CN101935050B - Method for synthesizing silicoaluminophosphate molecular sieve by utilizing crystallization mother liquor - Google Patents

Method for synthesizing silicoaluminophosphate molecular sieve by utilizing crystallization mother liquor Download PDF

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CN101935050B
CN101935050B CN 201010280116 CN201010280116A CN101935050B CN 101935050 B CN101935050 B CN 101935050B CN 201010280116 CN201010280116 CN 201010280116 CN 201010280116 A CN201010280116 A CN 201010280116A CN 101935050 B CN101935050 B CN 101935050B
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crystallization
source
mother liquor
hydrothermal
aluminum
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CN101935050A (en
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宋庆锋
张勇
潘蕊娟
王瑞
郭彦鑫
高亚娜
高俊文
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西北化工研究院
陕西省煤化工工程技术研究中心
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Abstract

The invention discloses a method for synthesizing a silicoaluminophosphate molecular sieve by utilizing crystallization mother liquor, which comprises the following steps: 1) mixing an aluminum source with deionized water for forming suspension A, or mixing the aluminum source with the crystallization mother liquor for forming the suspension A; 2) mixing a phosphorus source with the deionized water for forming solution B, or mixing the phosphorus source with the crystallization mother liquor for forming the solution B; 3) mixing the suspension A with the solution B, and then adding a templateagent, a silicon source, crystal seeds and the crystallization mother liquor for forming initial gel mixture; 4) placing the initial gel mixture in a crystallization kettle for hydrothermal crystallization, and then filtering for obtaining a filter cake and filtrate; 5) washing the filter cake, then drying and then calcining for obtaining the silicoaluminophosphate molecular sieve; and 6) recovering the filtrate, sealing and preserving. The method can reduce the using quantity of the template agent, realize zero emission of the crystallization mother liquor, and simultaneously regulate the grain size and the acid strength of the silicoaluminophosphate molecular sieve by fully utilizing the crystallization mother liquor.

Description

一种利用晶化母液合成磷酸硅铝分子筛的方法 A method for synthesis of crystalline silicoaluminophosphate molecular sieves mother liquor by

技术领域 FIELD

[0001] 本发明属于分子筛合成技术领域,具体涉及一种利用晶化母液合成磷酸硅铝分子筛的方法。 [0001] The present invention belongs to the field of molecular sieves synthesis technology, particularly relates to a method of using a synthetic mother liquor crystallized silicoaluminophosphate molecular sieve.

背景技术 Background technique

[0002] 低碳烯烃,尤其是乙烯和丙烯,作为基本有机化工原料,在现代石油和化学工业中起着举足轻重的作用。 [0002] The light olefins, particularly ethylene and propylene, as a basic organic chemicals, plays an important role in the modern petrochemical and chemical industries. 烯烃的生产方法可分为两类:一类是石油路线,另一类是非石油路线。 The method of producing an olefin can be divided into two categories: one is an oil line, the other non-petroleum routes. 但是对于石油而言,价格长期持续上涨,供应不稳定,且资源储藏量有限。 But for oil, the price continued to rise long-term, supply instability, limited resources and reserves. 因此增加乙烯、丙烯产量仅靠传统的石油路线是不够的,由甲醇制低碳烯烃(Methanol-to-Olefins,简称ΜΤ0)是以煤或天然气为原料经由甲醇制乙烯、丙烯等低碳烯烃的工艺过程,它是最有希望的非石油路线的新工艺。 Thus increasing ethylene, propylene production line conventional oil alone is not enough, by the MTO (Methanol-to-Olefins, referred ΜΤ0) based on coal or natural gas as raw material methanol via ethylene, propylene and other lower olefins process, it is the most promising non-oil route of the new technology. 而且甲醇是最丰富的化学产品之一,可以从煤、天然气和固体废物经由合成气得到。 And Methanol is one of the most abundant chemical product, may, natural gas and solid waste derived from coal via synthesis gas. MTO工艺过程的关键技术是催化剂,具有高活性、高选择性和再生性能好的催化剂是关键所在。 Key Technology MTO process is that the catalyst has high activity, high selectivity and good catalyst regeneration performance is key. 1984年,美国联合碳化物公司(UCC)发明了孔径在0.4nm左右的硅磷铝沸石分子筛(简称SAPO分子筛)。 In 1984, Union Carbide Corporation (UCC) of the invention, a silicon aluminum phosphate zeolite molecular sieve pore diameter of about 0.4nm (abbreviated SAPO molecular sieves). SAPO分子筛具有由氧原子连接的AlO4, SiO4和PO4四面体网络,晶体内的孔道因Si4+取代P5+或Al3+产生的酸性或用金属取代而产生酸性使该分子筛在MTO催化中起重要作用。 SAPO molecular sieves having AlO4 linked by an oxygen atom, SiO4 and PO4 tetrahedra networks, channels within the crystal by Si4 + substituted P5 + or Al3 + acid produced by or substituted with a metal to generate an acid so that the molecular sieve play an important role in the MTO catalysis. 在SAPO系列催化剂中,最为人瞩目的是SAP0-34分子筛,该分子筛的MTO催化性能优异:甲醇转化率近乎100%,乙烯和丙烯的选择性在60% 左右,几乎没有C4以上的产物。 SAPO catalysts in series, the most attention of the molecular sieve is SAP0-34 excellent catalytic performance of the molecular sieve MTO: nearly 100% conversion of methanol, ethylene and propylene selectivity at 60%, almost none of the above product C4.

[0003] 磷酸硅铝分子筛是除硅铝型沸石分子筛以外另一大类分子筛催化材料,已经广泛应用于石油化工和石油加工过程中。 [0003] The silicoaluminophosphate molecular sieve is an aluminosilicate zeolite molecular sieve other than another class of molecular sieve catalytic material, it has been widely used in the petrochemical and petroleum processing. 其中的SAP0-34分子筛具有类似菱沸石结构,属于小孔沸石,可用作吸附剂和催化剂,尤其在MTO的反应中表现出良好的催化活性和选择性。 Wherein the molecular sieve has a similar SAP0-34 chabazite structure, it is small pore zeolites, used as adsorbents and catalysts, in particular, exhibit good catalytic activity and selectivity in the MTO reaction. 经典制备SAP0-34分子筛的方法是水热合成法,美国专利说明书US4440871中公开了一种在高温水热体系中晶化而得到的磷酸硅铝凝胶。 The method of preparing SAP0-34 classical molecular sieve is a hydrothermal synthesis method, U.S. Patent Specification US4440871 discloses a system in a high temperature hydrothermal crystallization of silica-alumina gel obtained by acid. 通过改变合成条件和所用模板剂的种类,水热合成法可以得到很多具有不同结构的SAPO系列分子筛。 By varying the synthesis conditions and the type of templating agent used, hydrothermal synthesis method can be a lot SAPO family of molecular sieves having different structures. 但这种制备过程容易发生粘壁现象,需要在有聚四氟乙烯衬里的反应釜内进行,另外制备过程中还需要使用大量的有机模板剂。 However, this preparation process is prone to sticking phenomenon of wall required in a Teflon lined autoclave, additional manufacturing process also requires a large amount of organic templating agent.

[0004] 在2007年10月17日公开的发明专利CN101056708A中公开了一种合成硅铝磷酸盐分子筛的方法,该方法是将磷源和一种晶化导向剂混合后,引入铝源和硅源后进行晶化。 [0004] discloses a method of synthesizing silicoaluminophosphate molecular sieves in invention patent CN101056708A October 17, 2007 the disclosure, the method is after the phosphorus source and a crystalline mixed agent guide, the introduction of a source of aluminum and silicon after crystallization source. 研究发现,在制备分子筛晶化液时,如果反应温度高于50°C,易于发生不希望的副反应而生成杂质。 The study found that in the preparation of the molecular sieve crystallization solution, if the reaction temperature is higher than 50 ° C, and the generation of impurities prone to undesirable side reactions.

[0005] 气相晶化法作为制备分子筛的一种方法已经有深入的研究,但在磷酸硅铝分子筛的合成方面,目前报导的还不多。 [0005] vapor phase crystallization method as a method of preparing molecular sieves have been studied in depth, but in the synthesis of silicoaluminophosphate molecular sieves, currently reported to be not more. 气相晶化法具有可以大幅度减少有机模板剂的使用量,省去了产品与母液分离的繁杂步骤,不会产生大量母液,对环境很友好,便于进行连续生产, 有机模板剂可以重复使用等优点。 Having a vapor phase crystallization method can significantly reduce the amount of organic templating agent, eliminating the need for complicated separation step of the product from the mother liquor, the mother liquor will not produce a large amount, environmentally friendly, easy to continuous production, the organic templating agent and can be reused advantage. 在2007年5月9日公告的CN1314587C中公开了一种气相晶化法制备SAP0-34分子筛的方法,但该方法与水热合成法相比,存在结晶度相对较低, 制备的分子筛硅铝比与磷铝比的合成范围较小,而且设备复杂,不易放大等缺陷。 Publication 2007 May 9 announcement CN1314587C prepared in a method of vapor phase crystallization method SAP0-34 molecular sieve, but the method is compared with hydrothermal synthesis method, there is a relatively low crystallinity, molecular sieve prepared alumina ratio synthesis smaller range than aluminum and phosphorous, and complex equipment, and other defects easily enlarged. 发明内容 SUMMARY

[0006] 本发明所要解决的技术问题在于针对上述现有技术的不足,提供一种利用晶化母液合成磷酸硅铝分子筛的方法。 [0006] The present invention solves the technical problem that the deficiency of the prior art described above, there is provided a method of using a crystallization mother liquor synthesized silicoaluminophosphate molecular sieve.

