0.1 Fe 2 O 3 : 15 to 75H 2 O.
  • the templating agent in the step (2) is one or more of tetrapropylammonium bromide, tetraethylammonium bromide, tetrapropylammonium hydroxide and triethylamine.
  • a more preferred templating agent therein is tetrapropylammonium bromide.
  • the molar ratio of the templating agent to the SiO 2 in the synthesis system in the step (2) is 0.01 to 0.3:1.
  • the crystallization in the step (2) is crystallization at 140-220 ° C;
  • the crystallization time is preferably 30-80h
  • the crystallization is crystallization at 160-210 ° C;
  • the crystallization time is 36-72 h.
  • the present invention in order to further increase the crystallinity of the molecular sieve, the present invention further preferably mixes the mineral after the activation of the step (1) with sodium hydroxide, water and a templating agent, and then adjusts the pH to 9-14. Recrystallization.
  • the pH adjustment in the step (2) is a conventional operation in the art, and a common inorganic acid base is used.
  • the pH value can be adjusted by using a sulfuric acid solution.
  • the mixing of the mineral activated by the step (1) with the sodium hydroxide, water and the templating agent described in the step (2) is a conventional operation in the art, for example, direct feeding of all the above materials. mixing;
  • the appropriate amount of water can be judged according to actual production conditions, so that the materials can be mixed and dispersed uniformly.
  • the preferred ones in the present invention are high silicon aluminum ratio minerals, sodium hydroxide and 1/4-1/2 of the total water. Water mix.
  • the mass ratio of the low silicon aluminum to the mineral and the sodium hydroxide solution in the step (1) is 1:1-10.
  • the calcination temperature of step (1) is 600-1000 ° C;
  • the calcination temperature is preferably 600-900 ° C;
  • the calcination time is preferably 2-8 h.
  • sodium hydroxide solution is an aqueous sodium hydroxide solution
  • the sodium hydroxide aqueous solution has a sodium hydroxide to water mass ratio of 10-0.2:1;
  • the drying in the step (1) is to dry at 100-400 ° C;
  • the aging treatment is followed by crystallization.
  • the aging is aging at 50-80 ° C for 1-20 h;
  • the aging is aging at 60-80 ° C for 4-15 h.
  • the invention provides a FeZSM-5 molecular sieve prepared by the synthetic method of any of the preceding claims.
  • the FeZSM-5 molecular sieve of the present invention has a molar silicon to aluminum ratio of 2.0 to 48.0 and a Fe 2 O 3 content of 0.7 to 3.5% by weight; wherein preferably the FeZSM-5 molecular sieve is relative to pure
  • the crystallinity of the FeZSM-5 type molecular sieve synthesized by the chemical reagent is 70 to 98%.
  • silicon-aluminum ratio is further preferably 15-38;
  • the Fe 2 O 3 content may be preferably 0.7-1.5 wt%
  • the present invention provides a FeZSM-5 molecular sieve and a synthesis method thereof.
  • the FeZSM-5 molecular sieve of the present invention has the following advantages:
  • the method of the present invention provides all the silicon source, aluminum source and iron source required for synthesis from natural minerals, and hydrothermal crystallization to obtain FeZSM-5 type molecular sieve.
  • the FeZSM-5 molecular sieve with different crystallinity, different silicon-aluminum ratio and different iron content can be prepared by the method provided by the invention, and the relative crystallinity of the obtained FeZSM-5 molecular sieve is 70-98%, and the molar silicon-to-aluminum ratio is 2.0 to 48.0, wherein the natural mineral raw material is a mixture of a natural mineral of a low silicon to aluminum ratio and a natural mineral of a high silicon to aluminum ratio.
  • the synthetic route provided by the invention can not only greatly reduce the production cost of the molecular sieve synthesis, but also greatly improve the greenness and atomic utilization rate of the synthesis process, and the obtained molecular sieve has more excellent physical and chemical properties, such as higher crystallization.
  • the relative crystallinity of FeZSM-5 synthesized from aluminum source, silicon source and iron source with chemical reagents (NaAlO 2 , water glass and ferric nitrate instead of natural clay) is only 60%, and its synthesis cost is lower.
  • Figure 1 is an X-ray diffraction (XRD) spectrum of a FeZSM-5 molecular sieve obtained in Example 1 of the present invention.
  • Example 2 is a scanning electron microscope (SEM) photograph of a 40,000-fold magnification of a FeZSM-5 type molecular sieve obtained in Example 1 of the present invention.
  • the relative crystallinity referred to in the examples is the ratio of the sum of the characteristic peak areas of the 2 ⁇ angle between 22.5 and 25.0° in the XRD spectrum of the obtained product and the molecular sieve standard according to the ASTM D 3906-03 standard, expressed as a percentage.
  • the standard is a NaZSM-5 molecular sieve synthesized by a conventional chemical reagent (manufactured by Nankai University Catalyst Factory, having a silicon to aluminum molar ratio of 38), and its crystallinity is defined as 100%.
  • the product silicon-aluminum ratio is characterized by X-ray fluorescence (XRF) method, using the Japanese science ZSX-100e4580 type X-ray fluorescence spectrometer, the silica-alumina ratio of the molecular sieve described in the present invention refers to the molar ratio of SiO 2 to Al 2 O 3 .
  • the diatomaceous earth, kaolin and rector soil used are all commercially available products.
  • the main components of diatomaceous earth are: SiO 2 content of 93.2 wt.% and Al 2 O 3 content of 3.3 wt.%.
