WO2023230941A1 - Nanometer molecular sieve catalyst for cracking of endothermic hydrocarbon fuel, and preparation method therefor - Google Patents

Nanometer molecular sieve catalyst for cracking of endothermic hydrocarbon fuel, and preparation method therefor Download PDF

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WO2023230941A1
WO2023230941A1 PCT/CN2022/096504 CN2022096504W WO2023230941A1 WO 2023230941 A1 WO2023230941 A1 WO 2023230941A1 CN 2022096504 W CN2022096504 W CN 2022096504W WO 2023230941 A1 WO2023230941 A1 WO 2023230941A1
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parts
sieve catalyst
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molecular sieve
hydrocarbon fuel
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林果
刘琳
王鑫鑫
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天津大学滨海工业研究院有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/187—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/18—Phosphoric acid
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
    • C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
    • 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
    • C01B39/54—Phosphates, e.g. APO or SAPO compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
    • C07C2/66—Catalytic processes

Definitions

  • the invention relates to the technical field of active cooling of hypersonic aircraft, specifically a nanomolecular sieve catalyst for endothermic hydrocarbon fuel cracking and a preparation method thereof.
  • Endothermic hydrocarbon fuel is a new type of fuel that has emerged in recent years. It not only has excellent performance, but also can meet the cooling requirements of hypersonic flight. Nano-molecular sieve catalysts can accelerate the fuel cracking reaction rate and improve the endothermic hydrocarbon fuel. The conversion rate of fuel, lowering the starting temperature of cracking reaction, reducing side reactions, etc. are indispensable in the use of endothermic hydrocarbon fuels.
  • the present invention provides a nanomolecular sieve catalyst for endothermic hydrocarbon fuel cracking and a preparation method thereof, thereby solving the problems of high synthesis efficiency and high cost.
  • a nanomolecular sieve catalyst for endothermic hydrocarbon fuel cracking and its preparation method including the following main raw materials: silicon source, aluminum source, phosphorus source, template agent, sodium aluminate, modification agent, water and aqueous hexamethyleneimine solution.
  • the silicon source is silica sol
  • the aluminum source is aluminum alkoxide or boehmite
  • the phosphorus source is phosphoric acid or triethylphosphoric acid.
  • the template agent is tetrabutyl odorized phosphine
  • the modifying agent is sodium hydroxide
  • a method for preparing a nanomolecular sieve catalyst for endothermic hydrocarbon fuel cracking includes the following steps:
  • the main raw material parts are: 250-300 parts of silicon source, 150-200 parts of aluminum source, 300-350 parts of phosphorus source, 3.5-15 parts of template agent, 13.2-26 parts of sodium aluminate, and 2.1-2.1 parts of modifier. 4 parts, 366-400 parts of water and 103.3-200 parts of hexamethyleneimine aqueous solution.
  • the proportions of the alkaline silica sol, sesbania powder and nitric acid aqueous solution are 37.5-40 parts, 0.56-1 parts and 366-400 parts.
  • the nano-molecular sieve catalyst for endothermic hydrocarbon fuel cracking and its preparation method can replace the use of structural directing agents by adding different dosages of template agents and modifiers, thereby changing the pore size and particle size of the molecular sieve. In this way, try to avoid The use of structure directing agents significantly reduces costs and at the same time ensures the synthesis rate of nanomolecular sieve catalysts.
  • a nanomolecular sieve catalyst for endothermic hydrocarbon fuel cracking and its preparation method including the following parts of main raw materials: 250-300 parts of silicon source, 150-200 parts of aluminum source, 300-350 parts of phosphorus source, and 3.5-15 parts of template agent parts, 13.2-26 parts of sodium aluminate, 2.1-4 parts of modifier, 366-400 parts of water and 103.3-200 parts of hexamethyleneimine aqueous solution.
  • the silicon source is silica sol
  • the aluminum source is aluminum alkoxide or boehmite
  • the phosphorus source is phosphoric acid or triethylphosphoric acid.
