An organic-inorganic composite material catalyst, a preparation method thereof, and a method for preparing diols by hydrating an alkylene oxide

Abstract

The application discloses an organic-inorganic composite material catalyst, a preparation method thereof and a method for preparing diols by hydrating alkylene oxide. The organic-inorganic composite material catalyst has the following general structure: [M(Salen)X and / or M'(Salen)]@SC, wherein SC is a material with a cage-shaped pore; M(Salen)X and / or M'(Salen) is an active center, M and M' are metal ions, Salen is a Shiff base derivative, and X is an axial anion. The organic-inorganic composite material catalyst of the application uses a material with a specific cage-shaped pore structure and without strong acidity as a base material, and then introduces the active center into the cage-shaped pore through a'ship in a bottle' method, and is used in the hydration reaction of water and alkylene oxide, and has high activity and excellent recycling performance in the preparation of diols by hydrating alkylene oxide under high and low water ratios and short reaction time.

Description

Technical Field

[0001] This invention relates to the field of hydration of epoxides to diols, specifically to an organic-inorganic composite catalyst and its preparation method, and a method for hydration of epoxides to diols. Background Technology

[0002] Ethylene glycol, as an important organic chemical raw material and intermediate, is widely used in the production of polyester fibers, engineering plastics, bottle resins, films, antifreeze, and coolants. It is also commonly used in the production of plasticizers, desiccants, lubricants, and many other chemical products (Guangdong Chemical Industry, 2011, 38: 242). In 2017, the global production capacity of ethylene glycol was 39.25 million tons / year, while consumption was nearly 30 million tons / year. Currently, industrial production of ethylene glycol mainly involves the direct hydration of ethylene oxide. To reduce the yield of byproducts such as diethylene glycol and triethylene glycol, this technology requires the reaction to be carried out under conditions where the molar ratio of water to ethylene oxide feed (referred to as the water ratio) is 20-25:1, resulting in a water content in the product exceeding 85 wt.%. Removing such a large amount of water requires the use of a multi-effect evaporation system and consumes a significant amount of steam (e.g., when the water ratio is 20:1, producing 1 ton of ethylene glycol requires 2.4 tons of steam). This ultimately results in a long production process, complex equipment, and high energy consumption for ethylene glycol, leading to high production costs (Industrial Catalysis, 2002, 10:3; Petrochemicals, 2010, 39:562; Chemical Intermediates, 2009:59). Therefore, developing low-water-ratio catalytic hydration technology for ethylene oxide is imperative, and the core of this development lies in catalyst development.

[0003] To date, various acid and base catalysts have been developed, such as anion / cation exchange resins (CN102372815A), Sn zeolite (CN104437607A), and supported metal oxides (CN100413579A). However, the activity of these catalysts needs further improvement and still requires a relatively high water ratio (≥ 8:1) to achieve good catalytic performance. A recent breakthrough is the development of the pseudo-homogeneous nanocage catalyst FDU-12-[Co(Salen)X] (X = OAc- / OTs-) (CN102688776A) by the Dalian Institute of Chemical Physics, which can achieve a high ethylene glycol yield of over 98% under conditions where the water ratio is only 2:1. However, FDU-12-[Co(Salen)X](X = OAc- / OTs-) exhibits poor stability. On one hand, it requires activation and regeneration to achieve good recyclability; on the other hand, existing encapsulation techniques cause the active centers Co(Salen)X (X = OAc- / OTs-) to leak into the reaction system during use, affecting not only the catalyst's recyclability but also introducing impurities into the product, severely hindering its industrial application. Subsequently, Co(Salen)X (X = OAc- / OTs-)-based polymer catalysts were developed, exhibiting higher activity, but still requiring activation and regeneration for good recyclability (Chem. Eur. J. 2017, 23, 11504 - 11508; CN108129669A). Therefore, there is an urgent need in this field to develop catalysts with both high activity and stability for the hydration of epoxides to diols at low water ratios. Summary of the Invention

[0004] To address the problems existing in the prior art, this invention provides an organic-inorganic composite catalyst, its preparation method, and a method for the hydration of epoxides to produce diols. The catalyst used in the method for the hydration of epoxides to produce diols of this invention is an organic-inorganic composite material, expressed as: [M(Salen)X and / or M'(Salen)]@SC, where SC is a material with cage-like channels; M(Salen)X and / or M'(Salen) are active centers, M and M' are metal ions, Salen is a Shiff base derivative, and X is an axial anion.