[0007] 为解决上述技术问题,本发明采用的技术方案是:一种利用晶化母液合成磷酸硅铝分子筛的方法,其特征在于,该方法包括以下步骤: [0007] To solve the above problems, the present invention adopts the technical solution is: A method of using a mother liquid crystal in the synthesis of silicoaluminophosphate molecular sieves, characterized in that the method comprises the steps of:

[0008] 晶化母液的来源:水热合成法制备磷酸硅铝分子筛回收的滤液作为晶化母液; [0008] The mother liquor of crystallization of Origin: filtrate hydrothermal synthesis silicoaluminophosphate molecular sieves as a crystallization mother liquor recovered;

[0009] 晶种的来源:水热合成法制备的磷酸硅铝分子筛作为晶种; [0009] seed sources: hydrothermal synthesis of silicoaluminophosphate molecular sieve as a seed;

[0010] (1)将铝源与去离子水混合均勻形成悬浊液A,或将铝源与晶化母液混合均勻形成悬浊液A ;所述铝源为异丙醇铝、拟薄水铝石和氧化铝中的一种或几种,所述去离子水与铝源的摩尔比为1〜25 : 1,晶化母液与铝源的质量比为0.1〜5 : 1,其中铝源以Al2O3 计; [0010] (1) The source of aluminum with deionized water uniformly formed suspension A, or the aluminum source and the crystallization mother liquor was mixed uniformly formed suspension A; the aluminum source is aluminum isopropoxide, and pseudoboehmite one or more molar ratio of boehmite and aluminum oxide, deionized water and said aluminum source is 1~25: 1, mass ratio of the crystallization mother liquor with an aluminum source is 0.1~5: 1, wherein the aluminum source to Al2O3 meter;

[0011] (2)将磷源与去离子水混合均勻形成溶液B,或将磷源与晶化母液混合均勻形成溶液B;所述去离子水与磷源的摩尔比为1〜25 : 1,晶化母液与磷源的质量比为0.1〜 3.6 : 1,其中磷源以P2O5计; [0011] (2) the source of phosphorus mixed with deionized water to form a solution B, or by mixing a phosphorus source and the crystallization mother liquor solution B is formed uniformly; molar ratio of the phosphorus source and the deionized water is 1~25: 1 crystallization mother liquor with a mass ratio of phosphorus source 0.1~ 3.6: 1, wherein the source of phosphorus as P2O5;

[0012] (3)将步骤(1)中所述悬浊液A与步骤(¾中所述溶液B混合均勻,然后依次加入模板剂、硅源、晶种和晶化母液,搅拌形成初始凝胶混合物;所述初始凝胶混合物中模板剂、 硅源、磷源和铝源的摩尔比为0. 1〜2. 5 : 0.1〜1.5 : 0.2〜2.0 : 0.2〜2.0,初始凝胶混合物中晶化母液与铝源的质量比为0. 1〜10 : 1,初始凝胶混合物中晶种的质量为铝源质量的0.01%〜3.5%,其中硅源以SiO2计,磷源以P2O5计,铝源以Al2O3计; [0012] (3) Step (1) A suspension of the step (¾ B in the solution is mixed uniformly, followed by addition of the templating agent, a silicon source, a seed crystal and mother liquor, was stirred an initial condensate plastic mixture; initial molar ratio of the gel mixture the templating agent, a silicon source, a phosphorus source and an aluminum source 0. 5 ~ 2: 0.1~1.5: 0.2~2.0: 0.2~2.0, the initial gel mixture. crystallization mother liquid mass ratio of the aluminum source is 0. 1~10: 1, the initial seed mass gel mixture is 0.01% ~3.5% by mass of an aluminum source, wherein the source of silicon in terms of SiO2, a source of phosphorus as P2O5 , an aluminum source terms of Al2O3;

[0013] (4)将步骤(3)中所述初始凝胶混合物置于晶化釜中,先水热预晶化,然后水热晶化,或将步骤(3)中所述初始凝胶混合物置于晶化釜中,直接水热晶化,将水热晶化后的产物随炉冷却后过滤得到滤饼和滤液; [0013] (4) The step (3) of the initial gel mixture was placed in (3) in the crystallization vessel, to pre-heat the water of crystallization, and then hydrothermal crystallization step or the initial gel the mixture was placed in the crystallization autoclave, direct hydrothermal crystallization, the product after the hydrothermal subsequently cooling the furnace was filtered to obtain a cake and a filtrate;

[0014] (5)将步骤中所述滤饼用去离子水洗涤后置于烘箱中烘干;将烘干后的滤饼置于马弗炉中焙烧,随炉冷却后得到磷酸硅铝分子筛; [0014] (5) the step of washing the filter cake with deionized water were placed in a drying oven; After drying the filter cake was placed in a muffle furnace fired furnace cooling to obtain the silicoaluminophosphate molecular sieve ;

[0015] (6)将步骤中所述滤液回收并密封保存,作为晶化母液循环利用。 [0015] (6) The filtrate in the step of recovering and sealed, as the crystallization mother liquor recycling.

[0016] 上述步骤O)中所述磷源为正磷酸或/和亚磷酸。 [0016] The step O) of said phosphorus source is orthophosphoric acid and / or phosphorous acid.

[0017] 上述步骤(3)中所述硅源为正硅酸乙酯、白炭黑和硅溶胶中的一种或几种;上述步骤(3)中所述模板剂为四乙基氢氧化铵、三乙胺、二乙胺和吗啡啉中的一种或几种。 [0017] The step (3) in the one or more silicon source is tetraethylorthosilicate, silica and silica sol; above step (3) of the templating agent is tetraethylammonium hydroxide one or more ammonium, triethylamine, diethylamine and morpholine in.

[0018] 上述步骤中所述水热预晶化为三步水热预晶化,水热预晶化的制度为:第一步水热预晶化在温度为100°c的条件下水热预晶化Mi〜Mh,第二步水热预晶化在温度为120°C的条件下水热预晶化Ih〜他,第三步水热预晶化在温度为150°C的条件下水热预晶化Ih〜3h。 [0018] The above step is crystallized into a three-step pre-hydrothermal pre hydrothermal crystallization, the hydrothermal pre-crystallization system are: The first step of the hydrothermal pre-crystallization temperature of 100 ° c hydrothermal pre-conditions crystallization Mi~Mh, the second step of the hydrothermal pre-crystallization temperature to 120 ° C pre-conditions for hydrothermal crystallization Ih~ him, the third step of the hydrothermal pre-crystallization temperature of the water in the pre-heat to 150 ° C conditions crystallization Ih~3h.

[0019] 上述步骤中所述水热晶化的制度为:晶化温度为180°C,晶化时间为12h〜 36h。 [0019] The above step of hydrothermal system as: the crystallization temperature was 180 ° C, crystallization time is 12h~ 36h.

[0020] 上述步骤(5)中所述烘干的温度为120°C,焙烧的温度为550°C,焙烧的时间为5h。 [0020] The step (5) of the drying temperature is 120 ° C, calcined at a temperature of 550 ° C, the calcination time was 5h.

[0021] 本发明与现有技术相比具有以下优点:本发明通过将导晶沉淀法和溶胶凝胶法结合,对磷酸硅铝分子筛合成过程中伴生的晶化母液进行回收利用,从而减少了模板剂的用量,实现了晶化母液的零排放,同时通过对晶化母液的充分利用,调节了磷酸硅铝分子筛的晶粒和酸强度。 [0021] The present invention has the following advantages over the prior art: by combining conductive crystal precipitation and sol-gel method of the present invention, the crystallization of silicoaluminophosphate molecular sieve synthesis process associated mother liquor for recycling, thereby reducing the amount of templating agent to achieve zero emissions crystallization mother liquor, and by making full use of the crystallization mother liquor, and adjusting the acid strength of the grain silicoaluminophosphate molecular sieve. 本发明制备的磷酸硅铝分子筛用于甲醇或二甲醚制烯烃反应,能够提高乙烯和丙稀的选择性,并能大大提高催化剂的寿命。 Silicoaluminophosphate molecular sieves prepared in the present invention for the reaction of methanol or dimethyl ether to olefins, the selectivity to ethylene and propylene can be improved, and can greatly improve the life of the catalyst.

附图说明 BRIEF DESCRIPTION

[0022] 图1为按照本发明实施例7制备的磷酸硅铝分子筛EX-7的X射线衍射图(XRD谱图)。 [0022] FIG. 1 is a silicoaluminophosphate molecular sieve prepared in Example 7 X-ray diffraction (XRD spectrum) EX-7 according to the embodiment of the present invention.

具体实施方式 Detailed ways

[0023] 下面结合实施例对本发明做进一步说明。 [0023] The following embodiments in conjunction with embodiments of the present invention will be further described.

