WO2025113142A1 - 一种改性y型分子筛及其制备方法、加氢裂化催化剂 - Google Patents

一种改性y型分子筛及其制备方法、加氢裂化催化剂 Download PDF

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WO2025113142A1
WO2025113142A1 PCT/CN2024/130903 CN2024130903W WO2025113142A1 WO 2025113142 A1 WO2025113142 A1 WO 2025113142A1 CN 2024130903 W CN2024130903 W CN 2024130903W WO 2025113142 A1 WO2025113142 A1 WO 2025113142A1
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molecular sieve
type molecular
modified
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reaction
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French (fr)
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葛少辉
李荣观
王燕
侯远东
郭荣
雷俊伟
张占全
姜增琨
徐华
陈菲
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Petrochina Co Ltd
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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
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers

Definitions

  • the invention belongs to the field of molecular sieve modification, and specifically relates to a modified Y-type molecular sieve and a preparation method thereof, and a hydrocracking catalyst.
  • Y-type molecular sieve is a synthetic molecular sieve with a super cage surrounded by a ⁇ cage and a hexagonal prism cage. It is composed of 18 four-membered rings, 4 six-membered rings and 4 twelve-membered rings, forming a structure with a pore diameter of 0.74nm and an inner diameter of 1.2nm. Because it has a rich pore structure and a large number of cracking active centers required by solid acid catalysts. Since the hydrothermal stability of the Y-type molecular sieve with a low silicon-aluminum ratio affects the effect of subsequent use, the modified high silicon-aluminum ratio Y-type molecular sieve has good hydrothermal stability and acid stability.
  • the modified Y-type molecular sieve plays an irreplaceable role as a catalytic material in oil refining processes such as catalytic cracking and hydrocracking.
  • the high-temperature hydrothermal method is simple and easy to operate, and can produce some secondary pores.
  • the aluminum removed from the skeleton does not leave the molecular sieve, but exists in the molecular sieve pores in various forms, which leads to unreasonable pore distribution of the molecular sieve and large loss of crystallinity.
  • the chemical method is to treat it with chemical reagents to dealuminate part of the skeleton.
  • This method can be divided into two categories: one is dealumination and siliconization, that is, while dealumination is carried out with chemical reagents, silicon atoms are filled in the dealumination positions to maintain a high degree of crystallinity.
  • Typical methods are SiCl 4 gas phase dealumination and siliconization and (NH 4 ) 2 SiF 6 liquid phase dealumination and siliconization; the other is to use inorganic acid or organic acid to act with molecular sieve for simple dealumination.
  • Dealumination with inorganic acids such as HCl, HNO 3 , H 2 SO 4 , and citric acid only relies on H + dealumination, so the crystallinity decreases significantly.
  • CN106608643B aims at the problem that the total acid content of the molecular sieve is reduced during the hydrothermal superstabilization process of the molecular sieve, which affects the cracking activity or selectivity.
  • a modification method for a Y-type molecular sieve with a high framework silicon-aluminum ratio, good stability, and the ability to appropriately increase the number of acid centers is provided.
  • the method specifically comprises: (1) activating the NaY-type molecular sieve with a polyhydric alcohol at 80 to 200°C for 1 to 10 hours to obtain slurry A; (2) cooling the slurry A and mixing it with an organic base to obtain slurry B; (3) adding a silicon source and an aluminum source in the order of first adding a silicon source and then adding an aluminum source, and aging the mixture to obtain slurry C; (4) hydrothermally crystallizing the slurry C and recovering the product.
  • the technology activates the molecular sieve with a polyhydric alcohol to Si-OH and Al-OH, and then adds a silicon source and an aluminum source to re-hydrothermally crystallize it. The purpose is to increase the initial silicon-aluminum ratio and acid content of the NaY-type molecular sieve, and the external modification of the molecular sieve pores is not achieved.
  • the Y-type molecular sieve modification method specifically comprises: subjecting a NaY-type molecular sieve to ammonium exchange treatment to obtain an NH 4 Y-type molecular sieve, contacting the obtained NH 4 Y-type molecular sieve with a salt solution containing alkali metal ions and/or a salt solution containing alkaline earth metal ions, filtering, washing and drying, contacting the obtained product with an acid solution, and recovering the product to obtain a modified Y-type molecular sieve; the technical scheme mainly utilizes the steric hindrance generated by NH 4 + ions to promote the enrichment of alkali metals outside the molecular sieve and stabilize the framework, and then uses an acid solution to uniformly dealuminate, and its purpose is mainly to enhance the dealuminate degree of the molecular sieve bulk phase, and does not involve the modification of the molecular sieve
  • CN105498686B provides a molecular sieve modification method to solve the problems of poor adsorption effect and desorption and reuse of molecular sieves, which specifically includes: loading or exchanging the molecular sieve with a soluble metal salt or heteropoly acid, and using the modified molecular sieve to adsorb 2-heptanone in the cyclohexanone product; the technology aims to enhance the adsorption and desorption performance of the molecular sieve, and does not perform directional modulation on the pore structure of the molecular sieve to change its surface structure.