  • the template agent is tetrabutyl odorized phosphine
  • the modifying agent is sodium hydroxide
  • a method for preparing a nanomolecular sieve catalyst for endothermic hydrocarbon fuel cracking includes the following steps:
  • the proportions of alkaline silica sol, sesbania powder and nitric acid aqueous solution are 37.5-40 parts, 0.56-1 parts and 366-400 parts.
  • the crystal precipitation rate during the preparation process of the nanomolecular sieve catalyst is significantly improved.
  • controlling the amount of the template agent can control the size of the crystallization, which also affects the size of the nanomolecular sieve catalyst.
  • the introduction of modifiers can accelerate the crystallization process of the special phase of the nanomolecular sieve catalyst.
  • cations such as Na' and K* exist in the reactant gel
  • these cations will also appear in the nanomolecular sieve catalyst product, but they only exist in the reactant gel.
  • Molecular sieve pores may exist as structural cations on multiple faces of the crystal lattice to balance the negative charge of the skeleton.
  • the amount of modifier may change the size of the pores, thereby achieving the purpose of modifying the molecular sieve.
  • the modifier Alkali metal hydroxides can also adjust the pH value of the reactant gel, thereby improving the reaction conditions and better controlling the synthesis of molecular sieves. Therefore, the use of structure directing agents should be avoided as much as possible to significantly reduce costs.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
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Abstract

A nanometer molecular sieve catalyst for the cracking of an endothermic hydrocarbon fuel, and a preparation method therefor. The nanometer molecular sieve catalyst comprises the following main raw materials: a silicon source, an aluminum source, a phosphorus source, a templating agent, sodium aluminate, a modifier, water and an aqueous hexamethyleneimine solution, wherein the silicon source is a silica sol; the aluminum source is aluminum hydroxyl oxide or boehmite; the phosphorus source is phosphoric acid or triethyl phosphate; the templating agent is tetrabutylphosphonium bromide; and the modifier is sodium hydroxide.

Description

一种吸热碳氢燃料裂解用纳米分子筛催化剂及其制备方法A kind of nanomolecular sieve catalyst for endothermic hydrocarbon fuel cracking and preparation method thereof 技术领域Technical field
本发明涉及高超声速飞行器主动冷却技术领域，具体为一种吸热碳氢燃料裂解用纳米分子筛催化剂及其制备方法。The invention relates to the technical field of active cooling of hypersonic aircraft, specifically a nanomolecular sieve catalyst for endothermic hydrocarbon fuel cracking and a preparation method thereof.
背景技术Background technique
吸热型碳氢燃料是近年来崛起的一类新型燃料，它不但各项性能优良，而且能满足高超音速飞行的冷却要求，而纳米分子筛催化剂可以加快燃料裂解反应速率、提高吸热型碳氢燃料的转化率、降低裂解反应的起始温度、减少副反应等，是吸热型碳氢燃料在使用过程中不可或缺的。Endothermic hydrocarbon fuel is a new type of fuel that has emerged in recent years. It not only has excellent performance, but also can meet the cooling requirements of hypersonic flight. Nano-molecular sieve catalysts can accelerate the fuel cracking reaction rate and improve the endothermic hydrocarbon fuel. The conversion rate of fuel, lowering the starting temperature of cracking reaction, reducing side reactions, etc. are indispensable in the use of endothermic hydrocarbon fuels.
在实现本申请过程中，发明人发现该技术中至少存在如下问题，现有吸热碳氢燃料裂解用纳米分子筛催化剂在合成中会使用大量价格昂贵的结构导向剂，造成合成效率很低，同时会增加成本的支出，故而需要进一步的改进。In the process of realizing this application, the inventor found that there are at least the following problems in this technology. The existing nanomolecular sieve catalysts for endothermic hydrocarbon fuel cracking use a large amount of expensive structural directing agents in the synthesis, resulting in very low synthesis efficiency. At the same time, It will increase the cost and requires further improvement.