[0024] 实施例1 [0024] Example 1

[0025] 晶化母液的来源:水热合成法制备磷酸硅铝分子筛回收的滤液作为本实施例的晶化母液; [0025] Crystallization of the mother liquor source: Preparation of silicoaluminophosphate molecular sieves hydrothermal crystallization filtrate as mother liquor recovered according to the present embodiment;

[0026] 晶种的来源:水热合成法制备的磷酸硅铝分子筛作为本实施例的晶种; [0026] seed sources: hydrothermal synthesis of silicoaluminophosphate molecular sieve as the seed crystal according to the present embodiment;

[0027] (1)将铝源与去离子水混合均勻形成悬浊液A,去离子水与铝源(以Al2O3计)的摩尔比为25 : 1,所用铝源为拟薄水铝石; [0027] (1) The source of aluminum with deionized water uniformly formed suspension A, the molar ratio of the aluminum source with deionized water (in terms Al2O3) is from 25: 1, the aluminum source is a quasi boehmite;

[0028] (2)将磷源与去离子水混合均勻形成溶液B,去离子水与磷源(以P2O5计)的摩尔比为25 : 1,所用磷源为正磷酸; [0028] (2) the source of phosphorus mixed with deionized water to form a solution B, the molar ratio of deionized water and a source of phosphorus (as P2O5) 25: 1, the phosphorus source is orthophosphoric acid;

[0029] (3)将悬浊液A与溶液B混合均勻,然后依次加入模板剂、硅源、晶种和晶化母液, 搅拌形成初始凝胶混合物;所用模板剂为吗啡啉,所用硅源为硅溶胶,初始凝胶混合物中模板剂、硅源(以SiO2计)、磷源(以P2O5计)和铝源(以Al2O3计)的摩尔比为2. 5 : 1. 5 SiO2 : 2.0 P2O5 : 2. OAl2O3,初始凝胶混合物中晶化母液与铝源(以Al2O3计)的质量比为0. 1 : 1,初始凝胶混合物中晶种的质量为铝源(以Al2O3计)质量的3. 5% ; [0029] (3) A suspension was mixed with the solution B, followed by addition of the templating agent, a silicon source, a seed crystal and mother liquor, to form the initial gel mixture was stirred; the templating agent used is morpholine, used as the silicon source silica sol, the initial gel mixture the templating agent, a silicon source (in terms of SiO2), the molar ratio of the phosphorus source (as P2O5) and an aluminum source (in terms Al2O3) is from 2. 5: 1. 5 SiO2: 2.0 P2O5 : 2. OAl2O3, crystallization mother liquor mixture with an initial source of aluminum gel (in terms Al2O3) mass ratio of 0.1: 1, the initial gel mixture in the seed mass as aluminum source (in terms Al2O3) quality 3.5%;

[0030] (4)将初始凝胶混合物置于晶化釜中,在温度为180°C的条件下水热晶化36h ;将水热晶化后的产物随炉冷却后过滤得到滤饼和滤液; [0030] (4) The gel mixture was placed in the initial crystallization vessel at a temperature of to 180 ° C hydrothermal crystallization conditions for 36h; the product of the hydrothermal crystallization with the furnace was cooled and filtered to obtain a filtrate cake ;

[0031] (5)将滤饼用去离子水洗涤后置于烘箱中,在温度为120°C的条件下烘干;将烘干后的滤饼置于马弗炉中,在温度为550°C的条件下焙烧5h,随炉冷却后得到磷酸硅铝分子筛EX-I ; [0031] (5) The filter cake was washed with de-ionized water placed in an oven dried at a temperature condition to 120 ° C; the filter cake is dried in a muffle furnace at a temperature of 550 5h under calcination ° C., after the furnace was cooled with silicoaluminophosphate molecular sieves to give EX-I;

[0032] (6)将滤液回收并密封保存,作为晶化母液循环利用。 [0032] (6) The filtrate is recovered and sealed, as the crystallization mother liquor recycling.

[0033] 实施例2 [0033] Example 2

[0034] 本实施例与实施例1制备工艺相同,其中不同之处在于:所用晶化母液为实施例1中所用晶化母液和实施例1中回收的滤液的混合液,所用铝源为异丙醇铝或氧化铝,或者为异丙醇铝、拟薄水铝石和氧化铝中的至少两种,所用磷源为亚磷酸或亚磷酸和正磷酸,所用模板剂为四乙基氢氧化铵、三乙胺或二乙胺,或者为四乙基氢氧化铵、三乙胺、二乙胺和吗啡啉中的至少两种,所用硅源为正硅酸乙酯或白炭黑,或者为正硅酸乙酯、白炭黑和硅溶胶中的至少两种,温度为180°C的条件下水热晶化的时间为12h,制备得到磷酸硅铝分子筛EX-2。 [0034] The present embodiment is same as Example 1 Preparation process wherein except that: As used crystallization mother liquor to in Example 1 was crystallized mother liquor and a recovered filtrate embodiments mixture embodiments, the aluminum source is iso propanol or aluminum oxide, or aluminum isopropoxide, at least two of boehmite alumina and pseudo phosphorus source is phosphorous acid or phosphorous acid and phosphoric acid, the template agent is tetraethyl ammonium hydroxide used, diethylamine or triethylamine, or a tetraethylammonium hydroxide, triethylamine, diethylamine and morpholine at least two, the silicon source is tetraethyl orthosilicate or white carbon, or a positive ethyl silicate, silica sol, and at least two, a temperature of hot water to 180 ° C the crystallization time was 12h, silicoaluminophosphate molecular sieves prepared by EX-2.

[0035] 实施例3 [0035] Example 3

[0036] 本实施例与实施例1制备工艺相同,其中不同之处在于:所用晶化母液为实施例1和实施例2中回收的滤液的混合液,所用铝源为异丙醇铝或氧化铝,或者为异丙醇铝、拟薄水铝石和氧化铝中的至少两种,所用磷源为亚磷酸或亚磷酸和正磷酸,所用模板剂为四乙基氢氧化铵、三乙胺或二乙胺,或者为四乙基氢氧化铵、三乙胺、二乙胺和吗啡啉中的至少两种,所用硅源为正硅酸乙酯或白炭黑,或者为正硅酸乙酯、白炭黑和硅溶胶中的至少两种,温度为180°C的条件下水热晶化的时间为Mh,制备得到磷酸硅铝分子筛EX-3。 [0036] The present embodiment is the same as Preparation Example 1 process wherein except that: the crystallization mother liquor is used in Example 1 and a mixture of filtrate recovered in Example 2 embodiment, the source of aluminum oxide or aluminum isopropoxide aluminum isopropoxide or aluminum, at least two quasi-boehmite and alumina, the phosphorus source is phosphorous acid or phosphorous acid and phosphoric acid used, the template agent is tetraethyl ammonium hydroxide, triethylamine or di- ethylamine, or at least two tetraethylammonium hydroxide, triethylamine, diethylamine and morpholine is, the silicon source is tetraethyl orthosilicate or white carbon, or a TEOS silica sol and at least two, to 180 ° C temperature conditions of the hydrothermal crystallization time Mh, silicoaluminophosphate molecular sieves prepared EX-3.

[0037] 实施例4 [0037] Example 4

[0038] 晶化母液的来源:将实施例1至3中回收的滤液的混合液作为本实施例的晶化母液; [0038] Crystallization of the mother liquor sources: the crystallization mother liquor according to Example 1 of filtrate recovered in Example 3 as a mixture of the embodiment;

[0039] 晶种的来源:将实施例1制备的磷酸硅铝分子筛EX-I作为本实施例的晶种; Source [0039] The seed crystal: the embodiment silicoaluminophosphate molecular sieve prepared in Example 1 EX-I seed crystal in the present embodiment;

[0040] (1)将铝源与晶化母液混合均勻形成悬浊液A,晶化母液与铝源(以Al2O3计)的质量比为0.1 : 1,所用铝源为氧化铝; [0040] (1) the crystallization mother liquor with the aluminum source formed uniformly mixed suspension A, the aluminum source and the crystallization mother liquor (in terms Al2O3) mass ratio of 0.1: 1, the aluminum source is alumina;

[0041] (2)将磷源与晶化母液混合均勻形成溶液B,晶化母液与磷源(以P2O5计)的质量比为0.1 : 1,所用磷源为亚磷酸; [0041] (2) the crystallization mother liquor a source of phosphorus and mixed to form a solution B, the crystallization mother liquor a source of phosphorus (as P2O5) mass ratio of 0.1: 1, the phosphorus source is phosphorous acid;

[0042] (3)将悬浊液A与溶液B混合均勻,然后依次加入模板剂、硅源、晶种和晶化母液, 搅拌形成初始凝胶混合物;所用模板剂为四乙基氢氧化铵,所用硅源为硅溶胶,初始凝胶混合物中模板剂、硅源(以SiO2计)、磷源(以P2O5计)和铝源(以Al2O3计)的摩尔比为0.1 : 0. ISiO2 : 0. 2P205 : 0. 2A1203,初始凝胶混合物中晶化母液与铝源(以Al2O3计)的质量比为2 : 1,初始凝胶混合物中晶种的质量为铝源(以Al2O3计)质量的0. 01% ; [0042] (3) mixing the solution A and B uniform suspension, followed by addition of the templating agent, a silicon source, a seed crystal and mother liquor, to form the initial gel mixture was stirred; the template agent is tetraethyl ammonium hydroxide , the silicon source is silica sol, the initial gel mixture the templating agent, a silicon source (in terms of SiO2), the molar ratio of phosphorus source (as P2O5) and an aluminum source (in terms Al2O3) is from 0.1: 0. ISiO2: 0 . 2P205: 0. 2A1203, the initial gel mixture was crystallized mother liquor and the aluminum source (in terms Al2O3) mass ratio of 2: 1, the initial gel mixture in the seed mass as aluminum source (in terms Al2O3) quality 0.01%;

[0043] (4)将初始凝胶混合物置于晶化釜中,在温度为120°C的条件下水热预晶化他,然后在温度为150°C的条件下水热预晶化池,最后在温度为180°C的条件下水热晶化12h ;将水热晶化后的产物随炉冷却后过滤得到滤饼和滤液; [0043] (4) The gel mixture was placed in the initial crystallization vessel at a temperature of to 120 ° C pre hydrothermal crystallization conditions he then hydrothermally pre-crystallization temperature of the pool at conditions of 150 ° C, and finally in the temperature to 180 ° C hydrothermal crystallization conditions 12h; product after the hydrothermal crystallization with the furnace was filtered and the filtrate was cooled to obtain a cake;

[0044] (5)将滤饼用去离子水洗涤后置于烘箱中,在温度为120°C的条件下烘干;将烘干后的滤饼置于马弗炉中,在温度为550°C的条件下焙烧5h,随炉冷却后得到磷酸硅铝分子筛EX-4 ; [0044] (5) The filter cake was washed with de-ionized water placed in an oven dried at a temperature condition to 120 ° C; the filter cake is dried in a muffle furnace at a temperature of 550 5h under calcination ° C., after the furnace was cooled with silicoaluminophosphate molecular sieves EX-4;

[0045] (6)将滤液回收并密封保存,作为晶化母液循环利用。 [0045] (6) The filtrate is recovered and sealed, as the crystallization mother liquor recycling.