  • the present invention aims to provide a modified Y-type molecular sieve and a preparation method thereof.
  • the preparation method is safe and harmless, the obtained molecular sieve has a tunnel structure on the surface, and the molecular sieve has good catalytic activity.
  • the present invention provides a method for preparing a modified Y-type molecular sieve, which comprises:
  • an organic substance is first reacted with a Y-type molecular sieve to obtain a modified Y-type molecular sieve A; wherein the organic substance has one or a combination of two or more of amidine, benzyl, and thiol functional groups;
  • the modified Y-type molecular sieve A undergoes a second reaction, and then undergoes a calcination treatment to obtain the modified Y-type molecular sieve;
  • the mass ratio of the Y-type molecular sieve to the organic matter is 3-12.5:1.
  • the preparation method of the present invention completes the first step of modification of the modified Y-type molecular sieve, and the specific functional groups in the organic matter (including one or a combination of more than two of amidine, benzyl, and thiol functional groups) react with the surface structure of the molecular sieve to form a stable organic matter-Y-type molecular sieve structure, which can have a positive impact on the subsequent chemical treatment process.
  • the specific functional groups in the organic matter including one or a combination of more than two of amidine, benzyl, and thiol functional groups
  • the pore structure of the Y-type molecular sieve can be divided into a microporous structure formed by its crystal configuration and a mesoporous structure formed by the accumulation of molecular sieve particles.
  • the pore size in the Y-type molecular sieve crystal is 0.74nm, which is about the length of 5 CC bonds.
  • the size of the stacked pores formed by the Y-type molecular sieve is usually around 10-15nm, and the reaction of organic matter with the surface of the molecular sieve has almost no effect on the mass transfer performance of the mesoporous structure. Therefore, the adsorption of organic matter by the Y-type molecular sieve can make The subsequent acid treatment process is more likely to occur in the mesoporous channels of the Y-type molecular sieve.
  • the organic modification in the present invention can produce beneficial effects in three aspects: Y-type molecular sieve micropores, mesopores, and the outer surface of the molecular sieve.
  • micropores the adsorption of organic matter can achieve the protection of the microporous structure of the Y-type molecular sieve, reduce the crystallinity loss caused by chemical modification, and then cause the catalyst long-term operation life to be not guaranteed.
  • mesopores it is possible to achieve directional regulation of the molecular sieve mesoporous channel structure, and enhance the connectivity of the channel structure.
  • the outer surface of the molecular sieve can be oriented to carry out skeleton structure destruction, so as to produce a certain tunnel structure.
  • the generation of the tunnel structure is conducive to the preparation of the catalyst, so that the nearly spherical non-supported active phase falls into the tunnel, so as to improve the degree of combination of the non-supported active phase and the Y-type molecular sieve, and reach the purpose of improving the activity and selectivity of the non-supported catalyst.
  • the mass ratio of the Y-type molecular sieve to the organic matter is 3-12.5:1. Carrying out the first reaction according to this ratio is conducive to achieving the beneficial effects brought about by the modification of the organic matter.
  • the mass ratio of the Y-type molecular sieve to the organic matter is 5-10:1.
  • the temperature of the first reaction is 20-50° C., and the time is 0.5-3 h.
  • the temperature of the first reaction is 20-45°C.
  • the solvent in the liquid phase system in the first reaction, is water.
  • the solid-liquid mass ratio is 1:5-10.
  • the solid-liquid mass ratio is 1:10.
  • the preparation method further comprises:
  • the reaction product obtained from the first reaction is subjected to solid-liquid separation, washing and drying to obtain the modified Y-type molecular sieve A.
  • the solid-liquid separation method is filtration.
  • the methods of solid-liquid separation, washing and drying may be conventional methods in the art.
  • the above-mentioned solid-liquid separation, washing and drying treatments are optional.
  • the system obtained after the first reaction can be directly used for the second reaction, further simplifying the process and reducing costs.
  • a washing treatment is performed after the first reaction, preferably a water washing treatment is performed.
  • the specific functional groups in the amino acid react with the surface structure of the molecular sieve to form a stable organic-Y-type molecular sieve structure, so water washing will not cause a change in the content of amino acids adsorbed on the modified Y-type molecular sieve A.
  • the temperature of the second reaction is 35-60° C., and the time is 0.5-4 h.
