WO2018192530A1 - 一种复合结构分子筛及其制备方法与应用 - Google Patents

一种复合结构分子筛及其制备方法与应用 Download PDF

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WO2018192530A1
WO2018192530A1 PCT/CN2018/083583 CN2018083583W WO2018192530A1 WO 2018192530 A1 WO2018192530 A1 WO 2018192530A1 CN 2018083583 W CN2018083583 W CN 2018083583W WO 2018192530 A1 WO2018192530 A1 WO 2018192530A1
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molecular sieve
mtt
catalyst
bromide
alkali liquid
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张香文
李国柱
刘林林
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Tianjin University
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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
    • 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
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/74—Noble metals
    • B01J29/7492—MTT-type, e.g. ZSM-23, KZ-1, ISI-4 or EU-13
    • 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
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/74—Noble metals
    • B01J29/7476—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/2206—Catalytic processes not covered by C07C5/23 - C07C5/31
    • C07C5/222—Catalytic processes not covered by C07C5/23 - C07C5/31 with crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/2206—Catalytic processes not covered by C07C5/23 - C07C5/31
    • C07C5/226—Catalytic processes not covered by C07C5/23 - C07C5/31 with metals
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself

Definitions

  • the invention belongs to the technical field of catalysts, and in particular relates to a composite structure molecular sieve and a preparation method and application thereof.
  • Petroleum products such as lubricating oil, jet fuel point, freezing point, pour point, etc. are the focus of attention.
  • the products obtained by the Fischer-Tropsch synthesis method have been more clean, and have the characteristics of sulfur-free, nitrogen-free, and low aromatic hydrocarbons, and have attracted attention as raw material oils for producing jet fuels and lubricating oils.
  • Fischer-Tropsch products due to the presence of high levels of normal paraffins, Fischer-Tropsch products have disadvantages such as higher freezing point and poor low temperature fluidity.
  • a hydroisomerization process can be employed to rearrange the linear alkane to produce a branched product to achieve the desired effect.
  • the catalyst plays an important role in the hydroisomerization reaction.
  • the catalyst used in the hydroisomerization mostly uses a molecular sieve as a catalyst carrier to provide an acid site, and a hydrodehydrogenation function is achieved by supporting a noble metal.
  • Patent CN 104334271 A discloses a process for producing a hydroisomerization catalyst and a process for producing a lubricating base oil selected from the group consisting of ZSM-22 zeolite (TON structure), ZSM-23 zeolite (MTT structure), SSZ-32.
  • At least one of zeolite (MTT structure) and ZSM-48 zeolite is subjected to specific caulking treatment to finally obtain a hydroisomerization catalyst; and patent CN 104220169 A discloses a ZSM-22 zeolite hydroisomerization catalyst And a method for producing the same, the zeolite carrier of the hydroisomerization catalyst is at least one of ZSM-22 zeolite, ZSM-23 zeolite, SSZ-32 zeolite, and ZSM-48 zeolite; Patent CN200680036697.1 discloses a An isomerization dewaxing process using zeolite MTT and MTW, wherein the catalyst is preferably a combination of a hydrogen type zeolite MTT and MTW, and the MTT and MTW zeolites have a crystal size of less than 0.1 micron; and the patent US7390763 B2 discloses a The preparation method of small-grain MTT structure molecular sieve and its application
  • MTT molecular sieves Due to its unique pore structure and acidity and alkalinity, MTT molecular sieves are very suitable for the catalytic hydrogenation of alkane.
  • the regular ten-membered ring structure and adjustable acid properties in MTT molecular sieves provide a prerequisite for the hydrogen-isomerized pour point depressing reaction, and the change of grain size and morphology can further regulate its catalytic performance;
  • 103153860 A proposes a process for preparing small-grain molecular sieves in the absence of an amine component.
  • the pore size of MTT molecular sieve is 0.52nm ⁇ 0.45nm.
  • the pore structure of the molecular sieve of MTT structure Due to its unique pore structure and suitable acidity, it can optimize the pore properties and rational configuration of the active catalyst, and the heterogeneous pour point depressing reaction for normal paraffins Excellent catalytic performance.
