CN111298826B - Small-grain Ni @ Silicalite-1 encapsulated catalyst and synthesis method and application thereof - Google Patents
Small-grain Ni @ Silicalite-1 encapsulated catalyst and synthesis method and application thereof Download PDFInfo
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- CN111298826B CN111298826B CN201911225887.3A CN201911225887A CN111298826B CN 111298826 B CN111298826 B CN 111298826B CN 201911225887 A CN201911225887 A CN 201911225887A CN 111298826 B CN111298826 B CN 111298826B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
- B01J29/0352—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites containing iron group metals, noble metals or copper
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- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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- 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
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/334—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing molecular sieve catalysts
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
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- C—CHEMISTRY; METALLURGY
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a small-grain Ni @ Silicalite-1 encapsulated catalyst, a synthesis method and application thereof, wherein the catalyst is Silicalite-1 molecular sieve encapsulated metal Ni nano-particles, the maximum line width of the grains is 0.1-1.5 mu m, the mass percentage content of the metal Ni nano-particles is 0.1-5 wt%, and the metal Ni nano-particles are uniformly distributed and have the grain size of 2-5 nm; the synthesis of the catalyst adopts a three-step method, firstly, a silicon source is subjected to pre-depolymerization and/or alcohol-removing treatment, and a Ni precursor is added in the process and is uniformly mixed to obtain gel; secondly, pre-crystallizing and nucleating the gel at 80-100 ℃; thirdly, crystallizing, roasting and reducing the nucleated product at the temperature of 120-170 ℃ to obtain the catalyst; the obtained catalyst is used for catalyzing the reaction of phenol hydrodeoxygenation, and has good phenol conversion rate, aromatic selectivity and catalytic stability.
Description
Technical Field
The invention belongs to the field of catalytic materials, and relates to a small-grain Ni @ Silicalite-1 encapsulated catalyst, a synthesis method and application thereof.
Background
Benzene (B), toluene (T) and xylene (X) are BTX for short, and are very important basic chemical raw materials, and the price of the BTX is closely related to that of petroleum due to the fact that the BTX is mainly derived from petroleum; the current domestic market is in short supply. At present, most of medium-low temperature coal tar is directly combusted, so that resources are wasted and the environment is secondarily polluted; the preparation of gasoline and diesel oil by hydrogenation is a mainstream processing method for a moment. However, the operation rate is low due to the low price of crude oil and the problems of large hydrogen consumption, low yield, small capacity and dispersion. The phenol oil fraction is a main component of medium-low temperature coal tar, the mass ratio of the phenol oil fraction is 30-45%, and the phenol oil fraction comprises phenol compounds such as phenol, cresol and xylenol, and is difficult to separate due to similar physical and chemical properties. Theoretically, the direct hydrogenolysis deoxidation of the phenol oil fraction with lower hydrogen consumption to prepare BTX is an important direction for high-value utilization of the phenol oil fraction; among them, rational design and controllable preparation of high-efficiency catalysts are one of the key technologies.
At present, in the catalytic conversion reaction of phenols, gas phase reaction and liquid phase reaction are included, and metal catalysts prepared by a traditional impregnation method are mainly adopted; on the surface of the metal catalyst prepared by the traditional impregnation method, phenols are mainly adsorbed in a lying adsorption mode, hydrogenation metals (Pt, Ni and the like) are adsorbed to benzene rings to activate the benzene rings, and a few of oxophilic metals (Ru, Mo and the like) and/or oxophilic carriers (ZrO) are/is2、TiO2Etc.) the system then adsorbs and activates phenolic hydroxyl groups; however, the metal/molecular sieve catalyst prepared by the traditional wet impregnation method causes most of metals to be exposed on the outer surface of a carrier such as an oxide, a molecular sieve and the like, and the influence of the adsorption of a phenol-benzene ring lying down and the metal hydrogenation action on the outer surface is inevitable, so that the metal active center can simultaneously activate the phenol-benzene ring and the phenolic hydroxyl group under most conditions, which is the root cause of low BTX selectivity. Furthermore, it is more important that the metal particles have non-uniform size, and are prone to migration, agglomeration and loss, resulting in poor catalyst stability. For example Pt/SiO2As a catalyst for catalyzing the conversion of m-cresol, the conversion of m-cresol is only 17%, the selectivity of aromatic hydrocarbons in the product is only 28%, and the sum of the selectivities of ketones, alcohols and naphthenes is 72% (see document: j.catal.,2014,317, 22-29); to form Pt/ZrO2As a catalyst for catalyzing the conversion of m-cresol, the conversion rate of m-cresol is only 12%, the selectivity of aromatic hydrocarbon in the product is only 67.5%, and the sum of the selectivities of ketone, alcohol and naphthenic hydrocarbon is 29.4% (see the literature: J. Catal.,2014,317, 22-29); the two catalysts have low activity for catalyzing the conversion of m-cresol and produceThe selectivity of the compound to aromatic hydrocarbon is insufficient;
5% Ni/SiO prepared by traditional dipping method2Used for catalyzing the conversion of m-cresol, the conversion rate of the m-cresol is only 16.2 percent, the selectivity of aromatic hydrocarbon in the product is only 14.2 percent, and the sum of the selectivity of ketone, alcohol and naphthenic hydrocarbon is 44.4 percent (see the literature: J.Mole.Catal.A: chem.,2014,388-389, 47-55.); ru is taken as an active component and loaded on SiO2Prepared Ru/SiO2A catalyst which has a conversion rate of only 4.5% for the conversion of m-cresol, a selectivity to aromatics of 38.5% and a sum of selectivities to ketones, alcohols and naphthenes of 7.4% (see ACS Catal.,2015,5, 6271-6283.); MoOx/SiO2As a catalyst for catalyzing the conversion of m-cresol, the conversion rate of m-cresol in the catalytic process is 23.8 percent, the selectivity to aromatic hydrocarbon is 81.9 percent, and the sum of the selectivities to ketone, alcohol and naphthenic hydrocarbon is 18.1 percent (see the literature: appl.Catal. B: Environ,2017,214, 57-66.); 5 percent of Ni/H-ZSM-5 is used as a catalyst for catalyzing the conversion of phenol, the conversion rate of the phenol is 10 percent, the product does not contain aromatic hydrocarbon, and the sum of the selectivity to ketone, alcohol and naphthenic hydrocarbon is 100 percent (see the literature: J.Catal.,2012,296, 12-23.). 5 percent of Ni/H-Beta is taken as a catalyst for catalyzing the conversion of the phenolic mixture, wherein the conversion rate of phenolic substances is 32.2 percent, the selectivity to aromatic hydrocarbon is only 7.2 percent, and the sum of the selectivity to ketone, alcohol and naphthenic hydrocarbon is 21.4 percent (J.Ind.Eng.chem.,2016,35, 268-; 5% Fe/H-Beta is used as a catalyst for catalyzing the conversion of a phenolic mixture, wherein the conversion rate of phenolic substances is 23.8%, the selectivity to aromatic hydrocarbon is 20.2%, and the sum of the selectivities to ketone, alcohol and naphthenic hydrocarbon is 0.9% (see J.Ind.Eng.chem.,2016,35, 268-); the catalysts disclosed in the above documents all have the problems of low conversion rate of the phenols and/or low selectivity of the products to the aromatic hydrocarbon in the process of catalyzing the conversion of the phenols.