[0005] One objective of this invention is to provide an organic-inorganic composite catalyst having the following general structural formula:

[0006] [M(Salen)X and / or M'(Salen)]@SC

[0007] Wherein, SC is a material with cage-like channels; M(Salen)X and / or M'(Salen) are active centers, M and M' are metal ions, Salen is a Shiff base derivative, and X is an axial anion.

[0008] In the above technical solution,

[0009] The Si / Na atomic ratio of the material with cage-like channels is less than that of Si / Al, which makes the material with cage-like channels non-acidic, making it very suitable for the introduction of active centers and the maintenance of the high activity of the active centers.

[0010] In the above technical solution,

[0011] The pore size of the cage-like channels is greater than or equal to 1.1 nm in all three dimensions, preferably between 1.1 nm and 3.0 nm; and / or,

[0012] The cage-like channel has an opening size between 0.4 nm and 0.8 nm in all three dimensions.

[0013] In the above technical solution,

[0014] The material with cage-like channels is prepared by the following steps:

[0015] 1) Mix silicon source, aluminum source, sodium hydroxide and water evenly, and then age to obtain a directing agent solution;

[0016] 2) The material with cage-like channels is obtained by mixing the guiding agent solution, silicon source, aluminum source and water obtained in step 1), crystallizing and calcining.

[0017] In the above technical solution,

[0018] The silicon sources in steps 1) and 2) may be the same or different, and are independently selected from at least one of water glass, silica sol, silica fume, and tetraethyl orthosilicate; and / or,

[0019] The aluminum sources in steps 1) and 2) may be the same or different, and are independently selected from at least one of sodium aluminate, sodium metaaluminate, aluminum isopropoxide, aluminum hydroxide, aluminum sulfate, and aluminum nitrate.

[0020] In the above technical solution,

[0021] In step 1),

[0022] The ratio of silicon source, aluminum source, sodium hydroxide, and water is (15-35):1:(2-5):(10-20); and / or,

[0023] The aging time is 12-72 hours, and the aging temperature is 20-40℃.

[0024] In the above technical solution,

[0025] In step 2),

[0026] The mass ratio of the aluminum source to water is 1:(5-10); and / or,

[0027] The volume ratio of the directing agent solution, water, and silicon source is (0.05-0.3):1:(0.4-0.7); and / or,

[0028] The crystallization temperature is 60-120℃; and / or the crystallization time is 24-72 h; and / or the calcination temperature is 380-600℃; and / or the calcination time is 4-8 h.

[0029] In the above technical solution,

[0030] The M is selected from at least one trivalent ion of transition metals and Group IIIA metals, preferably from Co. 3+ Fe 3+ Ga 3+ Al 3+ Cr 3+ At least one of them; and / or,

[0031] The M' is selected from at least one divalent ion of a transition metal, preferably from Cu. 2+ Ni 2+ Zn 2+ At least one of them.

[0032] In the above technical solution,

[0033] X is selected from PF6. - BF4 - SbF6 - Cl - , Br - I - At least one of acetate, benzenesulfonate, benzoate, substituted acetate, substituted benzenesulfonate, and substituted benzoate.

[0034] In the above technical solution,

[0035] The Shiff base derivatives are at least one selected from N,N′-disalynyl-1,2-cyclohexanediamine, N,N′-disalynyl-1,2-ethylenediamine, N,N′-disalynyl-1,2-phenylenediamine, substituted N,N′-disalynyl-1,2-cyclohexanediamine, substituted N,N′-disalynyl-1,2-ethylenediamine, and substituted N,N′-disalynyl-1,2-phenylenediamine.

[0036] In the above technical solution,

[0037] The mass ratio of the material with cage-like channels to the active center is 1:(0.05-0.12), preferably 1:(0.2-0.8).

[0038] A second objective of this invention is to provide a method for preparing an organic-inorganic composite catalyst, which is one of the objectives of this invention, comprising assembling the material having cage-like channels with active centers M(Salen)X and / or M'(Salen) to obtain the organic-inorganic composite catalyst.

[0039] In the above technical solution,

[0040] The method includes:

[0041] (1) The material with cage-like channels is mixed and reacted with an aldehyde compound solution and a diamine compound solution to obtain a material with cage-like channels containing ligands;

[0042] (2) Disperse the ligand-containing material with cage-like channels obtained in step (1) in an organic solvent and react it with a metal compound containing M and / or a metal compound containing M';

[0043] When the metal compound in the above reaction raw materials is only a metal compound containing M', the reaction in step (2) yields the organic-inorganic composite catalyst;

[0044] When the metal compound in the above reaction raw materials includes a metal compound containing M, a compound containing X is simultaneously dispersed in the above organic solvent to participate in the reaction; or the reaction may further include the following steps:

[0045] (3) The reaction product of step (2) is mixed with the compound containing X, filtered, washed and dried to obtain the organic-inorganic composite catalyst.

