Molecular sieve catalyst, its preparation method and application

Abstract

The present application relates to a kind of molecular sieve catalyst and its preparation method and application, the molecular sieve catalyst includes M-X molecular sieve;Wherein, M includes Rh element, Co element, Ir element, Au element or Fe element any one or at least two combinations;X includes C element, N element or P element at least two combinations.The molecular sieve catalyst provided by the present application is applied to hydroformylation, the microenvironment of active metal M is regulated by adjuvant X, the nonlinear adsorption ratio of M and olefin is improved, then the generation of isomerized aldehyde is promoted, the normal / isomerized ratio of generated aldehyde is reduced, and new industrialized technology is provided for olefin hydroformylation reaction to produce isomerized aldehyde.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of catalyst technology, in particular to a molecular sieve catalyst and a preparation method and application thereof. BACKGROUND

[0002] Hydroformylation, also known as oxo synthesis or hydrocarbonylation, is an industrial process for converting alkenes to aldehydes in the presence of CO and H2. Since the discovery of the hydroformylation reaction by German scientist Otto Roelen in the Ruhrchemie laboratory in Oberhausen in 1938, and the construction of the first industrial unit in the early 1940s, the study of the hydroformylation of alkenes has never ceased. Hydroformylation technology has become one of the most important petrochemical technologies because the product aldehyde is a very useful chemical intermediate that can be used to synthesize carboxylic acids and their corresponding esters, and fatty amines, and most importantly, it can be hydrogenated to form alcohols, which can be used as organic solvents, plasticizers and surfactants, and widely used in the field of fine chemicals.

[0003] The process often uses transition metals as catalysts and requires treatment of alkenes with carbon monoxide and hydrogen, usually at high pressure (10 to 100 atmospheres), at temperatures of 40 to 200°C. The key consideration for hydroformylation is the "normal" versus "iso" selectivity. For example, the hydroformylation of propylene can provide two isomeric products, butyraldehyde or isobutyraldehyde. The product of traditional hydroformylation is mainly normal aldehyde, and most of the research on related catalysts focuses on increasing the proportion of straight-chain aldehyde. Existing processes mainly use homogeneous catalysis of rhodium-based and cobalt-based phosphine ligand systems, and the modification of the microenvironment of the active metal by the phosphine ligand promotes the formation of normal aldehydes. For example, CN101768060A discloses the application of a substituted bidentate phosphoramidite ligand with a benzophenone skeleton in the catalytic hydroformylation reaction and the isomerization-hydroformylation reaction of internal alkenes; the ligand is reacted with a Rh salt in an organic solvent under an inert gas or N2 atmosphere to obtain a ligand / Rh catalyst. The solution of the ligand / Rh catalyst is added to the solution of the ligand / Rh catalyst under an inert gas or N2 atmosphere, CO and H2 are filled, and the hydroformylation product, i.e., a compound containing an aldehyde group, is obtained. The reaction has high conversion rate and excellent selectivity of normal aldehyde product.

[0004] In recent years, the research results of heterogeneous hydroformylation have been emerging, and the common heterogeneous catalyst is a non-phosphine ligand system, which has the characteristics of high activity. For example, CN109876847A discloses a heterogeneous core-shell catalyst of molecular sieve encapsulated rhodium applied to olefin hydroformylation and a catalytic method thereof. Submicron Silicalite-1 (S-1) zeolite molecular sieve crystal grains are used to load rhodium ions as crystal seeds, and the S-1 shell layer is induced to grow, so that the rhodium catalytic active species is encapsulated in the S-1 zeolite molecular sieve to form a core-shell Rh@S-1 catalyst, which is applied to the synthesis of normal aldehydes by heterogeneous hydroformylation. The n / i ratio of the hydroformylation product is 1.1-2.0. However, there is still a lot of room for improvement in terms of long-term stability of the catalyst and regulation of aldehyde selectivity, especially in promoting the generation of isomeric aldehydes.

[0005] In recent years, the downstream applications of isomeric aldehydes have been continuously developed, including isobutyric acid, neopentyl glycol (NPG), 2,2,4-trimethyl-1,3-pentanediol, isovaleric acid, etc. Therefore, there is an urgent need in the art to develop a catalyst with excellent isomeric aldehyde selectivity to meet the current industrial needs. SUMMARY

[0006] To solve the above technical problems, the present application provides a molecular sieve catalyst and its preparation method and application. In the hydroformylation, the molecular sieve catalyst can promote the generation of isomeric aldehydes, has high aldehyde selectivity, ensures high conversion rate, and reduces the n / i ratio of the generated aldehydes, effectively solving the problem of high alkane selectivity of the non-phosphine ligand system heterogeneous catalyst.

[0007] To achieve this purpose, the present application adopts the following technical solutions:

[0008] In a first aspect, the present application provides a molecular sieve catalyst, which comprises M-X@ molecular sieve.

[0009] Wherein, M comprises any one or a combination of at least two of Rh element, Co element, Ir element, Au element or Fe element;

[0010] X comprises a combination of at least two of C element, N element or P element.

