CN113333016B - Nano-scale KL molecular sieve loaded metal catalyst, preparation method and application - Google Patents

Nano-scale KL molecular sieve loaded metal catalyst, preparation method and application Download PDF

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CN113333016B
CN113333016B CN202110559598.8A CN202110559598A CN113333016B CN 113333016 B CN113333016 B CN 113333016B CN 202110559598 A CN202110559598 A CN 202110559598A CN 113333016 B CN113333016 B CN 113333016B
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molecular sieve
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alkaline earth
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CN113333016A (en
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王树元
徐丹
朱地
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Energy Research Institute of Shandong Academy of Sciences
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    • 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
    • B01J29/60—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L, as exemplified by patent document US3216789
    • B01J29/61—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L, as exemplified by patent document US3216789 containing iron group metals, noble metals or copper
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    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/60—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L, as exemplified by patent document US3216789
    • B01J29/605—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L, as exemplified by patent document US3216789 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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    • 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
    • B01J29/60—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L, as exemplified by patent document US3216789
    • B01J29/61—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L, as exemplified by patent document US3216789 containing iron group metals, noble metals or copper
    • B01J29/63—Iron group metals or copper
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    • B01J35/391—Physical properties of the active metal ingredient
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    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/394—Metal dispersion value, e.g. percentage or fraction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • 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
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/373—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation
    • C07C5/393—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation with cyclisation to an aromatic six-membered ring, e.g. dehydrogenation of n-hexane to benzene
    • C07C5/41—Catalytic processes
    • C07C5/415—Catalytic processes with metals
    • 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
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/373—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation
    • C07C5/393—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation with cyclisation to an aromatic six-membered ring, e.g. dehydrogenation of n-hexane to benzene
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    • 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
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention relates to a nanometer KL molecular sieve loaded metal catalyst, a preparation method and application. The alkaline earth metal-doped KL molecular sieve comprises a nanoscale KL molecular sieve and metal, wherein the nanoscale KL molecular sieve is a KL molecular sieve doped with alkaline earth metal, the alkaline earth metal is formed on a coordination structure of the KL molecular sieve, the metal is adsorbed and combined with the alkaline earth metal of the nanoscale KL molecular sieve in an atomic form, and the metal exists in a single atom or cluster form. The preparation process comprises the steps of mixing an aluminum source, a silicon source, inorganic alkali, water and alkaline earth metal to obtain sol, crystallizing the sol to obtain the nanoscale KL molecular sieve, and obtaining the nanoscale KL molecular sieve supported metal catalyst by an atomic layer deposition method. Has better activity and selectivity of the straight paraffin hydrocarbon to C6-C8.

Description

Nano-scale KL molecular sieve loaded metal catalyst, preparation method and application
Technical Field
The invention belongs to the technical field of KL molecular sieve catalysts, and particularly relates to a nanoscale KL molecular sieve supported metal catalyst, a preparation method and application.
Background
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Aromatic hydrocarbons are important basic organic chemical raw materials, the economic value is high, the increasing aromatic hydrocarbon demand in China is difficult to meet through aromatic hydrocarbon production dominated by a petroleum route, and catalytic reforming is one of important ways for converting naphtha into aromatic hydrocarbons. In recent years, researchers have devoted their efforts to the study of molecular sieve supported metal type catalysts. Bernard research finds that the KL molecular sieve catalyst loaded by metals (Pt, fe, sn, co, la, tm and the like) is in the state of C 6 ～C 10 The aromatization reaction of straight-chain alkane shows higher activity and aromatic selectivity. The paraffin dehydrocyclization reaction follows a monofunctional reaction mechanism on metal-supported KL catalysts, i.e. the metal is uniqueA reactive center. Therefore, the position, particle size, dispersity, electron density and the like of the metal in the catalyst have important influence on the catalytic activity and the aromatic selectivity of the catalyst. Compared with an acidic molecular sieve carrier, the KL molecular sieve with the special one-dimensional twelve-membered ring through channel can effectively avoid cracking and isomerization reaction, and meanwhile, the limitation of the molecular sieve pore opening on reactant molecules enables alkane molecules to generate transition-state species matched with the channel, so that the aromatization performance is improved. Although the one-dimensional pore channel structure of the KL molecular sieve is beneficial to the aromatization reaction, the one-dimensional pore channel structure has certain limitation on the product diffusion, and meanwhile, the metal falling in the deep part of the molecular sieve pore cannot play an effective role. Researches have shown that the nano-scale KL molecular sieve is more beneficial to the diffusion of products, but the traditional preparation method cannot accurately regulate the falling position of metal inside and outside the molecular sieve pore channel, so that the function of the nano-scale KL molecular sieve cannot be fully exerted.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a nano KL molecular sieve supported platinum catalyst, a preparation method and application.