[0046] In the above technical solution,

[0047] In step (1),

[0048] The aldehyde compound is selected from at least one of salicylaldehyde, 3-methylsalicylaldehyde, and 3,5-dimethylsalicylaldehyde; and / or,

[0049] The diamine compound is selected from at least one of cyclohexanediamine, phenylenediamine, ethylenediamine, or substituted cyclohexanediamine, phenylenediamine, or ethylenediamine; and / or,

[0050] The mass ratio of the material with cage-like channels to the aldehyde compound and the diamine compound is 1:(0.05-0.3):(0.01-0.1); and / or,

[0051] The reaction temperature is 60-90℃; and / or the reaction time ranges from 3 to 12 h.

[0052] In the above technical solution,

[0053] In step (2),

[0054] The metal compound containing M is selected from at least one compound of transition metals and Group IIIA metals, preferably from at least one of Co(OAc)₂·4H₂O, Fe(OH)(CH₃COO)₂, Ga(CH₃COO)₃, and Al(CH₃COO)₃; wherein Co is divalent in the compound Co(OAc)₂·4H₂O, but becomes trivalent upon reaction with X by combining with oxygen from the air; and / or,

[0055] The M'-containing metal compound is selected from at least one of transition metal compounds, preferably from at least one of Cu(CH3COO)2·H2O, Ni(CH3COO)2, and Zn(CH3COO)2; and / or,

[0056] The compound containing X is selected from at least one of ferrocene hexafluorophosphate, ferrocene tetrafluoroboric acid, silver hexafluoroantimonate, NaCl, NaBr, NaI, acetic acid, benzenesulfonic acid, benzoic acid, substituted acetic acid, substituted benzenesulfonic acid, substituted benzoic acid, substituted ferrocene hexafluorophosphate, and substituted ferrocene tetrafluoroboric acid.

[0057] In the above technical solution,

[0058] Preferably, the compound containing X is dissolved in at least one of dichloromethane, acetonitrile, ethanol, and methanol and then mixed with the product of step (2) or participates in the reaction of step (2).

[0059] In the above technical solution,

[0060] In step (2),

[0061] The reaction temperature is 60-120℃; and / or the reaction time is 2-12 h.

[0062] In the above technical solution,

[0063] In step (3),

[0064] The mixing temperature is 20-60℃; and / or the mixing time is 10-24 h.

[0065] A third objective of this invention is to provide a method for hydrating epoxides to produce diols, comprising the step of contacting epoxides and water with an organic-inorganic composite catalyst according to one objective of this invention or an organic-inorganic composite catalyst obtained by the preparation method according to another objective of this invention.

[0066] In the above technical solution,

[0067] The epoxide alkane has the following general formula:

[0068]

[0069] R1, R2, R3, and R4 may be the same or different, and each is independently a hydrogen atom or an alkyl group having 1-6 carbon atoms, preferably a hydrogen atom or an alkyl group having 1-2 carbon atoms.

[0070] This invention relates to an organic-inorganic composite catalyst. By using a material with a specific cage-like pore structure and lacking strong acidity as the base material, and then introducing active centers into the cage-like pores using a "ship-in-a-bottle" method, it is used in the hydration reaction of water and epoxides. On the one hand, its specific-sized cage opening completely eliminates the problem of active center loss; on the other hand, its suitable pore size within the cage is very conducive to the catalytic reaction of active centers through synergistic intermediate states. It exhibits high activity and excellent recyclability for the hydration of epoxides to diols under high and low water ratios and short reaction times. This solves the problems of existing catalysts for the hydration of epoxides to diols, which require high water ratios, long reaction times, and have limited recyclability, achieving unexpected technical results. Attached Figure Description

[0071] Figure 1 This is the XRD pattern of the catalyst prepared in Example 1;

[0072] The horizontal axis represents the 2θ angle, in degrees; the vertical axis represents the cumulative intensity. Detailed Implementation

[0073] The present invention will now be described in detail with reference to specific embodiments and accompanying drawings. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0074] All raw materials used in the examples are conventional commercially available raw materials.

[0075] In this embodiment of the invention, the dimensions of the material pores and the opening of the cage-like channels were measured by a physical adsorption instrument.