  • the content of Fe 2 O 3 is 1.5 wt.%;
  • the main components of the rector soil are: SiO 2 content is 43.2 wt.%, Al 2 O 3 content is 37.2 wt.%, and Fe 2 O 3 content is 0.5 wt.%;
  • the main components of kaolin are: SiO 2 content of 50.5 wt.%, Al 2 O 3 content of 44.6 wt.%, and Fe 2 O 3 content of 0.5 wt.%.
  • Activation of minerals Commercially available diatomaceous earth and rector soil are separately dried and pulverized into powder. 50.00 g of diatomaceous earth powder was weighed and calcined at 800 ° C for 4 h, and was used. Weigh 12.00 g of rector soil powder, mix well with 24.00 g of sodium hydroxide solid, add 60.00 g of deionized water, and dry at 250 ° C for use.
  • Acid solution preparation Weigh 50.00 g of 98% concentrated sulfuric acid solution into 50.00 g of deionized water, cool to room temperature, and set aside.
  • Preparation of molecular sieve Weigh 5.20 g of the calcined diatomaceous earth powder, add 0.97 g of sodium hydroxide, 2.15 g of tetrapropylammonium bromide, and 58.30 g of deionized water, so that the molar ratio satisfies: 0.15 Na 2 O: 1 SiO 2 : 0.02Al 2 O 3 : 0.006Fe 2 O 3 : 40H 2 O, wherein the molar ratio of templating agent to SiO 2 in the synthesis system is 0.1:1; adjusting the pH of the mixture to 13 by using the above sulfuric acid solution at 60 ° C Mix and stir for 4 h.
  • the mixture was poured into a Teflon-lined stainless steel crystallizer and heated to 170 ° C for 48 h. After completion of the crystallization, the mother liquid was cooled and filtered, washed to neutrality, and dried at 120 ° C to obtain a crystallized product.
  • the product phase belongs to MFI type molecular sieve by XRD.
  • the relative crystallinity of FeZSM-5 molecular sieve is 90%, the product silica-alumina ratio is 48, and the Fe content in the product is 1.4wt.%.
  • the XRD spectrum is shown in the figure. 1, SEM photos are shown in Figure 2.
  • the pretreatment method of diatomaceous earth and rector soil and the preparation method of the sulfuric acid solution are the same as in the first embodiment.
  • the mixture was poured into a Teflon-lined stainless steel crystallizer, heated to 180 ° C, and statically crystallized for 36 h. After completion of the crystallization, the mother liquid was cooled and filtered, washed to neutrality, and dried at 120 ° C to obtain a crystallized product.
  • the product phase belongs to the MFI type molecular sieve as determined by XRD.
  • the relative crystallinity of the FeZSM-5 type molecular sieve in the product is 92%, the product silica-alumina ratio is 30, and the Fe content in the product is 0.9 wt.%.
  • the pretreatment method of the soil and the preparation method of the sulfuric acid solution are the same as those in the first embodiment.
  • the mixture was poured into a Teflon-lined stainless steel crystallizer and heated to 160 ° C for 72 h. After completion of the crystallization, the mother liquid was cooled and filtered, washed to neutrality, and dried at 120 ° C to obtain a crystallized product.
  • the product phase belongs to the MFI type molecular sieve as determined by XRD.
  • the relative crystallinity of the FeZSM-5 type molecular sieve in the product is 85%, the product silica-alumina ratio is 25, and the Fe content in the product is 1.0 wt.%.
  • the pretreatment method of diatomaceous earth and the preparation method of sulfuric acid solution were the same as in Example 1.
  • the mixture was poured into a stainless steel crystallizer with a polytetrafluoroethylene liner, heated to 200 ° C, and statically crystallized for 48 hours. After completion of the crystallization, the mother liquid was cooled and filtered, washed to neutrality, and dried at 120 ° C to obtain a crystallized product.
  • the product phase belongs to the MFI type molecular sieve as determined by XRD.
  • the relative crystallinity of the FeZSM-5 type molecular sieve in the product is 96%, the product silica-alumina ratio is 35, and the Fe content in the product is 0.8 wt.%.
  • the mixture was poured into a Teflon-lined stainless steel crystallizer, heated to 210 ° C, and statically crystallized for 48 h. After completion of the crystallization, the mother liquid was cooled and filtered, washed to neutrality, and dried at 120 ° C to obtain a crystallized product.
  • the product phase belongs to the MFI type molecular sieve as determined by XRD.
  • the relative crystallinity of the FeZSM-5 type molecular sieve in the product is 94%, the product silica-alumina ratio is 19, and the Fe content in the product is 0.9 wt.%.
  • the pretreatment method of the soil and the preparation method of the sulfuric acid solution are the same as those in the first embodiment.
  • the mixture was poured into a Teflon-lined stainless steel crystallizer and heated to 170 ° C for 48 h. After completion of the crystallization, the mother liquid was cooled and filtered, washed to neutrality, and dried at 120 ° C to obtain a crystallized product.
  • the product phase belongs to the MFI type molecular sieve as determined by XRD.
  • the relative crystallinity of the FeZSM-5 type molecular sieve in the product is 75%, the product silica-alumina ratio is 20, and the Fe content in the product is 0.7 wt.%.
  • the pretreatment method of diatomaceous earth and rector soil and the preparation method of the sulfuric acid solution are the same as in the first embodiment.
  • the mixture was poured into a Teflon-lined stainless steel crystallizer, heated to 170 ° C, and statically crystallized for 48 h. After completion of the crystallization, the mother liquid was cooled and filtered, washed to neutrality, and dried at 120 ° C to obtain a crystallized product.
  • the product phase belongs to the MFI type molecular sieve as determined by XRD.
  • the relative crystallinity of the FeZSM-5 type molecular sieve in the product is 72%, the product silica-alumina ratio is 18, and the Fe content in the product is 1.3 wt.%.