  • the pH of the acidic liquid phase system is ⁇ 1.
  • the acidic environment in the second reaction may be provided by an organic acid and/or an inorganic acid.
  • it can be oxalic acid, hydrochloric acid, citric acid, etc.
  • the concentration of the added acid is 0.1-1 mol/L.
  • the molecular sieve is an oxide of silicon and aluminum. Therefore, it is unstable in both acidic and alkaline media.
  • the Si and Al elements in the molecular sieve framework react to form Al 3+ ions and Si 4+ ions (the reaction performance of the Al element from the framework under acidic conditions is higher than that of the Si element). Through this etching action, tunnels are formed on the surface of the molecular sieve.
  • the structure of the acid is not the main factor and it is not immobilized on the molecular sieve.
  • the slurry is filtered, washed and dried.
  • the drying temperature is 80-120° C. and the drying time is 2-8 h.
  • the organic matter is one or a combination of two or more of arginine, phenylalanine, methionine, acetamidine hydrochloride, benzamidine hydrochloride, and 3-(carbamimidothio)-1-propanesulfonic acid.
  • the carbon chain length of the organic matter is greater than 5, it is easier to use the organic matter to occupy the micropores and complete the pore blocking.
  • the calcination temperature is 470-560°C and the time is 3-6 hours.
  • the calcination temperature here only needs to be able to burn all the modified amino acids.
  • a treatment temperature greater than 500°C can ensure that all organic matter is burned.
  • some organic matter has a low decomposition temperature, and there are also examples where treatment before 500°C can be achieved.
  • a modified Y-type molecular sieve obtained according to the above-mentioned preparation method, wherein the surface thereof has a tunnel structure.
  • the generation of the tunnel structure is conducive to making the nearly spherical cluster pellets (non-supported active phase) fall into the tunnel, thereby improving the degree of combination of the non-supported active phase and the Y-type molecular sieve, and achieving the purpose of improving the activity and selectivity of the non-supported catalyst.
  • the cluster pellet can have the effect of being used as the active phase of the hydrocracking catalyst after sulfurization.
  • the design goal of the molecular sieve surface tunnels is to form a tunnel structure of not less than 20 nm on the molecular sieve surface, preferably between 20-40 nm.
  • a hydrocracking catalyst the raw material of which includes the above-mentioned modified Y-type molecular sieve.
  • the hydrocracking catalyst further comprises a non-supported active phase, alumina, and optionally amorphous silicon-alumina, and is obtained by mixing, molding, drying, and calcining. Chemical catalyst.
  • the present invention also provides a hydrocracking process, which is carried out using the hydrocracking catalyst provided by the present invention.
  • the molecular sieve synthesized by the present invention has the following beneficial effects: the hydrocracking catalyst prepared by the modified Y-type molecular sieve of the present invention has a higher conversion rate, which means that the molecular sieve synthesized by the present invention has higher performance.
  • FIG1 shows a scanning electron microscope image of the modified Y1 molecular sieve according to Example 1 of the present invention.
  • FIG. 2 shows a scanning electron microscope image of the Y molecular sieve before modification according to Example 1 of the present invention.
  • FIG3 shows a scanning electron microscope image of the modified Y molecular sieve of Comparative Example 1 of the present invention.
  • FIG. 4 shows the UV spectra of the arginine solution and the water washing liquid of the Y-A2 molecular sieve in Example 2 of the present invention.
  • the Y-type molecular sieve used in the examples of the present invention is HY molecular sieve (SiO 2 : Al 2 O 3 molar ratio 10.7) produced by Nankai Catalyst Factory, hereinafter referred to as Y-type molecular sieve.
  • Scanning electron microscopy was used to characterize the molecular sieves before and after modification. Scanning electron microscopy images of the modified Y1 and the Y molecular sieve before modification are shown in Figures 1 and 2, respectively. It can be clearly identified that, compared with the Y molecular sieve before modification, a certain tunnel structure is generated on the surface of the molecular sieve modified by the method of this embodiment.
  • UV-visible spectroscopy was used to characterize the ability of water-washed Y-A2 molecular sieves to not cause changes in their organic content.
  • 1.5g of arginine dissolved in 80g of water at the initial stage of preparation has an obvious UV-visible absorption spectrum;
  • Y-A2 was added to 80g of water, stirred and filtered to obtain the washed solution, which did not have a significant UV-visible absorption spectrum (as shown in Figure 4), indicating that the modified organic matter has reacted chemically with the molecular sieve to form a stable organic matter-Y type molecular sieve structure. Therefore, it can be used for subsequent modification treatments in aqueous solution environments.
  • the physical adsorption characterization results of Y, Y1, Y2, Y3, Y4, D1, and D2 molecular sieves are shown in Table 1.