  • the pore structure of the molecular sieve of MTT structure has a restrictive effect on the formation and diffusion of multi-branched isomerization products, which leads to a secondary reaction of the isomerized product, that is, a cracking reaction, and the cracked product promotes the formation of carbon deposits, which easily blocks the catalyst pores. Therefore, the activity, selectivity and stability of the MTT molecular sieve catalyst used in the hydrogen isomerization reaction are not ideal and need to be further improved.
  • the present invention provides a core-shell molecular sieve having a micro-mesoporous composite structure and a high external specific surface area, a preparation method thereof and a hydroisomerization catalyst prepared therefrom.
  • the microporous-mesoporous composite molecular sieve has a micropore and mesoporous double model pore distribution, which combines the pores of the mesoporous material with the advantages of strong acidity and high hydrothermal stability of the microporous molecular sieve, so that the two materials can complement each other. Synergistic effect; the number of pores of the molecular sieve is closely related to the size of its external surface area.
  • the composite molecular sieve exhibits higher activity and selectivity in the hydroisomerization reaction due to its higher specific surface area and larger pore structure. And stability, reducing the formation of carbon deposits, increasing the heterogeneity of normal paraffins and the yield of target products, thereby reducing the freezing point of the product and improving the performance of the product.
  • the first aspect of the present invention provides a composite molecular sieve catalyst, which uses MTT microporous molecular sieve as a core and MCM-41 mesoporous molecular sieve as a shell, which can be abbreviated as MCM-41@MTT molecular sieve.
  • MTT microporous molecular sieve and the MCM-41 mesoporous molecular sieve are molecular sieves of a known type in the molecular sieve field, and the pore size and pore structure type and molecular sieve crystal form are already well-known information, and those skilled in the art can refer to the field.
  • a second aspect of the present invention provides a method for preparing the composite molecular sieve, comprising the steps of:
  • step (1) The solid obtained in the step (1) is calcined at 500 to 600 ° C for 3 to 5 hours, and then cooled to obtain the composite molecular sieve.
  • the alkali solution described in the step (1) is an inorganic alkali solution such as NaOH, KOH solution or the like; or an organic alkali solution such as tetramethylammonium hydroxide or tetraethylammonium hydroxide solution, the alkali solution
  • concentration of the alkali solution and the MTT molecular sieve is 5:1 to 25:1;
  • the surfactant described in the step (1) is a long-chain alkyltrimethylammonium bromide (CTAB) having three or more carbon atoms: such as decamethyltrimethylammonium bromide, twelve The alkyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, hexadecane and trimethylammonium bromide are added in an amount of from 1 to 4 times the mass of the MTT molecular sieve.
  • CTAB long-chain alkyltrimethylammonium bromide
  • a third aspect of the present invention provides a hydroisomerization catalyst comprising a support and a hydrogenation-dehydrogenation active component, wherein the support is MCM-41@MTT composite molecular sieve, and the hydrogenation-dehydrogenation active group Divided into Pt or Pd, the hydrogenation-dehydrogenation active component loading is 0.5 wt% of the total mass of the hydroisomerization catalyst.
  • the fourth aspect of the present invention provides the hydroisomerization catalyst for the hydroisomerization of normal paraffins to isoparaffins (such as isomeric depressing and isomerization dewaxing), hydrocracking and hydrodeoxygenation.
  • the invention has the beneficial effects that the core-shell molecular sieve catalyst MCM-41@MTT with micro-mesoporous composite structure and high specific surface area provided by the invention has suitable acidity, a large number of orifices and a high specific surface area. And pore volume, larger active sites.
  • the suitable acid concentration and acid strength are beneficial to reduce the occurrence of secondary reaction-cracking reaction, reduce the formation of cracking products while increasing the isomerization selectivity, reduce the formation of carbon deposits, and improve the isomerization rate of the catalyst and Stability; at the same time, the number of orifices of the catalyst increases, and the diffusibility of the pores is enhanced, which facilitates the diffusion of reactants and products out of the molecular sieve pores; increases the heterogeneous selectivity, reduces the formation of carbon deposits, and prolongs the life of the catalyst.