  • the pretreatment method of diatomaceous earth and the preparation method of sulfuric acid solution were the same as in Example 1.
  • the mixture was poured into a Teflon-lined stainless steel crystallizer, heated to 170 ° C, and statically crystallized for 48 h. After completion of the crystallization, the mother liquid was cooled and filtered, washed to neutrality, and dried at 120 ° C to obtain a crystallized product.
  • the product phase belongs to the MFI type molecular sieve as determined by XRD.
  • the relative crystallinity of the FeZSM-5 type molecular sieve in the product is 88%, the product silica-alumina ratio is 20, and the Fe content in the product is 1.1 wt.%.
  • the main component of the diatomaceous earth is: SiO 2 content is 90.0 wt.%, Al 2 O 3 content is 2.7 wt.%, Fe 2 O 3 content is 2.5 wt.%;
  • the pretreatment method of diatomaceous earth and rector soil and the preparation method of the sulfuric acid solution are the same as in the first embodiment.
  • the mixture was poured into a Teflon-lined stainless steel crystallizer, heated to 180 ° C, and statically crystallized for 36 h. After completion of the crystallization, the mother liquid was cooled and filtered, washed to neutrality, and dried at 120 ° C to obtain a crystallized product.
  • the product phase belongs to the MFI type molecular sieve as determined by XRD.
  • the relative crystallinity of the FeZSM-5 type molecular sieve in the product is 88%, the product silicon-aluminum ratio is 30, and the Fe content in the product is 1.4 wt.%.
  • the mixture was poured into a Teflon-lined stainless steel crystallizer, heated to 180 ° C, and statically crystallized for 36 h. After completion of the crystallization, the mother liquid was cooled and filtered, washed to neutrality, and dried at 120 ° C to obtain a crystallized product.
  • the product phase belongs to the MFI type molecular sieve as determined by XRD.
  • the relative crystallinity of the FeZSM-5 type molecular sieve in the product is 60%, the product silicon-aluminum ratio is 25, and the Fe content in the product is 0.4 wt.%.
  • the pretreatment method of diatomaceous earth and rector soil and the preparation method of the sulfuric acid solution are the same as in the first embodiment.
  • the mixture was poured into a Teflon-lined stainless steel crystallizer, heated to 170 ° C, and statically crystallized for 48 h. After completion of the crystallization, the mother liquid was cooled and filtered, washed to neutrality, and dried at 120 ° C to obtain a crystallized product.