  • the total specific surface area is calculated using the BET method.
  • the p/p0 range is selected to be no less than 3 points in the range of 0.01-0.30, and the BET specific surface area is obtained under the condition that the C value of the BET equation is greater than 0.
  • the characterization of the mesoporous and microporous specific surface areas is based on the BET specific surface area and is calculated using the t-Plot method.
  • the mesoporous specific surface areas of Y1, Y2, Y3, and Y4 molecular sieves are all improved to a certain extent compared with the Y molecular sieve, indicating that the method of the present invention can achieve directional regulation of the mesoporous channel structure of the molecular sieve and enhance the connectivity of the channel structure.
  • microporous specific surface areas of Y1, Y2, Y3, and Y4 molecular sieves are not much different from those of the Y molecular sieve, but the microporous specific surface areas of D1 and D2 molecular sieves have a large degree of decrease, indicating that the adsorption of amino acid organic matter in the method of the present invention can protect the microporous structure of the Y-type molecular sieve.
  • the prepared catalysts are used as straight-run diesel as raw materials, and catalyst evaluation experiments are carried out at 340°C, 8.0MPa, hydrogen-to-oil ratio of 800, and space velocity of 4.5h -1 .
  • the test results are shown in Table 3 below. Among them, the conversion rate is the mass fraction of the fraction product less than 180°C in all products.

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Abstract

一种改性Y型分子筛及其制备方法、加氢裂化催化剂；该制备方法包括：在液相体系中，使有机物与Y型分子筛发生第一反应，得到改性Y型分子筛A；其中，有机物具有脒基、苄基、巯基官能团中的一种或两种以上的组合；在酸性的液相体系中，使改性Y型分子筛A发生第二反应，其次进行焙烧处理，得到改性Y型分子筛；其中，Y型分子筛与有机物的质量比为3-12.5:1；所述制备方法安全无危害，所得分子筛表面具有坑道结构，该分子筛具有良好的催化活性。

Description

一种改性Y型分子筛及其制备方法、加氢裂化催化剂 技术领域
本发明属于分子筛改性领域，具体涉及一种改性Y型分子筛及其制备方法、加氢裂化催化剂。