In recent years, a metal-confined catalysis method of molecular sieve encapsulation can realize metal-confined catalysis, and the metal particles are uniformly distributed, so that agglomeration and loss of the metal particles are remarkably inhibited, and the method is recognized as an effective method for improving stability (see the documents: J.Catal.2014,311, 458-468.; J.Am.Chem.Soc.2014,136, 15280-15290.; J.Catal., 2016,342, 3370-3376.; J.Am.Chem.Soc.2016,138, 7484-7487.; nat.Mater.2017, 16, 132-138.; Angel.Chem.Ed.2017, 56, 1-6.; Angel.Int.Ed.2017, 56, 6594-6598.). A representative work is the Enrique Iglesia topic group (see the documents J.Cat. 2014,311, 458-468; J.Am. chem. Soc.2014,136,15280-15290.) which adopts noble metal precursor-ligand complexation or forms a transparent solution with a structure directing agent (the metal is amphoteric and can not be precipitated in an alkaline system), and the noble metal is encapsulated in a molecular sieve cage structure (such as an LTA structure molecular sieve, an SOD or CHA structure molecular sieve) by an in-situ synthesis mode of the molecular sieve.
US4552855 discloses the encapsulation of Fe-toluene polymers in Y molecular sieve 12MR supercage structures. US9938157B2 discloses the use of a molecular sieve transcrystalization method to achieve the encapsulation of noble metals in small pore molecular sieve structures, which comprises introducing a noble metal precursor onto a larger pore molecular sieve by a conventional wet impregnation method, such as wet impregnation of Pt, Pd, Ru, etc. onto Y and Beta molecular sieves to obtain M/Y or M/Beta (M ═ Pt, Pd, Ru, etc.), then adding a structure directing agent required for the synthesis of the small pore molecular sieve, hydrothermal crystallization for a period of time, where the crystalline phase is transcrystalized from FAU or BEA to the crystalline phase of the small pore molecular sieve, such as MFI or GIS, etc., and the small pore molecular sieve encapsulated metal is achieved in the transcrystalization process.
CN107020147A discloses an MFI structure lamellar molecular sieve catalyst for encapsulating metal oxides or metal nanoparticles, a preparation method and application, and the technical characteristics are that a lamellar MFI structure molecular sieve is synthesized, then a silicon support column is used for supporting the lamellar MFI structure molecular sieve and encapsulating the metal oxides or the metal nanoparticles between lamellae, namely, the method is equivalent to the method for encapsulating the metal oxides or the metal nanoparticles by adopting post-treatment modification, and the content of the metal oxides in the whole catalyst is 0.1-5 wt%; in addition, the method needs a plurality of steps and has long crystallization time.
Therefore, the development of a catalyst which has high catalytic efficiency and high selectivity to aromatic compounds and high structural stability in the process of catalyzing the hydrodeoxygenation reaction of phenolic substances and a preparation method thereof are still of great significance.
Disclosure of Invention
The invention aims to provide a small-grain Ni @ Silicalite-1 encapsulated catalyst, a synthesis method and application thereof, wherein the catalyst is an encapsulated catalyst formed by encapsulating metal Ni nano-particles by a Silicalite-1 molecular sieve, the maximum line width of the crystal grains of the catalyst is 0.1-1.5 mu m, the mass percentage content of the metal Ni nano-particles in the catalyst is 0.1-5 wt%, and the metal Ni nano-particles in the catalyst are uniformly distributed and have the grain size of 2-5 nm; the preparation process of the catalyst is synthesized by adopting a three-step method, the performance of the catalyst is obviously superior to that of a metal catalyst prepared by a traditional wet impregnation method, and the obtained catalyst is used for catalyzing the reaction of phenol hydrodeoxygenation and has good phenol conversion rate, aromatic selectivity and catalytic stability.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a small-grained Ni @ Silicalite-1 encapsulated catalyst, which is an encapsulated catalyst formed by encapsulating metallic Ni nanoparticles with a Silicalite-1 molecular sieve, wherein the grains of the catalyst have a maximum line width of 0.1 to 1.5 μm, such as 0.6 μm, 0.8 μm, 1 μm, 1.2 μm, 1.4 μm, etc.; the mass percentage content of the metal Ni nano particles in the catalyst is 0.1-5 wt%, such as 0.5 wt%, 1 wt%, 2 wt%, 3 wt% or 4 wt%; the particle size of the metal Ni nano-particles in the catalyst is 2-5nm, such as 2.5nm, 3nm, 3.5nm, 4nm or 4.5 nm.
The small crystal grains mean that the maximum line width of the crystal grains of the catalyst is 0.1-1.5 mu m.
The maximum line width of the crystal grain refers to a linear distance between two points which are farthest away on the crystal grain, and taking the crystal grain as a cylinder as an example, the maximum line width of the crystal grain refers to the length of a diagonal line of a cross section passing through a central axis of the cylinder.
The catalyst has small grain size, so that the catalyst has excellent catalytic activity and structural stability when being used for catalyzing the hydrogenation deoxidation of phenols, the conversion rate of phenol can reach more than 70 percent in the process of catalyzing the hydrogenation deoxidation reaction of the phenol, and the selectivity of the product benzene is also obviously improved; in the process of catalyzing the hydrogenation and deoxidation reaction of the m-cresol, the conversion rate of the m-cresol can reach more than 40 percent, and the product toluene also has high selectivity.
Preferably, the morphology of the catalyst grains is cylindrical-like.
Preferably, the maximum line width of the crystal grains of the catalyst is 0.5 to 1.5 μm, such as 0.6 μm, 0.8 μm, 1 μm, 1.2 μm, 1.4 μm, or the like.
In a second aspect, the present invention provides a method for synthesizing the small-grained Ni @ Silicalite-1 encapsulated catalyst according to the first aspect, the method comprising the steps of:
(1) sol-gel: carrying out pre-depolymerization and/or alcohol-removing treatment on a silicon source, adding a metal Ni precursor in the process, and stirring and mixing uniformly to obtain gel;
(2) low-temperature nucleation: transferring the gel obtained in the step (1) into a crystallization kettle, and carrying out pre-crystallization nucleation at 80-100 ℃, such as 90 ℃ or 100 ℃ and the like;
(3) high-temperature crystallization: and (3) crystallizing, carrying out solid-liquid separation, roasting and reducing the product obtained in the step (2) at the temperature of 120-170 ℃, such as 120 ℃, 140 ℃, 150 ℃ or 170 ℃ and the like to obtain the catalyst.