[0011] The molecular sieve catalyst provided by the present application comprises metal elements, non-metallic additives and a molecular sieve carrier, wherein the additives comprise at least two of C elements, N elements or P elements, the addition of which can effectively regulate the microenvironment of the active metal, promote the selective adsorption of olefins and realize the generation of isomeric aldehydes; the molecular sieve with different topological structures is used as the carrier, the porous structure of which ensures the uniform distribution of active sites and improves the stability of the catalyst. Compared with the traditional homogeneous catalyst, the molecular sieve catalyst provided by the present application is easier to separate, has higher catalytic activity and higher stability, and has mild and non-harsh operating conditions. In the hydrogenation reaction, the catalyst has excellent performance in selectively generating isomeric aldehydes, can avoid the generation of a large amount of normal aldehydes, can meet the demand for isomeric aldehydes and effectively reduces the production cost of isomeric aldehydes, thereby providing a new industrialized technology for promoting the generation of isomeric aldehydes in the olefin hydrogenation reaction.

[0012] The term "molecular sieve" can be understood as being loaded on a molecular sieve carrier. For example, "M-X@molecular sieve" can be understood as M-X loaded on a molecular sieve carrier. Other similar expressions are the same, and are not described in detail for the sake of brevity.

[0013] Preferably, the molecular sieve comprises any one or a combination of at least two of S-1, ZSM-5, SAPO-34, HY, SBA-15 or MCM-41.

[0014] Preferably, the mass content of M in the molecular sieve catalyst is 0.01-10%, for example, can be 0.02%, 0.05%, 0.1%, 0.2%, 0.5%, 1%, 2%, 5% or 8% and the like.

[0015] Preferably, the mass content of X in the molecular sieve catalyst is 0.1-50%, for example, can be 0.2%, 0.5%, 1%, 1.5%, 2%, 5%, 8%, 10%, 20%, 30% or 40% and the like.

[0016] Preferably, X in the molecular sieve catalyst comprises a combination of N elements and P elements.

[0017] Preferably, the molar ratio of the N elements to the P elements is (0.1-10):1, wherein the specific value of (0.1-10) can be 0.2, 0.5, 0.8, 1, 2, 3, 5, 7 or 9 and the like.

[0018] As a preferred technical solution of the present application, when the molecular formula catalyst simultaneously comprises N elements and P elements and the two are in a specific ratio range, the normal / isomeric ratio of the generated aldehyde is further reduced. The appropriate ratio of the N elements to the P elements is matched with the active metal, and the electronic effect is given to the catalyst to make the catalyst have excellent selectivity for the target product isomeric aldehyde.

[0019] In a second aspect, the present application provides a preparation method of the molecular sieve catalyst according to the first aspect, characterized in that the preparation method comprises the following steps:

[0020] (1) synthesis of M@molecular sieve: mixing a molecular sieve precursor with a M-containing compound to obtain the M@molecular sieve;

[0021] (2) synthesis of M-X@molecular sieve: mixing the M@molecular sieve obtained in step (1) with an X precursor to obtain the M-X@molecular sieve.

[0022] Preferably, the synthesis of the M@molecular sieve comprises the following steps:

[0023] mixing a silica-alumina gel with a M-containing compound solution and an organic template agent in sequence to obtain a mixed gel, and crystallizing and calcining the mixed gel to obtain the M@molecular sieve.

[0024] Preferably, the silica-alumina gel is obtained by mixing a silicon source, an aluminum source and a solvent.

[0025] Preferably, the silicon source comprises any one or a combination of at least two of silica gel, silica sol or organosilicate.

[0026] Preferably, the aluminum source is any one or a combination of at least two of pseudoboehmite, aluminum sesquioxide, sodium aluminate, variscite, gibbsite, aluminum isopropoxide or aluminum nitrate.

[0027] Preferably, the molar ratio of the silicon source to the aluminum source is 1:(0.05-0.4), and the specific value of (0.05-0.4) can be 0.08, 0.1, 0.15, 0.2 or 0.3, etc.

[0028] Preferably, the solvent comprises water.

[0029] Preferably, the mass ratio of the solvent to the silicon source is (1-10):1, and the specific value of (1-10) can be 2, 3, 4, 5, 6 or 8, etc. Preferably, the molar ratio of the M-containing compound to the silicon source is (10 -6 -10 -1 ):1, and the specific value of (10 -6 -10 -1 ) can be 10 -5 , 10 -4 , 10 -3 , 10 -2 or 0.05, etc.

[0030] Preferably, the M-containing compound comprises any one or a combination of at least two of rhodium chloride, rhodium nitrate, rhodium acetylacetonate, cobalt nitrate, cobalt chloride, cobalt acetate, iridium chloride, iridium carbonyl, iridium fluoride, hexachloro iridate, chloroauric acid, ferric nitrate or ferric chloride.

[0031] Preferably, the concentration of the M-containing compound in the M-containing compound solution is 0.1-5 g / L, for example, it can be 0.2 g / L, 0.5 g / L, 0.8 g / L, 1 g / L, 1.5 g / L, 2 g / L, 3 g / L or 4 g / L, etc.

[0032] Preferably, the solvent in the M-containing compound solution comprises water.

