CN116020518A - Spherical catalyst containing metal Silicate-1 molecular sieve, and forming method and application thereof - Google Patents

Abstract

A spherical catalyst comprising a metal Silicate-1 molecular sieve, characterized in that: the catalyst comprises 75-95 wt% of metal-containing Silicate-1 molecular sieve and 5-25 wt% of binder based on dry weight of the catalyst; the BET specific surface area of the metal-containing Silicate-1 molecular sieve is 400-500m ² /g, metal content 15-5000ppm; the particle size of the catalyst is 1-2.5mm, and the crushing strength sigma is 32.0-45.0N/particle. The catalyst has high crushing strength and is applied to the gas-phase Beckmann weight of cyclohexanone oxime in a fluidized bed processThe reaction can effectively prolong the service life of the catalyst and improve the conversion rate of cyclohexanone oxime and the selectivity of caprolactam.

Description

Spherical catalyst containing metal Silicate-1 molecular sieve, and forming method and application thereof

Technical Field

The invention relates to a Silicate-1 molecular sieve catalyst, a forming method and application, and further relates to a spherical catalyst containing metal Silicate-1 molecular sieve, a forming method and a method for preparing caprolactam from cyclohexanone oxime.

Background

The cyclohexanone oxime gas-phase Beckmann rearrangement reaction using solid acid catalyst is a new method for producing caprolactam without sulfation, and the method has the problems of no equipment corrosion, no environmental pollution, etc., and the separation and purification of the product are greatly simplified, so the method is greatly focused by the industry personnel. For commercial applications, the Silicate-1 molecular sieves must be shaped before use. Because various assistants added in the molding process often cause the activity or selectivity of the catalyst to be reduced, how to obtain the catalyst with high activity, high selectivity and high stability after molding is a key for realizing the preparation of caprolactam by gas-solid rearrangement reaction.

The process proposed in EP576295 is to prepare the molecular sieve into microspheres by spray drying without any addition of a binder and then to heat treat in water to increase the mechanical strength of the microspheres so that the microsphere catalyst can be used in a fluidized bed reactor for the conversion of cyclohexanone oxime to caprolactam.

CN1256967a discloses a method for preparing a full-silica molecular sieve catalyst containing MFI topology structure for the conversion of cyclohexanone oxime into caprolactam. The basic starting point of the method is that acidic silica gel is used as a binder, and the specific method is that siliceous oligomer prepared by acidic hydrolysis of alkoxy silicon is mixed with water or alcohol-water dispersion liquid of submicron particles of MFI structure molecular sieve with pH less than or equal to 5, and the mixture is emulsified, solidified, washed and baked to prepare gel microspheres. The catalyst prepared by the method is suitable for a fluidized bed reactor.

USP485985 discloses a process for preparing a titanium-containing silicalite catalyst using basic silica gel as a binder. The alkaline silica gel is prepared by hydrolyzing tetraalkyl silicate, preferably tetraalkyl orthosilicate, in tetraalkyl ammonium hydroxide aqueous solution at room temperature to 200deg.C for 0.2-10 hr, and has pH of not less than 10. The catalyst prepared by the method is a microsphere catalyst suitable for a fluidized bed reactor.

Since the fluidized bed process has high investment cost and only about 95% of cyclohexanone oxime is converted (100% conversion is required in terms of separation technology), development of a new fixed bed or moving bed method for the vapor phase Beckmann rearrangement reaction of cyclohexanone oxime is necessary for industrial application.

There have been no reports on spherical catalysts containing metal silicalite-1 molecular sieves and methods of preparation for use in fixed bed or moving bed processes.

Disclosure of Invention

The invention provides a spherical catalyst containing metal Silicate-1 molecular sieve, which aims at overcoming the defects that the crushing strength of the spherical molecular sieve catalyst in the prior art is not high enough, and the conversion rate of cyclohexanone oxime and the selectivity of caprolactam are not high enough when the spherical molecular sieve catalyst is applied to the preparation of caprolactam through the vapor phase Beckmann rearrangement of cyclohexanone oxime.

The second object of the present invention is to provide a process for preparing the same.

The invention further aims to provide a method for preparing caprolactam by the vapor phase Beckmann rearrangement of cyclohexanone oxime, which has higher conversion rate of cyclohexanone oxime, higher selectivity of caprolactam and better stability.

In order to achieve the above object, a first aspect of the present invention provides a spherical catalyst containing a metal Silicate-1 molecular sieve, characterized in that: the catalyst comprises 75-95 wt% of metal-containing Silicate-1 molecular sieve and 5-25 wt% of binder based on dry weight of the catalyst; the BET specific surface area of the metal-containing Silicate-1 molecular sieve is 400-500m ² /g, metal content 15-5000ppm; the particle size of the catalyst is 1-2.5mm, and the crushing strength sigma is 32.0-45.0N/particle.

The invention provides a spherical catalyst, wherein the metal-containing Silicate-1 molecular sieve, A _HB ：A _ISO Is (15-50): 1, A _HB And A _ISO Respectively represent 3400cm wave number in the infrared hydroxyl spectrogram of the metal-containing Silicate-1 molecular sieve ^-1 The summation wave number is 3725cm ^-1 Peak intensity at that point, expressed as peak area. The wave number in the infrared hydroxyl spectrogram is 3400cm ^-1 The peak at (highest value) represents hydrogen bonded silanol groups in the Silicate-1 molecular sieve; in the infrared hydroxy spectrogramWavenumber of 3725cm ^-1 The peak at (highest value) represents the isolated silicon hydroxyl groups in the Silicate-1 molecular sieve. The Silicate-1 molecular sieve provided by the invention is prepared by A _HB ：A _ISO The measurement of (2) may be characterized as having a higher hydrogen bonded silica hydroxyl ratio. The Silicate-1 molecular sieve with higher hydrogen bond and silicon hydroxyl ratio is used as a catalyst, so that various side reactions can be effectively reduced, and the selectivity of a target product can be improved. Preferably, A _HB ：A _ISO : is (15-25): 1. the infrared hydroxyl spectrogram is obtained by a Fourier transform infrared spectrometry.

Preferably, the catalyst comprises 85 to 90 wt% metal-containing Silicate-1 molecular sieve and 10 to 15 wt% binder, based on the weight of the dry basis of the catalyst; the particle size of the catalyst is 1.5-2mm, and the crushing strength sigma is 35.0-43.0N/particle.