[0046] 实施例5 [0046] Example 5

[0047] 本实施例与实施例4制备工艺相同,其中不同之处在于:所用晶化母液为实施例1至4中回收的滤液的混合液,所用铝源为异丙醇铝或拟薄水铝石,或者为异丙醇铝、拟薄水铝石和氧化铝中的至少两种,所用磷源为正磷酸或正磷酸和亚磷酸,所用模板剂为三乙胺、二乙胺或吗啡啉,或者为四乙基氢氧化铵、三乙胺、二乙胺和吗啡啉中的至少两种,所用硅源为正硅酸乙酯或白炭黑,或者为正硅酸乙酯、白炭黑和硅溶胶中的至少两种,温度为120°C的条件下水热预晶化的时间为lh,温度为150°C的条件下水热预晶化的时间为2h,温度为180°C的条件下水热晶化的时间为Mh,制备得到磷酸硅铝分子筛EX-5。 [0047] The present embodiment is the same as prepared in Example 4 process embodiment, except that wherein: crystallization mother liquor is used in 1 to 4 mixture recovered filtrate embodiment embodiment, the aluminum source is aluminum isopropoxide, or pseudoboehmite boehmite, or aluminum isopropoxide, at least two of boehmite alumina and Quasi, the phosphorus source is orthophosphoric acid and phosphorous acid or orthophosphoric acid, used as the template triethylamine, diethylamine or morpholine , or a tetraethylammonium hydroxide, triethylamine, diethylamine and morpholine at least two, the silicon source is tetraethyl orthosilicate or white carbon, or a TEOS, white carbon black and the silica sol at least two, a temperature of hot water to 120 ° C pre-crystallization time of LH, a temperature of hot water at 150 ° C pre-crystallization time was 2h, temperature to 180 ° C condition of hydrothermal crystallization time Mh, silicoaluminophosphate molecular sieves prepared EX-5.

[0048] 实施例6 [0048] Example 6

[0049] 本实施例与实施例4制备工艺相同,其中不同之处在于:所用晶化母液为实施例1至5中回收的滤液的混合液,所用铝源为异丙醇铝或拟薄水铝石,或者为异丙醇铝、拟薄水铝石和氧化铝中的至少两种,所用磷源为正磷酸或正磷酸和亚磷酸,所用模板剂为三乙胺、二乙胺或吗啡啉,或者为四乙基氢氧化铵、三乙胺、二乙胺和吗啡啉中的至少两种,所用硅源为正硅酸乙酯或白炭黑,或者为正硅酸乙酯、白炭黑和硅溶胶中的至少两种,温度为120°C的条件下水热预晶化的时间为3. 5h,温度为150°C的条件下水热预晶化的时间为lh,温度为180°C的条件下水热晶化的时间为36h,制备得到磷酸硅铝分子筛EX-6。 [0049] The present embodiment is the same as the procedure described in Preparation Example 4, except that wherein: crystallization mother liquor is used in 1 to 5 embodiments mixture recovered filtrate embodiment, the aluminum source is aluminum isopropoxide, or pseudoboehmite boehmite, or aluminum isopropoxide, at least two of boehmite alumina and Quasi, the phosphorus source is orthophosphoric acid and phosphorous acid or orthophosphoric acid, used as the template triethylamine, diethylamine or morpholine , or a tetraethylammonium hydroxide, triethylamine, diethylamine and morpholine at least two, the silicon source is tetraethyl orthosilicate or white carbon, or a TEOS, white carbon black and the silica sol at least two, a temperature of hot water to 120 ° C pre-crystallization time 3. 5h, a temperature of hot water at 150 ° C pre-crystallization time of LH, a temperature of 180 ° condition C hydrothermal crystallization time 36h, silicoaluminophosphate molecular sieves prepared EX-6.

[0050] 实施例7 [0050] Example 7

[0051] 晶化母液的来源:将实施例1至6中回收的滤液的混合液作为本实施例的晶化母液; [0051] Source crystallization mother liquor: 1-6 in the filtrate was recovered as a mixture of Example crystallization mother liquor according to the present embodiment;

[0052] 晶种的来源:将实施例4制备的磷酸硅铝分子筛EX-4作为本实施例的晶种; Source [0052] A seed crystal: The silicoaluminophosphate molecular sieves embodiment EX-4 prepared in Example 4 as a seed crystal according to the present embodiment;

[0053] (1)将铝源与去离子水混合均勻形成悬浊液A,去离子水与铝源(以Al2O3计)的摩尔比为1 : 1,所用铝源为异丙醇铝、拟薄水铝石和氧化铝的混合物; Molar ratio [0053] (1) mixing water with the aluminum source to form a uniform suspension of the ion A, deionized water and an aluminum source (in terms Al2O3) is 1: 1, the aluminum source is aluminum isopropoxide, Quasi a mixture of boehmite and aluminum oxide;

[0054] (2)将磷源与去离子水混合均勻形成溶液B,去离子水与磷源(以P2O5计)的摩尔比为1 : 1,所用磷源为正磷酸和亚磷酸的混合物; [0054] (2) the source of phosphorus and deionized water were mixed uniformly to form a solution B, the molar ratio of deionized water and a source of phosphorus (as P2O5) is 1: 1, the phosphorus source is a mixture of orthophosphoric acid and phosphorous acid;

[0055] (3)将悬浊液A与溶液B混合均勻,然后依次加入模板剂、硅源、晶种和晶化母液,搅拌形成初始凝胶混合物;所用模板剂为四乙基氢氧化铵、三乙胺和吗啡啉的混合物,所用硅源为正硅酸乙酯、白炭黑和硅溶胶的混合物,初始凝胶混合物中模板剂、硅源(以SiA计)、磷源(以P2O5计)和铝源(以Ai2O3计)的摩尔比为1.6 : 0. 4Si02 : 1. OP2O5 : 1. OAl2O3,初始凝胶混合物中晶化母液与铝源(以Al2O3计)的质量比为1 : 1,初始凝胶混合物中晶种的质量为铝源(以Al2O3计)质量的1.8% ; [0055] (3) mixing the solution A and B uniform suspension, followed by addition of the templating agent, a silicon source, a seed crystal and mother liquor, to form the initial gel mixture was stirred; the template agent is tetraethyl ammonium hydroxide , triethylamine and morpholine, and the silicon source is tetraethyl orthosilicate used, and a mixture of silica sol, the initial gel mixture the templating agent, a silicon source (in terms SiA), a source of phosphorus (as P2O5 molar ratio) and an aluminum source (in Ai2O3 basis) is 1.6: 0. 4Si02: 1. OP2O5: 1. OAl2O3, the initial gel mixture was crystallized mother liquor and the aluminum source (in terms Al2O3) mass ratio of 1: 1, the initial gel mixture in the seed mass as aluminum source (in terms Al2O3) of 1.8% by mass;

[0056] (4)将初始凝胶混合物置于晶化釜中,在温度为100°C的条件下水热预晶化Mh, 接着在温度为120°C的条件下水热预晶化lh,然后在温度为150°C的条件下水热预晶化lh, 最后在温度为180°C的条件下水热晶化36h ;将水热晶化后的产物随炉冷却后过滤得到滤饼和滤液; [0056] (4) The gel mixture was placed in the initial crystallization vessel, at a temperature of 100 ° C pre-conditions for hydrothermal crystallization Mh, followed by hydrothermal crystallization pre lh at temperatures to 120 ° C condition, then at a temperature of 150 ° C pre-conditions for hydrothermal crystallization lh, finally to 180 ° C temperature hydrothermal crystallization conditions 36h; product after the hydrothermal subsequently cooling the furnace was filtered to obtain a cake and a filtrate;

[0057] (5)将滤饼用去离子水洗涤后置于烘箱中,在温度为120°C的条件下烘干;将烘干后的滤饼置于马弗炉中,在温度为550°C的条件下焙烧5h,随炉冷却后得到磷酸硅铝分子筛EX-7 ; [0057] (5) The filter cake was washed with de-ionized water placed in an oven dried at a temperature condition to 120 ° C; the filter cake is dried in a muffle furnace at a temperature of 550 5h under calcination ° C., after the furnace was cooled with silicoaluminophosphate molecular sieves to give EX-7;

[0058] (6)将滤液回收并密封保存,作为晶化母液循环利用。 [0058] (6) The filtrate is recovered and sealed, as the crystallization mother liquor recycling.

[0059] 图1为本实施例制备的磷酸硅铝分子筛EX-7的XRD谱图。 Silicoaluminophosphate molecular sieve prepared in Example XRD spectrum of the EX-7 [0059] 1 of the present embodiment FIG. 磷酸硅铝分子筛EX_7 的主要成分为SAP0-34,其特征峰为图中标记的(1)、⑵和(3)处,其中⑴为在2Θ = 9.5°处有较强的单峰;(2)为在2 θ =¾°处有双峰;(3)为在2 θ =31°处有双峰。 Silicoaluminophosphate molecular sieves EX_7 main component SAP0-34, FIG characteristic peaks labeled (1), ⑵, and (3) at which there is a strong ⑴ single peak at 2Θ = 9.5 °; (2 ) is bimodal in at 2 θ = ¾ °; (3) as at 2 θ = 31 ° bimodal.