[0033] Preferably, the mass ratio of the organic template agent to the silicon source is 1:(0.5-5), wherein the specific value of (0.5-5) can be 0.8, 1, 2, 3 or 4, etc.

[0034] Preferably, the organic template agent comprises any one or a combination of at least two of tetraethylammonium hydroxide, tetrapropylammonium hydroxide or di-n-propylamine.

[0035] Preferably, the operation of mixing comprises stirring.

[0036] Preferably, the temperature of the mixing is 20-40℃, for example, it can be 22℃, 25℃, 28℃, 30℃, 32℃, 35℃ or 38℃, etc.

[0037] Preferably, the time of the mixing is 0.2-5h, for example, it can be 0.5h, 0.8h, 1h, 1.5h, 2h, 3h or 4h, etc.

[0038] Preferably, the temperature of the crystallization is 80-200℃, for example, it can be 100℃, 120℃, 140℃, 160℃ or 180℃, etc.

[0039] Preferably, the time of the crystallization is 2-6 days, for example, it can be 2.5 days, 3 days, 3.5 days, 4 days, 4.5 days, 5 days or 5.5 days, etc.

[0040] Preferably, after the crystallization, filtering, washing and drying are performed.

[0041] Preferably, the temperature of the drying is 50-150℃, for example, it can be 60℃, 80℃, 100℃, 120℃ or 140℃, etc.

[0042] Preferably, the time of the drying is 12-48h, for example, it can be 16h, 20h, 24h, 28h, 32h, 36h, 40h or 44h, etc.

[0043] Preferably, the temperature of the calcination is 200-800℃, for example, it can be 250℃, 300℃, 350℃, 400℃, 450℃, 500℃, 550℃, 600℃, 650℃, 700℃ or 750℃, etc.

[0044] Preferably, the time of the calcination is 6-48h, for example, it can be 8h, 10h, 12h, 24h or 36h, etc.

[0045] Preferably, the X precursor comprises any one or a combination of at least two of phosphorus trichloride, diphenylphosphine, triphenylphosphine, tributylphosphine, urea, ammonium chloride, biuret, melamine, glucose, carbon nitride or activated carbon.

[0046] Preferably, the mass ratio of the M@molecular sieve to the X precursor is 1:(0.1-3), wherein the specific value of (0.1-3) can be 0.2, 0.5, 0.8, 1, 1.5, 2 or 2.5, etc.

[0047] Preferably, in step (2), the operation of the mixing comprises grinding.

[0048] Preferably, in step (2), the reaction is carried out in a hydrogen gas and a protective gas atmosphere.

[0049] Preferably, the protective gas comprises any one or a combination of at least two of argon, nitrogen or helium.

[0050] Preferably, the volume fraction of hydrogen in the hydrogen gas and the protective gas is 1-10%, for example, it can be 3%, 5%, 7% or 9%, etc.

[0051] Preferably, in step (2), the temperature of the reaction is 300-800℃, for example, it can be 350℃, 400℃, 500℃, 600℃ or 700℃, etc.

[0052] Preferably, in step (2), the time of the reaction is 2-6h, for example, it can be 2.5h, 3h, 3.5h, 4h, 4.5h, 5h or 5.5h, etc.

[0053] Preferably, the preparation method comprises the following steps:

[0054] (1) Synthesis of M@molecular sieve: molecular sieve precursor and solvent are mixed under room temperature to obtain a mixed gel, the mixed gel is stirred with a solution containing M compound under room temperature, and then an organic template is added thereto under room temperature for 0.2-3h, and then transferred to a hydrothermal synthesis reactor, heated to 80-200℃ for crystallization for 2-6 days, filtered, washed, dried at 50-150℃ in an air atmosphere for 12-48h, and then calcined at 200-800℃ for 6-48h to obtain the M@molecular sieve.

[0055] (2) Synthesis of M-X@ molecular sieve: the M@ molecular sieve obtained in step (1) is ground with X precursor, and is reacted at 300-800℃ for 2-6h under a H2-protective gas atmosphere with a hydrogen volume fraction of 1-10%, and is naturally cooled to room temperature to obtain the M-X@ molecular sieve.

[0056] The preparation method of the molecular sieve catalyst provided by the present application first encapsulates the active metal M in the molecular sieve to obtain M@ molecular sieve, then grinds the M@ molecular sieve solid with the X precursor of the auxiliary agent, and finally obtains the M-X@ molecular sieve catalyst through reduction treatment. After high-temperature reduction treatment, the molecular sieve catalyst only leaves at least two of P, C or N elements as an auxiliary agent, and a nanocomposite catalyst is obtained. Compared with the traditional phosphine ligand homogeneous system hydroformylation catalyst, the heterogeneous catalyst has higher activity, is stable in an oxygen-containing and water-containing environment, and does not require harsh operating conditions.

[0057] In a third aspect, the present application provides a use of the molecular sieve catalyst according to the first aspect in catalyzing a hydroformylation reaction.