Preferably, the metal is at least one metal element selected from the group consisting of transition metal elements, group IIIA and group IVA elements. More preferably, the metal is at least one selected from group IVB and group VB elements. Further preferably, the metal is at least one of Ti, nb, ta, ga, la, ge, sn and Pb. The metal is contained in an amount of 10 to 5000ppm, preferably 15 to 4000ppm, more preferably 50 to 800ppm, and even more preferably 200 to 500ppm based on the dry weight of the metal-containing Silicate-1 molecular sieve.

Preferably, the spherical catalyst, wherein the metal-containing Silicate-1 molecular sieve has a BET specific surface area of 300-500m ² Per gram, preferably 350-500m ² /g, more preferably 440-480m ² /g; the external specific surface area is 20-100m ² /g, preferably 20-80m ² /g, more preferably 50-85m ² Preferably 55-75m per gram ² /g; particle size of 0.01-1 μm, preferably 0.1-0.3 μm, more preferably 0.15-0.3 μm; the relative crystallinity is 70% -110%. The preferred relative crystallinity is 80% to 90%.

Preferably, the binder is selected from one or more of ethanol, glycerol, silica sol, alumina sol and water glass. More preferably, the binder is silica sol having a sodium ion content of 10-500ppm，SiO ₂ The content is 20-45 wt%.

In order to achieve the object of the present invention, a second aspect of the present invention provides a method for molding a metal-containing silicalite-1 molecular sieve based spherical catalyst according to the first aspect of the present invention, comprising:

(1) Synthesizing metal-containing Silicate-1 molecular sieve: comprises mixing a silicon source, a metal source, a fluorine-containing compound, an organic template agent and water to obtain a colloid mixture; carrying out hydrothermal crystallization on the colloid mixture to obtain a crystallized product; washing, filtering, drying and roasting the crystallized product to obtain a metal-containing Silicate-1 molecular sieve; wherein, the silicon source: fluorine-containing compound: organic template agent: the molar ratio of water is 1 (0.01-0.50): 0.05-0.50): 5-100; the silicon source: the weight ratio of the metal source is (100-100000): 1, a step of; the silicon source is SiO ₂ A meter, wherein the metal source is calculated by metal element; and, a step of, in the first embodiment,

(2) Shaping: under the rotating operation condition of a turntable molding machine, placing a 200-500-mesh metal-containing Silicate-1 molecular sieve into the turntable molding machine, mixing and contacting with water and/or a first binder to obtain first spherical particles with the diameter of 0.1-1mm, and adding a 100-1000-mesh metal-containing Silicate-1 molecular sieve and a second binder to obtain second spherical particles with the diameter of 1-2.5 mm; and drying and roasting the second spherical particles to obtain the spherical catalyst containing the metal Silicate-1 molecular sieve.

In the molding method provided by the invention, in the step of synthesizing the metal-containing Silicate-1 molecular sieve (1), optionally, the silicon source is at least one selected from silica gel, silica sol and organosilicate. The organic silicate is methyl orthosilicate and/or ethyl orthosilicate.

Optionally, the metal source is a water-soluble compound or an oil-soluble compound containing metal ions. The metal source is at least one of metal-containing inorganic salt, alcohol metal compound and ester metal compound. For example, the metal source may be TiCl ₄ 、NbCl ₅ 、C ₁₀ H ₃₀ O ₅ Ta、Ga(NO ₃ ) ₃ 、La(NO ₃ ) ₃ 、GeCl ₄ 。

Optionally, the organic template agent is at least one selected from fatty amine compounds, alcohol amine compounds and quaternary amine alkali compounds. Preferably, the organic template agent is an alkyl quaternary ammonium base compound with 1-4 carbon atoms. More preferably, the alkyl quaternary ammonium base compound is tetraethylammonium hydroxide and/or tetrapropylammonium hydroxide.

Optionally, the fluorine-containing compound is selected from a water-soluble compound or an oil-soluble compound containing fluorine. Preferably, the fluorine-containing compound is at least one of hydrofluoric acid, ammonium fluoride, boron fluoride and fluosilicic acid.

Optionally, the material mixing sequence is: adding a metal source into a silicon source, adding an organic template agent and water after the metal source is completely dissolved, performing a hydrolysis process at normal temperature for 6-12h, performing alcohol removal at 50-90 ℃ for 12-48h after the hydrolysis is complete, and finally adding a fluorine-containing compound, and uniformly mixing to obtain a colloid mixture. The above material mixing sequence is helpful to obtain homogeneous crystallization mother liquor and avoid two-phase layering phenomenon. The water is preferably added in an amount of 20-40% by weight of the molecular sieve feedstock.

Optionally, the hydrothermal crystallization is carried out under the condition that the crystallization time is 40-60h at the temperature of 80-170 ℃ and preferably at the temperature of 100-150 ℃. The hydrothermal crystallization may be performed in an apparatus conventionally selected in the art, such as a hydrothermal reaction vessel.

Optionally, the drying is carried out at 80-120 ℃ for 12-36h; the conditions of the calcination treatment include: the roasting temperature is 400-600 ℃ for 4-12h, preferably 450-550 ℃ for 6-10h. The calcination may be carried out in a device conventionally selected in the art, such as a muffle furnace.

According to the forming method provided by the invention, metal and fluorine-containing compound are added in the synthesis process of the Silicate-1 molecular sieve, and trace metal elements with Lewis acid center characteristics are added, so that metal ions enter the Silicate-1 molecular sieve framework; the fluorine-containing compound can interact with the template agent and the metal ligand respectively, so that defects generated by self-assembly in the crystallization process are fewer, the difficulty of metal entering the framework is changed, and the catalytic performance of the full-silicon molecular sieve with the MFI topological structure can be effectively changed.

In the molding method provided by the invention, in the molding step (2), the inclination angle of the turntable is 40-55 degrees, and the rotating speed of the turntable is 10-50rpm in the rotating operation condition of the turntable molding machine. In the molding step (2), one or more selected from sesbania powder, graphite, active carbon, paraffin, stearic acid, glycerol, oxalic acid, tartaric acid, citric acid, starch, polyethylene glycol, polyvinyl alcohol, polyethylene oxide, polyacrylamide, cellulose, nitric acid, hydrochloric acid, acetic acid, formic acid, ammonia water, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide can be added as an auxiliary agent. The water accounts for 20-40% of the weight of the molecular sieve raw material.