  • Figure 1 is a powder XRD pattern of the molecular sieve prepared in Comparative Example and Example 1;
  • Figure 3 is a TEM image of the molecular sieve prepared in the comparative example
  • Figure 4 is a TEM image of the molecular sieve prepared in Example 1;
  • Figure 5 is a graph comparing the hydrodeoxygenation conversion of fatty acids in the comparative examples and examples.
  • Figure 6 is a graph comparing the hydrodeoxygenation selectivity of fatty acids in the comparative examples and examples.
  • the present comparative example provides a preparation method of a noble metal Pt catalyst supported by an MTT structure molecular sieve, and the specific steps are as follows:
  • the reactant gel was placed in a polytetrafluoroethylene-lined hydrothermal synthesis kettle, sealed, and crystallized at 175 ° C for 8 days under autogenous pressure; the crystallized product was taken out, cooled, centrifuged, and washed with deionized water to the middle. Drying in an oven at 120 ° C; then placing it in a muffle furnace and calcining at 600 ° C for 6 h to obtain the desired product. The precious metal Pt was loaded, and the loading amount was 0.5% by weight.
  • the present embodiment provides a core-shell MCM-41@MTT molecular sieve having a micro-mesoporous composite structure, and the preparation method thereof is as follows:
  • the molecular sieves were then placed in a muffle furnace and calcined at 550 ° C for 4 h to obtain MCM-41@MTT molecular sieves.
  • the precious metal Pt was then loaded using an equal volume impregnation method with a loading of 0.5 wt%.
  • the solid powder was dried in an oven at 120 ° C, and then the molecular sieve was placed in a muffle furnace and calcined at 550 ° C for 4 h to obtain MCM-41@MTT molecular sieve.
  • the precious metal Pd was supported by an excessive impregnation method using ethanol as a solvent, and the loading amount was 0.5% by weight.
  • the comparative example and the catalyst prepared in Example 1 were applied to the hydroisomerization pour point condensation reaction of nC 12 -nC 23 mixed normal paraffins; comparison was obtained at different reaction temperatures, Pt/MCM-41@
  • the conversion and isomerization ratio of the MTT catalyst are greatly improved compared with the conversion and the isomerization amount of the Pt/MTT catalyst, indicating that the micro-mesoporous composite molecular sieve MCM-41@MTT catalyst having the core-shell structure prepared by the present invention is applied to the positive
  • an isoparaffin mixture can be obtained with high activity and high selectivity, as shown in Table 1.
  • micro-mesoporous composite molecular sieve MCM-41@MTT catalyst having the core-shell structure prepared by the invention has stable isomerization yield for 7 days of continuous operation, as shown in Table 2.
  • the micromolecular composite molecular sieve MCM-41@MTT catalyst with core-shell structure of the invention has good stability performance, few carbon deposits are formed, and the isomerization yield of the catalyst is stable for 7 days.
  • the Pt/MCM-41@MTT catalyst prepared in the examples was applied to the isothermal dewaxing of nC 20 -nC 40 mixed normal paraffins to prepare a lubricating base oil, and the yield of the class III + lubricating base oil was obtained. above 50.
  • the micro-mesoporous composite molecular sieve MCM-41@MTT catalyst with core-shell structure prepared by the invention is applied to the isomerization dewaxing reaction of normal paraffins, and the lubricating base oil can be obtained with high activity and high selectivity.
  • the comparative examples and the catalysts prepared in the examples were applied to the hydrodeoxygenation of palmitic acid and stearic acid to produce a high quality diesel reaction, as shown in Figure 5, at low temperatures.
  • the total conversion of fatty acids was higher than that of the comparative examples (the conversion rates of Example 1 and Example 3 were the same), and the selectivity of the target carbon number C 15 -C 18 of the MCM-41@MTT catalyst was significantly higher than that of the MTT catalyst, as shown in Fig. 6. Shown.
  • the micromolecular composite molecular sieve MCM-41@MTT catalyst with core-shell structure prepared by the invention is applied to the hydrodeoxygenation reaction of fatty acids, and high-quality diesel oil can be prepared with high activity and high selectivity.