In order to solve the technical problems, the technical scheme of the invention is as follows:
in a first aspect, the invention provides a nanometer KL molecular sieve supported metal catalyst, which comprises a nanometer KL molecular sieve and metal, wherein the nanometer KL molecular sieve is a KL molecular sieve doped with alkaline earth metal, the alkaline earth metal exists on a coordination structure of the KL molecular sieve, the metal is adsorbed to form a bond with oxygen around the alkaline earth metal on the nanometer KL molecular sieve in an atomic form, and the metal exists in a form of a single atom or a cluster.
The invention utilizes the interaction between the alkaline earth metal coordinated on the KL molecular sieve framework and the atoms around the alkaline earth metal to ensure that the metal is adsorbed near the alkaline earth metal, and the framework oxygen atoms around the alkaline earth metal have larger adsorption and combination capacity on the metal, thereby improving the stability of the whole structure.
Because of the strong adsorption performance of oxygen atoms around the metal and the alkaline earth metal, the metal is not easy to agglomerate in the nano-scale KL molecular sieve, more active sites can be exposed, and the alkane aromatization reaction is favorably carried out.
The metal exists in the pore canal of the KL molecular sieve in the form of single atom or cluster, and because the alkaline earth metal is added in situ in the synthesis process of the molecular sieve, the alkaline earth metal can accelerate the nucleation of the molecular sieve to grow into the nano-scale KL molecular sieve, or serves as a structural guiding agent for the growth of the molecular sieve to replace the position of part K, and has stronger interaction with the oxygen of the molecular sieve framework, the metal can be stably adsorbed on the oxygen atom around the alkaline earth metal, and the highly dispersed metal single atom and cluster are obtained.
The alkaline earth metal replaces partial K ions to exist in a framework coordination structure of the KL molecular sieve, has strong interaction with oxygen atoms in the framework, and the alkalinity of the alkaline earth metal can neutralize the acidity of aluminum in the molecular sieve framework, so that the KL molecular sieve is neutral.
In some embodiments of the invention, the metal supported by the nanoscale KL molecular sieve is platinum, palladium, iron, cobalt, nickel, copper, manganese, zinc, gallium, or titanium.
In some embodiments of the invention, the nanoscale KL molecular sieve-supported metal catalyst has a diameter of 100-200nm. According to the invention, the adsorption effect of the nano-scale KL molecular sieve and platinum is utilized, so that the diameter of each structure of the formed catalyst is relatively small, the diameter is small, more exposed sites are exposed, and the alkane aromatization reaction can be improved.
In some embodiments of the invention, the nanoscale KL molecular sieve has a diameter of 50-100nm.
In some embodiments of the invention, the alkaline earth metal is one of beryllium, magnesium, calcium, strontium, barium.
In a second aspect, the invention provides a preparation method of the nano-scale KL molecular sieve supported metal catalyst, which comprises the following specific steps:
mixing an aluminum source, a silicon source, inorganic alkali, water and alkaline earth metal to obtain sol, crystallizing the sol, and drying and roasting the crystallized solid to obtain the nanoscale KL molecular sieve;
and controllably depositing metal on the nano-scale KL molecular sieve by the nano-scale KL molecular sieve through an atomic layer deposition method to obtain the nano-scale KL molecular sieve loaded metal catalyst.
During the crystallization of the sol, various substances form a framework structure, and the alkaline earth metal accelerates the nucleation of the molecular sieve or enters the framework coordination structure as a structure directing agent.
The nanoscale KL molecular sieve is synthesized, the scale range is small, and alkaline earth metals are fully exposed and dispersed. Under the adsorption action of oxygen atoms around the alkaline earth metal, the metal atoms and the clusters are distributed near the alkaline earth metal, and the atoms and the clusters coexist in the pore channels of the KL molecular sieve and are highly dispersed, so that the alkane aromatization reaction is favorably carried out; the occurrence of secondary hydrogenolysis reaction is reduced, and the selectivity of aromatic hydrocarbon is improved.
The atomic layer deposition method can control the placement of the metal on the carrier at the atomic level and can regulate the dispersion of metal single atoms on the carrier. Compared with other deposition methods, the method can reduce the metal loading amount by 0.15-0.3%, and reduce the catalyst cost by reducing the loading amount of the active metal.
In some embodiments of the invention, the molar ratio of the aluminum source, the silicon source, the inorganic base, the water, and the alkaline earth metal is 1: 2.5-20; further, 1: 2.5-6. The proportion of the alkaline earth metal and other substances influences the catalytic performance and the aromatic selectivity of the obtained nanoscale KL molecular sieve catalyst.