背景技术
Y型分子筛是人工合成的分子筛，具有β笼和六方柱笼围成的超笼，由18个四元环、4个六元环和4个十二元环组成，形成结构孔口直径为0.74nm，内径1.2nm。由于具有丰富的孔道结构，且具有大量固体酸催化剂所需的裂化活性中心。由于低硅铝比的Y型分子筛水热稳定性影响了后续使用的效果，经过改性得到的高硅铝比Y型分子筛具有良好的水热稳定性和酸稳定性，因此改性Y型分子筛作为一种催化材料在催化裂化及加氢裂化等炼油过程中发挥了不可替代的作用。Y型分子筛改性方法主要有三种：高温水热法、化学法、高温水热和化学法组合的方法。高温水热法简单易行，可以产生部分二次孔，从骨架脱除的铝并未离开分子筛，而是以各种形式存在于分子筛孔道中，因此导致分子筛的孔分布不合理，结晶度损失较大。化学法是用化学试剂对其进行处理而使骨架部分脱铝，此法可以分为两类：一种是脱铝补硅，即在用化学试剂法脱铝的同时，硅原子填充于脱了铝的位置上，可以保持较高的结晶度，典型的方法是SiCl4气相脱铝补硅和(NH4)2SiF6液相脱铝补硅；另一种是使用无机酸或有机酸与分子筛作用进行单纯的脱铝，HCl、HNO3、H2SO4、柠檬酸等无机酸脱铝只是依靠H+脱铝，因此结晶度下降较大。
CN106608643B针对分子筛水热超稳化过程中分子筛总酸量降低，影响裂化活性或选择性的不足，提供一种骨架硅铝比高、稳定性好、且可适当增加酸中心数量的Y型分子筛的改性方法，具体包括(1)在80～200℃下用多羟基醇对NaY型分子筛进行活化处理1～10h得到浆液A；(2)将浆液A冷却后与有机碱混合，得到浆液B；(3)按照先加硅源再加铝源的顺序加入硅源、铝源并将混合物经陈化处理得到浆液C；(4)将浆液C进行水热晶化并回收产物。该技术以多羟基醇将分子筛活化为的Si-OH和Al-OH，然后加入硅源、铝源使其重新进行水热晶化，目的在于提高NaY型分子筛的初始硅铝比和酸量，没有实现分子筛孔道的外部修饰。
CN110498424B针对化学脱铝法存在的脱铝不均匀的问题，提供一种均匀铝分布的 Y型分子筛改性方法，具体包括：将NaY型分子筛进行铵交换处理制得NH4Y型分子筛，将所得NH4Y型分子筛与含碱金属离子的盐溶液和/或含碱土金属离子的盐溶液接触，经过滤、洗涤、干燥后，将所得产物与一种酸溶液接触，并回收产物得到改性的Y型分子筛；该技术方案主要是利用NH4 +离子产生的空间位阻，促使碱金属在分子筛外部富集、稳定骨架，再用酸溶液进行均匀脱铝，其目的主要是增强分子筛体相脱铝程度，而不涉及对分子筛表面形貌的改性。
CN105498686B针对分子筛吸附效果不佳及脱附再利用问题，提供一种分子筛改性方法，具体包括：将分子筛用可溶性金属盐或杂多酸等进行负载或交换改性，用改性后的分子筛吸附环己酮成品中的2-庚酮；该技术旨在增强分子筛吸附、脱附性能，未对分子筛孔结构进行定向调变，进而改变其表面结构。
发明内容
为了解决上述的现有技术中的问题，本发明的目的在于提供一种改性Y型分子筛及其制备方法。该制备方法安全无危害，所得分子筛表面具有坑道结构，该分子筛具有良好的催化活性。
为了达到上述的目的，根据一方面，本发明提供了一种改性Y型分子筛的制备方法，其包括：
在液相体系中，使有机物与Y型分子筛发生第一反应，得到改性Y型分子筛A；其中，所述有机物具有脒基、苄基、巯基官能团中的一种或两种以上的组合；
在酸性的液相体系中，使所述改性Y型分子筛A发生第二反应，其次进行焙烧处理，得到所述改性Y型分子筛；
其中，所述Y型分子筛与所述有机物的质量比为3-12.5:1。
在第一反应中，本发明的制备方法完成了对改性Y型分子筛的第一步改性，有机物中的特定官能团(有脒基、苄基、巯基官能团中的一种或两种以上的组合)与分子筛表面结构发生了反应，形成了稳定的有机物-Y型分子筛结构，从而能够对后续的化学处理过程产生积极影响。
对于Y型分子筛的孔道结构，可以分为由其晶体构型而形成的微孔结构，以及由分子筛颗粒的堆积而形成的介孔结构。在微孔结构方面，Y型分子筛晶体中的孔道尺寸为0.74nm，约为5个C-C键的长度。有机物在与分子筛表面结构反应的过程中，会显著堵塞Y型分子筛中的微孔孔道，从而导致原微孔结构传质性能显著降低。在介孔结构方面，Y型分子筛所形成的堆积孔孔道尺寸通常在10-15nm左右，有机物与分子筛表面的反应对介孔结构的传质性能几乎不产生影响。由此，通过Y型分子筛吸附有机物，能够使得 后续的酸处理过程更容易发生在Y型分子筛的介孔孔道位置。