The preparation process of the catalyst adopts a three-step method, wherein the first step is sol-gel, namely, a silicon source is subjected to pre-depolymerization and/or alcohol-removing treatment, and a nickel source is added in the process and mixed to form gel; the second step is low-temperature nucleation, namely the obtained gel is subjected to pre-crystallization nucleation at the temperature of 80-100 ℃; the third step is high temperature crystallization, namely crystallization is carried out at the temperature of 120-170 ℃ to obtain the catalyst; performing pre-depolymerization and/or alcohol-removing treatment on a silicon source before pre-crystallization nucleation, and adding a metal Ni precursor to form gel, wherein the operation is favorable for forming uniformly distributed Ni nano-particles; meanwhile, before the crystallization in the step (3), the gel is placed at a lower temperature (80-100 ℃) for pre-crystallization nucleation, and then the crystallization treatment is carried out at a high temperature (120-170 ℃), which is beneficial to controlling the obtained catalyst with small grain size, the maximum line width of the crystal grains of the catalyst prepared by the method is 0.1-1.5 mu m, preferably 0.5-1.5 mu m, and the metal Ni nano-particles in the catalyst are uniformly distributed and have the grain size of 2-5 nm.
The catalyst is used in the process of catalyzing the hydrodeoxygenation of phenol and/or m-cresol, the conversion rate of raw materials is improved, and the selectivity of a product to benzene and/or toluene is obviously improved, so that the consumption of hydrogen in the reaction process is reduced, the energy consumption is reduced, the obvious economic advantage is achieved, and the catalyst has a good application prospect.
In the step (1) of the method of the present invention, the silicon source and the nickel source may be mixed and then subjected to preliminary depolymerization and/or alcohol removal, or the silicon source may be subjected to preliminary depolymerization and/or alcohol removal first and then the metallic Ni precursor may be added.
Preferably, the method of pre-depolymerization in step (1) includes mixing a silicon source, a structure directing agent, an alkali source and water, and heating.
Preferably, the alcohol removing treatment in the step (1) comprises mixing tetraethoxysilane, structure directing agent and water, and heating.
Preferably, the silicon source is selected from any one or a combination of at least two of solid silica gel, white carbon black, silica sol or ethyl orthosilicate, and the combination exemplarily comprises a combination of solid silica gel and white carbon black or a combination of silica sol and ethyl orthosilicate, and the like; preferably, the silica sol is one or a combination of at least two of silica white, silica sol and tetraethoxysilane, and more preferably tetraethoxysilane.
In the preparation process of the catalyst, the selection of the silicon source has higher influence on the crystallinity of the prepared catalyst, and compared with the white carbon black serving as the silicon source, the product obtained by taking the tetraethoxysilane as the silicon source has higher relative crystallinity.
Preferably, the structure directing agent is selected from any one of triethylamine, tributylamine, diisopropylamine, diisobutylamine, isobutylamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetramethylethyldiammonium, or dimethyldiethylammonium hydroxide, or a combination of at least two thereof, which illustratively includes a combination of triethylamine and tributylamine, a combination of diisopropylamine and diisobutylamine, a combination of isobutylamine and tetraethylammonium hydroxide, or a combination of tetrapropylammonium hydroxide, tetramethylethyldiammonium, and dimethyldiethylammonium hydroxide, and the like, preferably tetrapropylammonium hydroxide.
Preferably, the metal Ni precursor is selected from any one of or a combination of at least two of an aqueous nickel nitrate solution, an aqueous nickel chloride solution, an aqueous nickel sulfate solution, a transparent solution of a water-soluble nickel source complexed with ethylenediamine, or a transparent solution of a nickel hydroxide complexed with ethylenediamine, preferably a transparent solution of a water-soluble nickel source complexed with ethylenediamine or a transparent solution of a nickel hydroxide complexed with ethylenediamine, and more preferably a transparent solution of a nickel hydroxide complexed with ethylenediamine.
Preferably, the alkali source is selected from any one or a combination of at least two of sodium hydroxide, potassium hydroxide, ammonia water, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, dimethyldiethylammonium hydroxide or dimethyldipropylammonium hydroxide; the combination illustratively includes a combination of sodium hydroxide and potassium hydroxide, a combination of aqueous ammonia and tetramethylammonium hydroxide, a combination of tetraethylammonium hydroxide and tetrapropylammonium hydroxide, a combination of dimethyldiethylammonium hydroxide and dimethyldipropylammonium hydroxide, or the like, preferably any one of aqueous ammonia, tetramethylammonium hydroxide, tetraethylammonium hydroxide, or tetrapropylammonium hydroxide, or a combination of at least two thereof; the combination illustratively includes a combination of aqueous ammonia and tetramethylammonium hydroxide or a combination of tetraethylammonium hydroxide and tetrapropylammonium hydroxide, etc., preferably tetrapropylammonium hydroxide.
The structure directing agent and the alkali source can be the same substance, for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and dimethyldiethylammonium hydroxide are quaternary ammonium base substances which can be used as the structure directing agent and also can be used as the alkali source, and when monomolecular amine such as triethylamine, tributylamine, diisopropylamine, diisobutylamine or isobutylamine is used as the structure directing agent, the alkali source is required to be added.
Preferably, the heating temperature is 50-80 deg.C, such as 55 deg.C, 60 deg.C, 65 deg.C, 70 deg.C or 75 deg.C, etc., preferably 70-80 deg.C.
Preferably, the heating time is 2-12h, such as 6h, 8h or 10h, etc., preferably 6-12 h.
Preferably, the heating is accompanied by stirring.
Preferably, in the gel of step (1), OH is contained in-The molar ratio of ions to Si is 0.05-0.5, for example 0.1, 0.15, 0.2 or 0.25, preferably 0.1-0.3.
Preferably, in the gel of step (1), the molar ratio of the structure directing agent to Si is 0.05-0.5, such as 0.1, 0.15, 0.2 or 0.25, etc., preferably 0.1-0.3.
Preferably, the molar ratio of water to Si in the gel in step (1) is 10-60, such as 30, 40 or 50, etc., preferably 30-50.
Preferably, in the gel in the step (1), the molar ratio of the Ni element to the Si is 0.01 to 0.1, for example, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, etc., preferably 0.02 to 0.05.
Preferably, in the gel in the step (1), the molar ratio of Si, the structure directing agent, water and Ni element is 1 (0.05-0.5) to (10-60) to (0.01-0.1), such as 1:0.5:60:0.01, 1:0.3:30:0.04 or 1:0.1:10: 0.08.
Preferably, the temperature for nucleation of the pre-crystallization in the step (2) is 90-100 ℃, such as 90 ℃ or 100 ℃, and the like.
Preferably, the time for nucleation in the pre-crystallization in the step (2) is 6-36h, such as 8h, 12h, 16h, 24h or 32h, etc., preferably 12-36 h.
Preferably, the crystallization temperature in step (3) is 120-150 ℃, such as 120 ℃, 140 ℃ or 150 ℃, etc.