[0060] 实施例8 [0060] Example 8

[0061] 本实施例与实施例7制备工艺相同,其中不同之处在于:所用晶化母液为实施例1 至7中回收的滤液的混合液,所用铝源为异丙醇铝、拟薄水铝石和氧化铝中的一种或两种, 所用磷源为正磷酸或亚磷酸,所用模板剂为四乙基氢氧化铵、三乙胺、二乙胺和吗啡啉中的一种或两种,或者为四乙基氢氧化铵、三乙胺、二乙胺和吗啡啉,或者为四乙基氢氧化铵、三乙胺和二乙胺,或者为四乙基氢氧化铵、二乙胺和吗啡啉,或者为三乙胺、二乙胺和吗啡啉, 所用硅源为正硅酸乙酯、白炭黑和硅溶胶中的一种或两种,温度为100°C的条件下水热预晶化的时间为他,温度为120°C的条件下水热预晶化的时间为他,温度为150°C的条件下水热预晶化的时间为池,温度为180°C的条件下水热晶化的时间为Mh,制备得到磷酸硅铝分子筛EX-8。 [0061] The present embodiment is the same as in Example 7 preparation process, wherein except that: the crystallization mother liquor is used in 1 to 7 embodiments mixture recovered filtrate embodiment, the aluminum source is aluminum isopropoxide, and pseudoboehmite boehmite alumina and one or both of the phosphorus source is orthophosphoric acid or phosphorous acid, the template agent is tetraethyl ammonium hydroxide, a tri-ethylamine, diethylamine and morpholine or two , or a tetraethylammonium hydroxide, triethylamine, diethylamine and morpholine, or a tetraethyl ammonium hydroxide, diethylamine and triethylamine, or a tetraethyl ammonium hydroxide, diethylamine and morpholine, or triethylamine, diethylamine and morpholine, the silicon source is tetraethyl orthosilicate, the silica sol and one or both of a temperature of 100 ° C hydrothermal conditions pre-crystallization time for him, a temperature of to 120 ° C hydrothermal pre-crystallization time for him, a temperature condition of 150 ° C hydrothermal pre-crystallization time was pool temperature to 180 ° C condition water thermal crystallization time is Mh, silicoaluminophosphate molecular sieves prepared EX-8.

[0062] 实施例9 [0062] Example 9

[0063] 本实施例与实施例7制备工艺相同,其中不同之处在于:所用晶化母液为实施例1 至8中回收的滤液的混合液,所用铝源为异丙醇铝、拟薄水铝石和氧化铝中的一种或两种, [0063] The present embodiment is the same as in Example 7 preparation process, wherein except that: the crystallization mother liquor is used in 1 to Example 8 a mixture of recovered filtrate embodiment, the aluminum source is aluminum isopropoxide, and pseudoboehmite boehmite alumina and one or two,

7所用磷源为正磷酸或亚磷酸,所用模板剂为四乙基氢氧化铵、三乙胺、二乙胺和吗啡啉中的一种或两种,或者为四乙基氢氧化铵、三乙胺、二乙胺和吗啡啉,或者为四乙基氢氧化铵、三乙胺和二乙胺,或者为四乙基氢氧化铵、二乙胺和吗啡啉,或者为三乙胺、二乙胺和吗啡啉, 所用硅源为正硅酸乙酯、白炭黑和硅溶胶中的一种或两种,温度为100°C的条件下水热预晶化的时间为15h,温度为120°C的条件下水热预晶化的时间为3. 5h,温度为150°C的条件下水热预晶化的时间为池,温度为180°C的条件下水热晶化的时间为12h,制备得到磷酸硅铝分子筛EX-9。 7 with the phosphorus source is orthophosphoric acid or phosphorous acid, the template agent is tetraethyl ammonium hydroxide, triethylamine, diethylamine and morpholine in the one or two, or a tetraethylammonium hydroxide, tris ethylamine, diethylamine and morpholine, or a tetraethyl ammonium hydroxide, diethylamine and triethylamine, or a tetraethyl ammonium hydroxide, morpholine and diethylamine, or triethylamine, di- ethylamine and morpholine, the silicon source is tetraethyl orthosilicate, the silica sol and one or both of a temperature of hot water of 100 ° C the crystallization time is pre-15H, a temperature of 120 condition ° C. hydrothermal pre-crystallization time 3. 5h, a temperature of hot water at 150 ° C pre-crystallization time was pool, a temperature of hot water to 180 ° C the crystallization time was 12h, prepared silicoaluminophosphate molecular sieves to give EX-9.

[0064] 实施例10 [0064] Example 10

[0065] 晶化母液的来源:将实施例1至9中回收的滤液的混合液作为本实施例的晶化母液; [0065] Source crystallization mother liquor: 1 to 9 the filtrate recovered as a mixture of an embodiment of the present embodiment of the crystallization mother liquor;

[0066] 晶种的来源:将实施例7制备的磷酸硅铝分子筛EX-7作为本实施例的晶种; Source [0066] The seed crystal: the embodiment silicoaluminophosphate molecular sieve prepared in Example 7 EX-7 seed present embodiment;

[0067] (1)将铝源与去离子水混合均勻形成悬浊液A,去离子水与铝源(以Al2O3计)的摩尔比为13 : 1,所用铝源为拟薄水铝石; [0067] (1) The source of aluminum with deionized water uniformly formed suspension A, the molar ratio of the aluminum source with deionized water (in terms Al2O3) is from 13: 1, the aluminum source is a quasi boehmite;

[0068] (2)将磷源与去离子水混合均勻形成溶液B,去离子水与磷源(以P2O5计)的摩尔比为13 : 1,所用磷源为亚磷酸; [0068] (2) the source of phosphorus mixed with deionized water to form a solution B, the molar ratio of deionized water and a source of phosphorus (as P2O5) is 13: 1, the phosphorus source is phosphorous acid;

[0069] (3)将悬浊液A与溶液B混合均勻,然后依次加入模板剂、硅源和晶化母液,搅拌形成初始凝胶混合物;所用模板剂为二乙胺、三乙胺和吗啡啉的混合物,所用硅源为正硅酸乙酯和硅溶胶的混合物,初始凝胶混合物中模板剂、硅源(以S^2计)、磷源(以P2O5计) 和铝源(以Al2O3计)的摩尔比为1.55 : 0. 6Si02 : 1. IP2O5 : 1. IAl2O3,初始凝胶混合物中晶化母液与铝源(以Al2O3计)的质量比为3 : 1,初始凝胶混合物中晶种的质量为铝源(以Al2O3计)质量的2. 3% ; [0069] (3) mixing the solution A and B uniform suspension, followed by addition of the templating agent, silicon source and a crystallization mother liquor, to form the initial gel mixture was stirred; the templating agent used is diethylamine, triethylamine, and morphine morpholine mixture, a mixture of the silicon source is tetraethyl orthosilicate and colloidal silica, the initial gel mixture the templating agent, a silicon source (S ^ 2 in basis), a source of phosphorus (as P2O5) and an aluminum source (as Al2O3 meter) molar ratio of 1.55: 0. 6Si02: 1. IP2O5: 1. IAl2O3, the initial gel mixture was crystallized mother liquor and the aluminum source (in terms Al2O3) mass ratio of 3: 1, the initial crystallization gel mixture quality thereof as aluminum source (in terms Al2O3) of 2.3% by mass;

[0070] (4)将初始凝胶混合物置于晶化釜中,在温度为100°C的条件下水热预晶化Mh, 然后在温度为180°C的条件下水热晶化12h ;将水热晶化后的产物随炉冷却后过滤得到滤饼和滤液; [0070] (4) The gel mixture was placed in the initial crystallization vessel, at a temperature of 100 ° C pre-conditions for hydrothermal crystallization Mh, and then hydrothermally crystallized at 12h to 180 ° C temperature conditions; water the product was crystallized with the furnace heat was filtered and the filtrate was cooled to obtain a cake;

[0071] (5)将滤饼用去离子水洗涤后置于烘箱中,在温度为120°C的条件下烘干;将烘干后的滤饼置于马弗炉中,在温度为550°C的条件下焙烧5h,随炉冷却后得到磷酸硅铝分子蹄EX-10 ; [0071] (5) The filter cake was washed with de-ionized water placed in an oven dried at a temperature condition to 120 ° C; the filter cake is dried in a muffle furnace at a temperature of 550 5h under calcination ° C., after the furnace was cooled with silicoaluminophosphate molecular shoe EX-10;

[0072] (6)将滤液回收并密封保存,作为晶化母液循环利用。 [0072] (6) The filtrate is recovered and sealed, as the crystallization mother liquor recycling.

[0073] 实施例11 [0073] Example 11

[0074] 本实施例与实施例10制备工艺相同,其中不同之处在于:所用晶化母液为实施例1至10中回收的滤液的混合液,所用铝源为异丙醇铝或氧化铝,或者为异丙醇铝、拟薄水铝石和氧化铝中的至少两种,所用磷源为正磷酸或正磷酸和亚磷酸,所用模板剂为四乙基氢氧化铵、三乙胺、二乙胺和吗啡啉中的一种或两种,或者为四乙基氢氧化铵、三乙胺、二乙胺和吗啡啉,或者为四乙基氢氧化铵、三乙胺和二乙胺,或者为四乙基氢氧化铵、二乙胺和吗啡啉,或者为四乙基氢氧化铵、三乙胺和吗啡啉,所用硅源为正硅酸乙酯、白炭黑和硅溶胶中的一种或三种,或者为正硅酸乙酯和白炭黑,或者为白炭黑和硅溶胶,温度为100°c的条件下水热预晶化的时间为15h,温度为180°C的条件下水热晶化的时间为Mh,制备得到磷酸硅铝分子筛EX-Il。 [0074] The embodiment of the present embodiment is the same process of Example 10 was prepared, except that wherein: The mother liquor for the crystallization used in Example 1 to a mixture of filtrate 10 recovered, the aluminum source is aluminum isopropoxide or aluminum oxide, or aluminum isopropoxide, at least two of boehmite and pseudoboehmite alumina, the phosphorus source used is orthophosphoric acid or orthophosphoric acid and phosphorous acid, the template agent is tetraethyl ammonium hydroxide, triethylamine, diethyl amine, and morpholine in the one or two, or a tetraethylammonium hydroxide, triethylamine, diethylamine and morpholine, or a tetraethyl ammonium hydroxide, triethylamine, and diethylamine, or as tetraethyl ammonium hydroxide, diethylamine and morpholine, or a tetraethylammonium hydroxide, triethylamine and morpholine, the silicon source is tetraethyl orthosilicate, silica and a silica sol or three, or a TEOS and silica, or a silica sol and a temperature of 100 ° c hydrothermal conditions of the pre-crystallization time of 15H, a temperature of to 180 ° C hydrothermal crystallization time Mh, silicoaluminophosphate molecular sieves prepared EX-Il.