  • the product was quartz as determined by XRD.
  • the pretreatment method of diatomaceous earth and rector soil and the preparation method of the sulfuric acid solution are the same as in the first embodiment.
  • the mother liquid was cooled and filtered, washed to neutrality, and dried at 120 ° C to obtain a crystallized product.
  • the product phase belongs to the MFI type molecular sieve as determined by XRD, and the relative crystallinity of the FeZSM-5 type molecular sieve in the product is only 20%.

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Abstract

本发明提供了一种FeZSM-5分子筛及其合成方法，所述方法包括：取低硅铝比矿物和/或高硅铝比矿物分别进行活化；其中低硅铝比矿物的活化为与氢氧化钠溶液混合均匀，然后烘干；其中高硅铝比矿物的活化为焙烧处理；活化后的取低硅铝比矿物和/或高硅铝比矿物与氢氧化钠、水、模板剂混合进行晶化，并控制投料量使得摩尔配比满足：0.05～0.4Na2O:1SiO2:0.02-0.5Al2O3:0.004-0.1Fe2O3:10～80H2O；晶化得到的产物冷却、过滤，滤饼水洗至中性，干燥后得到FeZSM-5分子筛。本发明不仅可大幅降低分子筛合成的生产成本，而且可极大地提高合成过程的绿色性及原子利用率，所得到的分子筛具有更优异的物理化学性质。

Description

一种FeZSM-5分子筛及其合成方法 技术领域
本发明属于分子筛合成领域，涉及一种FeZSM-5分子筛及其合成方法，其以天然矿物为原料提供合成FeZSM-5分子筛所需要的全部硅源、铝源及铁源。
背景技术
分子筛骨架中的Si或Al被其他元素如Fe、B、Ti、Ga等取代可得到杂原子分子筛。利用杂原子取代分子筛中的骨架元素，是分子筛改性的重要方法之一，该法可以通过调变分子筛的酸性、孔结构进而改变分子筛的活性、稳定性和选择性。近年来，以过渡金属Fe改性的FeZSM-5分子筛作为催化剂已经成为研究的热点。FeZSM-5以其优异的催化性能引起了人们的广泛兴趣，在N2O直接分解、N2O选择催化还原和N2O氧化苯制苯酚等反应中都表现出了优异的催化性能。
将杂原子Fe引入到ZSM-5分子筛上制备FeZSM-5的方法很多，主要分为直接合成法和后改性法。直接合成法就是在合成过程中添加Fe物种制得FeZSM-5分子筛，后改性法是通过一些特殊的方法对已有的ZSM-5分子筛进行处理，主要包括：液态离子交换法、固态离子交换法、同晶取代法和化学蒸气相法。
CN1256243公开了一种小晶粒FeZSM-5分子筛的制备方法，以含硅物质、无机铁盐、无机钠盐、有机胺类、无机酸和去离子水为原料，采用水热合成法，在搅拌速度为400-500转/分钟、以2℃/min的速率由室温升至100～140℃，恒温130h，完成结晶。但是该方法必须在搅拌条件下完成，对设备要求较高，实验证明，用该方法在静态条件下并不能得到FeZSM-5分子筛；且晶化时间过长，达130h。
CN103183359 A公开了一种纳米级FeZSM-5分子筛及其制备方法和应用，具体制备方法是：将模板剂和铝源溶于去离子水中，在25～40℃下搅拌至澄清后滴加硅源，再加入碱源，待碱源完全溶解后加入铁盐，搅拌3～6h后置于水热反应釜中，密封后于40～60℃静态恒温老化1～4h；静态恒温老化后再在140～180℃下静态恒温晶化24～60h；晶化结束后，将合成体系冷却至室温，再将反应混合物过滤或离心分离，并将所得滤饼洗涤、干燥、焙烧后得到粒径小于50nm的颗粒纳米级FeZSM-5分子筛。
Pieterse(Applied Catalysis B,2004,51:215-228)等分别比较了以硫酸亚铁、莫尔盐、硝酸铁为铁源经离子交换制得的FeZSM-5的活性，实验结果表明，用莫尔盐作为铁源 制备的FeZSM-5分子筛的催化活性最佳。
以上专利或文献所报道的FeZSM-5分子筛的制备方法均是以无机化学品为硅源、铝源和铁源，这些无机化学品大多是从天然矿物经过繁杂的反应与分离过程制得，生产工艺路线长、物耗能耗高，且大多数过程存在严重的污染排放。因此，如果能够直接以富含硅、铝和铁的天然矿物为原料合成分子筛，不仅原料来源广泛，而且可以极大地缩短从原料到分子筛产物的合成路线，大幅降低分子筛生产过程的能耗、物耗和污染排放，并显著降低生产成本，从而为分子筛的合成开辟新的途径，具有广阔的发展前景。
高岭土属1:1型二八面体层状硅铝酸盐粘土矿物，其基本结构是由一层铝氧八面体和一层硅氧四面体构成的复层在c轴方向上周期性重复排列构成的，其典型的化学组成为Al2O3·2SiO2·2H2O，因而可以作为用于合成分子筛的硅源和铝源；同时天然高岭土矿物中伴生有铁杂质，可以为合成含杂原子FeZSM-5分子筛提供铁源。