Optionally, the second binder is 2-25% by weight of the 100-1000 mesh metal-containing Silicate-1 molecular sieve.

The invention also provides a spherical catalyst containing metal Silicate-1 molecular sieve obtained by the molding method.

In order to achieve the object of the present invention, a third aspect of the present invention provides a process for producing caprolactam comprising contacting cyclohexanone oxime in the presence of a solvent under rearrangement reaction conditions with the metal-containing silicalite-1 molecular sieve based spherical catalyst according to the first or second aspect of the present invention to carry out a gas phase Beckmann rearrangement reaction.

The invention provides a method for preparing caprolactam from cyclohexanone oxime, which is carried out in a nitrogen atmosphere, wherein the molar ratio of nitrogen to the cyclohexanone oxime is (10-80): 1. preferably, the molar ratio of said nitrogen to said cyclohexanone oxime is (30-60): 1.

optionally, the molar ratio of said solvent to said cyclohexanone oxime is (2-10): 1. more preferred molar ratios are (3-8): 1, a step of; preferably, the solvent is at least one selected from fatty alcohols with 1-6 carbon atoms, and more preferably the solvent is methanol and/or ethanol.

Optionally, the rearrangement reaction conditions include:the weight space velocity of cyclohexanone oxime is 0.1-20h ^-1 The reaction temperature is 300-500 ℃, and the reaction pressure is 0.1-0.5MPa. The method for preparing caprolactam provided by the invention further comprises the following steps: firstly, cyclohexanone oxime and water are mixed according to a mole ratio of 1: (0.01-2.5) mixing.

In the spherical catalyst provided by the invention, the active component is a metal-containing Silicate-1 molecular sieve, the molecular sieve takes trace metal as Lewis acid center, and fluorine-containing compound is added in the crystallization process. The fluorine-containing compound can interact with the template agent and the metal ligand respectively, so that defects generated by self-assembly in the crystallization process are fewer, the difficulty of metal entering the framework is changed, particularly the metal with +4 and/or +5 ionic valence is more susceptible to fluoride ions, and the obtained molecular sieve has special A _HB ：A _ISO The proportion relation, the ratio of the silicon hydroxyl groups of the hydrogen bond is high, which is favorable for the cyclohexanone oxime gas-phase Beckmann rearrangement reaction method to obtain higher cyclohexanone oxime conversion rate and caprolactam selectivity; the high crush strength is also advantageous for achieving long-cycle, continuous production of caprolactam.

Detailed Description

The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.

The following examples use X-ray fluorescence spectroscopy to determine the composition of the catalyst. The instrument manufacturer is Japanese motor Co, model 3031, test condition tungsten target, excitation voltage 40kV, excitation current 50mA.

The structure of the catalyst was determined by X-ray diffraction spectroscopy. The instrument manufacturer is the Dutch panaceae company, model X' Pert PRO, test condition Cu K ray, ni filter, 40kV power 40mA, scanning range 2 theta=5-35 deg.

The BET specific surface area and external specific surface area data of metal-containing Silicate-1 molecular sieve samples in the examples were determined by an automatic adsorption apparatus of U.S. Micromeritics ASAP-2020. The test conditions were: n (N) ₂ As an adsorbate, the adsorption temperature was-196.2℃and the deaeration was carried out at a constant temperature of 1.3Pa and 300℃for 6 hours.

The particle size of the metal-containing Silicate-1 molecular sieve samples in the examples was determined by Scanning Electron Microscopy (SEM) and the analysis was performed on a model QUANTA200F electron microscope from FEI company, magnification of 50000 to 100000.

The infrared hydroxyl characterization of the metal-containing Silicate-1 molecular sieve samples in the examples was performed on a model ten or ii fourier transform infrared spectrometer from Bruker, processing a self-supporting sample sheet at 400 ℃ for 2h and scanning at room temperature.

The crush strength (sigma) of the spherical catalyst was measured on a particle strength tester QCY-602 (manufactured by the Ministry of alkali industry research, producer) according to the RIPP25-90 method of petrochemical analysis method (Yang Cuiding et al, scientific Press, 1990).

In the following examples, all reagents used were commercially available ones unless otherwise specified.

In the following examples and comparative examples, the pressures are gauge pressures unless otherwise specified.

Examples 1-8 illustrate spherical catalysts provided by the present invention and methods of making the same.

Example 1

(1) 0.06kgC to 100kg of ethyl orthosilicate ₁₀ H ₃₀ O ₅ Ta, after dissolution, adding 120kg of 25 wt% tetrapropylammonium hydroxide and 150kg of water for mixing, and stirring for 8 hours at normal temperature to form a homogeneous colloid mixture;

(2) Alcohol expelling (water is continuously added in the middle of the process) is carried out at the temperature of 85 ℃ for 20 hours, and finally 2.7kg of ammonium fluoride is added to prepare crystallization mother liquor. The mole ratio of the mixture is SiO ₂ ∶NH ₄ F∶TPAOH∶H ₂ O＝1∶0.15∶0.3∶17，SiO ₂ With Ta ⁵⁺ The mass ratio of (2) is 1090:1;

(3) Transferring the mixture into a 500L reaction kettle, performing hydrothermal crystallization at 120 ℃ for 60 hours, washing, filtering, and drying at 120 ℃ for 24 hours to obtain a molecular sieve A1, wherein a sample A1 has an XRD spectrum of a standard MFI structure molecular sieve, the specific physicochemical properties of the XRD spectrum are shown in table 1, and the relative crystallinity of the XRD spectrum is measured by taking the MFI structure molecular sieve described in' Microporous Materials, vol22, p637, 1998) as a standard sample 100% crystallinity standard;

(4) 1kg of molecular sieve A1 with 200-500 meshes is placed in a rotary disk type forming machine, wherein the diameter of a rotary disk of the rotary disk type forming machine is 1.2m, the depth of the rotary disk is 450mm, the dip angle of the rotary disk is 50 degrees, and the rotating speed of the rotary disk is set to be 30rpm. Spraying deionized water 0.8kg into the mixture to obtain spherical particles with the diameter smaller than 1 mm;

(5) Taking 400-800 mesh molecular sieve A1 and 30% alkaline silica sol according to the ratio of 2.2:1 weight ratio, mixing uniformly and re-crushing, taking particles smaller than 30 meshes, and adding 60kg into a turntable molding machine at a constant speed. Sieving with 12 mesh and 9 mesh sieve to obtain spherical catalyst with diameter of 1.7-2.2mm, wet ball of about 45 kg; the wet pellets were dried at 120℃for 24 hours, and then calcined at 550℃for 6 hours. Finally, the spherical catalyst C1 with the molecular sieve content of 85% is obtained.