[0075] 实施例12[0076] 本实施例与实施例10制备工艺相同,其中不同之处在于:所用晶化母液为实施例1至11中回收的滤液的混合液,所用铝源为异丙醇铝或氧化铝,或者为异丙醇铝、拟薄水铝石和氧化铝中的至少两种,所用磷源为正磷酸或正磷酸和亚磷酸,所用模板剂为四乙基氢氧化铵、三乙胺、二乙胺和吗啡啉中的一种或两种,或者为四乙基氢氧化铵、三乙胺、二乙胺和吗啡啉,或者为四乙基氢氧化铵、三乙胺和二乙胺,或者为四乙基氢氧化铵、二乙胺和吗啡啉,或者为四乙基氢氧化铵、三乙胺和吗啡啉,所用硅源为正硅酸乙酯、白炭黑和硅溶胶中的一种或三种,或者为正硅酸乙酯和白炭黑,或者为白炭黑和硅溶胶,温度为100°c的条件下水热预晶化的时间为他,温度为180°c的条件下水热晶化的时间为36h,制备得到磷酸硅铝分子筛EX-12。 12 [0076] [0075] Example embodiments of the present embodiment is the same procedure described in Preparation Example 10, except that wherein: crystallization mother liquor is used in 1 to 11 in a mixture of recovered filtrate embodiment embodiment, the aluminum source is an isopropyl aluminum alkoxides or aluminum oxide, or aluminum isopropoxide, at least two of boehmite alumina and Quasi, the phosphorus source is orthophosphoric acid and phosphorous acid or orthophosphoric acid, the template agent is tetraethyl ammonium hydroxide, triethylamine, diethylamine and morpholine in the one or two, or a tetraethylammonium hydroxide, triethylamine, diethylamine and morpholine, or a tetraethyl ammonium hydroxide, triethylamine and diethylamine, or a tetraethyl ammonium hydroxide, diethylamine and morpholine, or a tetraethylammonium hydroxide, triethylamine and morpholine, the silicon source is tetraethyl orthosilicate, white carbon and one or three kinds of the silica sol, or a TEOS and silica, or a silica sol and a temperature of 100 ° c hydrothermal conditions of the pre-crystallization time his temperature 180 ° c for the conditions of hydrothermal crystallization time 36h, silicoaluminophosphate molecular sieves prepared EX-12.

[0077] 实施例13 [0077] Example 13

[0078] 晶化母液的来源:将实施例1至12中回收的滤液的混合液作为本实施例的晶化母液; [0078] Source crystallization mother liquor: 12 to 1 the filtrate was recovered as a mixture of an embodiment of the present embodiment of the crystallization mother liquor;

[0079] 晶种的来源:将实施例10制备的磷酸硅铝分子筛EX-10作为本实施例的晶种; Source [0079] The seed crystal: the embodiment silicoaluminophosphate molecular sieve prepared in Example 10 EX-10 as a seed of the present embodiment;

[0080] (1)将铝源与晶化母液混合均勻形成悬浊液A,晶化母液与铝源(以Al2O3计)的质量比为5 : 1,所用铝源为拟薄水铝石和异丙醇铝的混合物; [0080] (1) the aluminum source and the crystallization mother liquor was mixed uniformly formed suspension A, the aluminum source and the crystallization mother liquor (in terms Al2O3) mass ratio of 5: 1, the aluminum source is boehmite and pseudoboehmite iso mixture of aluminum-propanol;

[0081] (2)将磷源与晶化母液混合均勻形成溶液B,晶化母液与磷源(以P2O5计)的质量比为3. 6 : 1,所用磷源为亚磷酸; [0081] (2) the crystallization mother liquor a source of phosphorus and mixed to form a solution B, the crystallization mother liquor a source of phosphorus (as P2O5) mass ratio of 3.6: 1, the phosphorus source used is phosphorous acid;

[0082] (3)将悬浊液A与溶液B混合均勻,然后依次加入模板剂、硅源、晶种和晶化母液, 搅拌形成初始凝胶混合物;所用模板剂为四乙基氢氧化铵和吗啡啉的混合物,所用硅源为正硅酸乙酯和硅溶胶的混合物,初始凝胶混合物中模板剂、硅源(以SiOJ+)、磷源(以P2O5 计)和铝源(以Al2O3计)的摩尔比为1.12 : 0. 8Si02 : 0·8Ρ205 : 1. OAl2O3,初始凝胶混合物中晶化母液与铝源(以Al2O3计)的质量比为10 : 1,初始凝胶混合物中晶种的质量为铝源(以Al2O3计)质量的2. 5% ; [0082] (3) mixing the solution A and B uniform suspension, followed by addition of the templating agent, a silicon source, a seed crystal and mother liquor, to form the initial gel mixture was stirred; the template agent is tetraethyl ammonium hydroxide and a mixture of morpholine, the silicon source used is a mixture of silica sol and tetraethoxysilane, the initial gel mixture the templating agent, a silicon source (in SiOJ +), a source of phosphorus (as P2O5) and an aluminum source (in terms Al2O3 the molar ratio) of 1.12: 0. 8Si02: 0 · 8Ρ205: 1. OAl2O3, the initial gel mixture was crystallized mother liquor and the aluminum source (in terms Al2O3) mass ratio of 10: 1, the initial gel mixture was seeded the mass of the aluminum source (in terms Al2O3) of 2.5% by mass;

[0083] (4)将初始凝胶混合物置于晶化釜中,在温度为120°C的条件下水热预晶化他,然后在温度为180°C的条件下水热晶化Mh ;将水热晶化后的产物随炉冷却后过滤得到滤饼和滤液; [0083] (4) The gel mixture was placed in the initial crystallization vessel at a temperature of to 120 ° C pre hydrothermal crystallization conditions he then hydrothermally crystallized at a temperature Mh is the condition to 180 ° C; water the product was crystallized with the furnace heat was filtered and the filtrate was cooled to obtain a cake;

[0084] (5)将滤饼用去离子水洗涤后置于烘箱中,在温度为120°C的条件下烘干;将烘干后的滤饼置于马弗炉中,在温度为550°C的条件下焙烧5h,随炉冷却后得到磷酸硅铝分子蹄EX-13 ; [0084] (5) The filter cake was washed with de-ionized water placed in an oven dried at a temperature condition to 120 ° C; the filter cake is dried in a muffle furnace at a temperature of 550 5h under calcination ° C., after the furnace was cooled with silicoaluminophosphate molecular shoe EX-13;

[0085] (6)将滤液回收并密封保存,作为晶化母液循环利用。 [0085] (6) The filtrate is recovered and sealed, as the crystallization mother liquor recycling.

[0086] 实施例14 [0086] Example 14

[0087] 本实施例与实施例13制备工艺相同,其中不同之处在于:所用晶化母液为实施例1至13中回收的滤液的混合液,所用铝源为异丙醇铝、拟薄水铝石和氧化铝中的一种或三种,或者为异丙醇铝和氧化铝,或者为拟薄水铝石和氧化铝,所用磷源为正磷酸或正磷酸和亚磷酸,所用模板剂为四乙基氢氧化铵、三乙胺、二乙胺和吗啡啉中的一种或三种,或者为吗啡啉、三乙胺和二乙胺中的两种,或者为四乙基氢氧化铵和三乙胺,或者为四乙基氢氧化铵和二乙胺,或者为四乙基氢氧化铵、三乙胺、二乙胺和吗啡啉,所用硅源为正硅酸乙酯、白炭黑和硅溶胶中的一种或三种,或者为正硅酸乙酯和白炭黑,或者为白炭黑和硅溶胶,温度为120°C的条件下水热预晶化的时间为lh,温度为180°C的条件下水热晶化的时间为36h,制备得到磷酸硅铝分子筛EX-14。 [0087] The present embodiment is the same as prepared in Example 13 process, wherein except that: the crystallization mother liquor is used in 1 to Example 13 a mixture of recovered filtrate embodiment, the aluminum source is aluminum isopropoxide, and pseudoboehmite boehmite alumina and one or three, or aluminum oxide and aluminum isopropoxide, or a quasi boehmite and alumina, the phosphorus source used is orthophosphoric acid or orthophosphoric acid and phosphorous acid, as used as template four One or three kinds ethyl ammonium hydroxide, triethylamine, diethylamine and morpholine in, or a morpholine, diethylamine and triethylamine in two, or a tetraethyl ammonium hydroxide and triethylamine, or a tetraethyl ammonium hydroxide and diethylamine, or as tetraethylammonium hydroxide, triethylamine, morpholine and diethylamine, the silicon source is tetraethyl orthosilicate, white carbon silica sol and one or three, or a TEOS and white carbon, silica or a silica sol, a temperature of hot water to 120 ° C pre-crystallization time of LH, temperature condition to 180 ° C hydrothermal crystallization time 36h, silicoaluminophosphate molecular sieves prepared EX-14.