本发明中的有机物改性能够在Y型分子筛微孔、介孔、分子筛外表面三个方面产生有益效果。其一，在微孔方面，有机物的吸附能够实现对Y型分子筛微孔结构的保护，减少由化学改性所导致的结晶度损失，进而导致催化剂长周期运行寿命得不到保证。其二，在介孔方面，能够实现分子筛介孔孔道结构定向调控，增强孔道结构连通性。其三，在分子筛外表面方面，能够定向对分子筛的外表面进行骨架结构破坏，从而产生一定的坑道结构。该坑道结构的产生有利于在催化剂的制备中，使近球形的非负载型活性相落入到坑道中，从而提升非负载型活性相与Y型分子筛的结合程度，达到提升非负载型催化剂活性、选择性的目的。
将所述Y型分子筛与所述有机物的质量比为3-12.5:1，按照此比例进行第一反应，有利于实现有机物改性带来的有益效果。
进一步优选地，所述Y型分子筛与所述有机物的质量比为5-10:1。
在本发明的一些优选的实施方式中，所述第一反应的温度为20-50℃，时间为0.5-3h。
更为有利地，所述第一反应的温度为20-45℃。
在本发明的一些实施方式中，所述第一反应中的液相体系中，溶剂为水。优选地，固液质量比为1:5-10。优选地，固液质量比为1:10。
在本发明的一些实施方式中，在所述第一反应结束后，所述的制备方法还包括：
将所述第一反应所得反应产物进行固液分离、洗涤和干燥，得到所述改性Y型分子筛A。
优选地，所述固液分离的方法为过滤。
在本发明的制备方法中，固液分离、洗涤和干燥的方法可以是本领域常规的。
需要说明的是，在第一反应之后，上述的固液分离、洗涤和干燥处理是可选的，在本发明的一些实施方式中，可以直接将第一反应后所得到的体系用于第二反应，进一步简化流程、降低成本。
在本发明的一些实施方式中，在所述的第一反应后进行了洗涤处理，优选地，进行水洗处理。本发明的第一反应中，氨基酸中的特定官能团与分子筛表面结构发生了反应，形成了稳定的有机物-Y型分子筛结构，因此水洗不会导致改性Y型分子筛A上吸附的氨基酸含量发生变化。
在本发明的一些实施方式中，优选地，所述第二反应的温度为35-60℃，时间为0.5-4h。
在本发明的一些实施方式中，所述第二反应中，所述酸性的液相体系的pH为≤1。
在本发明的一些实施方式中，提供第二反应中酸性环境的可以是有机酸和/或无机酸。 举例而言，可以是草酸、盐酸、柠檬酸等。优选地，所加入的酸的浓度为0.1-1mol/L。由于分子筛是硅、铝的氧化物。因此在酸性介质和碱性介质中都不稳定。在酸性介质中，分子筛骨架中的Si、Al元素会发生反应，形成Al3+离子和Si4+离子(酸性条件下Al元素从骨架中脱离的反应性能高于Si元素)。通过这种刻蚀作用，在分子筛表面形成了坑道。
需要指明的是，在第二反应中，酸的结构不是主要因素，也并没有固载到分子筛上。
在本发明的一些实施方式中，优选地，在第二反应之后，对浆液进行过滤、洗涤、干燥。优选地，干燥的温度为80-120℃，时间为2-8h。
在本发明的一些实施方式中，优选地，所述有机物为精氨酸、苯丙氨酸、甲硫氨酸、盐酸乙脒、苄脒盐酸盐、3-(甲脒基硫代)-1-丙磺酸中的一种或两种以上的组合。当有机物的碳链长度大于5，则较容易利用有机物占据微孔，完成堵孔。
同样的，通过本发明技术开发中的实验发现，如果采用分子量、空间位阻较大的氨基酸对分子筛进行改性，较大分子量的分子难以进入到微孔孔道内，改性过程则较为难以发生。
在本发明的一些实施方式中，优选地，所述焙烧处理的温度为470-560℃，时间为3-6h。此处焙烧处理的温度只需能将所改性的氨基酸全部烧掉即可。通常情况下，处理温度大于500℃能够保证所有有机物都烧掉。但是，有些有机物分解温度低，也存在500℃之前处理也能够实现的实例。
在本发明的制备方法中，对于Y型分子筛的具体型号无额外的限定，市面常见的Y型分子筛不论其硅铝比，均可以适用于本发明提供的改性方法。
根据本发明的另一方面，提供了一种根据上述的制备方法得到的改性Y型分子筛，其表面具有坑道结构。在催化剂的制备中，该坑道结构的产生有利于使近球形的团簇小球(非负载型活性相)落入到坑道中，从而提升非负载型活性相与Y型分子筛的结合程度，达到提升非负载型催化剂活性、选择性的目的。该团簇小球能具有硫化之后作为加氢裂化催化剂活性相的作用。
本发明中，分子筛表面坑道的设计目标为在分子筛表面形成不小于20nm的坑道结构，优选在20-40nm之间。
根据本发明的另一方面，提供了一种加氢裂化催化剂，其原料包括上述的改性Y型分子筛。
在本发明的一些实施方式中，优选地，所述加氢裂化催化剂还包括非负载活性相、氧化铝、以及可选的无定型硅铝，通过混合、成型、干燥、焙烧，得到非负载型加氢裂 化催化剂。
本发明还提供了一种加氢裂化工艺，其是采用本发明所提供的上述加氢裂化催化剂进行的。