[0058] In a fourth aspect, the present application provides a preparation method of an isomeric aldehyde, which comprises the following steps:

[0059] reacting an olefin, carbon monoxide, hydrogen and a catalyst to obtain the isomeric aldehyde;

[0060] wherein the catalyst comprises the molecular sieve catalyst according to the first aspect.

[0061] Preferably, the molar ratio of the olefin to M in the catalyst is (1-10000):1, and the specific value of (1-10000) can be, for example, 5, 10, 50, 100, 500, 1000, 5000 or 8000, etc.

[0062] Preferably, the olefin comprises any one or a combination of at least two of C3-C20 olefins, such as C4, C5, C6, C8, C10, C12, C14, C16 or C18 olefin, etc.

[0063] Preferably, the olefin comprises any one or a combination of at least two of α-olefins.

[0064] Preferably, the total pressure of the carbon monoxide and hydrogen is 0.1-10MPa, which can be, for example, 0.5MPa, 0.8MPa, 1MPa, 1.5MPa, 2MPa, 3MPa, 5MPa or 8MPa, etc., and is further preferably 0.2-6MPa.

[0065] Preferably, the pressure ratio of hydrogen to carbon monoxide is (0.1-5):1, wherein the specific value of (0.1-5) can be 0.2, 0.5, 0.8, 1, 1.5, 2, 3 or 4, etc., and further preferably (0.1-2):1.

[0066] Preferably, the temperature of the reaction is 60-200℃, such as 80℃, 100℃, 120℃, 140℃, 160℃ or 180℃, etc.

[0067] Preferably, the time of the reaction is 1-24h, such as 2h, 4h, 6h, 10h, 12h, 16h or 20h, etc.

[0068] Preferably, the mixing is carried out in the presence of an organic solvent.

[0069] Preferably, the organic solvent comprises any one or a combination of at least two of toluene, tetrahydrofuran or ethyl acetate.

[0070] Preferably, the reaction is carried out under stirring.

[0071] Preferably, the rate of the stirring is 100-800rpm, such as 200rpm, 300rpm, 400rpm, 500rpm, 600rpm or 700rpm, etc.

[0072] Compared with the prior art, the present application has at least the following beneficial effects:

[0073] The molecular sieve catalyst provided by the present application introduces a combination of at least two of C, N or P as an additive to regulate the microenvironment of the active metal M, increase the nonlinear adsorption ratio of M and olefins, and further promote the generation of isomeric aldehydes, reduce the n-iso ratio (n / i ratio) of the generated aldehydes, the conversion rate in the product of hydroformylation is ≥83.1%, the aldehyde selectivity is ≥89.8%, the alkane selectivity in the product is ≤0.9mol%, the ratio of n-aldehyde and iso-aldehyde is below 0.32, the selectivity of iso-aldehyde is high, and the application effect in the olefin hydroformylation reaction is excellent. DETAILED DESCRIPTION

[0074] In order to facilitate the understanding of the present application, the present application lists the following embodiments. It should be understood by those skilled in the art that the embodiments are only to help understand the present application, and should not be regarded as a specific limitation on the present application.

[0075] In the following specific embodiments of the present application, the materials involved are all commercially available products.

[0076] Unless otherwise specified, in the present application, the "room temperature" refers to 20-40℃.

[0077] Example 1

[0078] A molecular sieve catalyst Rh-N-P@Zeolite is prepared by the following method:

[0079] (1) Synthesis of molecular sieve Rh@Zeolite

[0080] Take 8.4 g of tetraethyl orthosilicate and 0.4 g of pseudoboehmite (molecular weight 71) and add them to 30 g of water, stir for 2 h to form a mixed gel. Take 2.6 mg of rhodium trichloride trihydrate and add it to 5 mL of deionized water, mix well and then add it to the mixed gel, and stir at room temperature for 0.5 h; then add 4.5 g of the organic template tetraethylammonium hydroxide, stir at room temperature for 1 h; transfer to a 100 mL hydrothermal synthesis reactor, crystallize at 170 °C for 4 days; cool the autoclave to room temperature to obtain a crude molecular sieve; filter and wash the crude molecular sieve to obtain a white solid, place it in an oven at 100 °C for drying for 24 h, then place the sample in a muffle furnace and heat it to 550 °C for calcination for 12 h to obtain the molecular sieve Rh@Zeolite.

[0081] (2) Synthesis of molecular sieve catalyst Rh-N-P@Zeolite

[0082] Grind 1.0 g of the molecular sieve Rh@Zeolite solid with the additives ammonium chloride (0.5 g, n(N) = 0.01 mol) and phosphorus trichloride (0.3 g, n(P) = 0.002 mol), then heat treat at 400 °C for 4 h under a 5% H2 / Ar atmosphere, and then naturally cool to room temperature to obtain the molecular sieve catalyst.