[0076] In the embodiments of the present invention, the Si / Na atomic number and Si / Al atomic ratio of the material with cage-like channels are obtained through material calculations.

[0077] Example 1

[0078] 1.08 g of sodium aluminate and 3.759 g of sodium hydroxide were dissolved in 15 mL of deionized water at room temperature. After the solution was clear, 10.35 mL of water glass (Na₂SiO₃·9H₂O) was added dropwise, and the mixture was stirred until homogeneous. The solution was aged overnight at room temperature to obtain a directing agent solution. 6.02 g of sodium aluminate was dissolved in 40 mL of deionized water at room temperature, and 6 mL of the above directing agent was added. The mixture was stirred until homogeneous, and 20 mL of water glass was added dropwise. After stirring until homogeneous, the solution was placed in a reactor and crystallized at 90 °C for 24 h. After filtration and washing with deionized water until neutral, the solution was dried and calcined at 450 °C for 5 h to obtain a material with cage-like channels. The channel size was between 1.1 nm and 3.0 nm in all three dimensions, the cage opening size was between 0.4 nm and 0.8 nm in all three dimensions, the Si / Na atomic ratio was 0.41, and the Si / Al atomic ratio was 2.75.

[0079] Weigh 2 g of the above-mentioned material with cage-like channels and disperse it in 10 mL of ethanol containing 0.244 g (2 mmol) salicylaldehyde. Then add 4 mL of ethanol solution containing 0.114 g (1 mmol) cyclohexanediamine. React at 88 °C for 3 h. After cooling to room temperature, filter and wash with ethanol to obtain a material with cage-like channels containing ligands. Disperse the obtained material in 14 mL of toluene. Under N2 protection, add dropwise a mixed solution of 0.7 mL of water and 7 mL of ethanol containing 0.249 g (1 mmol) Co(OAc)2·4H2O. Heat to 120 °C and react for 2 h. After cooling to room temperature, filter and wash with cold methanol to obtain a material containing Co. II The ligand has a cage-like pore structure. It was dispersed together with 0.331 g (1 mmol) of ferrocene hexafluorophosphate in a mixed solution of 15 mL dichloromethane and 15 mL acetonitrile, stirred openly at room temperature for 12 h, filtered, and thoroughly washed with n-hexane and dried to obtain catalyst A: [Co(Salen)PF6]@SC.

[0080] The XRD pattern of catalyst A is as follows Figure 1 As shown, by Figure 1 It can be seen that the material is highly crystalline and has high stability.

[0081] Example 2

[0082] The preparation process of the material with cage-like channels is the same as in Example 1.

[0083] 2 g of the material with cage-like channels was weighed and dispersed in 10 mL of ethanol containing 0.268 g (2 mmol) of 3-methylsalicylaldehyde. Then, 4 mL of ethanol solution containing 0.03 g (0.5 mmol) of ethylenediamine and 0.054 g (0.5 mmol) of phenylenediamine was added. The mixture was reacted at 88 °C for 3 h, cooled to room temperature, filtered, washed with ethanol, and dried to obtain a material with cage-like channels containing ligands. The obtained material was dispersed in 14 mL of toluene. Under N2 protection, a mixed solution of 0.7 mL of water and 7 mL of ethanol containing 0.249 g (1 mmol) of Co(OAc)2·4H2O was added dropwise. The mixture was heated to 120 °C and reacted for 2 h. The mixture was cooled to room temperature, filtered, washed with cold methanol, and dried to obtain a material containing Co. II The ligand has a cage-like pore structure. It was dispersed together with 0.265 g (1 mmol) of ferrocene tetrafluoroboric acid in a mixed solution of 15 mL dichloromethane and 15 mL acetonitrile, stirred openly at room temperature for 12 h, filtered, and thoroughly washed with n-hexane and dried to obtain catalyst B: [Co(Salen)BF4]@SC.

[0084] Example 3

[0085] The preparation process of the material with cage-like channels is the same as in Example 1.