Crush strength σ=41.16N/particle for C1 samples.

Example 2

(1) 0.12. 0.12kgC to 100kg of ethyl orthosilicate ₁₀ H ₃₀ O ₅ Ta, after dissolution, adding 120kg of 25 wt% tetrapropylammonium hydroxide and 150kg of water for mixing, and stirring for 8 hours at normal temperature to form a homogeneous colloid mixture;

(2) Alcohol expelling (water is continuously added in the middle of the process) is carried out at the temperature of 85 ℃ for 20 hours, and finally 2.7kg of ammonium fluoride is added to prepare crystallization mother liquor. The mole ratio of the mixture is SiO ₂ ∶NH ₄ F∶TPAOH∶H ₂ O＝1∶0.15∶0.3∶17，SiO ₂ With Ta ⁵⁺ The mass ratio of (2) is 545:1;

(3) Transferring the mixture into a 500L reaction kettle, performing hydrothermal crystallization at 120 ℃ for 60 hours, washing, filtering, and drying at 120 ℃ for 24 hours to obtain a molecular sieve A2, wherein a sample A2 has a standard MFI structure molecular sieve XRD spectrum, and the specific physicochemical properties are shown in table 1;

the subsequent (4) - (5) molecular sieve molding processes were the same as in example 1, to prepare a spherical catalyst C2.

Crush strength σ=36.26N/particle for C2 samples.

Example 3

(1) 0.06kgC to 100kg of ethyl orthosilicate ₁₀ H ₃₀ O ₅ Ta, after dissolution, adding 120kg of 25 wt% tetrapropylammonium hydroxide and 150kg of water for mixing, and stirring for 8 hours at normal temperature to form a homogeneous colloid mixture;

(2) Alcohol expelling (water is continuously added in the middle of the process) is carried out at the temperature of 85 ℃ for 20 hours, and finally 3.6kg of ammonium fluoride is added to prepare crystallization mother liquor. The mole ratio of the mixture is SiO ₂ ∶NH ₄ F∶TPAOH∶H ₂ O＝1∶0.15∶0.3∶17，SiO ₂ With Ta ⁵⁺ The mass ratio of (2) is 1090:1;

(3) Transferring the mixture into a 500L reaction kettle, performing hydrothermal crystallization at 120 ℃ for 60 hours, washing, filtering, and drying at 120 ℃ for 24 hours to obtain a molecular sieve A3, wherein a sample A3 has a standard MFI structure molecular sieve XRD spectrum, and the specific physicochemical properties are shown in table 1;

the subsequent (4) - (5) molecular sieve molding processes were the same as in example 1, to prepare a spherical catalyst C3.

C3 samples had crush strength σ=38.22N/particle.

Example 4

(1) 0.12. 0.12kgC to 100kg of ethyl orthosilicate ₁₀ H ₃₀ O ₅ Ta, after dissolution, adding 120kg of 25 wt% tetrapropylammonium hydroxide and 150kg of water for mixing, and stirring for 8 hours at normal temperature to form a homogeneous colloid mixture;

(2) Alcohol expelling (water is continuously added in the middle of the process) is carried out at the temperature of 85 ℃ for 20 hours, and finally 3.6kg of ammonium fluoride is added to prepare crystallization mother liquor. The mole ratio of the mixture is SiO ₂ ∶NH ₄ F∶TPAOH∶H ₂ O＝1∶0.15∶0.3∶17，SiO ₂ With Ta ⁵⁺ The mass ratio of (2) is 1090:1;

(3) Transferring the mixture into a 500L reaction kettle, performing hydrothermal crystallization at 120 ℃ for 60 hours, washing, filtering, and drying at 120 ℃ for 24 hours to obtain a molecular sieve A4, wherein a sample A4 has a standard MFI structure molecular sieve XRD spectrum, and the specific physicochemical properties are shown in table 1;

the subsequent (4) - (5) molecular sieve molding processes were the same as in example 1, to prepare spherical catalyst C4.

C4 samples had crush strength σ= 34.30N/particle.

Example 5

(1) 0.06kgC to 100kg of ethyl orthosilicate ₁₀ H ₃₀ O ₅ Ta, after dissolution, adding 120kg of 25 wt% tetrapropylammonium hydroxide and 150kg of water for mixing, and stirring for 8 hours at normal temperature to form a homogeneous colloid mixture;

(2) Alcohol expelling (water is continuously added in the middle of the process) is carried out at the temperature of 85 ℃ for 20 hours, and finally 3.65kg of 40 wt% hydrofluoric acid is added to prepare crystallization mother liquor. The mole ratio of the mixture is SiO ₂ ∶HF∶TPAOH∶H ₂ O＝1∶0.15∶0.3∶17，SiO ₂ With Ta ⁵⁺ The mass ratio of (2) is 1090:1;

(3) Transferring the mixture into a 500L reaction kettle, performing hydrothermal crystallization at 120 ℃ for 60 hours, washing, filtering, and drying at 120 ℃ for 24 hours to obtain a molecular sieve A5, wherein a sample A5 has a standard MFI structure molecular sieve XRD spectrum, and the specific physicochemical properties are shown in table 1;

the subsequent (4) - (5) molecular sieve molding processes were the same as in example 1, to prepare spherical catalyst C5.

C5 samples had crush strength σ=35.28n/particle.

Example 6

(1) 0.12. 0.12kgC to 100kg of ethyl orthosilicate ₁₀ H ₃₀ O ₅ Ta, after dissolution, adding 120kg of 25 wt% tetrapropylammonium hydroxide and 150kg of water for mixing, and stirring for 8 hours at normal temperature to form a homogeneous colloid mixture;

(2) Alcohol expelling (water is continuously added in the middle of the process) is carried out at the temperature of 85 ℃ for 20 hours, and finally 3.65kg of 40 wt% hydrofluoric acid is added to prepare crystallization mother liquor. The mole ratio of the mixture is SiO ₂ ∶HF∶TPAOH∶H ₂ O＝1∶0.15∶0.3∶17，SiO ₂ With Ta ⁵⁺ The mass ratio of (2) is 545:1;

(3) Transferring the mixture into a 500L reaction kettle, performing hydrothermal crystallization at 120 ℃ for 60 hours, washing, filtering, and drying at 120 ℃ for 24 hours to obtain a molecular sieve A6, wherein a sample A6 has a standard MFI structure molecular sieve XRD spectrum, and the specific physicochemical properties are shown in table 1;

the subsequent (4) - (5) molecular sieve molding processes were the same as in example 1, to prepare spherical catalyst C6.