In some embodiments of the invention, the aluminum source is aluminum hydroxide. In some embodiments of the invention, the silicon source is a silica sol. In some embodiments of the invention, the inorganic base is potassium hydroxide. In some embodiments of the invention, the alkaline earth metal is barium chloride, barium nitrate, magnesium chloride, or magnesium nitrate.
In some embodiments of the present invention, the process of mixing the raw materials to obtain the sol is: mixing an aluminum source and an inorganic base, then adding silica sol and water, finally adding alkaline earth metal, and aging to obtain the sol. And finally adding the alkaline earth metal, wherein the alkaline earth metal is positioned on the coordination position of the nanometer KL molecular sieve framework, so that the alkaline earth metal is favorably dispersed and arranged.
Further, the mixing temperature of the aluminum source and the inorganic base is 90-110 ℃; further 100 ℃.
The raw materials are mixed to form sol, and then the sol is crystallized. In some embodiments of the present invention, the temperature of the crystallization process is 160-185 ℃ and the crystallization time is 18-35h.
In some embodiments of the present invention, the specific process of the nanoscale KL molecular sieve and the atomic layer deposition method is as follows: mixing the nano KL molecular sieve with a dispersing agent to obtain a suspension, dispersing the suspension on a matrix, drying, and performing pulse deposition on the surface of the dried substance to obtain the metal.
Further, the process of pulse deposition of metal is: firstly, carrying out pulse deposition and purging on the metal source, then carrying out pulse oxidation gas after purging, then carrying out oxidation gas purging, and repeating the pulse deposition and purging processes of the metal source for 3-8 times to obtain the nano KL molecular sieve loaded metal catalyst. The Atomic Layer Deposition (ALD) technology is a thin film growth technology, a nano catalyst with ultra-small nano ions is controlled and synthesized on a carrier, and the ALD technology has the characteristics of controllable metal particle size, uniform particle height dispersion and the like, and has outstanding advantages compared with the traditional catalyst preparation method.
Further, the conditions of pulse deposition and purging are as follows: the temperature is 200-250 ℃, the pulse time of the metal source is 0.02-0.8s, the deposition time is 10-70s, and the purging time is 25-105s; the pulse time of the oxidizing gas is 0.1-1.2s, the reaction time is 20-70s, and the purging time is 30-105s.
Further, the metal source is platinum (II) acetylacetonate, trimethyl-methylcyclopentadienyl platinum, nickelocene, cobaltocene, ferrocene, copper bis (2, 6-tetramethyl-3, 5-heptanedionate), manganese diethyldicyclopentadienyl, titanium tetraisopropoxide, diethyl zinc, trimethyl gallium, triethyl gallium, tin tetrakis (dimethylamine), tin tetrachloride, palladium hexafluoroacetylacetonate, and trimethyl indium.
In a third aspect, the nanometer KL molecular sieve loaded metal catalyst is applied to linear alkane reforming;
further, the linear alkane is C6-C8. The catalyst has better activity and aromatic selectivity for C6, C7 and C8, and the catalyst acts on the aromatization reaction process of straight-chain paraffin, taking C7 as an example, and can have better activity and aromatic selectivity for C6 and C8.
One or more technical schemes of the invention have the following beneficial effects:
1. the nanometer KL molecular sieve prepared by the invention has the advantages of simple method, easy regulation and control of grain size, good repeatability and uniform appearance.
2. According to the invention, an advanced atomic layer deposition technology is adopted to deposit metal species on the nano KL molecular sieve containing alkaline earth metal, and the metal monoatomic atoms fall on oxygen atoms near the alkaline earth metal source ion coordinated by the nano KL molecular sieve framework, so that the metal monoatomic atoms can stably exist, a catalytic system with coexisting metal monoatomic atoms and clusters is obtained, and the metal monoatomic atoms and the clusters are highly dispersed in the KL molecular sieve pore channels, so that the utilization rate of the metal is greatly improved.
3. The metal species falling in the pore canal of the nano-scale KL molecular sieve has stronger action with the carrier skeleton, can stably exist, is not easy to agglomerate at high temperature, and is beneficial to the alkane aromatization reaction. Meanwhile, the nano KL molecular sieve has a short pore channel, which is beneficial to the diffusion of aromatic hydrocarbon products, reduces the occurrence of secondary hydrogenolysis reaction, and greatly improves the selectivity of the aromatic hydrocarbon.
4. The metal monoatomic group in the catalyst system can effectively reduce the energy barrier of alkane terminal hydrogen desorption, and formed olefin species can complete cyclization reaction on the nearby metal cluster to generate a target product, so that the synergistic catalytic effect of the metal monoatomic group and the cluster is realized.
5. The method for obtaining the high-dispersion metal species on the nano-scale KL molecular sieve has important significance for preparing the aromatic hydrocarbon by reforming the long-chain alkane, particularly for C 8 The preparation of aromatic hydrocarbon, the catalytic system has wide application prospect.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description, serve to explain the invention and not to limit the invention.