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Abstract

一种复合分子筛及其制备方法，其中复合分子筛以MTT微孔分子筛为核，以MCM-41介孔分子筛为壳。以该复合分子筛为载体的催化剂可用于加氢异构化反应中。

Description

一种复合结构分子筛及其制备方法与应用 技术领域
本发明属于催化剂技术领域，具体涉及一种复合结构分子筛及其制备方法与应用。
背景技术
石油产品，如润滑油、喷气燃料的凝点、冰点、倾点等是人们关注的重点。近年来，利用煤通过费托合成法得到的产品更加洁净，具有无硫、无氮、低芳烃的特点，作为制造喷气燃料、润滑油等的原料油而受到瞩目。然而，由于高含量正构烷烃的存在，费托合成的产品具有较高的凝点和低温流动性差等缺点。为了降低倾点和凝点，可采用加氢异构化的方法，使直链烷烃重排产生支链产物来达到所希望的效果。
催化剂在加氢异构化反应中起到重要作用。加氢异构化所使用催化剂多以分子筛为催化剂载体来提供酸性位，并通过负载贵金属实现加氢脱氢功能。
专利CN 104334271 A公开了一种氢化异构化催化剂的制造方法和润滑油基础油的制造方法，该催化剂选自ZSM-22沸石(TON结构)、ZSM-23沸石(MTT结构)、SSZ-32沸石(MTT结构)和ZSM-48沸石中的至少一种，对其进行特定的敛缝处理，最后得到氢化异构化催化剂；专利CN 104220169 A公开了一种ZSM-22沸石氢化异构化催化剂及其制造方法，该氢化异构化催化剂的沸石载体为由ZSM-22沸石、ZSM-23沸石、SSZ-32沸石、以及ZSM-48沸石中的至少一种；专利CN200680036697.1公开了一种使用沸石MTT和MTW的异构脱蜡方法，其中所述的催化剂优选为氢型的沸石MTT与MTW的组合，且所述MTT和MTW沸石的晶体尺寸小于0.1微米；专利US7390763 B2公开了一种小晶粒MTT结构分子筛的制备方法及其在C 10+正构烷烃的异构降凝中的应用，使用小晶粒MTT结构分子筛可以使目标产物收率提高7.14％。
MTT结构分子筛由于其独特的孔结构和酸碱性，非常适合催化烷烃的加氢异构反应。MTT结构分子筛中规则的十元环孔道结构和可调节的酸性质，为临氢异构降凝反应提供了先决条件，其晶粒尺寸和形貌结构的变化可以进一步调控其催化性能；专利CN 103153860 A提出了一种不存在胺组分的情况下制备小晶粒分 子筛的方法。MTT结构分子筛的孔道尺寸为0.52nm×0.45nm，由于具有其独特的孔道结构和适宜的酸性，能够优化多孔催化剂的孔性质和活性位的合理配置，对正构烷烃的异构降凝反应具有优异的催化性能。但是MTT结构分子筛的孔道结构对多支链异构产物的生成和扩散有限制作用，会导致异构产物发生二次反应，即裂解反应，裂解产物促进积碳的生成，易堵塞催化剂孔道。因此临氢异构反应中使用的MTT分子筛催化剂的活性、选择性和稳定性还不够理想，有待进一步提高。
发明内容
为了解决上述问题，本发明提供了一种具有微介孔复合结构、高外比表面积的核壳结构分子筛其制备方法及由其制备的临氢异构化催化剂。微孔-介孔复合分子筛具有微孔和介孔双模型孔分布，结合了介孔材料的孔道可调与微孔分子筛酸性较强和高水热稳定性的优势，可使两种材料优势互补、起到协同作用；分子筛的孔口数量与其外表面积的大小密切相关，复合分子筛因其较高的比表面积和较大的孔道结构，加氢异构反应中表现出更高的活性、选择性和稳定性，减少了积碳的生成，提高正构烷烃的异构率和目标产品收率，从而降低产物的凝点，提高产品的性能。
本发明第一方面提供一种复合分子筛催化剂，所述催化剂以MTT微孔分子筛为核，以MCM-41介孔分子筛为壳，可简写为MCM-41@MTT分子筛。