累托土的基本结构单元为硅氧四面体和铝氧八面体，硅氧四面体以其底部的三个氧，分别与其相邻的三个四面体以共角顶氧的方式相连，形成层状硅酸盐矿物的单元晶层。在单元晶层中，四面体片与八面体片的结合可以是1:1型或者2:1型，其单位晶胞的化学式为Al4[Si8O20](OH)4，因而也可以作为用于合成分子筛的硅源和铝源；同时，天然累托土矿物中也伴生有铁杂质，可以为合成含杂原子FeZSM-5分子筛提供铁源。
硅藻土是硅藻在一定的光、温度和营养物质等物理化学条件下通过生物吸收水中的可溶性氧化硅，而以硅藻遗骸形式保存下来的一种生物沉积岩。硅藻土通用的理论结构式为Mg8[Si12O30](OH)4(OH2)4·8H2O，呈2:1型的链层状结构。硅藻土的化学成分主要是无定形SiO2，同时还含有少量的Al2O3和Fe2O3，经活化可作为合成分子筛的硅源、铝源及铁源。硅藻土在工业上主要用于助滤剂、填料和催化剂载体，而利用硅藻土作为原料合成沸石主要集中在低硅铝比的LTA、SOD和MOR沸石，尚未见将其用于合成含杂原子Fe的分子筛的报道。
近年来，随着绿色化学与化工浪潮的兴起，使用无毒无害的原料，提高原料利用率、降低生产过程的能耗和减少污染排放等已成为新型化工过程研究开发关注的焦点。在分子筛合成领域，如果能够完全利用天然矿物中的硅铝铁源，并以富含无定形氧化硅的天然矿物作为外加硅源来调节投料硅铝比，可望形成环境友好的分子筛绿色合成新技术路线。
目前，已经有以天然矿物为原料制备ZSM-5型分子筛的报道，但仅利用了矿物中的部分硅铝，尚需要添加一定量的外加化学硅源或者铝源来调节硅铝比，且现有 FeZSM-5的合成无一例外地需要外加化学铁源。无外加化学硅源、铝源和铁源，完全以天然矿物为原料制备硅铝比可调、铁含量可调的FeZSM-5分子筛的技术尚未见报道。FeZSM-5型分子筛是脱硝领域中应用广泛的分子筛材料，研究开发完全以天然矿物为原料合成FeZSM-5型分子筛的技术，有着广阔的应用前景。
发明内容
本发明的一个目的在于提供一种FeZSM-5分子筛；本发明的FeZSM-5分子筛由天然矿物提供合成所需要的全部硅源、铝源和铁源，经水热晶化而获得FeZSM-5型分子筛。
本发明的另一目的在于提供所述FeZSM-5分子筛的合成方法。
为达上述目的，一方面，本发明提供了一种FeZSM-5分子筛的合成方法，所述方法包括如下步骤：
(1)矿物的活化：取低硅铝比矿物和/或高硅铝比矿物分别进行活化；其中低硅铝比矿物的活化为与氢氧化钠溶液混合均匀，然后烘干；其中高硅铝比矿物的活化为焙烧处理；
(2)晶化：将步骤(1)活化后的低硅铝比矿物和/或高硅铝比矿物与氢氧化钠、水、模板剂混合后晶化，并控制投料量使得摩尔配比满足：0.05～0.4Na2O:1SiO2:0.02-0.5Al2O3:0.004-0.1Fe2O3:10～80H2O；
(3)后处理：将步骤(2)晶化得到的产物冷却、过滤，滤饼水洗至中性，经过干燥后得到FeZSM-5分子筛。
根据本发明所述的合成方法，其中步骤(1)所述的低硅铝比矿物与高硅铝比矿物为本领域技术人员所惯用的术语，本领域技术人员均清楚知晓其含义；而在本发明中优选的是其中所述低硅铝比矿物的硅铝摩尔比在10以下，所述高硅铝比矿物的硅铝比在30以上；
根据本发明所述的合成方法，步骤(1)所述低硅铝比矿物为高岭土和/或累托土；所述高硅铝比矿物为硅藻土和/或白炭黑。
本发明由天然矿物原料提供合成分子筛所需要的全部硅源、铝源和铁源，不需要添加其他形式的化学硅源、铝源和铁源，拓宽了天然矿物的应用领域和合成分子筛的原料来源。
本发明的低硅铝比矿物和高硅铝比矿物的加入比例需满足摩尔配比1SiO2: 0.02-0.5Al2O3；在满足上述摩尔配比条件下，可以根据所选用的低硅铝比矿物和高硅铝比矿物的硅铝比而计算出二者的用量比例，其中可以是低硅铝比矿物和高硅铝比矿物的适当混合，甚至是二者之一。
根据本发明所述的合成方法，步骤(2)还可以优选控制投料量使得摩尔配比满足：0.15～0.35Na2O:1SiO2:0.02-0.06Al2O3:0.005-0.1Fe2O3:15～75H2O。
根据本发明所述的合成方法，步骤(2)所述模板剂为四丙基溴化铵、四乙基溴化铵、四丙基氢氧化铵和三乙胺中的一种或二种以上的组合；
其中更优选的模板剂为四丙基溴化铵。
根据本发明所述的合成方法，本发明进一步优选步骤(2)所述模板剂的用量与合成体系中SiO2的摩尔配比为0.01～0.3:1。
根据本发明所述的合成方法，步骤(2)所述晶化是在140-220℃下晶化；
其中晶化时间优选为30-80h；
其中还可以优选所述晶化是在160-210℃下晶化；
进一步优选晶化时间为36-72h。
根据本发明所述的合成方法，为进一步提高分子筛的结晶度，本发明进一步优选将步骤(1)活化后的矿物与氢氧化钠、水、模板剂混合后，先调节pH为9-14后再晶化。
根据本发明所述的合成方法，步骤(2)中所述调节pH值为本领域常规操作，采用常用的无机酸碱即可，譬如本发明可以采用硫酸溶液调节pH值。
根据本发明所述的合成方法，其中步骤(2)所述的将步骤(1)活化后的矿物与氢氧化钠、水、模板剂混合为本领域常规操作，譬如直接投料将上述全部物料进行混合；
甚至也可以分批投料，譬如本发明还可以是，将高硅铝比矿物、氢氧化钠和适量水混合后，在60-80℃下搅拌2-6h(优选为70℃下搅拌4h)，再加入低硅铝比矿物、模板剂和剩余水。
所述的适量的水可以根据实际生产情况来判断决定，以使得物料能够混合分散均匀，譬如本发明优选的是将高硅铝比矿物、氢氧化钠和占总水量1/4-1/2的水混合。
根据本发明所述的合成方法，步骤(1)中低硅铝比矿物与氢氧化钠溶液的质量比为1：1-10。