[0083] Example 2

[0084] A molecular sieve catalyst Rh-C-P@Zeolite is prepared by the following method:

[0085] (1) Synthesis of molecular sieve Rh@Zeolite

[0086] Take 8.4 g of tetraethyl orthosilicate and 0.5 g of pseudoboehmite (molecular weight 71) and add them to 30 g of water, stir for 1 h to form a mixed gel. Take 3.7 mg of rhodium trichloride trihydrate and add it to 5 mL of deionized water, mix well and then add it to the mixed gel, and stir at room temperature for 1 h; then add 4.9 g of the organic template tetrapropylammonium hydroxide, stir at room temperature for 1 h; transfer to a 100 mL hydrothermal synthesis reactor, crystallize at 180 °C for 3 days; cool the autoclave to room temperature to obtain a crude molecular sieve; filter and wash the crude molecular sieve to obtain a white solid, place it in an oven at 100 °C for drying for 12 h, then place the sample in a muffle furnace and heat it to 500 °C for calcination for 6 h to obtain the molecular sieve Rh@Zeolite.

[0087] (2) Synthesis of a molecular sieve catalyst Rh-C-P@Zeolite

[0088] The molecular sieve catalyst Rh-C-P@Zeolite was prepared by the following method: 1.0 g of the molecular sieve Rh@Zeolite solid was ground with the co-catalyst glucose (0.5 g) and triphenylphosphine (0.3 g), and then heat-treated at 450°C for 6 h under a 5% H2 / Ar atmosphere, and naturally cooled to room temperature to obtain the molecular sieve catalyst.

[0089] Example 3

[0090] A molecular sieve catalyst Rh-C-N@Zeolite was prepared by the following method:

[0091] (1) Synthesis of a molecular sieve Rh@Zeolite

[0092] A mixed gel was formed by adding 8.4 g of tetraethyl orthosilicate and 0.3 g of pseudoboehmite (molecular weight 71) to 30 g of water and stirring for 0.5 h. 2.7 mg of rhodium trichloride trihydrate was added to 5 mL of deionized water, mixed, and then added to the mixed gel and stirred at room temperature for 1 h. 4.9 g of the organic template tetrapropylammonium hydroxide was added, and stirred at room temperature for 1 h. The mixture was transferred to a 100 mL hydrothermal synthesis reactor, and crystallized at 170°C for 5 days. The reactor was cooled to room temperature to obtain a crude molecular sieve. The crude molecular sieve was filtered, washed, and dried as a white solid in an oven at 100°C for 18 h. The sample was then placed in a muffle furnace and heated to 550°C for 6 h to obtain the molecular sieve Rh@Zeolite.

[0093] (2) Synthesis of a molecular sieve catalyst Rh-C-P@Zeolite

[0094] The molecular sieve catalyst Rh-C-P@Zeolite was prepared by the following method: 1.0 g of the molecular sieve Rh@Zeolite solid was ground with the co-catalyst activated carbon (0.5 g) and biuret (0.3 g), and then heat-treated at 450°C for 6 h under a 5% H2 / Ar atmosphere, and naturally cooled to room temperature to obtain the molecular sieve catalyst.

[0095] Example 4

[0096] A molecular sieve catalyst Co-C-N@Zeolite was prepared by the following method:

[0097] (1) Synthesis of a molecular sieve Co@Zeolite

[0098] Take tetraethyl orthosilicate 8.4 g and 0.6 g of pseudo-boehmite (molecular weight 71) into 30 g of water, stir for 0.5 h to form a mixed gel. Take 9.8 mg of cobalt nitrate into 5 mL of deionized water, mix well and add to the mixed gel, and stir at room temperature for 0.5 h; then add 4.5 g of organic template tetraethylammonium hydroxide, stir at room temperature for 1 h; transfer to a 100 mL hydrothermal synthesis reactor, crystallize at 180 ℃ for 4 days; cool the autoclave to room temperature to obtain a crude molecular sieve; the crude molecular sieve is filtered, washed to obtain a white solid, and then dried in an oven at 100 ℃ for 6 h; then the sample is placed in a muffle furnace and heated to 550 ℃ and calcined for 6 h to obtain the molecular sieve Co@Zeolite.

[0099] (2) Synthesis of the molecular sieve catalyst Co-C-N@Zeolite

[0100] Grind 1.0 g of the molecular sieve Co@Zeolite solid with the auxiliary active carbon (0.5 g) and biuret (0.3 g), and then heat treat at 500 ℃ for 6 h under a 5% H2 / Ar atmosphere, and then naturally cool to room temperature to obtain the molecular sieve catalyst.

[0101] Example 5

[0102] A molecular sieve catalyst Rh-N-P@Zeolite, which is different from Example 1 only in that the amount of ammonium chloride added in step (2) is 0.053 g, n(N) = 0.001 mol, the amount of phosphorus trichloride added is 1.51 g, n(P) = 0.011 mol, and the other materials and preparation methods are the same as in Example 1.

[0103] Example 6

[0104] A molecular sieve catalyst Rh-N-P@Zeolite, which is different from Example 1 only in that the amount of ammonium chloride added in step (2) is 1.1 g, n(N) = 0.01125 mol, the amount of phosphorus trichloride added is 0.1 g, n(P) = 0.00075 mol, and the other materials and preparation methods are the same as in Example 1.

[0105] Example 7

[0106] A molecular sieve catalyst Rh-C-P@Zeolite, which is different from Example 1 only in that the ammonium chloride in step (2) is replaced by active carbon (0.12 g, n(C) = 0.01 mol), and the other materials and preparation methods are the same as in Example 1.