本发明合成的分子筛与现有技术相比，具有的有益效果包括：经由本发明的改性Y型分子筛所制备的加氢裂化催化剂存在更高的转化率，意味着利用本发明所合成的分子筛具有更高的性能。
附图说明
图1示出了本发明实施例1的改性后的Y1分子筛的扫描电镜图。
图2示出了本发明实施例1的改性前的Y分子筛的扫描电镜图。
图3示出了本发明对比例1的改性后的Y分子筛的扫描电镜图。
图4示出了精氨酸溶液与本发明的实施例2中的Y-A2分子筛的水洗液紫外光谱图。
具体实施方式
为了对本发明的技术特征、目的和有益效果有更加清楚的理解，现对本发明的技术方案进行以下详细说明，但不能理解为对本发明的可实施范围的限定。
本发明实施例中所使用Y型分子筛为通过南开催化剂厂生产的HY分子筛(SiO2、Al2O3摩尔比10.7)，以下简称Y型分子筛。
实施例1
称取10g Y型分子筛加入到100g去离子水中，搅拌均匀，再加入1g 3-(甲脒基硫代)-1-丙磺酸、1g苄脒盐酸盐，并在20℃下进行第一反应，反应时长3h，然后对形成的浆液进行过滤、洗涤，并于120℃干燥3h，得到改性Y型分子筛A，记为Y-A1。
称取9g Y-A1加入到90g去离子水中，搅拌均匀；再加入4g的草酸，pH＜1，并升温至50℃进行反应3h后，对浆液进行过滤、洗涤，并于120℃干燥3h，于550℃焙烧，得到改性Y型分子筛，记为Y1分子筛。
利用扫描电镜表征改性前后的分子筛。改性后的Y1和改性前的Y分子筛的扫描电镜图分别如图1、图2所示。可清晰识别出，相对于改性前的Y分子筛，经过本实施例的方法改性的分子筛表面产生了一定的坑道结构。
实施例2
称取10g Y型分子筛加入到80g去离子水中，搅拌均匀，再加入1.5g精氨酸，并在 25℃下进行反应，反应时长2h，后对形成的浆液进行过滤、洗涤，并于120℃干燥3h，得到改性Y型分子筛A，记为Y-A2。
利用紫外可见光谱表征水洗Y-A2分子筛不会导致其有机物含量发生变化的能力。如图4所示，制备初期1.5g精氨酸溶解在80g的水中存在明显的紫外可见吸收光谱；将Y-A2加入80g水中，搅拌后过滤取水洗后的溶液，其不具备显著的紫外可见吸收光谱(如图4所示)，说明改性有机物已经与分子筛发生了化学反应，形成了稳定的有机物-Y型分子筛结构。由此，可用于后续水溶液环境下的改性处理。
称取9g Y-A2加入到90g去离子水中，搅拌均匀；再加入14.0g的柠檬酸，并升温至60℃进行反应2h后，对浆液进行过滤、洗涤，并于120℃干燥3h，于550℃焙烧，得到改性Y型分子筛，记为Y2分子筛。
实施例3
称取10g Y型分子筛加入到50g去离子水中，搅拌均匀，再加入0.6g甲硫氨酸、0.6g盐酸乙脒，并在35℃下进行反应，反应时长1h，后对形成的浆液进行过滤、洗涤，并于120℃干燥3h，得到改性Y型分子筛A，记为Y-A3。
称取9g Y-A3加入到90g去离子水中，搅拌均匀；再加入1.87g的盐酸(浓度36％)，pH为<1，并升温至55℃进行反应1h后，对浆液进行过滤、洗涤，并于120℃干燥3h，于550℃焙烧，得到改性Y型分子筛，记为Y3分子筛。
实施例4
称取10g Y型分子筛加入到100g去离子水中，搅拌均匀，再加入0.83g苯丙氨酸，并在45℃下进行反应，反应时长2h，后对形成的浆液进行过滤、洗涤，并于120℃干燥3h，得到改性Y型分子筛A，记为Y-A4。
称取9g Y-A4加入到90g去离子水中，搅拌均匀；再加入8.6g的柠檬酸，pH为<1，并升温至45℃反应4h后，对浆液进行过滤、洗涤，并于120℃干燥3h，于550℃焙烧，得到改性Y型分子筛，记为Y4分子筛。
对比例1
称取9g Y型分子筛加入到90g去离子水中，搅拌均匀，再加入14g的柠檬酸，pH为<1，并升温至60℃进行恒温，反应2h后，对浆液进行过滤、洗涤，并于120℃干燥3h，于550℃焙烧，得到改性D1分子筛。
利用扫描电镜表征是否利用本发明的技术方案进行改性的分子筛的差异。改性后的Y1和D1分子筛的扫描电镜图分别如图1、图3所示。由图可清晰识别出，本实施例的方法改性的分子筛Y1表面产生了一定的坑道结构，未使用本方法改性的分子筛D1由 于酸性溶液能够进入到分子筛的微孔中，无法实现在酸性溶液在分子筛的表面靶向刻蚀，因此形成了无特征形貌的改性分子筛。
对比例2
称取9g Y型分子筛加入到90g去离子水中，搅拌均匀，再加入1.87g的盐酸(浓度36％)，pH为<1，并升温至55℃进行恒温，反应1h后，对浆液进行过滤、洗涤，并于120℃干燥3h，于550℃焙烧，得到改性D2分子筛。
对比例3