Fig. 1 is an SEM photograph of a comparative example preparation of a conventional KL molecular sieve.
Figure 2 is an XRD pattern of a conventional KL molecular sieve prepared by comparative example.
FIG. 3 is an SEM photograph of a nano-scale KL molecular sieve prepared in inventive example 1.
FIG. 4 is an XRD pattern of the nano-scale KL molecular sieve prepared in inventive example 1.
FIG. 5 is an SEM photograph of a nano-sized KL molecular sieve prepared in inventive example 2.
FIG. 6 is an XRD pattern of the nano-scale KL molecular sieve prepared in inventive example 2.
FIG. 7 is an SEM photograph of nanoscale KL molecular sieve prepared in inventive example 3.
FIG. 8 is an XRD pattern of the nano-scale KL molecular sieve prepared in inventive example 3.
FIG. 9 is a TEM photograph of a Pt/KL catalyst prepared by the comparative example.
FIG. 10 is a TEM photograph of Pt/KL catalyst prepared in inventive example 8.
FIG. 11 is a TEM photograph of Pt/KL catalyst prepared in inventive example 9.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an", and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise. The invention will be further illustrated by the following examples
Comparative example
Weighing 22.6g Al (OH) 3 Dissolving in 400g deionized water, weighing 93.2g KOH, dissolving in 275g deionized waterAnd (3) transferring the two solutions into a three-neck flask in water, heating to 100 ℃ under the condition of stirring, and cooling to room temperature after the solution is clarified. Then, 334g of silica Sol (SiO) was added dropwise to the above-mentioned transparent solution with stirring 2 Content of 30%) and 100g of deionized water, fully stirring after dropwise adding to obtain molecular sieve initial sol, transferring the molecular sieve initial sol into a crystallization kettle, placing the crystallization kettle into a 180 ℃ oven for 22 hours, then cooling to room temperature, carrying out suction filtration, washing the deionized water to be neutral, transferring the molecular sieve initial sol into a 120 ℃ oven for drying for 12 hours, and finally roasting the molecular sieve sol in a muffle furnace at 500 ℃ for 4 hours to obtain the conventional KL molecular sieve carrier.
Dissolving the conventional KL molecular sieve prepared by the comparative example in ethanol, uniformly dispersing the dissolved conventional KL molecular sieve on a quartz plate, drying the solution in air at room temperature for 2 hours, and transferring the solution to a reaction chamber of atomic layer deposition equipment, wherein the ALD deposition parameters are as follows: the reaction chamber temperature is 220 ℃, and the platinum source adopts trimethyl-methyl cyclopentadiene platinum (MeCpPtMe) 3 ) As precursor, a temperature of 65 ℃ was used, O 3 As the oxidizing agent, high-purity nitrogen gas having a temperature of room temperature and a flow rate of 50sccm was used as a carrier gas. First MeCpPtMe was performed 3 The pulse time of (1) was 0.5s, the deposition time was 60s, the purge time was 100s, and then O was performed 3 The pulse time of (2) was 1s, the reaction time was 60s, and the purge time was 100s. After 6 Pt cycles were repeated successively, a Pt/KL catalyst was obtained.
Example 1
Weighing 22.6g Al (OH) 3 Dissolving in 400g of deionized water, weighing 93.2g of KOH, dissolving in 275g of deionized water, transferring the two solutions into a three-neck flask, heating to 100 ℃ under the condition of stirring, and cooling to room temperature after the solution is clear. Then, 334g of silica Sol (SiO) was added dropwise to the above-mentioned transparent solution with stirring 2 Content 30%) and 100g of deionized water, and fully stirring to obtain the molecular sieve initial sol after the dropwise addition. Weighing a certain amount of 0.18g BaCl 2 Dissolving in 15g of deionized water, continuously stirring and aging for 1h after dripping, transferring into a crystallization kettle, placing into a 175 ℃ oven for 24h, cooling to room temperature, performing suction filtration, washing with deionized water to neutrality, transferring into a 120 ℃ oven for drying for 12h, and finally roasting in a muffle furnace at 500 ℃ for 4h to obtain the nano-scale KL molecular sieve carrier。
Example 2
Weighing 22.6g Al (OH) 3 Dissolving in 400g deionized water, weighing 93.2g KOH, dissolving in 275g deionized water, transferring the two solutions into a three-neck flask, heating to 100 ℃ under the condition of stirring, and cooling to room temperature after the solution is clear. Then, 334g of silica Sol (SiO) was added dropwise to the above-mentioned transparent solution with stirring 2 Content 30%) and 100g of deionized water, and fully stirring to obtain the molecular sieve initial sol after the dropwise addition. Weigh 0.36g Ba (NO) 3 ) 2 Dissolving in 18g of deionized water, continuing stirring and aging for 1h after the dropwise addition is finished, then transferring into a crystallization kettle, placing into a 175 ℃ oven for keeping for 24h, then cooling to room temperature, carrying out suction filtration, washing with deionized water to be neutral, transferring into a 120 ℃ oven for drying for 12h, and finally roasting in a muffle furnace at 500 ℃ for 4h to obtain the nano KL molecular sieve carrier.