技术解决方案Technical solutions
本发明针对现有技术中存在的技术问题，提供一种吸热碳氢燃料裂解用纳米分子筛催化剂及其制备方法，解决了合成效率，成本支出高问题。In view of the technical problems existing in the prior art, the present invention provides a nanomolecular sieve catalyst for endothermic hydrocarbon fuel cracking and a preparation method thereof, thereby solving the problems of high synthesis efficiency and high cost.
本发明解决上述技术问题的技术方案如下：一种吸热碳氢燃料裂解用纳米分子筛催化剂及其制备方法，包括以下主要原料：硅源、铝源、磷源、模板剂，铝酸钠、修饰剂、水和六亚甲基亚胺水溶液。The technical solution of the present invention to solve the above technical problems is as follows: a nanomolecular sieve catalyst for endothermic hydrocarbon fuel cracking and its preparation method, including the following main raw materials: silicon source, aluminum source, phosphorus source, template agent, sodium aluminate, modification agent, water and aqueous hexamethyleneimine solution.
进一步，所述硅源为硅溶胶，所述铝源为烃氧基铝或勃姆石，所述磷源为磷酸或三乙基磷酸。Further, the silicon source is silica sol, the aluminum source is aluminum alkoxide or boehmite, and the phosphorus source is phosphoric acid or triethylphosphoric acid.
进一步，所述模板剂为四丁基臭化膦，所述修饰剂为氢氧化钠。Further, the template agent is tetrabutyl odorized phosphine, and the modifying agent is sodium hydroxide.
一种吸热碳氢燃料裂解用纳米分子筛催化剂制备方法，其制备方法包括以下步骤：A method for preparing a nanomolecular sieve catalyst for endothermic hydrocarbon fuel cracking. The preparation method includes the following steps:
1）首先将硅源、铝源、磷源、模板剂依次充分搅拌混合均匀，然后再依次加入铝酸钠、修饰剂、水和六亚甲基亚胺水溶液搅拌均匀，并装入不锈钢反应釜中，密闭后加热至150-250℃，晶化5天，在此期间仍然需要进行搅拌；1) First, stir the silicon source, aluminum source, phosphorus source, and template agent thoroughly in sequence, and then add sodium aluminate, modifier, water, and hexamethyleneimine aqueous solution in sequence, stir well, and put it into a stainless steel reaction kettle. 2. After sealing, heat to 150-250°C and crystallize for 5 days. During this period, stirring is still required;
2）晶化完成后，将固体产物过滤出，并使用离子水对其进行洗涤，洗涤完成后将固体产物放置于50-60℃的环境下进行干燥，最后，再将固体物放置于空气中进行焙烧，使模板剂被完全去除，也就得到合成态分子筛；2) After the crystallization is completed, filter out the solid product and wash it with ionized water. After the washing is completed, place the solid product in an environment of 50-60°C for drying. Finally, place the solid product in the air. Perform roasting to completely remove the template agent, thereby obtaining the synthetic molecular sieve;
3）将合成态分子筛、碱性硅溶胶、田菁粉和硝酸水溶液混合均匀，通过挤条成型设备将其制备成分子筛催化剂前体；3) Mix the synthetic molecular sieve, alkaline silica sol, sesbania powder and nitric acid aqueous solution evenly, and prepare it into a molecular sieve catalyst precursor through extrusion molding equipment;
4）将分子筛催化剂前体放置于氢氧化钠水溶液中浸泡3h，此时浸泡温度为150-250℃，浸泡结束后，将固体产物滤出，并放置于50-60℃的环境下进行干燥，最后，将其放置于550-600°C空气气氛下焙烧5-8.5h得分子筛催化剂。4) Soak the molecular sieve catalyst precursor in the sodium hydroxide aqueous solution for 3 hours. At this time, the soaking temperature is 150-250°C. After the soaking is completed, filter out the solid product and place it in an environment of 50-60°C for drying. Finally, it is placed in an air atmosphere of 550-600°C and calcined for 5-8.5 hours to obtain a molecular sieve catalyst.