其中所述MTT微孔分子筛和MCM-41介孔分子筛均是分子筛领域中已知类型的分子筛，其孔径大小和孔结构类型以及分子筛晶型早已经是公知信息，本领域技术人员可查阅本领域专利和论文来知晓。
本发明第二方面提供所述复合分子筛的制备方法，包括如下步骤：
(1)将MTT分子筛粉末、碱液和表面活性剂混合均匀，升温至150～180℃反应12～48h后降温，滴加酸液使pH为8～9，再升温至110～130℃反应12～72h后降温，分离出固体，用去离子水洗至中性，在110～130℃下干燥得到固体物；
(2)将步骤(1)得到的固体物在500～600℃下煅烧3～5h后降温，得到所述复合分子筛。
优选地，步骤(1)所述的碱液为无机碱液，如NaOH、KOH溶液等；或有 机碱液，如四甲基氢氧化铵、四乙基氢氧化铵溶液等，所述碱液的浓度为0.2～1.0mol/L，所述碱液与所述MTT分子筛的质量比为5:1～25:1；
优选地，步骤(1)所述的表面活性剂为碳原子个数为三个以上的长链烷基三甲基溴化铵(CTAB)：如十烷基三甲基溴化铵、十二烷基三甲基溴化铵、十四烷基三甲基溴化铵、十六烷及三甲基溴化铵等，其加入量为所述MTT分子筛的质量的1～4倍。
本发明第三方面提供一种加氢异构化催化剂，其包括载体和加氢-脱氢活性组分，其中所述载体为MCM-41@MTT复合分子筛，所述加氢-脱氢活性组分为Pt或Pd，加氢-脱氢活性组分负载量为该加氢异构化催化剂总质量的0.5wt％。
本发明第四方面提供所述的加氢异构化催化剂用于将正构烷烃临氢异构化为异构烷烃(如异构降凝和异构脱蜡)、加氢裂化和加氢脱氧的用途，其用于增加催化活性和/或提高选择性和/或减少积碳和/或延长催化剂寿命。
本发明的有益效果：本发明提供的一种具有微介孔复合结构、高比表面积的核壳分子筛催化剂MCM-41@MTT，具有适宜的酸性、较多的孔口数量、较高的比表面积和孔容、较大的活性位。较适宜的的酸性位浓度和酸强度有利于减少二次反应-裂解反应的发生，在提高异构选择性的同时降低裂解产物的生成，减少积碳生成，提高了催化剂的异构化率和稳定性；同时，催化剂的孔口数量增多，孔道扩散性增强，有利于反应物和生成物扩散出分子筛孔道；在增加了异构选择性，减少了积碳的生成，延长了催化剂寿命。
附图说明
图1为对比例和实施例1制得的分子筛的粉末XRD图；
图2为对比例和实施例1制得的分子筛的N 2吸附-脱附等温曲线；
图3为对比例制得的分子筛的TEM图；
图4为实施例1制得的分子筛的TEM图；
图5为对比例和实施例对脂肪酸的加氢脱氧转化率的对比图。
图6为对比例和实施例对脂肪酸的加氢脱氧选择性的对比图。
具体实施方式
为了对本发明的技术特征、目的和有益效果更加清楚的理解，现对本发明的技术方案进行以下详细说明，下面的实施例体现了本发明描述的过程，但本发明 并不局限于这些实例。
对比例1：
本对比例提供了一种MTT结构分子筛负载贵金属Pt催化剂的制备方法，具体的步骤如下：
称取1.53g的1,3-二异丙基咪唑氯(1mol/L))于聚四氟釜衬中，再向其中加入22.52g高纯水，摇匀；然后加入12.03g氢氧化钾溶液(1mol/L)，室温下搅拌30min；向上述的碱性溶液中加入7.62g的硅溶胶、2.5g硅铝溶胶、0.9g异丁胺，搅拌均匀。然后反应物凝胶装入带聚四氟乙烯内衬水热合成釜中，密封，在自生压力下175℃，晶化8天；取出晶化产物，冷却，离心分离，并用去离子水洗至中性，在120℃烘箱中干燥；然后将其置于马弗炉中，600℃煅烧6h，得到目标产物。负载贵金属Pt，负载量为0.5wt％。
该类分子筛的粉末XRD衍射图谱如图1中的曲线所示，N 2吸附-脱附等温曲线如图2中的曲线所示，TEM图如图3所示。
实施例1
本实施例提供了一种具有微介孔复合结构的核壳MCM-41@MTT分子筛，其制备方法如下：