Example 3
Weighing 22.6g Al (OH) 3 Dissolving in 400g deionized water, weighing 93.2g KOH, dissolving in 275g deionized water, transferring the two solutions into a three-neck flask, heating to 100 ℃ under the condition of stirring, and cooling to room temperature after the solution is clear. Then, 334g of silica Sol (SiO) was added dropwise to the above-mentioned transparent solution with stirring 2 Content 30%) and 100g of deionized water, and fully stirring to obtain the molecular sieve initial sol after the dropwise addition. Weigh 0.54g of BaCl 2 Dissolving in 20g of deionized water, continuing stirring and aging for 1h after the dropwise addition is finished, then transferring into a crystallization kettle, placing into a 175 ℃ oven for keeping for 24h, then cooling to room temperature, carrying out suction filtration, washing with deionized water to be neutral, transferring into a 120 ℃ oven for drying for 12h, and finally roasting in a muffle furnace at 500 ℃ for 4h to obtain the nano KL molecular sieve carrier.
Example 4
Weighing 22.6g Al (OH) 3 Dissolving in 400g deionized water, weighing 93.2g KOH, dissolving in 275g deionized water, transferring the two solutions into a three-neck flask, heating to 100 ℃ under the condition of stirring, and cooling to room temperature after the solution is clear. Then 314g of silica Sol (SiO) was added dropwise to the above-mentioned transparent solution with stirring 2 Content 30%) and 100g deionizationAnd fully stirring the mixed solution of water after the dropwise addition is finished to obtain the molecular sieve initial sol. 0.44g MgCl was weighed 2 Dissolving in 20g of deionized water, continuing stirring and aging for 1h after the dripping is finished, then transferring into a crystallization kettle, placing into an oven at 170 ℃ for maintaining for 14h, then cooling to room temperature, carrying out suction filtration, washing with deionized water to be neutral, transferring into an oven at 120 ℃ for drying overnight, and finally roasting in a muffle furnace at 550 ℃ for 3h to obtain the nano-scale KL molecular sieve carrier.
Example 5
Weighing 22.6g Al (OH) 3 Dissolving in 400g of deionized water, weighing 93.2g of KOH, dissolving in 275g of deionized water, transferring the two solutions into a three-neck flask, heating to 100 ℃ under the condition of stirring, and cooling to room temperature after the solution is clear. Then 354g of silica Sol (SiO) was added dropwise to the above-mentioned transparent solution with stirring 2 Content 30%) and 100g of deionized water, and fully stirring to obtain the molecular sieve initial sol after the dropwise addition. Weighing 0.44g Mg (NO) 3 ) 2 Dissolving in 20g of deionized water, continuing stirring and aging for 1h after the dropwise addition is finished, then transferring into a crystallization kettle, placing into a 175 ℃ oven for keeping for 35h, then cooling to room temperature, carrying out suction filtration, washing with deionized water to be neutral, transferring into a 120 ℃ oven for drying overnight, and finally roasting in a muffle furnace at 520 ℃ for 6h to obtain the nano-scale KL molecular sieve carrier.
Example 6
Dissolving the nano-scale KL molecular sieve prepared in the embodiment 1 in ethanol, uniformly dispersing the dissolved nano-scale KL molecular sieve on a quartz plate, drying the obtained product in air at room temperature for 2 hours, and transferring the obtained product to a reaction chamber of atomic layer deposition equipment, wherein the ALD deposition parameters are as follows: the temperature of the reaction cavity is 220 ℃, palladium hexafluoroacetylacetone is used as a metal precursor, the use temperature is 70 ℃, formaldehyde is used as an oxidant, the use temperature is room temperature, and the carrier gas is high-purity nitrogen with the flow rate of 50 sccm. First, the pulse time of hexafluoroacetylacetonatopalladium was 0.5s, the deposition time was 20s, and the purge time was 40s, and then the pulse time of formaldehyde was 1s, the reaction time was 20s, and the purge time was 40s. After 6 times of Pd circulation, the Pd/KL catalyst is obtained.