进一步，所述主要原料份数为：硅源250-300份、铝源150-200份、磷源300-350份、模板剂3.5-15份，铝酸钠13.2-26份、修饰剂2.1-4份、水366-400份和六亚甲基亚胺水溶液103.3-200份。Further, the main raw material parts are: 250-300 parts of silicon source, 150-200 parts of aluminum source, 300-350 parts of phosphorus source, 3.5-15 parts of template agent, 13.2-26 parts of sodium aluminate, and 2.1-2.1 parts of modifier. 4 parts, 366-400 parts of water and 103.3-200 parts of hexamethyleneimine aqueous solution.
进一步，所述碱性硅溶胶、田菁粉和硝酸水溶液的份数为37.5-40份、0.56-1份和366-400份。Further, the proportions of the alkaline silica sol, sesbania powder and nitric acid aqueous solution are 37.5-40 parts, 0.56-1 parts and 366-400 parts.
有益效果beneficial effects
与现有技术相比，本申请的技术方案具有以下有益技术效果：Compared with the existing technology, the technical solution of this application has the following beneficial technical effects:
该吸热碳氢燃料裂解用纳米分子筛催化剂及其制备方法，通过模板剂和修饰剂不同剂量的添加，使之代替结构导向剂的使用，从而能够改变分子筛的孔径和粒径，如此，尽量避免结构导向剂使用，显著降低成本，同时，也保证纳米分子筛催化剂的合成率。The nano-molecular sieve catalyst for endothermic hydrocarbon fuel cracking and its preparation method can replace the use of structural directing agents by adding different dosages of template agents and modifiers, thereby changing the pore size and particle size of the molecular sieve. In this way, try to avoid The use of structure directing agents significantly reduces costs and at the same time ensures the synthesis rate of nanomolecular sieve catalysts.
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在此处键入附图说明描述段落。Type the figure description paragraph here.
本发明的最佳实施方式Best Mode of Carrying Out the Invention
在此处键入本发明的最佳实施方式描述段落。Type here the paragraph describing the best mode for carrying out the invention.
本发明的实施方式Embodiments of the invention
下面将结合本发明的实施例，对本发明的原理和特征进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。The principles and features of the present invention will be described below with reference to the embodiments of the present invention. The examples cited are only used to explain the present invention and are not intended to limit the scope of the present invention.
一种吸热碳氢燃料裂解用纳米分子筛催化剂及其制备方法，包括以下份数主要原料：硅源250-300份、铝源150-200份、磷源300-350份、模板剂3.5-15份，铝酸钠13.2-26份、修饰剂2.1-4份、水366-400份和六亚甲基亚胺水溶液103.3-200份。A nanomolecular sieve catalyst for endothermic hydrocarbon fuel cracking and its preparation method, including the following parts of main raw materials: 250-300 parts of silicon source, 150-200 parts of aluminum source, 300-350 parts of phosphorus source, and 3.5-15 parts of template agent parts, 13.2-26 parts of sodium aluminate, 2.1-4 parts of modifier, 366-400 parts of water and 103.3-200 parts of hexamethyleneimine aqueous solution.
本实施例中，硅源为硅溶胶，铝源为烃氧基铝或勃姆石，磷源为磷酸或三乙基磷酸。In this embodiment, the silicon source is silica sol, the aluminum source is aluminum alkoxide or boehmite, and the phosphorus source is phosphoric acid or triethylphosphoric acid.
本实施例中，模板剂为四丁基臭化膦，修饰剂为氢氧化钠。In this embodiment, the template agent is tetrabutyl odorized phosphine, and the modifying agent is sodium hydroxide.