[0088] 实施例15 [0088] Example 15

[0089] 本实施例与实施例13制备工艺相同,其中不同之处在于:所用晶化母液为实施例1至14中回收的滤液的混合液,所用铝源为异丙醇铝、拟薄水铝石和氧化铝中的一种或三种,或者为异丙醇铝和氧化铝,或者为拟薄水铝石和氧化铝,所用磷源为正磷酸或正磷酸和亚磷酸,所用模板剂为四乙基氢氧化铵、三乙胺、二乙胺和吗啡啉中的一种或三种,或者为吗啡啉、三乙胺和二乙胺中的两种,或者为四乙基氢氧化铵和三乙胺,或者为四乙基氢氧化铵和二乙胺,或者为四乙基氢氧化铵、三乙胺、二乙胺和吗啡啉,所用硅源为正硅酸乙酯、 白炭黑和硅溶胶中的一种或三种,或者为正硅酸乙酯和白炭黑,或者为白炭黑和硅溶胶,温度为120°C的条件下水热预晶化的时间为3. 5h,温度为180°C的条件下水热晶化的时间为12h,制备得到磷酸硅铝分子筛EX-15。 [0089] The present embodiment is the same as Example 13 preparation, wherein except that: the crystallization mother liquor with a mixture of filtrate recovered in Example 1 to 14 of the embodiment, the aluminum source is aluminum isopropoxide, and pseudoboehmite boehmite alumina and one or three, or aluminum oxide and aluminum isopropoxide, or a quasi boehmite and alumina, the phosphorus source used is orthophosphoric acid or orthophosphoric acid and phosphorous acid, as used as template four One or three kinds ethyl ammonium hydroxide, triethylamine, diethylamine and morpholine in, or a morpholine, diethylamine and triethylamine in two, or a tetraethyl ammonium hydroxide and triethylamine, or a tetraethyl ammonium hydroxide and diethylamine, or as tetraethylammonium hydroxide, triethylamine, morpholine and diethylamine, the silicon source is tetraethyl orthosilicate, white carbon silica sol and one or three, or a TEOS and white carbon, silica or a silica sol, a temperature of hot water to 120 ° C pre-crystallization time 3. 5h , to 180 ° C temperature conditions of the hydrothermal crystallization time 12h, silicoaluminophosphate molecular sieves prepared EX-15.

[0090] 实施例16 [0090] Example 16

[0091] 晶化母液的来源:将实施例1至15中回收的滤液的混合液作为本实施例的晶化母液; [0091] Source crystallization mother liquor: 1 to 15 recover the filtrate as a mixture of an embodiment according to the present embodiment of the crystallization mother liquor;

[0092] 晶种的来源:将实施例13制备中的磷酸硅铝分子筛EX-13作为本实施例的晶种; Source [0092] The seed crystal: the embodiment silicoaluminophosphate molecular sieve prepared in Example 13 EX-13 as the seed of the present embodiment;

[0093] (1)将铝源与晶化母液混合均勻形成悬浊液A,晶化母液与铝源(以Al2O3计)的质量比为2. 5 : 1,所用铝源为氧化铝和异丙醇铝的混合物; [0093] (1) the aluminum source and the crystallization mother liquor was mixed uniformly formed suspension A, the aluminum source and the crystallization mother liquor (in terms Al2O3) mass ratio of 2.5: 1, the source of alumina and aluminum iso mixture of aluminum-propanol;

[0094] (2)将磷源与晶化母液混合均勻形成溶液B,晶化母液与磷源(以P2O5计)的质量比为1.8 : 1,所用磷源为正磷酸; [0094] (2) mixing a source of phosphorus and crystallization mother liquor solution B is formed uniformly, the crystallization mother liquor a source of phosphorus (as P2O5) mass ratio of 1.8: 1, with the phosphorus source is orthophosphoric acid;

[0095] (3)将悬浊液A与溶液B混合均勻,然后依次加入模板剂、硅源、晶种和晶化母液, 搅拌形成初始凝胶混合物;所用模板剂为四乙基氢氧化铵,所用硅源为正硅酸乙酯和硅溶胶的混合物,初始凝胶混合物中模板剂、硅源(以S^2计)、磷源(以P2O5计)和铝源(以Al2O3计)的摩尔比为1.3 : 0. 2Si02 : 0. 9P205 : 1. OAl2O3,初始凝胶混合物中晶化母液与铝源(以Al2O3计)的质量比为5 : 1,初始凝胶混合物中晶种的质量为铝源(以Al2O3计) 质量的3.0% ; [0095] (3) mixing the solution A and B uniform suspension, followed by addition of the templating agent, a silicon source, a seed crystal and mother liquor, to form the initial gel mixture was stirred; the template agent is tetraethyl ammonium hydroxide , the silicon source is tetraethyl orthosilicate and mixtures of silica, the initial gel mixture the templating agent, a silicon source (S ^ 2 in basis), a source of phosphorus (as P2O5) and an aluminum source (as Al2O3 basis) molar ratio of 1.3: 0. 2Si02: 0. 9P205: 1. OAl2O3, the initial gel mixture was crystallized mother liquor and the aluminum source (in terms Al2O3) mass ratio of 5: 1, the quality of the initial seed crystal gel mixture a source of aluminum (in terms Al2O3) of 3.0% by mass;

[0096] (4)将初始凝胶混合物置于晶化釜中,在温度为150°C的条件下水热预晶化池,然后在温度为180°C的条件下水热晶化Mh ;将水热晶化后的产物随炉冷却后过滤得到滤饼和滤液; [0096] (4) The initial crystallization gel mixture was placed in the autoclave, hydrothermal pre-crystallization temperature of the pool at conditions of 150 ° C, and then hydrothermal crystallization at a temperature Mh is the condition to 180 ° C; water the product was crystallized with the furnace heat was filtered and the filtrate was cooled to obtain a cake;

[0097] (5)将滤饼用去离子水洗涤后置于烘箱中,在温度为120°C的条件下烘干;将烘干后的滤饼置于马弗炉中,在温度为550°C的条件下焙烧5h,随炉冷却后得到磷酸硅铝分子蹄EX-16 ; [0097] (5) The filter cake was washed with de-ionized water placed in an oven dried at a temperature condition to 120 ° C; the filter cake is dried in a muffle furnace at a temperature of 550 5h under calcination ° C., after the furnace was cooled with silicoaluminophosphate molecular shoe EX-16;

[0098] (6)将滤液回收并密封保存,作为晶化母液循环利用。 [0098] (6) The filtrate is recovered and sealed, as the crystallization mother liquor recycling.

[0099] 实施例17 [0099] Example 17

[0100] 本实施例与实施例16制备工艺相同,其中不同之处在于:所用晶化母液为实施例1至16中回收的滤液的混合液,所用铝源为异丙醇铝、拟薄水铝石和氧化铝中的一种或三种,或者为异丙醇铝和拟薄水铝石,或者为拟薄水铝石和氧化铝,所用磷源为亚磷酸或亚磷酸和正磷酸,所用模板剂为三乙胺、二乙胺和吗啡啉中的一种,或者为四乙基氢氧化铵、三乙胺、二乙胺和吗啡啉中的至少两种,所用硅源为正硅酸乙酯、白炭黑和硅溶胶中的一种或三种,或者为正硅酸乙酯和白炭黑,或者为白炭黑和硅溶胶,温度为150°C的条件下水热预晶化的时间为池,温度为180°C的条件下水热晶化的时间为12h,制备得到磷酸硅铝分子筛EX-17。 [0100] The present embodiment is prepared in the same procedure described in Example 16, except that wherein: crystallization mother liquor is used in 1 to 16 Example mixture recovered filtrate embodiment, the aluminum source is aluminum isopropoxide, and pseudoboehmite One or three kinds of boehmite and aluminum oxide, or aluminum isopropoxide and pseudo-boehmite, or a quasi boehmite and aluminum oxide, a phosphorus source is phosphorous acid or phosphorous acid and phosphoric acid used, the templating agent used as a triethylamine, diethylamine and morpholine in, at least two or tetraethylammonium hydroxide, triethylamine, diethylamine and morpholine in, that the silicon source used is TEOS , silica sol and one or three, or a TEOS and white carbon, silica or a silica sol, a temperature of 150 ° C pre-conditions for hydrothermal crystallization time for the pool, to 180 ° C temperature conditions of the hydrothermal crystallization time 12h, silicoaluminophosphate molecular sieves prepared EX-17.

[0101] 实施例18 [0101] Example 18

[0102] 本实施例与实施例16制备工艺相同,其中不同之处在于:所用晶化母液为实施例1至17中回收的滤液的混合液,所用铝源为异丙醇铝、拟薄水铝石和氧化铝中的一种或三种,或者为异丙醇铝和拟薄水铝石,或者为拟薄水铝石和氧化铝,所用磷源为亚磷酸或亚磷酸和正磷酸,所用模板剂为三乙胺、二乙胺和吗啡啉中的一种,或者为四乙基氢氧化铵、三乙胺、二乙胺和吗啡啉中的至少两种,所用硅源为正硅酸乙酯、白炭黑和硅溶胶中的一种或三种,或者为正硅酸乙酯和白炭黑,或者为白炭黑和硅溶胶,温度为150°C的条件下水热预晶化的时间为lh,温度为180°C的条件下水热晶化的时间为36h,制备得到磷酸硅铝分子筛EX-18。 [0102] The present embodiment is prepared in the same procedure described in Example 16, except that wherein: crystallization mother liquor is used in 1 to 17 in a mixture of recovered filtrate embodiment embodiment, the aluminum source is aluminum isopropoxide, and pseudoboehmite One or three kinds of boehmite and aluminum oxide, or aluminum isopropoxide and pseudo-boehmite, or a quasi boehmite and aluminum oxide, a phosphorus source is phosphorous acid or phosphorous acid and phosphoric acid used, the templating agent used as a triethylamine, diethylamine and morpholine in, at least two or tetraethylammonium hydroxide, triethylamine, diethylamine and morpholine in, that the silicon source used is TEOS , silica sol and one or three, or a TEOS and white carbon, silica or a silica sol, a temperature of 150 ° C pre-conditions for hydrothermal crystallization time to lh, to 180 ° C temperature conditions of hydrothermal crystallization time 36h, silicoaluminophosphate molecular sieves prepared EX-18.