[0086] 2 g of the material with cage-like channels was weighed and dispersed in 10 mL of ethanol containing 0.146 g (1 mmol) of 3,5-dimethylsalicylaldehyde and 0.134 g (1 mmol) of 3-methylsalicylaldehyde. Then, 4 mL of ethanol solution containing 0.0507 g (0.5 mmol) of cyclohexanediamine and 0.03 g (0.5 mmol) of ethylenediamine was added. The mixture was reacted at 88 °C for 3 h, cooled to room temperature, filtered, washed with ethanol, and dried to obtain a material with cage-like channels containing ligands. The obtained material was dispersed in 14 mL of toluene. Under N2 protection, a mixed solution of 0.7 mL of water and 7 mL of ethanol containing 0.249 g (1 mmol) of Co(OAc)2·4H2O was added dropwise. The mixture was heated to 120 °C and reacted for 2 h. The mixture was cooled to room temperature, filtered, washed with cold methanol, and dried to obtain a material containing Co. II The ligand has cage-like channels. It was dispersed together with 0.331 g (1 mmol) of ferrocene hexafluorophosphate in a mixed solution of 15 mL dichloromethane and 15 mL acetonitrile, stirred openly at room temperature for 12 h, filtered, and thoroughly washed with n-hexane and dried to obtain catalyst C: [Co(Salen)PF6]@SC.

[0087] Example 4

[0088] The preparation process of the material with cage-like channels is the same as in Example 1.

[0089] 2 g of the material with cage-like channels was weighed and dispersed in 10 mL of ethanol containing 0.146 g (1 mmol) of 3,5-dimethylsalicylaldehyde and 0.134 g (1 mmol) of 3-methylsalicylaldehyde. Then, 4 mL of ethanol solution containing 0.0507 g (0.5 mmol) of cyclohexanediamine and 0.03 g (0.5 mmol) of ethylenediamine was added. The mixture was reacted at 88 °C for 3 h, cooled to room temperature, filtered, washed with ethanol, and dried to obtain a material with cage-like channels containing ligands. The obtained material was dispersed in 14 mL of toluene. Under N2 protection, a mixed solution of 0.7 mL of water and 7 mL of ethanol containing 0.249 g (1 mmol) of Co(OAc)2·4H2O was added dropwise. The mixture was heated to 120 °C and reacted for 2 h. The mixture was cooled to room temperature, filtered, washed with cold methanol, and dried to obtain a material containing Co. II The ligand has a cage-like pore structure. It was dispersed together with 0.1655 g (0.5 mmol) of ferrocene hexafluorophosphate and 0.1325 g (0.5 mmol) of ferrocene tetrafluoroboric acid in a mixed solution of 15 mL dichloromethane and 15 mL acetonitrile. The mixture was stirred openly at room temperature for 12 h, filtered, and thoroughly washed with n-hexane and dried to obtain catalyst D: [Co(Salen)PF6, Co(Salen)BF4]@SC.

[0090] Example 5

[0091] The preparation process of the material with cage-like channels is the same as in Example 1.

[0092] 2 g of the material with cage-like channels was weighed and dispersed in 10 mL of ethanol containing 0.146 g (1 mmol) of 3,5-dimethylsalicylaldehyde and 0.122 g (1 mmol) of salicylaldehyde. Then, 4 mL of ethanol solution containing 0.054 g (0.5 mmol) of phenylenediamine and 0.03 g (0.5 mmol) of ethylenediamine was added. The mixture was reacted at 88 °C for 3 h, cooled to room temperature, filtered, washed with ethanol, and dried to obtain the material with cage-like channels containing ligands. The obtained material was dispersed in 14 mL of toluene, and 0.060 g (1 mmol) of CH3COOH was added. Then, a mixed solution of 0.7 mL of water and 7 mL of ethanol containing 0.194 g (1 mmol) of Fe(OH)(CH3COO)2 was added dropwise. The mixture was heated to 120 °C and reacted for 12 h. After filtration and separation, the catalyst E: [Fe(Salen)CH3COO]@SC was obtained after thorough washing and drying with ethanol.

[0093] Example 6

[0094] The preparation process of the material with cage-like channels is the same as in Example 1.

[0095] 2 g of the material with cage-like channels was weighed and dispersed in 10 mL of ethanol containing 0.146 g (1 mmol) of 3,5-dimethylsalicylaldehyde and 0.122 g (1 mmol) of salicylaldehyde. Then, 4 mL of ethanol solution containing 0.054 g (0.5 mmol) of phenylenediamine and 0.03 g (0.5 mmol) of ethylenediamine was added. The mixture was reacted at 88 °C for 3 h, cooled to room temperature, filtered, washed with ethanol, and dried to obtain the material with cage-like channels containing ligands. The obtained material was dispersed in 14 mL of toluene, and then 7 mL of ethanol solution containing 0.2 g (1 mmol) of Cu(CH3COO)2·H2O was added dropwise. The mixture was heated to 120 °C and reacted for 12 h. After filtration and separation, the catalyst F: [Cu(Salen)]@SC was obtained after thorough washing with ethanol and drying.