根据本发明所述的合成方法，步骤(1)的焙烧温度为600-1000℃；
其中还优选焙烧温度为600-900℃；
其中优选焙烧时间为2-8h。
根据本发明所述的合成方法，其中优选步骤(1)氢氧化钠溶液为氢氧化钠水溶液；
其中更优选所述氢氧化钠水溶液中氢氧化钠与水质量比为10-0.2：1；
根据本发明所述的合成方法，其中还优选步骤(1)所述烘干为在100-400℃下烘干；
其中还优选是在250-350℃下烘干；
根据本发明任意一项所述的合成方法，步骤(2)中调节pH为9-14后，先老化处理再进行晶化。
根据本发明所述的合成方法，所述老化为在50-80℃下老化1-20h；
其中进一步优选老化为在60-80℃下老化4-15h。
另一方面，本发明还提供了前面任意一项所述的合成方法制备得到的FeZSM-5分子筛。
根据本发明所述的FeZSM-5分子筛，所述FeZSM-5分子筛的摩尔硅铝比为2.0-48.0，Fe2O3含量为0.7-3.5wt％；其中优选所述FeZSM-5分子筛相对于以纯化学试剂为原料合成的FeZSM-5型分子筛的结晶度为70～98％。
其中进一步优选所述硅铝比为15-38；
其中还可以优选所述Fe2O3含量为0.7-1.5wt％；
综上所述，本发明提供了一种FeZSM-5分子筛及其合成方法。本发明的FeZSM-5分子筛具有如下优点：
本发明的方法由天然矿物提供合成所需要的全部硅源、铝源和铁源，经水热晶化而获得FeZSM-5型分子筛。采用本发明提供的方法可以制备具有不同结晶度、不同硅铝比、不同铁含量的FeZSM-5型分子筛，所得到的FeZSM-5分子筛的相对结晶度为70～98％，摩尔硅铝比为2.0～48.0，其中所述的天然矿物原料为低硅铝比的天然矿物与高硅铝比的天然矿物的混合物。
本发明所提供的合成工艺路线不仅可大幅降低分子筛合成的生产成本，而且可极大地提高合成过程的绿色性及原子利用率，所得到的分子筛具有更优异的物理化学性质，如更高的结晶度，以化学试剂(NaAlO2、水玻璃和硝酸铁来替代天然粘土)为铝源、硅源和铁源合成的FeZSM-5的相对结晶度仅为60％，且其合成成本更低。
附图说明
图1为本发明实施例1所得FeZSM-5分子筛的X射线衍射(XRD)谱图。
图2为本发明实施例1所得FeZSM-5型分子筛放大40000倍的扫描电镜(SEM)照片。
具体实施方式
以下结合附图及实施例详细说明本发明的技术方案，但本发明的保护范围包括但是不限于此。
实施例中所说的相对结晶度是根据ASTM D 3906-03标准，以所得产物与分子筛标样的XRD谱图中2θ角在22.5～25.0°间的特征峰面积之和的比值，以百分数表示，标样为以常规化学试剂为原料合成的NaZSM-5分子筛(南开大学催化剂厂生产，其硅铝摩尔比为38)，将其结晶度定义为100％。
产物硅铝比通过X-射线荧光(XRF)方法进行表征，采用日本理学ZSX-100e4580型X射线荧光光谱仪，本发明中描述的分子筛的硅铝比是指SiO2与Al2O3的摩尔比。
实施例1
试剂的准备：
矿物的选择：所用的硅藻土、高岭土和累托土均为市售产品，硅藻土的主要成分为：SiO2的含量为93.2wt.％，Al2O3的含量为3.3wt.％，Fe2O3的含量为1.5wt.％；累托土的主要成分为：SiO2的含量为43.2wt.％，Al2O3的含量为37.2wt.％，Fe2O3的含量为0.5wt.％；高岭土的主要成分为：SiO2的含量为50.5wt.％，Al2O3的含量为44.6wt.％，Fe2O3的含量为0.5wt.％。
矿物的活化：将市售的硅藻土和累托土分别烘干、粉碎成粉末。称取50.00g硅藻土粉末在800℃焙烧4h，备用。称取12.00g累托土粉末，与24.00g氢氧化钠固体混合均匀，加入60.00g去离子水，在250℃下烘干，备用。
酸液配制：称取50.00g质量分数为98％的浓硫酸溶液加入到50.00g去离子水中，冷却至室温，备用。
分子筛制备：称取上述焙烧后的硅藻土粉末5.20g，加入0.97g氢氧化钠、2.15g四丙基溴化铵，58.30g去离子水，使得摩尔配比满足：0.15Na2O:1SiO2:0.02Al2O3:0.006Fe2O3:40H2O，其中模板剂与合成体系中SiO2摩尔比为0.1：1；用上述的硫酸溶液调节混合物的pH为13，在60℃下混合搅拌4h。将该混合物倒入带聚四氟乙烯内衬的不锈钢晶化釜内，升温至170℃静止晶化48h。晶化结束后，冷却、过滤除去母液，洗涤至中性，于120℃下干燥，得到晶化产物。经XRD测定，产物物相属于MFI型分子筛，产物中FeZSM-5型分子筛的相对结晶度为90％，产物硅铝比为48，产物中Fe含量为1.4wt.％，其XRD谱图见图1，SEM照片见图2。
实施例2
硅藻土和累托土的预处理方法以及硫酸溶液的配制方法均同实施例1。
称取上述焙烧后的硅藻土粉末5.20g，加入0.67g氢氧化钠、0.45g上述处理过的累托土粉末、4.30g四丙基溴化铵，46.58g去离子水，使得摩尔配比满足：0.15Na2O:1SiO2:0.03Al2O3:0.006Fe2O3:32H2O，其中模板剂与合成体系中SiO2摩尔比为0.2：1；用上述的硫酸溶液调节混合物的pH为12，在60℃下混合搅拌8h。将该混合物倒入带聚四氟乙烯内衬的不锈钢晶化釜内，升温至180℃，静止晶化36h。晶化结束后，冷却、过滤除去母液，洗涤至中性，于120℃下干燥，得到晶化产物。经XRD测定，产物物相属于MFI型分子筛，产物中FeZSM-5型分子筛的相对结晶度为92％，产物硅铝比为30，产物中Fe含量为0.9wt.％。
实施例3
累托土的预处理方法以及硫酸溶液的配制方法均同实施例1。
称取50.00g硅藻土粉末在600℃焙烧8h，备用。