C6 samples have crush strength σ= 34.30N/particle.

Example 7

The preparation process was the same as in examples 1 (1), (2), (3) and (4), with the following modifications in the molding process (5):

(5) Taking 400-800 mesh molecular sieve and 30% alkaline silica sol according to 2.2:1 weight ratio, mixing uniformly and re-crushing, taking particles smaller than 40 meshes, and adding 60kg into a turntable molding machine at a constant speed. Sieving with 13 mesh and 10 mesh sieve to obtain spherical catalyst with diameter of 1.5-2.0mm, and wet ball of about 45 kg; the wet pellets were dried at 120℃for 24 hours, and then calcined at 550℃for 6 hours. Finally, the spherical catalyst C7 with the molecular sieve content of 85% is obtained.

C7 samples had crush strength σ= 34.30N/particle.

Example 8

The preparation process was the same as in examples 1 (1), (2), (3) and (4), with the following modifications in the molding process (5):

(5) The molecular sieve of 400-800 meshes and 30% alkaline silica sol are mixed according to the proportion of 2.1:1 weight ratio, mixing uniformly and re-crushing, taking particles smaller than 40 meshes, and adding 60kg into a turntable molding machine at a constant speed. Sieving with 13 mesh and 10 mesh sieve to obtain spherical catalyst with diameter of 1.5-2.0mm, and wet ball of about 45 kg; (3) 45kg of the wet pellets obtained above were dried at 120℃for 24 hours, and then calcined at 550℃for 6 hours. Finally, the spherical catalyst C8 with the molecular sieve content of 89% is obtained.

C8 samples had crush strength σ= 33.30N/particle.

Comparative example 1

(1) Method of CN103896839A for synthesizing Silicate-1 molecular sieve: pouring ethyl orthosilicate into a beaker at room temperature, stirring for 30 minutes, adding 22.5% tetrapropylammonium hydroxide solution into the ethyl orthosilicate, stirring and hydrolyzing for 3-5 hours at room temperature, adding water to form sol, stirring uniformly, transferring the mixture into a stainless steel reaction kettle lined with polytetrafluoroethylene, crystallizing for 3 days at 100 ℃, filtering, washing, and drying at 120 ℃ for 24 hours to obtain a Silicate-1 molecular sieve;

(2) 1kg of molecular sieve with 200-500 meshes is placed in a rotary table type forming machine, wherein the diameter of a rotary table of the rotary table type forming machine is 1.2m, the depth of the rotary table is 450mm, the dip angle of the rotary table is determined to be 50 degrees, and the rotating speed of the rotary table is set to be 30rpm. Spraying deionized water 0.8kg into the mixture to obtain spherical particles with the diameter smaller than 1 mm;

(3) Taking 400-800 mesh molecular sieve and 30% alkaline silica sol according to 2.2:1 weight ratio, mixing uniformly and re-crushing, taking particles smaller than 40 meshes, and adding 60kg into a turntable molding machine at a constant speed. Sieving with 12 mesh and 9 mesh sieve to obtain spherical catalyst with diameter of 1.7-2.2mm, about 45kg wet bulb, drying wet bulb at 120deg.C for 24 hr, and roasting at 550deg.C for 6 hr;

(4) 95kg of the molecular sieve and 950kg of an alkaline buffer solution of a nitrogen-containing compound (the alkaline buffer solution of the nitrogen-containing compound is a mixed solution of ammonia water and an aqueous solution of ammonium nitrate) are added into a reaction kettle with pressure, and the temperature is 80 ℃ and 2.3kg/cm ³ Stirring for 1 hour under pressure, filtering, washing and drying to finally obtain the spherical catalyst D-C1 with the molecular sieve content of 85%.

The crush strength σ=27.44N/particle of the D-C1 sample.

Comparative example 2

The same preparation as in example 1 was used, except that no fluorine-containing compound was added. The product obtained was designated as comparative sample D-C2.

Crush strength σ=24.50N/particle for D-C2 samples.

TABLE 1

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Examples 9 to 16

Examples 9-16 are provided to illustrate the catalytic reaction results of the metal-containing silicalite-1-containing spherical molecular sieve catalysts prepared in examples 1-8 in a gas phase Beckmann rearrangement reaction.

Test conditions: the reaction device is a constant pressure continuous flow fixed bed, the inner diameter of the reactor is 5mm, the loading of the catalyst is 0.469 g, coarse quartz sand with the height of 30mm and 30 meshes is filled on the upper surface of the catalyst bed, and fine quartz sand with the size of 50 meshes is filled below the catalyst bed. The granularity of the catalyst is 40-60 meshes. After the catalysts (catalysts A1 to A6 and D1 to D2) were charged into the reaction tube, they were pretreated for 1 hour under a nitrogen atmosphere at 350℃under normal pressure. The concentration of the raw material cyclohexanone oxime was 35%, and the weight space velocity (WHSV) was 16h ^-1 The solvent is ethanol, the reaction temperature is 380 ℃, the nitrogen flow is 45ml/min, the reaction product is cooled by an ice-water mixture and then enters a collecting bottle for gas-liquid separation, and the reaction time is 12 hours for product composition analysis.

The reaction product was quantitatively analyzed by Agilent 6890 gas chromatograph (hydrogen flame ion detector, PEG20M capillary chromatography column, column length 50M), vaporization chamber temperature 250 ℃, detection chamber temperature 240 ℃, column temperature programmed temperature, constant temperature of 110 ℃ for 8 minutes, 15 ℃/min to 230 ℃ and constant temperature again for 14 minutes.

After the reaction, the rearrangement product content of caprolactam and cyclohexenone is calculated by adopting an area normalization method, and the solvent does not participate in integration.

The mole percent of cyclohexanone oxime in the reaction product and the mole percent of caprolactam in the reaction product are obtained through the analysis, and the cyclohexanone oxime conversion and caprolactam selectivity are determined according to the following formula. The results are shown in Table 2.