[0096] Example 7

[0097] 1.08 g of sodium aluminate and 3.759 g of sodium hydroxide were dissolved in 15 mL of deionized water at room temperature. After the solution was clarified, 10.35 mL of water glass was added dropwise, and the mixture was stirred until homogeneous. The solution was aged overnight at room temperature to obtain a directing agent solution. Then, 7 mL of the directing agent, 35 mL of water glass, 11 mL of aluminum sulfate solution (Al2(SO4)3 / 62.5H2O), 10 mL of sodium aluminate solution (Al2O3 / 1.76Na2O / 38.6H2O), and 16 mL of deionized water were stirred until homogeneous and placed in a reactor. The mixture was crystallized at 100 °C for 24 h, filtered, washed with deionized water until neutral, dried, and calcined at 450 °C for 5 h to obtain a material with cage-like channels. The channel size was between 1.1 nm and 3.0 nm in all three dimensions, the cage opening size was between 0.4 nm and 0.8 nm in all three dimensions, the Si / Na atom ratio was 0.44, and the Si / Al atom ratio was 5.94.

[0098] Weigh 2 g of the above-mentioned material with cage-like channels and disperse it in 10 mL of ethanol containing 0.244 g (2 mmol) salicylaldehyde. Then add 4 mL of ethanol solution containing 0.114 g (1 mmol) cyclohexanediamine. React at 88 °C for 3 h. After cooling to room temperature, filter and wash with ethanol to obtain a material with cage-like channels containing ligands. Disperse the obtained material in 14 mL of toluene. Under N2 protection, add dropwise a mixed solution of 0.7 mL of water and 7 mL of ethanol containing 0.249 g (1 mmol) Co(OAc)2·4H2O. Heat to 120 °C and react for 2 h. After cooling to room temperature, filter and wash with cold methanol to obtain a material containing Co. IIThe ligand has cage-like channels. It was dispersed together with 0.331 g (1 mmol) of ferrocene hexafluorophosphate in a mixed solution of 15 mL dichloromethane and 15 mL acetonitrile, stirred openly at room temperature for 12 h, filtered, and thoroughly washed with n-hexane and dried to obtain catalyst G: [Co(Salen)PF6]@SC.

[0099] Comparative Example 1

[0100] 1.08 g sodium aluminate and 3.759 g sodium hydroxide were dissolved in 15 mL of deionized water at room temperature. After the solution was clear, 10.35 mL of water glass was added dropwise, and the mixture was stirred until homogeneous. The solution was aged overnight at room temperature to obtain the directing agent solution. At room temperature, 6.02 g of sodium aluminate was dissolved in 40 mL of deionized water, and 6 mL of the above-mentioned directing agent was added. The mixture was stirred until homogeneous, and 20 mL of water glass was added dropwise. After stirring until homogeneous, the mixture was placed in a reactor and crystallized at 90 °C for 24 h. After filtration, the mixture was washed with deionized water until neutral and dried. Then, it was subjected to ion exchange five times with 0.1 mol / L ammonium chloride solution at a solid-liquid ratio of 1:10. After thorough washing with deionized water and drying, the mixture was calcined at 450 °C for 5 h to obtain an acidic material with cage-like channels. The channel size was between 1.1 nm and 3.0 nm in all three dimensions, the cage opening size was between 0.4 nm and 0.8 nm in all three dimensions, the Si / Al atomic number was 2.75, and it did not contain Na. Weigh 2 g of the above-mentioned cage-like porous material and disperse it in 10 mL of ethanol containing 0.146 g (1 mmol) of 3,5-dimethylsalicylaldehyde and 0.122 g (1 mmol) of salicylaldehyde. Then add 4 mL of ethanol solution containing 0.054 g (0.5 mmol) of phenylenediamine and 0.03 g (0.5 mmol) of ethylenediamine. React at 88 °C for 3 h. After cooling to room temperature, filter, wash and dry with ethanol to obtain a cage-like porous material containing ligands. Disperse the obtained material in 14 mL of toluene, then add dropwise 7 mL of ethanol solution containing 0.2 g (1 mmol) of Cu(CH3COO)2·H2O. Heat to 120 °C and react for 12 h. Filter and separate, wash thoroughly with ethanol and dry to obtain catalyst H.