一种吸热碳氢燃料裂解用纳米分子筛催化剂制备方法，其制备方法包括以下步骤：A method for preparing a nanomolecular sieve catalyst for endothermic hydrocarbon fuel cracking. The preparation method includes the following steps:
1）首先将硅源、铝源、磷源、模板剂依次充分搅拌混合均匀，然后再依次加入铝酸钠、修饰剂、水和六亚甲基亚胺水溶液搅拌均匀，并装入不锈钢反应釜中，密闭后加热至150-250℃，晶化5天，在此期间仍然需要进行搅拌；1) First, stir the silicon source, aluminum source, phosphorus source, and template agent thoroughly in sequence, and then add sodium aluminate, modifier, water, and hexamethyleneimine aqueous solution in sequence, stir well, and put it into a stainless steel reaction kettle. 2. After sealing, heat to 150-250°C and crystallize for 5 days. During this period, stirring is still required;
2）晶化完成后，将固体产物过滤出，并使用离子水对其进行洗涤，洗涤完成后将固体产物放置于50-60℃的环境下进行干燥，最后，再将固体物放置于空气中进行焙烧，使模板剂被完全去除，也就得到合成态分子筛；2) After the crystallization is completed, filter out the solid product and wash it with ionized water. After the washing is completed, place the solid product in an environment of 50-60°C for drying. Finally, place the solid product in the air. Perform roasting to completely remove the template agent, thereby obtaining the synthetic molecular sieve;
3）将合成态分子筛、碱性硅溶胶、田菁粉和硝酸水溶液混合均匀，通过挤条成型设备将其制备成分子筛催化剂前体；3) Mix the synthetic molecular sieve, alkaline silica sol, sesbania powder and nitric acid aqueous solution evenly, and prepare it into a molecular sieve catalyst precursor through extrusion molding equipment;
其中，碱性硅溶胶、田菁粉和硝酸水溶液的份数为37.5-40份、0.56-1份和366-400份。Among them, the proportions of alkaline silica sol, sesbania powder and nitric acid aqueous solution are 37.5-40 parts, 0.56-1 parts and 366-400 parts.
4）将分子筛催化剂前体放置于氢氧化钠水溶液中浸泡3h，此时浸泡温度为150-250℃，浸泡结束后，将固体产物滤出，并放置于50-60℃的环境下进行干燥，最后，将其放置于550-600°C空气气氛下焙烧5-8.5h得分子筛催化剂。4) Soak the molecular sieve catalyst precursor in the sodium hydroxide aqueous solution for 3 hours. At this time, the soaking temperature is 150-250°C. After the soaking is completed, filter out the solid product and place it in an environment of 50-60°C for drying. Finally, it is placed in an air atmosphere of 550-600°C and calcined for 5-8.5 hours to obtain a molecular sieve catalyst.
上述实施例的工作原理为：The working principle of the above embodiment is:
在使用中，通过加入模板剂使纳米分子筛催化剂制备过程中的晶体析出率得到显著提升，同时控制模板剂的加入量，可以使得晶体析出大小得以控制，也就影响了纳米分子筛催化剂的大小，通过修饰剂的引入可以加速纳米分子筛催化剂特殊相的晶化过程，当Na'、K*等阳离子存在于反应物凝胶中时，这些阳离子也会出现在纳米分子筛催化剂产物中，只不过仅仅存在于分子筛孔口或作为构造阳离子存在于晶格的多面位以平衡骨架负电荷，此时，将修饰剂的多少，有可能改变孔口的大小，从而达到对分子筛改性的目的，同时，修饰剂属于碱金属的氢氧化物还可以调节反应物凝胶的PH值，从而改善反应条件，更好地控制分子筛的合成，故而，尽量避免结构导向剂使用，显著降低成本。In use, by adding a template agent, the crystal precipitation rate during the preparation process of the nanomolecular sieve catalyst is significantly improved. At the same time, controlling the amount of the template agent can control the size of the crystallization, which also affects the size of the nanomolecular sieve catalyst. The introduction of modifiers can accelerate the crystallization process of the special phase of the nanomolecular sieve catalyst. When cations such as Na' and K* exist in the reactant gel, these cations will also appear in the nanomolecular sieve catalyst product, but they only exist in the reactant gel. Molecular sieve pores may exist as structural cations on multiple faces of the crystal lattice to balance the negative charge of the skeleton. At this time, the amount of modifier may change the size of the pores, thereby achieving the purpose of modifying the molecular sieve. At the same time, the modifier Alkali metal hydroxides can also adjust the pH value of the reactant gel, thereby improving the reaction conditions and better controlling the synthesis of molecular sieves. Therefore, the use of structure directing agents should be avoided as much as possible to significantly reduce costs.