[0103] 实施例19 :磷酸硅铝分子筛催化甲醇转化制烯烃试验 [0103] Example 19: silicoaluminophosphate molecular sieves catalytic conversion of methanol to olefins Test

[0104] 将实施例1,4,7,10,13和16制备的磷酸硅铝分子筛压片后破碎;各取20目〜40 目破碎后的磷酸硅铝分子筛4. 5g装入固定床反应器,在温度为500°C的条件下通氮气活化lh,然后在温度为400°C的条件下进行反应,质量分数为50%的甲醇由氮气携带,氮气流量为50mL/min,甲醇空速为2. OtT1,反应产物由在线气相色谱进行分析。 After [0104] Examples 1,4,7,10,13 and silicoaluminophosphate molecular sieves prepared in tablet crushing embodiment 16; silicoaluminophosphate depicting the mesh 20 ~ 40 mesh was charged crushed zeolite fixed-bed reactor 4. 5g , a pass at a temperature of 500 ° C in a nitrogen activation of LH, followed by reaction at a temperature condition of 400 ° C, mass fraction of 50% methanol carried by nitrogen gas, the nitrogen flow rate was 50mL / min, methanol airspeed is 2. OtT1, the reaction product was analyzed by online gas chromatography. 试验结果如表1所 The test results in Table 1

7J\ ο 7J \ ο

[0105] 表1磷酸硅铝分子筛的甲醇转化制烯烃(MTO)反应结果* [0105] Table 1 silicoaluminophosphate molecular sieve conversion of methanol to olefins (MTO) reaction Results *

[0106] [0106]

Figure CN101935050BD00111

[0107] 甲醇转化率时最高的乙烯和丙烯的选择性。 [0107] The highest selectivity of ethylene and propylene in the conversion of methanol.

Claims (6)

1. 一种利用晶化母液合成磷酸硅铝分子筛的方法,其特征在于,该方法包括以下步骤:晶化母液的来源:水热合成法制备磷酸硅铝分子筛回收的滤液作为晶化母液;晶种的来源:水热合成法制备的磷酸硅铝分子筛作为晶种;(1)将铝源与去离子水混合均勻形成悬浊液A,或将铝源与晶化母液混合均勻形成悬浊液A ;所述铝源为异丙醇铝、拟薄水铝石和氧化铝中的一种或几种,所述去离子水与铝源的摩尔比为1〜25 : 1,晶化母液与铝源的质量比为0.1〜5 : 1,其中铝源以Al2O3计;(2)将磷源与去离子水混合均勻形成溶液B,或将磷源与晶化母液混合均勻形成溶液B;所述去离子水与磷源的摩尔比为1〜25 : 1,晶化母液与磷源的质量比为0.1〜 3.6 : 1,其中磷源以I32O5计;(3)将步骤(1)中所述悬浊液A与步骤O)中所述溶液B混合均勻,然后依次加入模板剂、硅源、晶种和 1. A method for the synthesis of phosphoric acid crystallization mother liquor using a silicoaluminophosphate molecular sieve, characterized in that the method comprises the steps of: the source of mother liquor of crystallization: Hydrothermal synthesis of silicoaluminophosphate molecular sieves recovering filtrate as mother liquor crystallization; Jing species source: silicoaluminophosphate molecular sieves prepared by hydrothermal synthesis as a seed crystal; (1) the aluminum source with deionized water to form a uniform suspension a, or the aluminum source and the crystallization mother liquor was mixed uniformly formed suspension a; the molar ratio of aluminum isopropoxide as aluminum source, to be one or more of boehmite and aluminum oxide, deionized water and said aluminum source is 1~25: 1, mother liquor and crystallization of aluminum mass ratio source is 0.1~5: 1, wherein the aluminum source terms of Al2O3; (2) the source of phosphorus mixed with deionized water to form a solution B, or by mixing a phosphorus source and the crystallization mother liquor solution B is formed uniformly; the the molar ratio of water to phosphorus ion source is 1~25: 1, the crystallization mother liquor with a mass ratio of phosphorus source 0.1~ 3.6: 1, wherein the source of phosphorus in terms I32O5; (3) the step (1) in the A suspension in step O) in the solution is mixed uniformly B, followed by addition of the templating agent, a source of silicon, and the seed 化母液,搅拌形成初始凝胶混合物;所述初始凝胶混合物中模板剂、硅源、磷源和铝源的摩尔比为0. 1〜2. 5 : 0.1〜1.5 : 0.2〜2.0 : 0.2〜2.0,初始凝胶混合物中晶化母液与铝源的质量比为0. 1〜10 : 1,初始凝胶混合物中晶种的质量为铝源质量的0.01%〜3.5%,其中硅源以SiO2计,磷源以P2O5计,铝源以Al2O3计;(4)将步骤(3)中所述初始凝胶混合物置于晶化釜中,先水热预晶化,然后水热晶化, 或将步骤(3)中所述初始凝胶混合物置于晶化釜中,直接水热晶化,将水热晶化后的产物随炉冷却后过滤得到滤饼和滤液;(5)将步骤中所述滤饼用去离子水洗涤后置于烘箱中烘干;将烘干后的滤饼置于马弗炉中焙烧,随炉冷却后得到磷酸硅铝分子筛;(6)将步骤中所述滤液回收并密封保存,作为晶化母液循环利用。 Mother liquor, to form the initial gel mixture was stirred; the molar ratio of the initial gel mixture the templating agent, a silicon source, a phosphorus source and an aluminum source 0. 5 ~ 2: 0.1~1.5: 0.2~2.0: 0.2~. 2.0, the crystallization mother liquor with an aluminum source in a mass ratio of the initial gel mixture to 0. 1~10: 1, the quality of the initial gel mixture was seeded as the aluminum source ~3.5% 0.01 mass%, wherein the silicon source is SiO2 meter, as P2O5 phosphorus source, aluminum source terms of Al2O3; (4) the step (3) of the initial gel mixture was placed in a crystallizing vessel, a pre-heat the water before crystallization, and then hydrothermal crystallization, or the step (3) of the initial gel mixture was placed in the crystallization tank, the direct hydrothermal crystallization, the product after the hydrothermal subsequently cooling the furnace was filtered to obtain a cake and a filtrate; (5) the step the filter cake was washed with de-ionized water was placed in a drying oven; after drying the filter cake was placed in a muffle furnace fired furnace cooling to obtain the silicoaluminophosphate molecular sieve; (6) the step of The filtrate was recovered and sealed, as the crystallization mother liquor recycling.
2.根据权利要求1所述的一种利用晶化母液合成磷酸硅铝分子筛的方法,其特征在于,步骤O)中所述磷源为正磷酸或/和亚磷酸。 The mother liquor synthesized silicoaluminophosphate molecular sieve of claim 1 utilizing crystallization, characterized in that, in step O) of said phosphorus source is orthophosphoric acid and / or phosphorous claims.
3.根据权利要求1所述的一种利用晶化母液合成磷酸硅铝分子筛的方法,其特征在于,步骤(3)中所述硅源为正硅酸乙酯、白炭黑和硅溶胶中的一种或几种;步骤(3)中所述模板剂为四乙基氢氧化铵、三乙胺、二乙胺和吗啡啉中的一种或几种。 3. The method of claim 1 utilizing the synthetic mother liquor crystallized silicoaluminophosphate molecular sieve as claimed in claim, wherein step (3) in the silicon source is tetraethyl orthosilicate, the silica and silica sol one or more; step (3) in the templating agent is tetraethyl ammonium hydroxide, one or more of triethylamine, diethylamine and morpholine in.
4.根据权利要求1所述的一种利用晶化母液合成磷酸硅铝分子筛的方法,其特征在于,步骤中所述水热预晶化为三步水热预晶化,水热预晶化的制度为:第一步水热预晶化在温度为100°C的条件下水热预晶化Mi〜Mh,第二步水热预晶化在温度为120°C的条件下水热预晶化Ih〜他,第三步水热预晶化在温度为150°C的条件下水热预晶化Ih〜池。 A method according crystallization mother liquor silicoaluminophosphate molecular sieves using synthesis according to claim 1, wherein said step of hydrothermally crystallized into a three-step pre-heat pre-water crystallization, the hydrothermal pre-crystallization the system as: the first step of the hydrothermal pre-crystallization Mi~Mh hydrothermal pre-crystallization temperature of at conditions of 100 ° C, the second step of the hydrothermal pre-crystallization temperature to 120 ° C pre hydrothermal crystallization conditions he Ih~, the third step of the hydrothermal pre-crystallization hydrothermal crystallization Ih~ pre-pool of 150 ° C temperature conditions.
5.根据权利要求1所述的一种利用晶化母液合成磷酸硅铝分子筛的方法,其特征在于,步骤⑷中所述水热晶化的制度为:晶化温度为180°C,晶化时间为12h〜36h。 A method according crystallization mother liquor was synthesized using the silicoaluminophosphate molecular sieve as claimed in claim 1, wherein said step of ⑷ hydrothermal system as: the crystallization temperature was 180 ° C, crystallization time 12h~36h.
6.根据权利要求1所述的一种利用晶化母液合成磷酸硅铝分子筛的方法,其特征在于,步骤(5)中所述烘干的温度为120°C,焙烧的温度为550°C,焙烧的时间为证。 6. A method for the synthesis of phosphoric acid crystallization mother liquor with the silicoaluminophosphate molecular sieve as claimed in claim 1, wherein the step (5) of the drying temperature is 120 ° C, calcined at a temperature of 550 ° C roasting time to prove it.
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