Preferably, the crystallization time in step (3) is 12-48h, such as 12h, 24h, 30h, 36h, 42h or 48h, etc., preferably 12-24 h.
Preferably, the solid-liquid separation method in step (3) comprises filtration.
Preferably, the solid-liquid separation further comprises washing.
Preferably, the detergent for washing is water.
Preferably, the temperature of the calcination in step (3) is 500-700 ℃, such as 550 ℃, 600 ℃ or 650 ℃, preferably 550-600 ℃.
Preferably, the roasting time in the step (3) is 5-15h, such as 5h, 8h, 10h, 12h or 14h, etc., preferably 5-10 h.
Preferably, the method for reducing in step (3) comprises heating the reduction under a hydrogen atmosphere.
Preferably, the temperature of the reduction in step (3) is 500-700 ℃, such as 550 ℃, 600 ℃ or 650 ℃, etc.
Preferably, the reduction in step (3) is carried out for a period of 4 to 10 hours, such as 5 hours, 6 hours, 7 hours, 8 hours, 10 hours, or the like.
As a preferred technical scheme of the invention, the method comprises the following steps:
(1) sol-gel: mixing a silicon source, a structure directing agent, water and an alkali source, heating and stirring for 2-12h at 50-80 ℃, adding a metal Ni precursor in the process, and mixing to obtain gel;
OH in the resulting gel-The mol ratio of ions to Si is 0.05-0.5, the mol ratio of the structure directing agent to Si is 0.05-0.5, the mol ratio of water to Si is 10-60, and the mol ratio of Ni element to Si is 0.01-0.1;
(2) low-temperature nucleation: carrying out pre-crystallization nucleation on the gel obtained in the step (1) at the temperature of 80-100 ℃, wherein the time of the pre-crystallization nucleation is 6-36 h;
(3) high-temperature crystallization: crystallizing the product obtained in the step (2) at the temperature of 120-170 ℃, wherein the crystallization time is 12-48h, and carrying out solid-liquid separation, roasting and reduction to obtain the catalyst.
In a third aspect, the present invention provides the use of a catalyst as described in the first aspect for catalysing the hydrodeoxygenation reaction of a phenol, ether or fatty acid.
Preferably, the catalyst is used for phenol gas phase hydrodeoxygenation reactions.
Preferably, the catalyst is used for preparing gasoline and/or diesel oil from the phenol oil.
Preferably, the catalyst is used in the process of the phenol gas phase hydrodeoxygenation reaction, and the reaction temperature is 180-.
Preferably, the catalyst is used in the phenol gas phase hydrodeoxygenation reaction, and the pressure of hydrogen is 0.1-2MPa, such as 0.2MPa, 0.4MPa, 0.6MPa, 0.8MPa, 1MPa, 1.2MPa, 1.4MPa, 1.6MPa or 1.8MPa, and the like, preferably 0.25-0.5 MPa.
Preferably, the phenols comprise phenol and/or m-cresol.
Preferably, the weight space velocity of the phenol is 1-8h-1E.g. 1.5h-1、2h-1、2.5h-1、3h-1、 3.5h-1、4h-1、4.5h-1、5h-1、5.5h-1、6h-1、6.5h-1、7h-1Or 7.5h-1Etc., preferably 4 to 7h-1。
Preferably, the molar ratio of phenol to hydrogen is from 5 to 50, such as 10, 20, 25, 30, 35, 40 or 45, etc., preferably from 10 to 30.
Compared with the prior art, the invention has the following beneficial effects:
(1) the catalyst is a packaged catalyst formed by packaging metal Ni nano-particles by a Silicalite-1 molecular sieve, the catalyst is prepared by a three-step method in the preparation process, the maximum line width of crystal grains of the obtained catalyst is 0.1-1.5 mu m, the mass percentage content of the metal Ni nano-particles in the catalyst is 0.1-5 wt%, and the particle size of the metal Ni nano-particles in the catalyst is 2-5nm, so that the problems of uneven distribution, uneven particle size, easy migration, agglomeration and loss of the metal nano-particles of the catalyst prepared by the traditional impregnation method are solved;
(2) the catalyst has higher activity in the process of catalyzing the phenol hydrodeoxygenation reaction, the conversion rate of the phenol can reach more than 70 percent, and the selectivity of the product benzene can reach more than 90 percent in the process of catalyzing the phenol hydrodeoxygenation reaction by the catalyst; when the catalyst is used for catalyzing the hydrogenation and deoxidation reaction of m-cresol, the conversion rate of p-m-cresol can reach more than 40%, and the selectivity of the product benzene and toluene can reach more than 80%, so that the catalyst is obviously superior to a metal catalyst prepared by an impregnation method.
Drawings
FIG. 1 is an X-ray diffraction pattern of the catalyst prepared in comparative example 1 of the present invention;
FIG. 2 is an SEM photograph of the catalyst prepared in comparative example 1 of the present invention;
FIG. 3 is an X-ray diffraction pattern of the catalyst prepared in comparative example 2 of the present invention;
FIG. 4 is an SEM photograph of the catalyst prepared in comparative example 2 of the present invention;
FIG. 5 is a TEM image of the catalyst prepared in comparative example 2 of the present invention;
FIG. 6 is an X-ray diffraction pattern of the catalyst prepared in example 1 of the present invention;
FIG. 7 is an SEM photograph of the catalyst prepared in example 1 of the present invention;
FIG. 8 is a TEM image of the catalyst prepared in example 1 of the present invention;
FIG. 9 is an X-ray diffraction pattern of the catalyst prepared in example 3 of the present invention;
FIG. 10 is an SEM photograph of the catalyst prepared in example 3 of the present invention;
FIG. 11 is a TEM image of the catalyst prepared in example 3 of the present invention;
FIG. 12 is an X-ray diffraction pattern of the catalyst prepared in example 5 of the present invention;
FIG. 13 is a bar graph of the conversion of phenol and the selectivity values of the products during the use of the catalysts of example 1 and comparative example 2 of the present invention for catalyzing the gas phase hydrodeoxygenation of phenol;
FIG. 14 is a bar graph of the conversion of metacresol and the selectivity value of the product in the process of using the catalysts in example 1 and comparative example 2 of the present invention for catalyzing the gas phase hydrodeoxygenation of metacresol.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. But not to limit the scope of the invention accordingly.
In the examples and comparative examples, the X-ray diffraction (XRD) phase diagrams of the samples were measured on a Siemens D5005 type X-ray diffractometer. The crystallinity of the sample relative to the reference sample, that is, the relative crystallinity, is expressed as the ratio of the sum of diffraction intensities (peak heights) of diffraction characteristic peaks between 22.5 ° and 25.0 ° in 2 θ of the sample and the reference sample. The crystallinity was 100% based on the sample of comparative example 1.