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention shall be included in the protection of the present invention. within the range.

Claims (6)

  1. 一种吸热碳氢燃料裂解用纳米分子筛催化剂，其特征在于，包括以下主要原料：硅源、铝源、磷源、模板剂，铝酸钠、修饰剂、水和六亚甲基亚胺水溶液。A nanomolecular sieve catalyst for endothermic hydrocarbon fuel cracking, characterized by including the following main raw materials: silicon source, aluminum source, phosphorus source, template agent, sodium aluminate, modifier, water and hexamethyleneimine aqueous solution .
  2. 根据权利要求1所述的一种吸热碳氢燃料裂解用纳米分子筛催化剂，其特征在于，所述硅源为硅溶胶，所述铝源为烃氧基铝或勃姆石，所述磷源为磷酸或三乙基磷酸。A nanomolecular sieve catalyst for endothermic hydrocarbon fuel cracking according to claim 1, characterized in that the silicon source is silica sol, the aluminum source is aluminum alkoxide or boehmite, and the phosphorus source It is phosphoric acid or triethyl phosphate.
  3. 根据权利要求2所述的一种吸热碳氢燃料裂解用纳米分子筛催化剂，其特征在于，所述模板剂为四丁基臭化膦，所述修饰剂为氢氧化钠。A nanomolecular sieve catalyst for endothermic hydrocarbon fuel cracking according to claim 2, characterized in that the template agent is tetrabutyl odorized phosphine and the modifying agent is sodium hydroxide.
  4. 根据权利要求3所述的一种吸热碳氢燃料裂解用纳米分子筛催化剂制备方法，其特征在于，其制备方法包括以下步骤：A method for preparing a nanomolecular sieve catalyst for endothermic hydrocarbon fuel cracking according to claim 3, characterized in that the preparation method includes the following steps:
    1）首先将硅源、铝源、磷源、模板剂依次充分搅拌混合均匀，然后再依次加入铝酸钠、修饰剂、水和六亚甲基亚胺水溶液搅拌均匀，并装入不锈钢反应釜中，密闭后加热至150-250℃，晶化5天，在此期间仍然需要进行搅拌；1) First, stir the silicon source, aluminum source, phosphorus source, and template agent thoroughly in sequence, and then add sodium aluminate, modifier, water, and hexamethyleneimine aqueous solution in sequence, stir well, and put it into a stainless steel reaction kettle. 2. After sealing, heat to 150-250°C and crystallize for 5 days. During this period, stirring is still required;
    2）晶化完成后，将固体产物过滤出，并使用离子水对其进行洗涤，洗涤完成后将固体产物放置于50-60℃的环境下进行干燥，最后，再将固体物放置于空气中进行焙烧，使模板剂被完全去除，也就得到合成态分子筛；2) After the crystallization is completed, filter out the solid product and wash it with ionized water. After the washing is completed, place the solid product in an environment of 50-60°C for drying. Finally, place the solid product in the air. Perform roasting to completely remove the template agent, thereby obtaining the synthetic molecular sieve;
    3）将合成态分子筛、碱性硅溶胶、田菁粉和硝酸水溶液混合均匀，通过挤条成型设备将其制备成分子筛催化剂前体；3) Mix the synthetic molecular sieve, alkaline silica sol, sesbania powder and nitric acid aqueous solution evenly, and prepare it into a molecular sieve catalyst precursor through extrusion molding equipment;
    4）将分子筛催化剂前体放置于氢氧化钠水溶液中浸泡3h，此时浸泡温度为150-250℃，浸泡结束后，将固体产物滤出，并放置于50-60℃的环境下进行干燥，最后，将其放置于550-600°C空气气氛下焙烧5-8.5h得分子筛催化剂。4) Soak the molecular sieve catalyst precursor in the sodium hydroxide aqueous solution for 3 hours. At this time, the soaking temperature is 150-250°C. After the soaking is completed, filter out the solid product and place it in an environment of 50-60°C for drying. Finally, it is placed in an air atmosphere of 550-600°C and calcined for 5-8.5 hours to obtain a molecular sieve catalyst.