称取上述焙烧后的硅藻土粉末5.20g，加入1.0g氢氧化钠、20.00g去离子水，在70℃下混合搅拌4h。然后加入0.90g上述处理过的累托土粉末、3.23g四丙基溴化铵、43.32g去离子水，使得摩尔配比满足：0.24Na2O:1SiO2:0.033Al2O3:0.006Fe2O3:42.4H2O，其中模板剂与合成体系中SiO2摩尔比为0.15：1；用上述的硫酸溶液调节混合物的pH为14，在60℃下混合搅拌12h。将该混合物倒入带聚四氟乙烯内衬的不锈钢晶化釜内，升温至160℃静止晶化72h。晶化结束后，冷却、过滤除去母液，洗涤至中性，于120℃下干燥，得到晶化产物。经XRD测定，产物物相属于MFI型分子筛，产物中FeZSM-5型分子筛的相对结晶度为85％，产物硅铝比为25，产物中Fe含量为1.0wt.％。
实施例4
硅藻土的预处理方法和硫酸溶液配制方法均同实施例1。
称取20.00g市售的高岭土粉末，与32.00g氢氧化钠固体混合均匀，加入24.00g去离子水，在250℃下烘干，备用。
称取上述焙烧后的硅藻土粉末5.20g，加入0.67g氢氧化钠、0.50g上述处理过的高岭土粉末、4.30g四丙基溴化铵，105.58g去离子水，使得摩尔配比满足：0.15Na2O:1SiO2:0.027Al2O3:0.006Fe2O3:71H2O，其中模板剂与合成体系中SiO2摩尔比为0.2：1；用上述的硫酸溶液调节混合物的pH为13，在80℃下混合搅拌6h。将该混合物倒入带 聚四氟乙烯内衬的不锈钢晶化釜内，升温至200℃，静止晶化48h。晶化结束后，冷却、过滤除去母液，洗涤至中性，于120℃下干燥，得到晶化产物。经XRD测定，产物物相属于MFI型分子筛，产物中FeZSM-5型分子筛的相对结晶度为96％，产物硅铝比为35，产物中Fe含量为0.8wt.％。
实施例5
硫酸溶液及硅藻土的预处理方法均同实施例1。
称取12.00g高岭土粉末，与16.00g氢氧化钠固体混合均匀，加入64.00g去离子水，于200℃下烘干，备用。
称取上述焙烧后的硅藻土粉末5.20g，加入0.7g氢氧化钠、1.56g上述处理过的高岭土粉末、1.08g四丙基溴化铵，43.32g去离子水，使得摩尔配比满足：0.24Na2O:1SiO2:0.05Al2O3:0.0059Fe2O3:28H2O，其中模板剂与合成体系中SiO2摩尔比为0.047：1；用上述的硫酸溶液调节混合物的pH为12左右，在70℃下混合搅拌4h。将该混合物倒入带聚四氟乙烯内衬的不锈钢晶化釜内，升温至210℃，静止晶化48h。晶化结束后，冷却、过滤除去母液，洗涤至中性，于120℃下干燥，得到晶化产物。经XRD测定，产物物相属于MFI型分子筛，产物中FeZSM-5型分子筛的相对结晶度为94％，产物硅铝比为19，产物中Fe含量为0.9wt.％。
实施例6
累托土的预处理方法及硫酸溶液的配制方法均同实施例1。
称取50.00g硅藻土粉末在900℃焙烧2h，备用。
称取上述焙烧后的硅藻土粉末5.20g，加入0.97g氢氧化钠、2.15g四丙基溴化铵、1.5g上述处理过的累托土粉末、28.30g去离子水，使得摩尔配比满足：0.3Na2O:1SiO2:0.04Al2O3:0.006Fe2O3:18.6H2O，其中模板剂与合成体系中SiO2摩尔比为0.1：1；在60℃下混合搅拌4h。将该混合物倒入带聚四氟乙烯内衬的不锈钢晶化釜内，升温至170℃静止晶化48h。晶化结束后，冷却、过滤除去母液，洗涤至中性，于120℃下干燥，得到晶化产物。经XRD测定，产物物相属于MFI型分子筛，产物中FeZSM-5型分子筛的相对结晶度为75％，产物硅铝比为20，产物中Fe含量为0.7wt.％。
实施例7
硅藻土和累托土的预处理方法以及硫酸溶液的配制方法均同实施例1。
称取上述焙烧后的硅藻土粉末8.41g，加入1.32g氢氧化钠、3.9g上述处理过的累托土粉末、11.17g四丙基溴化铵，51.34g去离子水，使得摩尔配比满足：0.35Na2O:1SiO2: 0.053Al2O3:0.0059Fe2O3:20H2O，其中模板剂与合成体系中SiO2摩尔比为0.3：1；用上述的硫酸溶液调节混合物的pH为12。将该混合物倒入带聚四氟乙烯内衬的不锈钢晶化釜内，升温至170℃，静止晶化48h。晶化结束后，冷却、过滤除去母液，洗涤至中性，于120℃下干燥，得到晶化产物。经XRD测定，产物物相属于MFI型分子筛，产物中FeZSM-5型分子筛的相对结晶度为72％，产物硅铝比为18，产物中Fe含量为1.3wt.％。
实施例8
硅藻土的预处理方法和硫酸溶液配制方法均同实施例1。
称取20.00g市售的累托土粉末，与30.00g氢氧化钠固体混合均匀，加入3.00g去离子水，在350℃下烘干，备用。
称取上述焙烧后的硅藻土粉末5.20g，加入0.67g氢氧化钠、1.0g上述处理过的累托土粉末、4.30g四丙基溴化铵，60.00g去离子水，使得摩尔配比满足：0.19Na2O:1SiO2:0.046Al2O3:0.006Fe2O3:40H2O，其中模板剂与合成体系中SiO2摩尔比为0.19：1；用上述的硫酸溶液调节混合物的pH为13，在60℃下混合搅拌4h。将该混合物倒入带聚四氟乙烯内衬的不锈钢晶化釜内，升温至170℃，静止晶化48h。晶化结束后，冷却、过滤除去母液，洗涤至中性，于120℃下干燥，得到晶化产物。经XRD测定，产物物相属于MFI型分子筛，产物中FeZSM-5型分子筛的相对结晶度为88％，产物硅铝比为20，产物中Fe含量为1.1wt.％。
实施例9
为了调节反应体系投料Fe的含量，我们采用市售的劣质硅藻土为原料进行合成。其中硅藻土的主要成分为：SiO2的含量为90.0wt.％，Al2O3的含量为2.7wt.％，Fe2O3的含量为2.5wt.％；