将2g MTT分子筛核、20ml 0.3mol/L的碱液加入到反应釜中，搅拌30min，然后再加入4g表面活性剂，继续搅拌30min，在150℃均相反应器中搅拌反应24h；降温，通过滴加3mol/L的盐酸溶液，调节混合液的pH为8～9之间，再在120℃下，晶化48h；取出晶化产物，水冷后取出其中的混合物进行离心分离，并用去离子水洗至中性，在120℃烘箱中干燥。
然后将分子筛置于马弗炉中，550℃煅烧4h，得到MCM-41@MTT分子筛。然后采用等体积浸渍法负载贵金属Pt，负载量为0.5wt％。
实施例2
将2g MTT分子筛核、20ml的0.2mol/L无机碱(NaOH或KOH)溶液加入到反应釜中，搅拌30min，然后再加入3g表面活性剂，其他操作类同于实施例1，得到MCM-41@MTT分子筛。负载贵金属Pt，负载量为0.5wt％。
实施例3
将2g MTT结构分子筛粉末及4g表面活性剂加入到20mL、0.5mol/L的有机 碱TAAOH(四甲基氢氧化铵或四乙基氢氧化铵)溶液中，充分混合后在室温下搅拌30min，然后转移到晶化釜中，于180℃搅拌反应24h。降温，通过逐滴加入3mol/L的HCl溶液，将混合体系的pH值调至8.5，之后于120℃晶化24h；将晶化釜取出，水冷后取出其中的混合物进行离心分离、将固体水洗至中性。最后将固体粉末于120℃烘箱中干燥，然后将分子筛置于马弗炉中，550℃煅烧4h，得到MCM-41@MTT分子筛。用乙醇作溶剂的过量浸渍法负载贵金属Pd，负载量为0.5wt％。
该类分子筛的粉末XRD衍射图谱如图1中的曲线所示，N 2吸附-脱附等温曲线如图2中的曲线所示，TEM图如图4所示。
实施例4：正构烷烃加氢异构反应
将对比例和实施例1中制得的催化剂应用到n-C 12～n-C 23混合正构烷烃的加氢异构降凝反应中；对比可得，在不同的反应温度下，Pt/MCM-41@MTT催化剂的转化率和异构量比Pt/MTT催化剂的转化率和异构量均大幅提升，说明本发明制得的具有核壳结构的微介孔复合分子筛MCM-41@MTT催化剂应用到正构烷烃的异构反应中，可以高活性、高选择性地制得异构烷烃混合物，如表1所示。并且本发明制得的具有核壳结构的微介孔复合分子筛MCM-41@MTT催化剂连续运行7天异构化收率稳定，如表2所示。说明本发明的具有核壳结构的微介孔复合分子筛MCM-41@MTT催化剂具有良好的稳定性能，积碳生成的很少，催化剂连续运行7天异构化收率稳定。
表1 催化性能评价结果
Figure PCTCN2018083583-appb-000001
表2 Pt/MCM-41@MTT催化剂的稳定性评价
运行时间 270℃，异构产物液相收率，％
1d 96.0％
2d 96.2％
3d 95.7％
4d 95.8％
5d 96.4％
6d 95.5％
7d 96.1％
实施例5：正构烷烃的异构脱蜡
将实施例中制得的Pt/MCM-41@MTT催化剂应用到n-C 20～n-C 40混合正构烷烃的异构脱蜡制备润滑油基础油中，得到III类+润滑油基础油的收率在50％以上。说明本发明制得的具有核壳结构的微介孔复合分子筛MCM-41@MTT催化剂应用到正构烷烃的异构脱蜡反应中，可以高活性、高选择性地制得润滑油基础油。
实施例6：脂肪酸的加氢脱氧
将对比例和实施例(实施例1和实施例3)制得的催化剂应用到棕榈酸和硬脂酸的加氢脱氧制备高品质柴油反应中，如图5所示，在低温时实施例的脂肪酸总转化率高于对比例(实施例1和实施例3的转化率相同)，且MCM-41@MTT催化剂的目标碳数C 15～C 18的选择性明显高于MTT催化剂，如图6所示。说明本发明制得的具有核壳结构的微介孔复合分子筛MCM-41@MTT催化剂应用到脂肪酸的加氢脱氧反应中，可以高活性、高选择性地制得高品质柴油。