Example 7
Nanoscale scale prepared from example 1The KL molecular sieve is dissolved in ethanol and then uniformly dispersed on a quartz plate, and is transferred to a reaction chamber of atomic layer deposition equipment after being dried in air at room temperature for 2 hours, and ALD deposition parameters are set as follows: the reaction chamber temperature is 220 ℃, and the platinum source adopts trimethyl-methyl cyclopentadiene platinum (MeCpPtMe) 3 ) As precursor, a temperature of 65 ℃ was used, O 3 As the oxidizing agent, high-purity nitrogen gas having a temperature of room temperature and a flow rate of 50sccm was used as a carrier gas. First, meCpPtMe was performed 3 The pulse time of (1) was 0.5s, the deposition time was 60s, the purge time was 100s, and then O was performed 3 The pulse time of (2) was 1s, the reaction time was 60s, and the purge time was 100s. After 6 Pt cycles were repeated successively, a Pt/KL catalyst was obtained.
Example 8
The nanometer KL molecular sieve prepared in example 2 is dissolved in ethanol and then uniformly dispersed on a quartz plate, and is dried in air at room temperature for 2 hours and then transferred to a reaction chamber of atomic layer deposition equipment, wherein the set ALD deposition parameters are as follows: the reaction chamber temperature is 220 ℃, and the platinum source adopts trimethyl-methyl cyclopentadiene platinum (MeCpPtMe) 3 ) As precursor, a temperature of 65 ℃ was used, O 3 As the oxidizing agent, high-purity nitrogen gas having a flow rate of 50sccm was used as the carrier gas at room temperature. First MeCpPtMe was performed 3 The pulse time of (1) was 0.5s, the deposition time was 60s, the purge time was 100s, and then O was performed 3 The pulse time of (2) was 1s, the reaction time was 60s, and the purge time was 100s. After 6 Pt cycles were repeated successively, a Pt/KL catalyst was obtained.
Example 9
The nanometer KL molecular sieve prepared in example 3 is dissolved in ethanol and then uniformly dispersed on a quartz plate, and is dried in air at room temperature for 2 hours and then transferred to a reaction chamber of atomic layer deposition equipment, wherein the set ALD deposition parameters are as follows: the reaction chamber temperature is 220 ℃, and the platinum source adopts trimethyl-methyl cyclopentadiene platinum (MeCpPtMe) 3 ) As precursor, a temperature of 65 ℃ was used, O 3 As the oxidizing agent, high-purity nitrogen gas having a flow rate of 50sccm was used as the carrier gas at room temperature. First MeCpPtMe was performed 3 The pulse time of (1) was 0.5s, the deposition time was 60s, the purge time was 100s, and then O was performed 3 The pulse time of (2) was 1s, the reaction time was 60s, and the purge time was 100s. ContinuousAfter 6 repeated Pt cycles, the Pt/KL catalyst is obtained.
Example 10
The nanometer KL molecular sieve prepared in the embodiment 1 is dissolved in ethanol and then uniformly dispersed on a quartz plate, and is transferred to a reaction chamber of atomic layer deposition equipment after being dried in air at room temperature for 2 hours, wherein the ALD deposition parameters are set as follows: the temperature of the reaction cavity is 220 ℃, cobaltocene is used as a metal precursor, the use temperature is 70 ℃, and O 3 As the oxidizing agent, high-purity nitrogen gas having a flow rate of 50sccm was used as the carrier gas at room temperature. Firstly, the pulse time of cobaltocene is 0.5s, the deposition time is 20s, the purging time is 40s, and then O is carried out 3 The pulse time of (2) was 1s, the reaction time was 20s, and the purge time was 40s. After continuously repeating the Co circulation for 3 times, the Co/KL catalyst is obtained.
Example 11
The nanometer KL molecular sieve prepared in example 2 is dissolved in ethanol and then uniformly dispersed on a quartz plate, and is dried in air at room temperature for 2 hours and then transferred to a reaction chamber of atomic layer deposition equipment, wherein the set ALD deposition parameters are as follows: the temperature of the reaction cavity is 220 ℃, the nickel-metallocene is adopted as a metal precursor, the use temperature is 70 ℃, and O 3 As the oxidizing agent, high-purity nitrogen gas having a flow rate of 50sccm was used as the carrier gas at room temperature. Firstly, the pulse time of nickelocene is 0.5s, the deposition time is 20s, the purging time is 40s, and then O is carried out 3 The pulse time of (2) was 1s, the reaction time was 20s, and the purge time was 40s. After repeating the cycle of Ni for 5 times continuously, the Ni/KL catalyst is obtained.