Conversion of cyclohexanone oxime (mol%) = (mole% cyclohexanone oxime in 100-reaction product)/100×100%

Caprolactam selectivity (mol%) =mole% caprolactam in reaction product/(mole% cyclohexanone oxime in 100-reaction product) ×100%

The reaction results are shown in Table 2.

Comparative example 3 and comparative example 4

Comparative example 3 and comparative example 4 are used to illustrate the catalytic reaction results of comparative spherical catalysts D-C1 and D-C2 prepared in comparative example 1 and comparative example 2, respectively, in a vapor phase beckmann rearrangement reaction.

The reaction results are shown in Table 2.

TABLE 2

As can be seen from Table 2, the metal-containing Silicate-1 spherical molecular sieve catalyst synthesized by the preparation method provided by the invention has better catalytic performance, the conversion rate of cyclohexanone oxime is higher in the vapor phase Beckmann rearrangement reaction of cyclohexanone oxime, the highest conversion rate of cyclohexanone oxime can reach more than 99.9% after 12 hours of reaction, the selectivity of caprolactam is higher, the crushing strength of caprolactam can reach more than 96%, and the crushing strength of caprolactam can reach 41.16N/particle.

Example 17

(1) To 100kg of ethyl orthosilicate was added 0.06kg of TiCl ₄ After the dissolution is completed, 120kg of tetrapropylammonium hydroxide with 25 wt% and 150kg of water are added to be mixed, and the mixture is stirred for 8 hours at normal temperature to form a homogeneous colloid mixture;

(2) Alcohol expelling (water is continuously added in the middle of the process) is carried out at the temperature of 85 ℃ for 20 hours, and finally 2.7kg of ammonium fluoride is added to prepare crystallization mother liquor. The mole ratio of the mixture is SiO ₂ ∶NH ₄ F∶TPAOH∶H ₂ O＝1∶0.15∶0.3∶17，SiO ₂ With Ti ⁴⁺ The mass ratio of (3) is 1902:1;

(3) Transferring the mixture into a 500L reaction kettle, performing hydrothermal crystallization at 120 ℃ for 60 hours, washing, filtering, and drying at 120 ℃ for 24 hours to obtain a molecular sieve A7, wherein a sample A7 has a standard MFI structure molecular sieve XRD spectrum, and the specific physicochemical properties are shown in Table 3;

(4) 1kg of a molecular sieve of 200-500 mesh was placed in a rotary disk type molding machine, wherein the rotary disk diameter of the rotary disk type rotary molding machine used was 1.2m, the depth of the rotary disk was 450mm, the tilt angle of the rotary disk was determined to be 50℃and the rotational speed of the rotary disk was set to 30rpm. Spraying deionized water 0.8kg into the mixture to obtain spherical particles with the diameter smaller than 1 mm;

(5) The molecular sieve of 400-800 meshes and 30% alkaline silica sol are mixed according to the proportion of 2.2:1 weight ratio, mixing uniformly and re-crushing, taking particles smaller than 30 meshes, and adding 60kg into a turntable molding machine at a constant speed. Sieving with 12 mesh and 9 mesh sieve to obtain spherical catalyst with diameter of 1.7-2.2mm, wet ball of about 45 kg; 45kg of the wet pellets obtained above were dried at 120℃for 24 hours, and then calcined at 550℃for 6 hours. Finally, the spherical catalyst C9 with the molecular sieve content of 85% is obtained.

C9 samples had crush strength σ= 40.18N/particle.

Example 18

(1) To 100kg of ethyl orthosilicate was added 0.06kg of GeCl ₄ After the dissolution is completed, 120kg of tetrapropylammonium hydroxide with 25 wt% and 150kg of water are added to be mixed, and the mixture is stirred for 8 hours at normal temperature to form a homogeneous colloid mixture;

(2) Alcohol expelling (water is continuously added in the middle of the process) is carried out at the temperature of 85 ℃ for 20 hours, and finally 2.7kg of ammonium fluoride is added to prepare crystallization mother liquor. The mole ratio of the mixture is SiO ₂ ∶NH ₄ F∶TPAOH∶H ₂ O＝1∶0.15∶0.3∶17，SiO ₂ With Ge ⁴⁺ The mass ratio of (2) is 1419:1;

(3) Transferring the mixture into a 500L reaction kettle, performing hydrothermal crystallization at 120 ℃ for 60 hours, washing, filtering, and drying at 120 ℃ for 24 hours to obtain a molecular sieve A8, wherein a sample A8 has a standard MFI structure molecular sieve XRD spectrum, and the specific physicochemical properties are shown in Table 3;

(4) 1kg of a molecular sieve of 200-500 mesh was placed in a rotary disk type molding machine, wherein the rotary disk diameter of the rotary disk type rotary molding machine used was 1.2m, the depth of the rotary disk was 450mm, the tilt angle of the rotary disk was determined to be 50℃and the rotational speed of the rotary disk was set to 30rpm. Spraying deionized water 0.8kg into the mixture to obtain spherical particles with the diameter smaller than 1 mm;

(5) The molecular sieve of 400-800 meshes and 30% alkaline silica sol are mixed according to the proportion of 2.2:1 weight ratio, mixing uniformly and re-crushing, taking particles smaller than 30 meshes, and adding 60kg into a turntable molding machine at a constant speed. Sieving with 12 mesh and 9 mesh sieve to obtain spherical catalyst with diameter of 1.7-2.2mm, wet ball of about 45 kg; 45kg of the wet pellets obtained above were dried at 120℃for 24 hours, and then calcined at 550℃for 6 hours. Finally, the spherical catalyst C10 with the molecular sieve content of 85% is obtained.

C10 samples had crush strength σ=42.14N/particle.