Claims (7)

  1. 一种复合分子筛，其特征在于，所述复合分子筛以MTT微孔分子筛为核，以MCM-41介孔分子筛为壳。
  2. 一种根据权利要求1所述复合分子筛的制备方法，其特征在于，包括如下步骤：
    (1)将MTT分子筛粉末、碱液和表面活性剂混合均匀，升温至150～180℃反应12～48h后降温，滴加酸液使pH为8～9，再升温至110～130℃反应12～72h后降温，分离出固体，用去离子水洗至中性，在110～130℃下干燥得到固体物；
    (2)将步骤(1)得到的固体物在500～600℃下煅烧3～5h后降温，得到所述复合分子筛。
  3. 根据权利要求2所述的制备方法，其特征在于，步骤(1)所述的碱液为无机碱液或有机碱液，所述碱液的浓度为0.2～1.0mol/L，所述碱液与所述MTT分子筛的质量比为5:1～25:1。
  4. 根据权利要求2所述的制备方法，其特征在于，步骤(1)所述的表面活性剂为碳原子个数为三个以上的长链烷基三甲基溴化铵，其加入量为所述MTT分子筛的质量的1～4倍。
  5. 根据权利要求4所述的制备方法，其特征在于，所述长链烷基三甲基溴化铵为十烷基三甲基溴化铵、十二烷基三甲基溴化铵、十四烷基三甲基溴化铵或十六烷基三甲基溴化铵。
  6. 一种加氢异构化催化剂，其特征在于，其包括载体和加氢-脱氢活性组分，其中所述载体为权利要求1所述的复合分子筛，所述加氢-脱氢活性组分为Pt或Pd，加氢-脱氢活性组分负载量为该加氢异构化催化剂总质量的0.5％。
  7. 根据权利要求6所述的加氢异构化催化剂用于将正构烷烃加氢异构化为异构烷烃的用途，其用于增加催化活性和/或提高选择性和/或减少积碳和/或延长催化剂寿命。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118002194A (zh) * 2024-02-02 2024-05-10 山东丰嘉生物科技发展有限公司 一种核壳结构的生物航煤催化剂及其应用

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106955734A (zh) * 2017-04-21 2017-07-18 天津大学 一种复合结构分子筛及其制备方法与应用
CN110560148B (zh) * 2019-08-26 2021-09-21 天津大学 一种短柱状、单分散的负载型钯催化剂及其制备方法和用途
CN112717995B (zh) * 2021-01-19 2021-11-26 天津大学 一种mcm-41和ssz-32复合分子筛催化剂、其制备及用途
CN117399065B (zh) * 2022-07-08 2025-09-09 国家能源投资集团有限责任公司 加氢异构催化剂及其制备方法和用途

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1597516A (zh) * 2004-09-21 2005-03-23 太原理工大学 微孔－介孔复合分子筛及制备方法
CN101094719A (zh) * 2004-12-28 2007-12-26 耐思特石油公司 催化材料及其制备方法
GB2451863A (en) * 2007-08-15 2009-02-18 Exxonmobil Chem Patents Inc Core-shell catalysts and absorbents
CN105032478A (zh) * 2015-07-13 2015-11-11 中科合成油技术有限公司 一种用于f-t合成中间馏分油异构降凝的催化剂与其专用的核壳结构复合分子筛
CN106513035A (zh) * 2016-11-16 2017-03-22 中国海洋石油总公司 一种介孔‑微孔复合加氢异构脱蜡催化剂的制备方法
CN106955734A (zh) * 2017-04-21 2017-07-18 天津大学 一种复合结构分子筛及其制备方法与应用

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105214716A (zh) * 2014-05-30 2016-01-06 中国科学院大连化学物理研究所 一种废塑料转化用多级孔分子筛催化剂及其制备方法
CN106566589A (zh) * 2016-11-13 2017-04-19 中国海洋石油总公司 一种加工高蜡含量润滑油基础油的方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1597516A (zh) * 2004-09-21 2005-03-23 太原理工大学 微孔－介孔复合分子筛及制备方法
CN101094719A (zh) * 2004-12-28 2007-12-26 耐思特石油公司 催化材料及其制备方法
GB2451863A (en) * 2007-08-15 2009-02-18 Exxonmobil Chem Patents Inc Core-shell catalysts and absorbents
CN105032478A (zh) * 2015-07-13 2015-11-11 中科合成油技术有限公司 一种用于f-t合成中间馏分油异构降凝的催化剂与其专用的核壳结构复合分子筛
CN106513035A (zh) * 2016-11-16 2017-03-22 中国海洋石油总公司 一种介孔‑微孔复合加氢异构脱蜡催化剂的制备方法
CN106955734A (zh) * 2017-04-21 2017-07-18 天津大学 一种复合结构分子筛及其制备方法与应用

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118002194A (zh) * 2024-02-02 2024-05-10 山东丰嘉生物科技发展有限公司 一种核壳结构的生物航煤催化剂及其应用

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