Example 12
Dissolving the nano-scale KL molecular sieve prepared in the embodiment 3 in ethanol, uniformly dispersing the dissolved nano-scale KL molecular sieve on a quartz plate, drying the obtained product in air at room temperature for 2 hours, and transferring the obtained product to a reaction chamber of atomic layer deposition equipment, wherein the ALD deposition parameters are as follows: the temperature of the reaction cavity is 200 ℃, diethyl zinc is adopted as a metal precursor, the using temperature is room temperature, and H 2 O is an oxidant, the using temperature is room temperature, and the carrier gas is high-purity nitrogen with the flow rate of 50 sccm. Firstly, the pulse time of diethyl zinc is 0.02s, the deposition time is 10s, the purging time is 25s, and then H is carried out 2 Pulse time of O was 0.1s, reaction time was 10s, purgingThe time is 30s. After continuously repeating the Zn circulation for 3 times, zn/KL catalyst is obtained.
Example 13
Dissolving the nanometer KL molecular sieve prepared in the embodiment 4 in ethanol, uniformly dispersing the dissolved nanometer KL molecular sieve on a quartz plate, drying the obtained product in air at room temperature for 2 hours, and transferring the obtained product to a reaction chamber of atomic layer deposition equipment, wherein the ALD deposition parameters are as follows: the temperature of the reaction cavity is 220 ℃, palladium hexafluoroacetylacetonate is adopted as a metal precursor, the use temperature is 70 ℃, formaldehyde is adopted as an oxidant, the use temperature is room temperature, and the carrier gas is high-purity nitrogen with the flow of 50 sccm. First, the pulse time of hexafluoroacetylacetonatopalladium was 0.5s, the deposition time was 20s, and the purge time was 40s, and then the pulse time of formaldehyde was 1s, the reaction time was 20s, and the purge time was 40s. After continuously repeating the Pd circulation for 3 times, the Pd/KL catalyst is obtained.
Example 14
The nanometer KL molecular sieve prepared in example 5 is dissolved in ethanol and then uniformly dispersed on a quartz plate, and is dried in air at room temperature for 2 hours and then transferred to a reaction chamber of atomic layer deposition equipment, wherein the set ALD deposition parameters are as follows: the temperature of the reaction cavity is 220 ℃, tin tetrachloride is used as a metal precursor, the using temperature is room temperature, water is used as an oxidant, the using temperature is room temperature, and the carrier gas is high-purity nitrogen with the flow rate of 50 sccm. The pulse time for tin tetrachloride was 0.5s, the deposition time was 20s, and the purge time was 40s, and the pulse time for water was 1s, the reaction time was 20s, and the purge time was 40s. After continuously repeating the Sn circulation for 5 times, the Sn/KL catalyst is obtained.
Example 15
Evaluation of reaction Performance
The atomic layer deposition technology described in the comparative example and examples 7-9 is used to prepare Pt supported KL molecular sieve supported catalysts with different sizes, and the aromatization performance of the Pt supported KL molecular sieve supported catalysts is evaluated in a fixed bed microreactor by using n-heptane as a raw material. Mass airspeed WHSV =1h -1 Reaction temperature 420 ℃ and H 2 n-Heptane =6, the reaction pressure was 0.1MPa, all products were analyzed by on-line chromatography, and the reaction results are shown in Table 1.
TABLE 1 results of evaluation of catalytic Performance of each catalyst
Figure BDA0003078441800000111
As can be seen from the data in Table 1, the nano-scale KL molecular sieve loaded Pt monatomic and cluster catalyst shows higher catalytic performance and aromatic selectivity for heptane aromatization.
The n-heptane conversion and aromatic selectivity of examples 7 and 8 were better than those of example 9. Examples 7 and 8 correspond to the nano-sized KL molecular sieve supports prepared in examples 1 and 2, respectively, and it can be seen that the effect is best when the loading amount of alkaline earth metal is not as large as possible, but when a certain amount is reached, the catalytic performance and the selectivity of aromatic hydrocarbon are rather reduced when the loading amount is more.
As can be seen from the SEM images in fig. 1, 3,5, and 7, if no alkaline earth metal is added during the preparation of the KL molecular sieve support, the nucleation rate of the molecular sieve is slow, and the diameter of the obtained KL molecular sieve support is large, the diameter of the KL molecular sieve support in fig. 1 is 600-800nm, the diameter of fig. 3 is 200-300nm, the diameter of fig. 5 is 100-300nm, and the diameter of fig. 7 is 50-200nm.
The prepared nanometer KL molecular sieve can be seen from figures 4, 6 and 8, and shows that the KL molecular sieve comprises the KL molecular sieve and alkaline earth metal barium element.