[0107] Example 8

[0108] A molecular sieve catalyst Rh-C-N@Zeolite, which is only different from Example 1 in that the phosphorus trichloride in step (2) is replaced by activated carbon (0.024 g, n(C) = 0.002 mol), and other materials and preparation methods are the same as those in Example 1.

[0109] Comparative Example 1

[0110] A molecular sieve catalyst Rh@Zeolite, which is prepared by the same method as step (1) in Example 1.

[0111] Comparative Example 2

[0112] A molecular sieve catalyst Co@Zeolite, which is prepared by the same method as step (1) in Example 4.

[0113] Comparative Example 3

[0114] A molecular sieve catalyst Rh-N@Zeolite, which is only different from Example 1 in that no triphenylphosphine is added in step (2), and only ammonium chloride (0.8 g) is added, and other materials and preparation methods are the same as those in Example 1.

[0115] Comparative Example 4

[0116] A molecular sieve catalyst Rh-P@Zeolite, which is only different from Example 1 in that no urea is added in step (2), and only phosphorus trichloride (0.8 g) is added, and other materials and preparation methods are the same as those in Example 1.

[0117] Comparative Example 5

[0118] A molecular sieve catalyst Rh-C@Zeolite, which is only different from Example 1 in that the ammonium chloride (0.5 g) and the phosphorus trichloride (0.3 g) in step (2) are replaced by activated carbon (0.8 g), and other materials and preparation methods are the same as those in Example 1.

[0119] Application Example 1

[0120] A preparation method of an isomeric aldehyde, which uses the molecular sieve catalyst obtained in Example 1 as a catalyst, and the preparation method comprises the following steps:

[0121] 100 mg of the catalyst and 20 mL of toluene were added to a 100 mL (mechanically stirred) stainless steel high-pressure reaction kettle, and the reactor was sealed. A hydrogen and carbon monoxide mixed gas H2 / CO (v:v = 1:1) at 1.0 MPa was introduced into the reaction kettle, and the reactor was fully replaced. 1.0 g of the reactant 1-hexene was weighed and added, and then a hydrogen and carbon monoxide mixed gas H2 / CO (v:v = 1:1) at 3.0 MPa was filled. The stirring speed was set to 400 rpm, the reaction temperature was set to 80°C, and the reaction time was set to 4 h.

[0122] Application Example 2

[0123] A method for preparing an isomerized aldehyde using the molecular sieve catalyst obtained in Example 1 as a catalyst, the method comprising the steps of:

[0124] A 100 mL (mechanically stirred) stainless steel autoclave was charged with 100 mg of the catalyst and 20 mL of toluene, and the reactor was sealed. A hydrogen and carbon monoxide mixed gas H2 / CO (v:v = 1 : 1) at 1.0 MPa was introduced into the reactor, and the reactor was sufficiently replaced. 1.0 g of the reactant 1-decene was weighed and added, and then a hydrogen and carbon monoxide mixed gas H2 / CO (v:v = 1 : 1) at 4.0 MPa was charged. The stirring rate was set to 400 rpm, the reaction temperature was set to 100°C, and the reaction time was set to 6 h.

[0125] Application Example 3

[0126] A method for preparing an isomerized aldehyde using the molecular sieve catalyst obtained in Example 2 as a catalyst, the method comprising the steps of:

[0127] A 100 mL (mechanically stirred) stainless steel autoclave was charged with 100 mg of the catalyst and 20 mL of toluene, and the reactor was sealed. A hydrogen and carbon monoxide mixed gas H2 / CO (v:v = 1 : 1) at 1.0 MPa was introduced into the reactor, and the reactor was sufficiently replaced. 1.0 g of the reactant 1-hexene was weighed and added, and then a hydrogen and carbon monoxide mixed gas H2 / CO (v:v = 1 : 1) at 3.5 MPa was charged. The stirring rate was set to 400 rpm, the reaction temperature was set to 90°C, and the reaction time was set to 4 h.

[0128] Application Example 4

[0129] A method for preparing an isomerized aldehyde using the molecular sieve catalyst obtained in Example 3 as a catalyst, the method comprising the steps of:

[0130] A 100 mL (mechanically stirred) stainless steel autoclave was charged with 100 mg of the catalyst and 20 mL of toluene, and the reactor was sealed. A hydrogen and carbon monoxide mixed gas H2 / CO (v:v = 1 : 1) at 1.0 MPa was introduced into the reactor, and the reactor was sufficiently replaced. 1.0 g of the reactant 1-hexene was weighed and added, and then a hydrogen and carbon monoxide mixed gas H2 / CO (v:v = 1 : 1) at 3.5 MPa was charged. The stirring rate was set to 400 rpm, the reaction temperature was set to 90°C, and the reaction time was set to 4 h.