称取10g Y型分子筛加入100g去离子水中，搅拌均匀，再加入2g葡萄糖，并在20℃下进行反应，反应时长2h，后对形成的浆液进行过滤、洗涤，并于120℃干燥3h，得到Y-D3分子筛；对前一步骤得到Y-D3进行与实施例2相同的水洗试验，取水洗后滤液10mL加入10mL 0.05mol/L碘标准溶液，再缓慢滴加0.2mol/L氢氧化钠溶液，至溶液呈淡黄色，用pH试纸检测发现溶液为弱酸性，说明水洗液中含有葡萄糖，因此此过程未能得到吸附稳定的改性Y分子筛。
Y、Y1、Y2、Y3、Y4、D1、D2分子筛的物理吸附表征结果如表1所示。其中，总比表面积利用BET方法计算得到，为了使得BET方程成立，选择p/p0范围在0.01-0.30中不小于3个点，满足BET方程的C值大于0的条件下，得到BET比表面积。介孔、微孔比表面积的表征以BET比表面积为基础，利用t-Plot方法计算得到。
由表1数据可知，Y1、Y2、Y3、Y4分子筛的介孔比表面积均比Y分子筛有一定程度的提升，说明本发明的方法能够实现分子筛介孔孔道结构定向调控，增强孔道结构连通性。Y1、Y2、Y3、Y4分子筛的微孔比表面积与Y分子筛相比差别不大，但是D1、D2分子筛的微孔比表面积存在较大程度的下降，说明本发明的方法中氨基酸有机物的吸附能够实现对Y型分子筛微孔结构的保护。
表1
Y、Y1、Y2、Y3、Y4、D1、D2分子筛的相对结晶度结果如表2所示。由表2中数据可以看出，Y1、Y2、Y3、Y4分子筛相较于D1、D2分子筛存在更高的相对结晶度。由此说明，本发明方法利用氨基酸有机物的吸附能够实现对Y型分子筛结构的保护，减少其由化学改性所导致的结晶度损失。
表2
分别称取10g Y1、Y2、Y3、Y4、D1、D2分子筛，与60g氧化铝、30g非负载型活性相、2g田菁粉混合均匀，利用硝酸水溶液进行湿混，而后挤条成型，成型产品在120℃干燥4h、500℃焙烧3h后，分别得到加氢裂化催化剂CAT-Y1、CAT-Y2、CAT-Y3、CAT-Y4、CAT-D1、CAT-D2。将制备的各催化剂以直馏柴油为原料，在340℃，8.0MPa，氢油比800，空速4.5h-1的条件下开展催化剂评价实验，试验结果如下表3所示。其中，转化率为小于180℃馏分产品占全部产品的质量分数。
表3
由表3中各催化剂评价结果可以看出，利用本发明合成的分子筛与对比技术相比，所制备的加氢裂化催化剂存在更高的转化率，意味着利用本发明所合成的分子筛具有更高的性能。
当然，本发明还可有其它多种实施例，在不背离本发明精神及其实质的情况下，熟悉本领域的技术人员可根据本发明作出各种相应的改变和变形，但这些相应的改变和变 形都应属于本发明权利要求的保护范围。

Claims (11)

  1. 一种改性Y型分子筛的制备方法，其中，包括：
    在液相体系中，使有机物与Y型分子筛发生第一反应，得到改性Y型分子筛A；其中，所述有机物具有脒基、苄基、巯基官能团中的一种或两种以上的组合；
    在酸性的液相体系中，使所述改性Y型分子筛A发生第二反应，其次进行焙烧处理，得到所述改性Y型分子筛；
    其中，所述Y型分子筛与所述有机物的质量比为3-12.5:1。
  2. 根据权利要求1所述的制备方法，其中，所述Y型分子筛与所述有机物的质量比为5-10:1。
  3. 根据权利要求1所述的制备方法，其中，所述第一反应的温度为20-50℃，时间为0.5-3h。
  4. 根据权利要求1所述的制备方法，其中，在所述第一反应结束后，所述的制备方法还包括：
    将所述第一反应所得反应产物进行固液分离、洗涤和干燥，得到所述改性Y型分子筛A。
  5. 根据权利要求1所述的制备方法，其中，所述第二反应的温度为35-60℃，时间为0.5-4h。
  6. 根据权利要求1所述的制备方法，其中，所述第二反应中，所述酸性的液相体系的pH≤1。
  7. 根据权利要求1所述的制备方法，其中，所述有机物为精氨酸、苯丙氨酸、甲硫氨酸、盐酸乙脒、苄脒盐酸盐、3-(甲脒基硫代)-1-丙磺酸中的一种或两种以上的组合。
  8. 根据权利要求1所述的制备方法，其中，所述焙烧处理的温度为470-560℃，时间为3-6h。
  9. 一种权利要求1至8中任一项所述的制备方法得到的改性Y型分子筛。
  10. 一种加氢裂化催化剂，其中，其原料包含权利要求9所述的改性Y型分子筛。
  11. 一种加氢裂化工艺，其是采用权利要求10所述的加氢裂化催化剂进行的。
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