And (3) testing of an SEM spectrogram: scanning electron microscope Quanta 200F type produced by FEI company is adopted; and (3) testing conditions are as follows: and after the sample is dried, evaporating in vacuum to increase the conductivity and the contrast effect, and analyzing the accelerating voltage of an electron microscope to be 20.0kV and the magnification to be 1-30K.
Testing a TEM spectrogram: adopting a JEOL JEM2010F type field emission electron microscope; and (3) testing conditions are as follows: and after the sample is dried, evaporating in vacuum to increase the conductivity and the contrast effect, and analyzing the accelerating voltage of the electron microscope to be 20.0kV and the magnification of 1-20K.
Comparative example 1
The synthesis method of the Silicalite-1 molecular sieve catalyst comprises the following steps:
(1) adding tetraethoxysilane, TPAOH and deionized water into a beaker according to a certain ratio, stirring to remove alcohol, and obtaining uniform silica gel; the mixture ratio is as follows: si, TPAOH and H2The molar ratio of O is 1:0.1: 30;
(2) and transferring the obtained silica gel into a closed crystallization kettle, dynamically crystallizing for 12 hours at the temperature of 170.5 ℃, cooling, taking out a product, and filtering, washing, drying and roasting to obtain the Silicalite-1 molecular sieve.
The X-ray diffraction pattern of the Silicalite-1 molecular sieve prepared in the comparative example is shown in fig. 1, it can be seen from fig. 1 that the product is the Silicalite-1 molecular sieve, the crystallinity of the sample is set as 100%, relative crystallinity data of the catalysts obtained in the other examples and comparative examples are based on the relative crystallinity data, SEM analysis of the pure silicon Silicalite-1 molecular sieve is shown in fig. 2, it can be seen from fig. 2 that the molecular sieve has a uniform appearance, a cylindrical-like shape, the maximum line width of crystal grains is 0.4-1.0 μm, and elemental analysis shows no metal elements, and the pure silicon Silicalite-1 molecular sieve is used.
The catalyst prepared by the comparative example is used for catalyzing the phenol gas-phase hydrodeoxygenation reaction, and the test method is as follows:
the testing process is carried out in a fixed bed reactor, the granularity of the catalyst is 20-40 meshes, the loading amount of the catalyst is 2mL, and the catalytic process conditions are as follows: the reaction pressure is 0.25MPa H2The weight space velocity of phenol is 6.0h-1The molar ratio of hydrogen to phenol is 12.5, and the reaction temperature is 300 ℃;
the detection method comprises the following steps: an instantaneous sample is taken, the product composition is analyzed by using chromatography, and then the phenol conversion rate and the benzene selectivity are calculated.
The catalyst obtained in the comparative example is used for catalyzing the reaction of phenol gas-phase hydrodeoxygenation, phenol is not converted, and the pure silicon Silicalite-1 molecular sieve is proved to have no catalytic activity.
Comparative example 2
In the comparative example, the Silicalite-1 molecular sieve prepared in the comparative example 1 is used as a catalyst carrier, and a Ni/Silicalite-1 catalyst is obtained by loading nickel by an impregnation method; the specific operation mode is as follows:
adding the Silicalite-1 molecular sieve prepared in the comparative example 1 into a nickel nitrate solution, wherein the mass ratio of the Silicalite-1 molecular sieve to nickel element to water is 1:0.1:10, stirring at room temperature for 5 hours to obtain a mixture, drying the mixture in an oven at 105 ℃ for 20 hours, cooling, grinding, roasting at 550 ℃ for 5 hours, and reducing at 500 ℃ for 4 hours in a hydrogen atmosphere to obtain the catalyst.
The X-ray diffraction pattern of the catalyst obtained in this comparative example is shown in fig. 3, and it can be seen from fig. 3 that characteristic diffraction peaks of metallic Ni particles are evident in the diffraction pattern in addition to the Silicalite-1 molecular sieve diffraction peaks, and the relative crystallinity of the catalyst is 75%, thus illustrating that the loss of crystallinity is evident during the preparation of the catalyst by the impregnation method, and SEM and TEM analyses thereof are shown in fig. 4 and 5: more metal Ni particles are distributed on the outer surface of the pure silicon Silicalite-1 molecular sieve, the particles are not uniformly distributed, and the particle size is not uniform and is about 20-50 nm.
The evaluation method of the performance of the catalyst obtained in the comparative example for the phenol gas phase hydrodeoxygenation reaction is exactly the same as that in comparative example 1, and the test results are shown in table 1 and fig. 13.
The catalyst obtained in the comparative example is used for catalyzing the gas-phase hydrodeoxygenation catalytic reaction of m-cresol; the test method comprises the following steps:
the test process is carried out in a fixed bed reactor, the loading amount of the catalyst is 2mL, and the catalytic process conditions are as follows: the reaction pressure is 0.25MPa H2The weight space velocity of m-cresol is 6h-1The molar ratio of hydrogen to m-cresol was 12.5, the reaction temperature was 350 ℃, and the test results are shown in table 2 and fig. 14.
Example 1
The synthesis method of the small-grain Ni @ Silicalite-1 encapsulated catalyst comprises the following steps:
(1) sol-gel: mixing ethyl orthosilicate, tetrapropylammonium hydroxide, nickel nitrate and deionized water, and heating and stirring for 8 hours at the temperature of 80 ℃ to obtain gel without obvious precipitation;
wherein the molar ratio of Si, tetrapropylammonium hydroxide, deionized water and nickel nitrate is 1:0.15:30: 0.04;
(2) low-temperature nucleation: transferring the gel obtained in the step (1) into a crystallization kettle with a polytetrafluoroethylene lining, and carrying out pre-crystallization nucleation at the temperature of 100 ℃, wherein the time of the pre-crystallization nucleation is 24 hours;
(3) high-temperature crystallization: and (3) crystallizing the product obtained in the step (2) at 120 ℃, wherein the crystallization time is 24h, filtering, washing with water until the pH value is close to 7, drying at 100 ℃, heating to 550 ℃ at the heating rate of 2 ℃/min, roasting for 10h, and reducing for 4h under the hydrogen atmosphere at the heating rate of 10 ℃/min to 500 ℃ to obtain the catalyst.
The X-ray diffraction pattern of the catalyst obtained in the example is shown in FIG. 6, and as can be seen from FIG. 6, the diffraction pattern shows that the pure silicon Silicalite-1 molecular sieve has no obvious characteristic diffraction peak of metallic nickel particles, and the relative crystallinity is 106 percent; SEM and TEM analysis are shown in FIG. 7 and FIG. 8, and it can be seen from the figures that the catalyst obtained in this example has uniform morphology, is cylindrical, has a maximum line width of crystal grains of 0.5-1.5 μm, has uniform distribution and particle size of metal Ni nanoparticles of 2-5nm, has smooth surface and no obvious granular substances; the content of metallic Ni in the catalyst was 4.01 wt% by elemental analysis.
The evaluation method of the performance of the catalyst obtained in this example for the gas phase hydrodeoxygenation of phenol was exactly the same as that in comparative example 1, and the test results are shown in table 1 and fig. 13.