硅藻土和累托土的预处理方法以及硫酸溶液的配制方法均同实施例1。
称取上述焙烧后的硅藻土粉末5.40g，加入0.67g氢氧化钠、0.45g上述处理过的累托土粉末、4.30g四丙基溴化铵，46.58g去离子水，使得摩尔配比满足：0.15Na2O:1SiO2:0.024Al2O3:0.10Fe2O3:32H2O，其中模板剂与合成体系中SiO2摩尔比为0.2：1；用上述的硫酸溶液调节混合物的pH为12，在60℃下混合搅拌8h。将该混合物倒入带聚四氟乙烯内衬的不锈钢晶化釜内，升温至180℃，静止晶化36h。晶化结束后，冷却、过滤除去母液，洗涤至中性，于120℃下干燥，得到晶化产物。经XRD测定，产物物相属于MFI型分子筛，产物中FeZSM-5型分子筛的相对结晶度为88％，产物硅铝比为30，产物中Fe含量为1.4wt.％。
对比例1
称取0.356g偏铝酸钠、0.574g硝酸铁、16.56g水玻璃(含26wt.％SiO2)、1.73g四丙基溴化铵、41.76g去离子水，使得摩尔配比满足：0.15Na2O:1SiO2:0.03Al2O3:0.006Fe2O3:32H2O，其中模板剂与合成体系中SiO2摩尔比为0.2：1；用上述的硫酸溶液调节混合物的pH为12，在60℃下混合搅拌8h。将该混合物倒入带聚四氟乙烯内衬的不锈钢晶化釜内，升温至180℃，静止晶化36h。晶化结束后，冷却、过滤除去母液，洗涤至中性，于120℃下干燥，得到晶化产物。经XRD测定，产物物相属于MFI型分子筛，产物中FeZSM-5型分子筛的相对结晶度为60％，产物硅铝比为25，产物中Fe含量为0.4wt.％。
对比例2
硅藻土和累托土的预处理方法以及硫酸溶液的配制方法均同实施例1。
称取上述焙烧后的硅藻土粉末8.41g，加入2.44g氢氧化钠、3.9g上述处理过的累托土粉末、11.17g四丙基溴化铵，51.34g去离子水，使得摩尔配比满足：0.45Na2O:1SiO2:0.053Al2O3:0.0059Fe2O3:20H2O，其中模板剂与合成体系中SiO2摩尔比为0.3：1；用上述的硫酸溶液调节混合物的pH为12。将该混合物倒入带聚四氟乙烯内衬的不锈钢晶化釜内，升温至170℃，静止晶化48h。晶化结束后，冷却、过滤除去母液，洗涤至中性，于120℃下干燥，得到晶化产物。经XRD测定，产物为石英。
对比例3
硅藻土和累托土的预处理方法以及硫酸溶液的配制方法均同实施例1。
称取上述焙烧后的硅藻土粉末5.20g，加入0.67g氢氧化钠、0.45g上述处理过的累托土粉末、46.58g去离子水，使得摩尔配比满足：0.15Na2O:1SiO2:0.03Al2O3:0.006Fe2O3:32H2O；用上述的硫酸溶液调节混合物的pH为12，在60℃下混合搅拌4h。将该混合物倒入带聚四氟乙烯内衬的不锈钢晶化釜内，升温至180℃，静止晶化48h。晶化结束后，冷却、过滤除去母液，洗涤至中性，于120℃下干燥，得到晶化产物。经XRD测定，产物物相属于MFI型分子筛，产物中FeZSM-5型分子筛的相对结晶度仅为20％。

Claims (10)

  1. 一种FeZSM-5分子筛的合成方法，其特征在于，所述方法包括如下步骤：
    (1)矿物的活化：取低硅铝比矿物和/或高硅铝比矿物分别进行活化；其中低硅铝比矿物的活化为与氢氧化钠溶液混合均匀，然后烘干；其中高硅铝比矿物的活化为焙烧处理；其中优选所述低硅铝比矿物的硅铝摩尔比在10以下，所述高硅铝比矿物的硅铝比在30以上；其中还优选氢氧化钠溶液为氢氧化钠水溶液；更优选所述氢氧化钠水溶液中氢氧化钠与水质量比为10-0.2：1；其中还优选所述烘干为在100-400℃下烘干；
    (2)晶化：将步骤(1)活化后的低硅铝比矿物和/或高硅铝比矿物与氢氧化钠、水、模板剂混合后晶化，并控制投料量使得摩尔配比满足：0.05～0.4Na2O:1SiO2:0.02-0.5Al2O3:0.004-0.1Fe2O3:10～80H2O；其中还优选将步骤(1)活化后的矿物与氢氧化钠、水、模板剂混合，先调节pH为9-14后再晶化；
    (3)后处理：将步骤(2)晶化得到的产物冷却、过滤，滤饼水洗至中性，经过干燥后得到FeZSM-5分子筛。
  2. 根据权利要求1所述的合成方法，其特征在于，步骤(1)所述低硅铝比矿物为高岭土和/或累托土；所述高硅铝比矿物为硅藻土和/或白炭黑。
  3. 根据权利要求1所述的合成方法，其特征在于，步骤(2)所述模板剂为四丙基溴化铵、四乙基溴化铵、四丙基氢氧化铵和三乙胺中的一种或二种以上的组合。
  4. 根据权利要求1所述的合成方法，其特征在于，步骤(2)所述晶化是在140-220℃下晶化6-96h。
  5. 根据权利要求1所述的合成方法，其特征在于，步骤(1)中低硅铝比矿物与氢氧化钠溶液的质量比为1：1-10。
  6. 根据权利要求1所述的合成方法，其特征在于，步骤(1)的焙烧温度为600-1000℃，焙烧时间为1-10h。
  7. 根据权利要求1-6任意一项所述的合成方法，其特征在于，步骤(2)中调节pH为9-14后，先老化处理再进行晶化。
  8. 根据权利要求7所述的合成方法，其特征在于，所述老化为在50-80℃下老化1-20h。
  9. 权利要求1～8任意一项所述的合成方法制备得到的FeZSM-5分子筛。
  10. 根据权利要求9所述的FeZSM-5分子筛，其特征在于，所述FeZSM-5分子筛的摩尔硅铝比为2.0-48.0，Fe2O3含量为0.7-3.5wt％；其中优选所述FeZSM-5分子筛相对于以纯化学试剂为原料合成的NaZSM-5型分子筛的结晶度为70～98％。
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