As can be seen from fig. 9, the internal structure stripes of the Pt/KL catalyst prepared by the comparative example are thicker, and the internal structure stripes of the Pt/KL catalyst in fig. 10 and 11 are cleaned and have uniform structure.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (16)

1. A nanometer KL molecular sieve loaded metal catalyst is characterized in that: the alkaline earth metal-doped KL molecular sieve comprises a nanoscale KL molecular sieve and metal, wherein the nanoscale KL molecular sieve is a KL molecular sieve doped with alkaline earth metal, the alkaline earth metal is formed on a coordination structure of the KL molecular sieve, the metal is adsorbed and combined with the alkaline earth metal of the nanoscale KL molecular sieve in an atomic form, and the metal exists in a form of a single atom or a cluster; the diameter of the nanometer KL molecular sieve loaded metal catalyst is 100-200nm;
the preparation method of the nanometer KL molecular sieve loaded metal catalyst comprises the following specific steps:
mixing an aluminum source, a silicon source, inorganic alkali, water and alkaline earth metal to obtain sol, crystallizing the sol, and drying and roasting the crystallized solid to obtain the nanoscale KL molecular sieve;
depositing metal on the nano KL molecular sieve by using an atomic layer deposition method to obtain a nano KL molecular sieve loaded metal catalyst;
the process of mixing the raw materials to obtain the sol comprises the following steps: mixing an aluminum source and an inorganic base, then adding silica sol and water, finally adding alkaline earth metal, and aging to obtain sol, wherein the mixing temperature of the aluminum source and the inorganic base is 90-110 ℃;
the temperature of the crystallization process is 160-180 ℃, and the crystallization time is 18-35h.
2. The nanoscale KL molecular sieve supported metal catalyst of claim 1, wherein: the metal loaded by the nanoscale KL molecular sieve is platinum, palladium, iron, cobalt, nickel, copper, manganese, zinc, gallium or titanium.
3. The nanoscale KL molecular sieve supported metal catalyst of claim 1, wherein: the alkaline earth metal is one of beryllium, magnesium, calcium, strontium and barium.
4. The nanoscale KL molecular sieve supported metal catalyst of claim 1, wherein: the molar ratio of the aluminum source to the silicon source to the inorganic alkali to the water to the alkaline earth metal is 1:2.5 to 20, wherein the weight ratio of the (C).
5. The nanoscale KL molecular sieve supported metal catalyst of claim 1, wherein: the molar ratio of the aluminum source to the silicon source to the inorganic alkali to the water to the alkaline earth metal is 1:2.5 to 6.
6. The nanoscale KL molecular sieve supported metal catalyst of claim 1, wherein: the aluminum source is aluminum hydroxide.
7. The nanoscale KL molecular sieve supported metal catalyst of claim 1, wherein: the silicon source is silica sol.
8. The nanoscale KL molecular sieve supported metal catalyst of claim 1, wherein: the inorganic base is potassium hydroxide.
9. The nanoscale KL molecular sieve supported metal catalyst of claim 1, wherein: the alkaline earth metal is barium chloride, barium nitrate, magnesium chloride or magnesium nitrate.
10. The nanoscale KL molecular sieve supported metal catalyst of claim 1, wherein: the temperature at which the aluminum source and the inorganic base are mixed is 100 ℃.
11. The nanoscale KL molecular sieve supported metal catalyst of claim 1, wherein: the specific process of the nano KL molecular sieve and the atomic layer deposition method comprises the following steps: mixing the nano KL molecular sieve with a dispersing agent to obtain a suspension, dispersing the suspension on a matrix, drying, and performing pulse deposition on the surface of the dried substance to obtain the metal.
12. The nanoscale KL molecular sieve supported metal catalyst of claim 11, wherein: the process of pulse deposition of metal is as follows: firstly, carrying out pulse deposition and purging on the metal source, then carrying out pulse oxidation gas after purging, then carrying out oxidation gas purging, and repeating the pulse deposition and purging processes of the metal source for 3-8 times to obtain the nano KL molecular sieve supported platinum catalyst.
13. The nanoscale KL molecular sieve supported metal catalyst of claim 12, wherein: the conditions of pulse deposition and purging are as follows: the temperature is 200-250 ℃, the pulse time of the metal source is 0.02-0.8s, the deposition time is 10-70s, and the purging time is 25-105s; the pulse time of the oxidant is 0.1-1.2s, the reaction time is 20-70s, and the purging time is 30-105s.
14. The nanoscale KL molecular sieve supported metal catalyst of claim 12, wherein: the metal source is one or more of platinum (II) acetylacetonate, trimethyl-methyl cyclopentadienyl platinum, nickelocene, cobaltocene, ferrocene, copper bis (2, 2,6, 6-tetramethyl-3, 5-heptanedionate), diethyl manganese dicyclopentadienyl, titanium tetraisopropoxide, diethyl zinc, trimethyl gallium, triethyl gallium, tetra (dimethyl) tin, tin tetrachloride, palladium hexafluoroacetylacetonate and trimethyl indium.
15. Use of the nano-sized KL molecular sieve supported metal catalyst of any of claims 1-14 for linear alkane reforming.
16. The use of claim 15, wherein: the straight-chain alkane is C6-C8.
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