The performance evaluation method of the catalyst obtained in this example for catalyzing the gas-phase hydrodeoxygenation catalytic reaction of m-cresol is exactly the same as that in comparative example 2, and the test results are shown in table 2 and fig. 14.
Example 2
The difference between the embodiment and the embodiment 1 is that in the step (1), the adding amount of the raw materials is adjusted to ensure that the molar ratio of Si, tetrapropylammonium hydroxide, deionized water and nickel nitrate is 1:0.1:45: 0.02; and the heating and stirring time in the step (1) is replaced by 6h, and other conditions are completely the same as those in the example 1.
The X-ray diffraction curve of the catalyst in the embodiment shows that the catalyst is a pure silicon Silicalite-1 molecular sieve, has no obvious characteristic diffraction peak of metal nickel particles, the relative crystallinity of the nickel particles is 101 percent, the obtained catalyst is uniform in appearance and similar to a cylinder, the maximum line width of crystal grains is 1.0-1.5 mu m, metal Ni nano particles are uniformly distributed and uniform in particle size, the particle size is 2-5nm, the surface of the catalyst is smooth, and no obvious granular substance exists; the content of metallic Ni in the catalyst was 2 wt% by elemental analysis.
Example 3
This example differs from example 1 in that in step (1), white carbon black, tetrapropylammonium hydroxide and deionized water were mixed, stirred and mixed at 100 ℃ for 10 hours to give a mixture, and then nickel nitrate was added and treated at 60 ℃ for 6 hours to give a gel without significant precipitation, wherein SiO is SiO2The molar ratio of tetrapropylammonium hydroxide, deionized water and nickel nitrate was 1:0.2:45:0.04, and other conditions were exactly the same as compared with example 1.
The X-ray diffraction pattern of the catalyst prepared in this example is shown in fig. 9, and as can be seen from fig. 9, the diffraction pattern shows a pure silicon Silicalite-1 molecular sieve, no characteristic diffraction peak of metallic nickel particles is evident, and the relative crystallinity is 90%; SEM and TEM analysis are shown in FIG. 10 and FIG. 11, and it can be seen from the figures that the catalyst obtained in this example has uniform morphology, is cylindrical, has a maximum line width of crystal grains of 1.0-1.5 μm, has uniform distribution and particle size of metal Ni nanoparticles of 2-5nm, has smooth surface and no obvious granular substances; by element analysis, the content of metal Ni in the catalyst is 4.11 wt%, which is in line with the theoretical feeding.
Example 4
The difference between this example and example 1 is that in step (1), tetraethoxysilane is replaced by alkaline silica sol, and the addition ratio of each raw material is adjusted so that SiO is formed2The molar ratio of tetrapropylammonium hydroxide to deionized water to nickel nitrate was 1:0.1:50:0.04, the heating and stirring temperature was changed to 100 ℃ and the heating and stirring time was changed to 12 hours, and the other conditions were completely the same as those in example 1.
The X-ray diffraction curve of the catalyst in the embodiment shows that the catalyst is a pure silicon Silicalite-1 molecular sieve, has no obvious characteristic diffraction peak of metal nickel particles, the relative crystallinity of the nickel particles is 95%, the SEM and TEM analysis of the obtained catalyst shows that the catalyst is uniform in appearance and cylindrical, the maximum line width of crystal grains is 1.0-1.5 mu m, metal Ni nano particles are uniformly distributed and uniform in particle size, the particle size is 2-5nm, the surface of the catalyst is smooth, and no obvious granular substances exist; by element analysis, the content of metal Ni in the catalyst is 4.07 wt%, which is in line with the theoretical feeding.
Example 5
This example differs from example 1 in that in step (1), holy silica gel, tetrapropylammonium hydroxide and deionized water were mixed, stirred and mixed at 100 ℃ for 10 hours to give a mixture, and then nickel nitrate was added and treated at 60 ℃ for 120 hours to give a gel without significant precipitation, wherein SiO was used as the SiO-phase inhibitor2The molar ratio of tetrapropylammonium hydroxide, deionized water and nickel nitrate was 1:0.3:30:0.04, and other conditions were exactly the same as compared with example 1.
The X-ray diffraction pattern of the catalyst prepared in this example is shown in fig. 12, from which it can be seen that the diffraction pattern shows a pure silicon Silicalite-1 molecular sieve with no distinct diffraction peaks characteristic of metallic nickel particles, but with a relative crystallinity of only 53% and with a maximum line width of the crystallites in the range of 1.0 to 1.5 μm.
Example 6
The difference between this example and example 1 is that the temperature for pre-crystallization nucleation in step (2) is replaced by 80 ℃, the crystallization time is 36h, and other conditions are exactly the same as those in example 1.
The X-ray diffraction curve of the catalyst in the embodiment shows that the catalyst is a pure silicon Silicalite-1 molecular sieve, has no obvious characteristic diffraction peak of metal nickel particles, has 97% relative crystallinity, is uniform in appearance and cylindrical, the maximum line width of crystal grains is 0.2-0.8 mu m, metal Ni nano particles are uniformly distributed and uniform in particle size, the particle size is 2-5nm, the surface of the catalyst is smooth, and no obvious granular substance exists.
Comparative example 3
The comparative example is different from example 1 in that the temperature for crystallization in step (3) is 180 deg.c, and other conditions are identical to those of example 1.
The X-ray diffraction curve of the catalyst in the comparative example shows that the catalyst is a pure silicon Silicalite-1 molecular sieve, has no obvious characteristic diffraction peak of metal nickel particles, has the relative crystallinity of 108 percent, has uniform appearance and cylindrical shape, the maximum line width of crystal grains is 2.0 to 4.0 mu m, the metal Ni nano particles are uniformly distributed and have uniform particle size, the particle size is 2 to 5nm, the surface of the catalyst is smooth, and no obvious granular substance exists.
The evaluation method of the performance of the catalyst obtained in the comparative example for the phenol gas phase hydrodeoxygenation reaction is completely the same as that in the comparative example 1, and the test results are shown in table 1.
The performance evaluation method of the catalyst obtained in the comparative example for catalyzing the gas-phase hydrodeoxygenation catalytic reaction of m-cresol is completely the same as that in the comparative example 2, and the test results are shown in Table 2.
Comparative example 4
This comparative example is different from example 1 in that the operation of step (2) is not performed during the preparation of the catalyst, and other conditions are exactly the same as those in example 1.
The relative crystallinity of the catalyst described in this comparative example was 105%, the maximum line width of the catalyst grains was 3.0 to 6.0 μm, and the particle size of the metallic Ni nanoparticles was 3 to 6 nm.
TABLE 1
As can be seen from the above table, when the catalyst of the present invention is used in the reaction process of catalyzing the hydrodeoxygenation of phenol, the conversion rate of phenol is significantly higher than that of the catalysts obtained in comparative example 2 and comparative example 3, and the product has high selectivity to benzene, wherein the selectivity to benzene can reach more than 90%, so that the cost of product separation is reduced, and the catalyst has significant economic benefits.