[0131] Application Example 5

[0132] A preparation method of isomeric aldehydes, using the molecular sieve catalyst obtained in Example 4 as catalyst, comprising the following steps:

[0133] A 100-mL (mechanically stirred) stainless steel autoclave was charged with 100 mg of catalyst and 20 mL of toluene, and the reactor was sealed. The reactor was filled with 1.0 MPa of hydrogen and carbon monoxide mixed gas H2 / CO (v:v = 1:1), and the reactor was fully replaced. 1.0 g of reactant 1-heptene was weighed and added, and then 4 MPa of hydrogen and carbon monoxide mixed gas H2 / CO (v:v = 1:1) was filled. The stirring rate was set to 400 rpm, the reaction temperature was set to 120°C, and the reaction time was set to 8 h.

[0134] Application Examples 6-9, Comparative Application Examples 1-5

[0135] A preparation method of isomeric aldehydes, which is different from Application Example 1 only in that the molecular sieve catalysts obtained in Examples 5-8 and Comparative Examples 1-5 are used as catalysts, and other materials and preparation methods are the same as those in Application Example 1.

[0136] The products obtained in the above application examples and comparative application examples were quantitatively analyzed by using an Agilent 6890 gas chromatograph (hydrogen flame ionization detector, PEG20M capillary column, column length 50 m). The specific detection method was as follows: injection volume 0.5 μL; column temperature 50°C for 2 min; temperature increased to 80°C at a rate of 5°C / min, and maintained for 4 min; temperature increased to 200°C at a rate of 15°C / min, and maintained for 5 min; injection port temperature 250°C; detector temperature 280°C. The detection results are summarized in Table 1. The contents of alkanes, alkenes, aldehydes, alcohols and other compounds after the reaction were calculated by area normalization method, and the solvent was not integrated.

[0137] Olefins conversion rate (mol%) = (100 - molar percentage content of olefins in reaction products) / 100 x 100%;

[0138] Aldehyde selectivity (mol%) = (molar percentage content of aldehydes in reaction products) / (100 - molar percentage content of olefins in reaction products) x 100%;

[0139] Alkane selectivity (mol%) = (molar percentage content of alkanes in reaction products) / (100 - molar percentage content of olefins in reaction products) x 100%;

[0140] n-Aldehyde:isomeric aldehyde = (molar percentage content of n-aldehyde in reaction products) / (molar percentage content of isomeric aldehyde in reaction products).

[0141] Table 1

[0142]

[0143]

[0144] It can be seen from the test results that the molecular sieve catalyst provided by the present application promotes the generation of isomeric aldehydes by introducing a combination of at least two of C, N or P as an auxiliary agent, reduces the n / i ratio of the generated aldehydes, the conversion rate of the hydrogenation product is ≥83.1 mol%, the aldehyde selectivity is ≥89.8 mol%, the alkane selectivity is ≤0.9 mol%, the ratio of normal aldehyde and isomeric aldehyde is below 0.38, the selectivity of isomeric aldehyde is high, and the application effect in the olefin hydroformylation reaction is excellent.

[0145] It can be seen from the comparison of application example 1 and application examples 8 and 9 that the present application improves the conversion rate of olefins and the selectivity of aldehydes by using a combination of N and P as an auxiliary agent, while the n / i ratio is reduced, and the reaction is beneficial to the formation of isomeric aldehydes. It can be seen from the comparison of application example 1 and application examples 6 and 7 that the present application further optimizes the element ratio of N and P to obtain more excellent catalytic effect of isomeric aldehyde.

[0146] It can be seen from the comparison of application example 1 and comparative application examples 1-5 that when the molecular sieve catalyst lacks a non-metallic element auxiliary agent or an auxiliary agent of a combination of at least two elements, the n / i ratio of the generated aldehydes is significantly increased, and a large amount of normal aldehyde is produced in the reaction.

[0147] The applicant declares that the above is only a specific embodiment of the present application, but the protection scope of the present application is not limited thereto. It should be understood by those skilled in the art that any changes or replacements within the technical scope disclosed by the present application can be easily thought of by any person skilled in the art, and all fall within the protection scope and disclosure scope of the present application.

Claims

1. A process for the preparation of a molecular sieve catalyst, characterized by, The preparation method comprises the following steps: (1) synthesis of M@ molecular sieve: mixing molecular sieve precursor and M-containing compound to obtain the M@ molecular sieve; (2) synthesis of M-X@ molecular sieve: mixing the M@ molecular sieve obtained in step (1) and X precursor to obtain the M-X@ molecular sieve; In step (2), the mixing operation comprises grinding, and the reaction is carried out in a hydrogen and protective gas atmosphere, and the reaction temperature is 300-800 ℃; The molecular sieve catalyst comprises M-X@ molecular sieve; M comprises any one or a combination of at least two of Rh element, Co element, Ir element, Au element or Fe element; The molecular sieve comprises any one or a combination of at least two of S-1, ZSM-5, SAPO-34, HY, SBA-15 or MCM-41; The mass ratio of the M@ molecular sieve to the X precursor is 1:(0.1-3).

2. The production method according to claim 1, characterized by, The mass content of M in the molecular sieve catalyst is 0.01-10%.

3. The preparation method according to claim 1, characterized in that, The mass content of X in the molecular sieve catalyst is 0.1-50%.

4. The method of claim 1, wherein, X in the molecular sieve catalyst comprises a combination of N element and P element.

5. The preparation method according to claim 1, characterized in that, The molar ratio of the N element to the P element is (0.1-10):

1.