Example 19

(1) To 100kg of ethyl orthosilicate was added 0.06kg of Ga (NO) ₃ ) ₃ After the dissolution is completed, 120kg of tetrapropylammonium hydroxide with 25 wt% and 150kg of water are added to be mixed, and the mixture is stirred for 8 hours at normal temperature to form a homogeneous colloid mixture;

(2) Alcohol expelling (water is continuously added in the middle of the process) is carried out at the temperature of 85 ℃ for 20 hours, and finally 2.7kg of ammonium fluoride is added to prepare crystallization mother liquor. The mole ratio of the mixture is SiO ₂ ∶NH ₄ F∶TPAOH∶H ₂ O＝1∶0.15∶0.3∶17，SiO ₂ With Ga ³⁺ The mass ratio of (3) is 907:1;

(3) Transferring the mixture into a 500L reaction kettle, performing hydrothermal crystallization at 120 ℃ for 60 hours, washing, filtering, and drying at 120 ℃ for 24 hours to obtain a molecular sieve A9, wherein a sample A9 has a standard MFI structure molecular sieve XRD spectrum, and the specific physicochemical properties are shown in Table 3;

(4) 1kg of a molecular sieve of 200-500 mesh was placed in a rotary disk type molding machine, wherein the rotary disk diameter of the rotary disk type rotary molding machine used was 1.2m, the depth of the rotary disk was 450mm, the tilt angle of the rotary disk was determined to be 50℃and the rotational speed of the rotary disk was set to 30rpm. Spraying deionized water 0.8kg into the mixture to obtain spherical particles with the diameter smaller than 1 mm;

(5) The molecular sieve of 400-800 meshes and 30% alkaline silica sol are mixed according to the proportion of 2.2:1 weight ratio, mixing uniformly and re-crushing, taking particles smaller than 30 meshes, and adding 60kg into a turntable molding machine at a constant speed. Sieving with 12 mesh and 9 mesh sieve to obtain spherical catalyst with diameter of 1.7-2.2mm, wet ball of about 45 kg;

45kg of the wet pellets obtained above were dried at 120℃for 24 hours, and then calcined at 550℃for 6 hours. Finally, the spherical catalyst C11 with the molecular sieve content of 85% is obtained.

C11 samples had crush strength σ=38.22N/particle.

Example 20

(1) To 100kg of ethyl orthosilicate was added 0.06kg of La (NO) ₃ ) ₃ .6H ₂ O, after the dissolution is completed, 120kg of tetrapropylammonium hydroxide with 25 weight percent and 150kg of water are added for mixing, and stirring is carried out for 8 hours at normal temperature to form a homogeneous phaseA colloid mixture;

(2) Alcohol expelling (water is continuously added in the middle of the process) is carried out at the temperature of 85 ℃ for 20 hours, and finally 2.7kg of ammonium fluoride is added to prepare crystallization mother liquor. The mole ratio of the mixture is SiO ₂ ∶NH ₄ F∶TPAOH∶H ₂ O＝1∶0.15∶0.3∶17，SiO ₂ With La ³⁺ The mass ratio of (2) is 1496:1;

(3) Transferring the mixture into a 500L reaction kettle, performing hydrothermal crystallization at 120 ℃ for 60 hours, washing, filtering, and drying at 120 ℃ for 24 hours to obtain a molecular sieve A10, wherein a sample A10 has a standard MFI structure molecular sieve XRD spectrum, and the specific physicochemical properties are shown in Table 3;

(4) 1kg of a molecular sieve of 200-500 mesh was placed in a rotary disk type molding machine, wherein the rotary disk diameter of the rotary disk type rotary molding machine used was 1.2m, the depth of the rotary disk was 450mm, the tilt angle of the rotary disk was determined to be 50℃and the rotational speed of the rotary disk was set to 30rpm. Spraying deionized water 0.8kg into the mixture to obtain spherical particles with the diameter smaller than 1 mm;

(5) The molecular sieve of 400-800 meshes and 30% alkaline silica sol are mixed according to the proportion of 2.2:1 weight ratio, mixing uniformly and re-crushing, taking particles smaller than 30 meshes, and adding 60kg into a turntable molding machine at a constant speed. Sieving with 12 mesh and 9 mesh sieve to obtain spherical catalyst with diameter of 1.7-2.2mm, wet ball of about 45 kg;

45kg of the wet pellets obtained above were dried at 120℃for 24 hours, and then calcined at 550℃for 6 hours. Finally, the spherical catalyst C12 with the molecular sieve content of 85% is obtained.

C12 samples have crush strength σ= 40.18N/particle.

TABLE 3 Table 3

Examples 21 to 24

Examples 21 to 24 are provided to illustrate the catalytic reaction results of the metal-containing Silicate-1 molecular sieve-containing spherical catalysts prepared in examples 17 to 20 in a vapor phase Beckmann rearrangement reaction.

The reaction conditions were the same as in example 9. The results are shown in Table 4.

TABLE 4 Table 4

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Claims (36)

1. A spherical catalyst comprising a metal Silicate-1 molecular sieve, characterized in that: the catalyst comprises 75-95 wt% of metal-containing Silicate-1 molecular sieve and 5-25 wt% of binder based on dry weight of the catalyst; the BET specific surface area of the metal-containing Silicate-1 molecular sieve is 400-500m ² /g, metal content 15-5000ppm; the particle size of the catalyst is 1-2.5mm, and the crushing strength sigma is 32.0-45.0N/particle.

2. The spherical catalyst according to claim 1, wherein the metal-containing Silicate-1 molecular sieve, A _HB ：A _ISO Is (15-50): 1, A _HB And A _ISO Respectively represent 3400cm wave number in the infrared spectrogram of the metal-containing Silicate-1 molecular sieve ^-1 The summation wave number is 3725cm ^-1 Peak intensity at that point, expressed as peak area.

3. The spherical catalyst according to claim 1, wherein the catalyst comprises 85-90 wt% metal-containing silicalite-1 molecular sieve and 10-15 wt% binder on a dry basis, based on the weight of the catalyst on a dry basis; the particle size of the catalyst is 1.5-2mm, and the crushing strength sigma is 35.0-43.0N/particle.

4. The spherical catalyst according to claim 1, wherein the metal is at least one metal element selected from transition metal elements, group IIIA and group IVA elements.

5. The spherical catalyst according to claim 1, wherein the metal-containing Silicate-1 molecular sieve is at least one metal selected from group IVB and group VB elements.

6. The spherical catalyst according to claim 1, wherein the metal is at least one of Ti, nb, ta, ga, la, ge, sn and Pb.

7. The spherical catalyst according to claim 1, wherein the metal is present in an amount of 15-4000ppm, preferably in an amount of 50-800ppm, more preferably in an amount of 200-500ppm.

8. The spherical catalyst according to claim 1, wherein the BET specific surface area is 300 to 500m ² /g; the external specific surface area is 20-100m ² /g; the grain diameter is 0.01-1 mu m; the relative crystallinity is 70% -110%.