  5. 根据权利要求4所述的一种吸热碳氢燃料裂解用纳米分子筛催化剂制备方法，其特征在于，所述主要原料份数为：硅源250-300份、铝源150-200份、磷源300-350份、模板剂3.5-15份，铝酸钠13.2-26份、修饰剂2.1-4份、水366-400份和六亚甲基亚胺水溶液103.3-200份。A method for preparing a nanomolecular sieve catalyst for endothermic hydrocarbon fuel cracking according to claim 4, characterized in that the parts of the main raw materials are: 250-300 parts of silicon source, 150-200 parts of aluminum source, and phosphorus source 300-350 parts, template agent 3.5-15 parts, sodium aluminate 13.2-26 parts, modifier 2.1-4 parts, water 366-400 parts and hexamethyleneimine aqueous solution 103.3-200 parts.
  6. 根据权利要求4所述的一种吸热碳氢燃料裂解用纳米分子筛催化剂制备方法，其特征在于，所述碱性硅溶胶、田菁粉和硝酸水溶液的份数为37.5-40份、0.56-1份和366-400份。A method for preparing a nanomolecular sieve catalyst for endothermic hydrocarbon fuel cracking according to claim 4, characterized in that the proportions of the alkaline silica sol, sesbania powder and nitric acid aqueous solution are 37.5-40 parts, 0.56- 1 serving and 366-400 servings.
PCT/CN2022/096504 2022-06-01 2022-06-01 Nanometer molecular sieve catalyst for cracking of endothermic hydrocarbon fuel, and preparation method therefor WO2023230941A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060147364A1 (en) * 2004-12-30 2006-07-06 Council Of Scientific And Industrial Research Process for synthesising porous crystalline aluminophosphate molecular sieves
CN101417811A (en) * 2007-10-25 2009-04-29 中国石油化工股份有限公司 Method for synthesizing SAPO-35 molecular sieve by using bi-template
CN107434252A (en) * 2016-05-27 2017-12-05 中国科学院大连化学物理研究所 The preparation method of the low molecular sieves of silicon nanometer SAPO 34
CN110642262A (en) * 2019-11-15 2020-01-03 广西师范大学 Method for synthesizing SAPO-35 molecular sieve by using double templates
CN112705252A (en) * 2019-10-24 2021-04-27 中国石油化工股份有限公司 Liquid-phase alkylation catalyst, preparation method and application thereof, and method for carrying out liquid-phase alkylation reaction on benzene and ethylene

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060147364A1 (en) * 2004-12-30 2006-07-06 Council Of Scientific And Industrial Research Process for synthesising porous crystalline aluminophosphate molecular sieves
CN101417811A (en) * 2007-10-25 2009-04-29 中国石油化工股份有限公司 Method for synthesizing SAPO-35 molecular sieve by using bi-template
CN107434252A (en) * 2016-05-27 2017-12-05 中国科学院大连化学物理研究所 The preparation method of the low molecular sieves of silicon nanometer SAPO 34
CN112705252A (en) * 2019-10-24 2021-04-27 中国石油化工股份有限公司 Liquid-phase alkylation catalyst, preparation method and application thereof, and method for carrying out liquid-phase alkylation reaction on benzene and ethylene
CN110642262A (en) * 2019-11-15 2020-01-03 广西师范大学 Method for synthesizing SAPO-35 molecular sieve by using double templates

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