6. The method of claim 1, wherein, The synthesis of the M@ molecular sieve comprises the following steps: Mixing silica-alumina gel, M-containing compound solution and organic template agent in sequence to obtain mixed gel, and crystallizing and calcining the mixed gel to obtain the M@ molecular sieve.

7. The production method according to claim 6, wherein The silica-alumina gel is obtained by mixing silica source, aluminum source and solvent.

8. The preparation method according to claim 7, characterized in that, The silica source comprises any one or a combination of at least two of silica gel, silica sol or organic silicate.

9. The preparation method according to claim 7, characterized in that, The aluminum source is any one or a combination of at least two selected from pseudoboehmite, di-aluminum trioxide, sodium aluminate, variscite, gibbsite, aluminum isopropylate or aluminum nitrate.

10. The preparation method according to claim 7, characterized in that, The molar ratio of the silica source to the aluminum source is 1:(0.05-0.4).

11. The preparation method according to claim 7, characterized in that, The solvent comprises water.

12. The method of claim 7, wherein, The mass ratio of the solvent to the silica source is (1-10):

1.

13. The preparation method according to claim 7, characterized in that, The molar ratio of the M-containing compound to the silicon source is (10 -6 -10 -1 ):

1.

14. The method of claim 6, wherein, The M-containing compound comprises any one or a combination of at least two of rhodium chloride, rhodium nitrate, rhodium acetylacetonate, cobalt nitrate, cobalt chloride, cobalt acetate, iridium chloride, carbonyl iridium, iridium fluoride, hexachloro iridic acid, chloroauric acid, iron nitrate or iron chloride.

15. The method of claim 6, wherein the method further comprises, The concentration of the M-containing compound in the M-containing compound solution is 0.1-5 g / L.

16. The method of claim 6, wherein, The solvent in the M-containing compound solution comprises water.

17. The method of claim 7, wherein the method further comprises, The mass ratio of the organic template agent to the silica source is 1:(0.5-5).

18. The method of claim 6, wherein, The organic template agent comprises any one or a combination of at least two of tetraethylammonium hydroxide, tetrapropylammonium hydroxide or di-n-propylamine.

19. The method of claim 6, wherein, The mixing operation comprises stirring.

20. The method of claim 6, wherein, The mixing temperature is 20-40 ℃.

21. The method of claim 6, wherein, The mixing time is 0.2-5 h.

22. The method of claim 6, wherein, The crystallization temperature is 80-200 ℃.

23. The method of claim 6, wherein the method further comprises, The crystallization time is 2-6 days.

24. The method of claim 6, wherein, After crystallization, filtration, washing and drying are carried out.

25. The method of claim 24, wherein, The drying temperature is 50-150 ℃.

26. The method of claim 25, wherein, The drying time is 12-48 h.

27. The method of claim 6, wherein, The calcination temperature is 200-800 ℃.

28. The method of claim 6, wherein, The calcination time is 6-48 h.

29. The method of claim 1, wherein, The X precursor includes any one or a combination of at least two of phosphorus trichloride, diphenylphosphine, triphenylphosphine, tributylphosphine, urea, ammonium chloride, biuret, melamine, glucose, carbon nitride, or activated carbon.

30. The method of claim 1, wherein, The protective gas includes any one or a combination of at least two of argon, nitrogen, or helium.

31. The method of claim 1, wherein, The volume fraction of hydrogen in the protective gas is 1-10%.

32. The method of claim 1, wherein, In step (2), the reaction time is 2-6 h.

33. Use of the molecular sieve catalyst prepared by the preparation method of any one of claims 1-32 in a catalytic hydroformylation reaction.

34. A method of preparing a heteroaldehyde, characterized by, The preparation method includes the following steps: mixing an olefin, carbon monoxide, hydrogen, and a catalyst to react, to obtain the isomeric aldehyde; the catalyst is the molecular sieve catalyst prepared by the preparation method of any one of claims 1-32.

35. The method of claim 34, wherein the method further comprises, The molar ratio of the olefin to M in the catalyst is (1-10000):

1.

36. The preparation method according to claim 34, characterized in that, The olefin includes any one or a combination of at least two of C3-C20 olefins.

37. The method of claim 36, wherein the method is performed in a single step. The olefin includes any one or a combination of at least two of α-olefins.

38. The preparation method according to claim 34, characterized in that, The total pressure of the carbon monoxide and hydrogen is 0.1-10 MPa.

39. The method of claim 38, wherein the method is performed in a single step. The total pressure of the carbon monoxide and hydrogen is 0.2-6 MPa.

40. The method of claim 34, wherein, The pressure ratio of the hydrogen to the carbon monoxide is (0.1-5):

1.

41. The method of claim 40, wherein the method is performed in a single step. The pressure ratio of the hydrogen to the carbon monoxide is (0.1-2):

1.

42. The method of claim 34, wherein, The reaction temperature is 60-200℃.

43. The method of claim 34, wherein the method is carried out at a temperature of about 20°C to about 30°C. The reaction time is 1-24 h.

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