[0101] Comparative Example 2

[0102] 4.1 g NaAlO2 and 2.325 g Na2O were dissolved in 360 g H2O under stirring at room temperature. Then, 29.7 g hexamethyleneimine and 150 g Si sol were added sequentially. After stirring until a homogeneous solution was obtained, the solution was transferred to a homogeneous reactor and reacted at 150 °C for 72 hours at 20 rpm. After filtration, the solution was thoroughly washed with deionized water and dried. Then, it was calcined at 550 °C for 6 hours to obtain a material with cage-like channels having a pore size between 1.1 nm and 3.0 nm in one dimension, between 0.6 nm and 0.9 nm in two dimensions, and a cage opening size between 0.4 nm and 0.8 nm in all three dimensions. Weigh 2 g of the above-mentioned cage-like porous material and disperse it in 10 mL of ethanol containing 0.146 g (1 mmol) of 3,5-dimethylsalicylaldehyde and 0.122 g (1 mmol) of salicylaldehyde. Then add 4 mL of ethanol solution containing 0.054 g (0.5 mmol) of phenylenediamine and 0.03 g (0.5 mmol) of ethylenediamine. React at 88 °C for 3 h, cool to room temperature, filter, wash with ethanol, and dry to obtain a cage-like porous material containing ligands. Disperse the obtained material in 14 mL of toluene, then add dropwise 7 mL of ethanol solution containing 0.2 g (1 mmol) of Cu(CH3COO)2·H2O. Heat to 120 °C and react for 12 h. Filter to separate, wash thoroughly with ethanol, and dry to obtain catalyst I.

[0103] Example 7-21

[0104] 1.32 g of ethylene oxide was weighed, and the performance of catalysts A, B, and C was investigated under the following conditions: temperature 20℃, pressure 1.0 MPa, water ratio 2:1, catalyst-to-ethylene oxide molar ratio 1:1000, and reaction time 7 h. Ethanol was added to terminate the reaction, and after centrifugation and drying, the used catalysts A, B, and C were directly used in the next catalytic reaction under the same conditions without activation or regeneration (this cycle was repeated four times). The results are shown in Table 1.

[0105] Table 1. Recyclability of Catalysts A, B, and C

[0106]

[0107] Examples 22-41

[0108] 1.32 g of ethylene oxide was weighed, and the performance of catalysts D, E, F, and G was investigated under the following conditions: temperature 40 ℃, pressure 1.0 MPa, water ratio 6:1, catalyst-to-ethylene oxide molar ratio 1:500, and reaction time 4 h. The reaction was terminated by adding ethanol, and after centrifugation and drying, the used catalysts D, E, F, and G were directly used in the next catalytic reaction under the same conditions without activation or regeneration (this cycle was repeated four times). The results are shown in Table 2.

[0109] Table 2. Recyclability of catalysts D, E, F, and G

[0110]

[0111] Examples 42-56

[0112] 1.74 g of propylene oxide was weighed and the performance of catalysts A, B, and C was investigated under the following conditions: temperature 40 ℃, pressure 1.0 MPa, water ratio 2:1, catalyst-to-propylene oxide molar ratio 1:1000, and reaction time 7 h. Ethanol was added to terminate the reaction. After centrifugation and drying, the used catalysts A, B, and C were directly used in the next catalytic reaction under the same conditions without activation or regeneration (this cycle was repeated four times). The results are shown in Table 3.

[0113] Table 3. Recyclability of Catalysts A, B, and C

[0114]

[0115] Examples 57-76

[0116] 1.74 g of propylene oxide was weighed and the performance of catalysts D, E, F, and G was investigated under the following conditions: temperature 60 ℃, pressure 1.0 MPa, water ratio 8:1, catalyst-to-propylene oxide molar ratio 1:500, and reaction time 4 h. Ethanol was added to terminate the reaction. After centrifugation and drying, the used catalysts D, E, F, and G were directly used in the next catalytic reaction under the same conditions without activation or regeneration (this cycle was repeated four times). The results are shown in Table 4.

[0117] Table 4. Recyclability of Catalysts D, E, F, and G

[0118]

[0119] Comparative Examples 3 and 4

[0120] 1.74 g of propylene oxide was weighed, and the performance of catalysts H and I was investigated under the following conditions: temperature 40 ℃, pressure 1.0 MPa, water ratio 2:1, catalyst-to-propylene oxide molar ratio 1:1000, and reaction time 7 h. The reaction was terminated by adding ethanol, and after centrifugation and drying, the used catalysts H and I were directly used in the next catalytic reaction under the same conditions without activation or regeneration. The results are shown in Table 6.

[0121] Table 6. Recyclability of Catalysts G and H

[0122]

[0123] As can be seen from Examples and Comparative Examples 1 and 3, the Si / Na atomic ratio of the material with cage-like channels prepared in Comparative Example 1 is not less than the Si / Al atomic ratio, and it is acidic, which is not suitable for the introduction of active centers and the maintenance of high activity of active centers. Therefore, compared with the catalyst in Example 6, its catalyst activity is low and its recyclability is also poor.