9. The spherical catalyst according to claim 1, wherein the BET specific surface area is 350 to 500m ² Per gram, the external specific surface area is 50-85m ² Preferably, the BET specific surface area is 440 to 480m, per gram, of 0.1 to 0.3 mu m ² Per gram, external specific surface area of 20-80m ² The grain diameter is 0.15-0.3 mu m, and the relative crystallinity is 80-90%; more preferably, the external specific surface area is 50-85m ² /g; most preferably, the external specific surface area is 55-75m ² /g。

10. The spherical catalyst according to claim 1, wherein the binder is selected from one or more of ethanol, glycerin, silica sol, alumina sol and water glass.

11. The spherical catalyst according to claim 1, wherein the binder is silica sol having a sodium ion content of 10 to 500ppm, siO ₂ The content is 20-45 wt%.

12. A method of forming a spherical catalyst comprising a metal Silicate-1 molecular sieve according to any one of claims 1 to 10, comprising:

(1) Synthesizing metal-containing Silicate-1 molecular sieve: a silicon source,Carrying out hydrothermal crystallization on a colloid mixture obtained by mixing a metal source, a fluorine-containing compound, an organic template agent and water to obtain a crystallized product, and washing, separating, drying and roasting to obtain the metal-containing Silicate-1 molecular sieve, wherein the silicon source is as follows: fluorine-containing compound: organic template agent: the molar ratio of water is 1 (0.01-0.50): 0.05-0.50): 5-100; the silicon source: the weight ratio of the metal source is (100-100000): 1, a step of; the silicon source is SiO ₂ A meter, wherein the metal source is calculated by metal element; and, a step of, in the first embodiment,

(2) Shaping: under the rotating operation condition of a turntable molding machine, placing a 200-500-mesh metal-containing Silicate-1 molecular sieve into the turntable molding machine, mixing and contacting with water and/or a first binder to obtain first spherical particles with the diameter of 0.1-1mm, and adding a 100-1000-mesh metal-containing Silicate-1 molecular sieve and a second binder to obtain second spherical particles with the diameter of 1-2.5 mm; and drying and roasting the second spherical particles to obtain the spherical catalyst containing the metal Silicate-1 molecular sieve.

13. The method of claim 12, wherein the silicon source is at least one selected from the group consisting of silica gel, silica sol, and organosilicate.

14. The method of claim 13, wherein the organosilicate is methyl orthosilicate and/or ethyl orthosilicate.

15. The method of claim 12, wherein the metal source is a water-soluble compound or an oil-soluble compound containing metal ions.

16. The method of claim 15, wherein the metal source is at least one of a metal-containing inorganic salt, an alcohol metal compound, and an ester metal compound.

17. The method of claim 16 wherein the metal source is TiCl ₄ 、NbCl ₅ 、C ₁₀ H ₃₀ O ₅ Ta、Ga(NO ₃ ) ₃ 、La(NO ₃ ) ₃ 、GeCl ₄ 。

18. The method of claim 12, wherein the organic template is at least one selected from the group consisting of fatty amine compounds, alcohol amine compounds, and quaternary amine base compounds.

19. The method of claim 18, wherein the organic templating agent is an alkyl quaternary ammonium base having 1-4 carbon atoms.

20. The method of claim 19, wherein the alkyl quaternary ammonium base compound is tetraethylammonium hydroxide and/or tetrapropylammonium hydroxide.

21. The method of claim 12, wherein the fluorine-containing compound is selected from the group consisting of a water-soluble compound containing fluorine and an oil-soluble compound.

22. The method of claim 21, wherein the fluorine-containing compound is at least one of hydrofluoric acid, ammonium fluoride, boron fluoride, and fluosilicic acid.

23. The method of claim 12, wherein the mixing sequence of (1) is: adding a metal source into a silicon source, adding an organic template agent and water after the metal source is completely dissolved, performing a hydrolysis process at normal temperature for 6-12h, performing alcohol removal at 50-90 ℃ for 12-48h after the hydrolysis is complete, and finally adding a fluorine-containing compound, and uniformly mixing to obtain a colloid mixture.

24. The process of claim 12 wherein said water of (1) is added in an amount of 20-40% by weight of the molecular sieve feedstock.

25. The method of claim 12, wherein the hydrothermal crystallization is performed at a temperature of 80-170 ℃ for 20-100 hours.

26. The method of claim 12, wherein in the rotational operating condition of the rotary table forming machine in (2), the inclination angle of the rotary table is 40-55 ° and the rotational speed of the rotary table is 10-50rpm.

27. The method according to claim 12, wherein one or more selected from sesbania powder, graphite, activated carbon, paraffin, stearic acid, glycerin, oxalic acid, tartaric acid, citric acid, starch, polyethylene glycol, polyvinyl alcohol, polyethylene oxide, polyacrylamide, cellulose methyl cool, cellulose, nitric acid, hydrochloric acid, acetic acid, formic acid, ammonia water, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide are further added as an auxiliary agent for the molding in (2).

28. The method of claim 12 wherein the water is added in an amount of 20-40% by weight of the molecular sieve feedstock.

29. The method of claim 12 wherein said second binder comprises 2-25% by weight of said 100-1000 mesh metal-containing Silicate-1 molecular sieve.

30. A metal-containing silicalite-1 molecular sieve based catalyst prepared by the method of any one of claims 12-29.

31. A process for preparing caprolactam from cyclohexanone oxime, characterized in that it comprises carrying out a gas phase beckmann rearrangement reaction under rearrangement reaction conditions by contacting cyclohexanone oxime in the presence of a solvent with the spherical catalyst comprising metal Silicate-1 molecular sieve according to any one of claims 1-11 and 30.

32. Process according to claim 31, characterized in that it is carried out under a nitrogen atmosphere, the molar ratio of said nitrogen to said cyclohexanone oxime being (10-80): 1. the preferred molar ratio is (30-60): 1

33. Process according to claim 31, wherein the molar ratio of solvent to cyclohexanone oxime is (2-10): 1. preferably, the molar ratio of said solvent to said cyclohexanone oxime is (3-8): 1, a step of;

34. the method according to claim 31, wherein the solvent is at least one selected from fatty alcohols having 1 to 6 carbon atoms, preferably methanol and/or ethanol.

35. The method of claim 31, wherein the rearrangement reaction conditions comprise: the weight space velocity of cyclohexanone oxime is 0.1-20h ^-1 The reaction temperature is 300-500 ℃, and the reaction pressure is 0.1-0.5MPa.

36. Process according to claim 31, further comprising first mixing cyclohexanone oxime with water at 1: (0.01-2.5) in a molar ratio.