TABLE 2
As can be seen from the table above, when the catalyst of the invention is used for catalyzing the hydrodeoxygenation reaction of m-cresol, the conversion rate of m-cresol is obviously higher than that of the catalysts prepared by the impregnation method in the comparative examples 2 and 3, and the selectivity of the catalyst to the product toluene is obviously improved and can reach more than 80%.
With respect to the stability of the catalyst, the catalyst in example 1 of the present invention has high stability, and no obvious deactivation phenomenon is observed when the reaction is continuously carried out for 15 hours in the process of catalyzing the gas-phase hydrodeoxygenation of phenol or the gas-phase hydrodeoxygenation of m-cresol, while the catalyst in comparative example 2 has poor stability and gradually deactivates as the catalytic reaction is carried out.
The conversion rate of phenol and the selectivity value of each product in the process of catalyzing the gas-phase hydrodeoxygenation reaction of phenol by using the catalyst obtained in the example 1 are shown in fig. 13, and as can be seen from fig. 13, under the same test conditions, compared with the catalyst prepared by adopting the impregnation method in the comparative example 2, the catalytic activity and the selectivity to the product benzene of the catalyst are both obviously improved.
The conversion rate of the intermediate cresol and the selectivity value of each product in the process of using the catalyst obtained in the example 1 of the invention to catalyze the gas-phase hydrodeoxygenation reaction of the intermediate cresol are shown in fig. 14, and as can be seen from fig. 14, under the same test conditions, compared with the catalyst prepared by adopting the impregnation method in the comparative example 2, the catalyst of the invention has obviously improved catalytic activity and selectivity to the product toluene.
The above description is only for the specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the protection scope and the disclosure of the present invention.
Claims (39)
1. A synthetic method of a small-grain Ni @ Silicalite-1 encapsulated catalyst is characterized by comprising the following steps of:
(1) sol-gel: carrying out pre-depolymerization and/or alcohol-removing treatment on a silicon source, adding a metal Ni precursor in the process, and stirring and mixing uniformly to obtain gel;
(2) low-temperature nucleation: transferring the gel obtained in the step (1) into a crystallization kettle to perform pre-crystallization nucleation for 6-36h at 90-100 ℃;
(3) high-temperature crystallization: crystallizing the product obtained in the step (2) at the temperature of 120-150 ℃, for 12-48h, carrying out solid-liquid separation, roasting and reducing to obtain the catalyst;
the catalyst is an encapsulated catalyst formed by encapsulating metallic Ni nano-particles by a Silicalite-1 molecular sieve, the maximum line width of crystal grains of the catalyst is 0.5-1.5 mu m, the mass percentage content of the metallic Ni nano-particles in the catalyst is 0.1-5 wt%, and the particle size of the metallic Ni nano-particles in the catalyst is 2-5 nm.
2. The method of claim 1, wherein the pre-depolymerization process of step (1) includes mixing a silicon source, a structure directing agent, an alkali source, and water, and heating.
3. The method of claim 2, wherein the silicon source is selected from any one of solid silica gel, silica white, silica sol or ethyl orthosilicate or a combination of at least two of the above.
4. The method according to claim 2, wherein the silicon source is any one of white carbon black, silica sol or ethyl orthosilicate or a combination of at least two of the white carbon black, the silica sol and the ethyl orthosilicate.
5. The method of claim 2, wherein the structure directing agent is selected from the group consisting of any one or a combination of at least two of triethylamine, tributylamine, diisopropylamine, diisobutylamine, isobutylamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetramethylethyldiammonium, or dimethyldiethylammonium hydroxide.
6. The method of claim 5, wherein the structure directing agent is tetrapropylammonium hydroxide.
7. The method of claim 2, wherein the alkali source is selected from the group consisting of sodium hydroxide, potassium hydroxide, aqueous ammonia, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, dimethyldiethylammonium hydroxide, and dimethyldipropylammonium hydroxide, either alone or in combination with at least two thereof.
8. The method of claim 7, wherein the alkali source is selected from the group consisting of any one of ammonia, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropylammonium hydroxide, or a combination of at least two thereof.
9. The method of claim 8, wherein the alkali source is tetrapropylammonium hydroxide.
10. The method of claim 2, wherein the heating is at a temperature of 50-80 ℃.
11. The method of claim 10, wherein the heating is at a temperature of 70-80 ℃.
12. The method of claim 2, wherein the heating time is from 2 to 12 hours.
13. The method of claim 12, wherein the heating time is 6-12 hours.
14. The method of claim 2, wherein the heating is accompanied by stirring.
15. The method of claim 1, wherein in step (1) the gel is OH-The molar ratio of the ions to the Si is 0.05-0.5.
16. The method of claim 15, wherein in step (1) the gel is OH-The molar ratio of the ions to the Si is 0.1-0.3.
17. The method of claim 1, wherein the molar ratio of structure directing agent to Si in the gel of step (1) is from 0.05 to 0.5.
18. The method of claim 17, wherein the molar ratio of structure directing agent to Si in the gel of step (1) is from 0.1 to 0.3.
19. The method of claim 1, wherein the molar ratio of water to Si in the gel of step (1) is 10 to 60.
20. The method of claim 19, wherein the molar ratio of water to Si in the gel of step (1) is from 30 to 50.
21. The method according to claim 1, wherein the molar ratio of the Ni element to the Si in the gel in the step (1) is 0.01 to 0.1.
22. The method of claim 21, wherein the molar ratio of Ni element to Si in the gel of step (1) is 0.02 to 0.05.
23. The method of claim 1, wherein the time for nucleation for pre-crystallization in step (2) is 12-36 h.
24. The method of claim 1, wherein the crystallization time of step (3) is 12-24 hours.
25. The method of claim 1, wherein the method comprises the steps of:
(1) sol-gel: mixing a silicon source, a structure directing agent, water and an alkali source, heating and stirring for 2-12h at 50-80 ℃, adding a metal Ni precursor in the process, and mixing to obtain gel;
OH in the resulting gel-The mol ratio of ions to Si is 0.05-0.5, the mol ratio of the structure directing agent to Si is 0.05-0.5, the mol ratio of water to Si is 10-60, and the mol ratio of Ni element to Si is 0.01-0.1;
(2) low-temperature nucleation: carrying out pre-crystallization nucleation on the gel obtained in the step (1) at the temperature of 90-100 ℃, wherein the time of the pre-crystallization nucleation is 6-36 h;
(3) high-temperature crystallization: crystallizing the product obtained in the step (2) at the temperature of 120-150 ℃, wherein the crystallization time is 12-48h, and carrying out solid-liquid separation, roasting and reduction to obtain the catalyst.
26. A small-grained Ni @ Silicalite-1 encapsulated catalyst obtained by the method of any one of claims 1 to 25, wherein the catalyst is an encapsulated catalyst formed by encapsulating metallic Ni nanoparticles with a Silicalite-1 molecular sieve, the maximum line width of the grains of the catalyst is 0.5 to 1.5 μm, the mass percentage of the metallic Ni nanoparticles in the catalyst is 0.1 to 5 wt%, and the particle size of the metallic Ni nanoparticles in the catalyst is 2 to 5 nm.
27. The catalyst of claim 26, wherein the catalyst has a columnar-like morphology.
28. Use of a catalyst according to claim 26 or 27 for catalysing the hydrodeoxygenation of phenols, ethers or fatty acids.
29. The use of claim 28, wherein the catalyst is used in a phenol gas phase hydrodeoxygenation reaction.
30. The use of claim 28, wherein the catalyst is used in the production of gasoline and/or diesel from phenolic oil.
31. The use of claim 28, wherein the catalyst is used in a phenol gas phase hydrodeoxygenation reaction at a temperature of 180 ℃ to 480 ℃.
32. The use of claim 31, wherein the reaction temperature is 250-350 ℃.
33. The use according to claim 29, wherein the catalyst is used in a phenol gas phase hydrodeoxygenation process at a hydrogen pressure of from 0.1 to 2 MPa.
34. The use of claim 33, wherein the catalyst is used in a phenol gas phase hydrodeoxygenation process at a hydrogen pressure of from 0.25 to 0.5 MPa.
35. Use according to claim 29, wherein the phenol comprises phenol and/or m-cresol.
36. As claimed in claim35, characterized in that the weight space velocity of the phenol is 1-8h-1。
37. The use of claim 36, wherein the phenol has a weight space velocity of 1.5 to 6h-1。
38. The use of claim 35, wherein the phenol to hydrogen molar ratio is from 5 to 50.
39. The use according to claim 38, wherein the molar ratio of phenol to hydrogen is from 10 to 30.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103100415A (en) * | 2012-12-03 | 2013-05-15 | 北京化工大学 | Catalyst with active component nano particles embedded in molecular sieve to crystallize, method and application |
| CN106669768A (en) * | 2017-01-09 | 2017-05-17 | 吉林大学 | Metal@Sillicalite-1 molecular sieve loading super-small noble metal particles, preparation method and application |
| CN106745025A (en) * | 2016-11-17 | 2017-05-31 | 阳泉煤业（集团）有限责任公司 | A kind of synthetic method of the HTSs of TS 1 |
| CN107790170A (en) * | 2017-11-02 | 2018-03-13 | 中国科学院上海高等研究院 | Methane dry reforming catalyst and its production and use |
| CN109231235A (en) * | 2018-06-04 | 2019-01-18 | 吉林化工学院 | A kind of preparation method of nano-ZSM-5 molecular sieve |
| CN109277112A (en) * | 2017-07-20 | 2019-01-29 | 万华化学集团股份有限公司 | A method of catalyst based on silicalite-1 molecular sieve and 1,2- pentanediol is prepared with it |
| CN109647495A (en) * | 2018-11-16 | 2019-04-19 | 天津大学 | A kind of preparation method of Ni-based methane dry reforming catalyst |
| CN109647493A (en) * | 2019-01-30 | 2019-04-19 | 中国科学院过程工程研究所 | A kind of pure silicon S-1 molecular sieve catalyst of package metals nano particle, preparation method and applications |
| CN109731608A (en) * | 2019-01-30 | 2019-05-10 | 中国科学院过程工程研究所 | A kind of bifunctional catalyst and preparation method thereof without sodium Si-Al molecular sieve of package metals nano particle |
| CN110028983A (en) * | 2019-04-26 | 2019-07-19 | 河南百优福生物能源有限公司 | A kind of method that biomass pyrolysis liquid hydrogenation deoxidation oil prepares aromatic hydrocarbons |
| CN110368982A (en) * | 2019-07-25 | 2019-10-25 | 大连理工大学 | Non-noble metal nano cluster catalyst and preparation method and application are stablized in Silicalite-1 molecular sieve pore passage confinement |
| CN110479353A (en) * | 2019-08-08 | 2019-11-22 | 吉林大学 | A kind of catalyst and its preparation method and application |
-
2019
- 2019-12-04 CN CN201911225887.3A patent/CN111298826B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103100415A (en) * | 2012-12-03 | 2013-05-15 | 北京化工大学 | Catalyst with active component nano particles embedded in molecular sieve to crystallize, method and application |
| CN106745025A (en) * | 2016-11-17 | 2017-05-31 | 阳泉煤业（集团）有限责任公司 | A kind of synthetic method of the HTSs of TS 1 |
| CN106669768A (en) * | 2017-01-09 | 2017-05-17 | 吉林大学 | Metal@Sillicalite-1 molecular sieve loading super-small noble metal particles, preparation method and application |
| CN109277112A (en) * | 2017-07-20 | 2019-01-29 | 万华化学集团股份有限公司 | A method of catalyst based on silicalite-1 molecular sieve and 1,2- pentanediol is prepared with it |
| CN107790170A (en) * | 2017-11-02 | 2018-03-13 | 中国科学院上海高等研究院 | Methane dry reforming catalyst and its production and use |
| CN109231235A (en) * | 2018-06-04 | 2019-01-18 | 吉林化工学院 | A kind of preparation method of nano-ZSM-5 molecular sieve |
| CN109647495A (en) * | 2018-11-16 | 2019-04-19 | 天津大学 | A kind of preparation method of Ni-based methane dry reforming catalyst |
| CN109647493A (en) * | 2019-01-30 | 2019-04-19 | 中国科学院过程工程研究所 | A kind of pure silicon S-1 molecular sieve catalyst of package metals nano particle, preparation method and applications |
| CN109731608A (en) * | 2019-01-30 | 2019-05-10 | 中国科学院过程工程研究所 | A kind of bifunctional catalyst and preparation method thereof without sodium Si-Al molecular sieve of package metals nano particle |
| CN110028983A (en) * | 2019-04-26 | 2019-07-19 | 河南百优福生物能源有限公司 | A kind of method that biomass pyrolysis liquid hydrogenation deoxidation oil prepares aromatic hydrocarbons |
| CN110368982A (en) * | 2019-07-25 | 2019-10-25 | 大连理工大学 | Non-noble metal nano cluster catalyst and preparation method and application are stablized in Silicalite-1 molecular sieve pore passage confinement |
| CN110479353A (en) * | 2019-08-08 | 2019-11-22 | 吉林大学 | A kind of catalyst and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| "Silicalite-1晶体形貌和尺寸的调控及MFI型分子筛膜的制备";鲁慧彬;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》;20160315(第03期);第30-31、40-41页 * |
| "Temperature-Dependent Selectivity of Hydrogenation/Hydrogenolysis during Phenol Conversion over Ni Catalysts";Yanchun Shi et al.;《ACS Sustainable Chemistry & Engineering》;20190422;第7卷;实验部分、摘要和表1 * |
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