[0124] As can be seen from Examples and Comparative Examples 2 and 4, the appropriate cage-like pore size is very conducive to the catalytic reaction of the active center through the cooperative intermediate state. However, the material with cage-like pores prepared in Comparative Example 1 has two dimensions of pore size that are less than 1.1 nm, which is not within the scope of this invention. Therefore, the activity of its catalyst is also very low compared to the catalyst in Example 6.

[0125] As can be seen from Examples 1-76, the organic-inorganic composite catalyst of the present invention, by using a material with a specific cage-like pore structure and without strong acidity as the base material, and then introducing active centers into its cage-like pores through the "shipbuilding in a bottle" method, exhibits high activity and excellent recyclability in the hydration reaction of water and epoxide alkanes under high and low water ratios and short reaction times.

Claims

1. An organic-inorganic composite catalyst having the following general structural formula: [M(Salen)X and / or M'(Salen)]@SC in, SC is a material with cage-like channels, wherein the Si / Na atomic ratio of the material with cage-like channels is less than the Si / Al atomic ratio, the pore size of the cage-like channels is between 1.1 nm and 3.0 nm in all three dimensions, and the cage opening size of the cage-like channels is between 0.4 nm and 0.8 nm in all three dimensions; M(Salen)X and / or M'(Salen) are active centers, M and M' are metal ions, wherein M is selected from Co. 3+ Fe 3+ Ga 3+ Al 3+ Cr 3+ At least one of them, wherein M' is selected from Cu 2+ Ni 2+ Zn 2+ At least one of the following: Salen is a Shiff base derivative, wherein the Shiff base derivative is at least one of N,N′-disalicylate-1,2-cyclohexanediamine, N,N′-disalicylate-1,2-ethylenediamine, N,N′-disalicylate-1,2-phenylenediamine, substituted N,N′-disalicylate-1,2-cyclohexanediamine, substituted N,N′-disalicylate-1,2-ethylenediamine, or substituted N,N′-disalicylate-1,2-phenylenediamine; X is an axial anion, wherein X is selected from PF6. - BF4 - SbF6 - Cl - ,Br - I - At least one of acetate, benzenesulfonate, benzoate, substituted acetate, substituted benzenesulfonate, and substituted benzoate.

2. The organic-inorganic composite catalyst as described in claim 1, characterized in that: The material with cage-like channels is prepared by the following steps: 1) Mix silicon source, aluminum source, sodium hydroxide and water evenly, and then age to obtain a directing agent solution; 2) The material with cage-like channels is obtained by mixing the guiding agent solution, silicon source, aluminum source and water obtained in step 1), crystallizing and calcining.

3. The organic-inorganic composite catalyst as described in claim 2, characterized in that: The silicon sources in steps 1) and 2) may be the same or different, and are independently selected from at least one of water glass, silica sol, silica fume, and tetraethyl orthosilicate; and / or, The aluminum sources in steps 1) and 2) may be the same or different, and are independently selected from at least one of sodium aluminate, sodium metaaluminate, aluminum isopropoxide, aluminum hydroxide, aluminum sulfate, and aluminum nitrate.

4. The organic-inorganic composite catalyst as described in claim 2, characterized in that: In step 1), The ratio of silicon source, aluminum source, sodium hydroxide and water is (10-40):1:(2-5):(10-20).

5. The organic-inorganic composite catalyst as described in claim 2, characterized in that: In step 2), The ratio of silicon source, aluminum source, and water is (3-12):1:(5-10); and / or, The volume ratio of the directing agent solution to water is (0.05-0.7):1; and / or, The crystallization temperature is 60-120℃; and / or the crystallization time is 24-72 h; and / or the calcination temperature is 380-600℃; and / or the calcination time is 4-8 h.

6. The organic-inorganic composite catalyst as described in claim 1, characterized in that: The mass ratio of the material with cage-like channels to the active centers is 1:(0.05-0.12).

7. A method for preparing an organic-inorganic composite catalyst as described in any one of claims 1-6, comprising introducing the active center into the material having cage-like channels to obtain the organic-inorganic composite catalyst.

8. The method for preparing the organic-inorganic composite catalyst as described in claim 7, characterized in that... The method includes: (1) The material with cage-like channels is mixed and reacted with an aldehyde compound solution and a diamine compound solution to obtain a material with cage-like channels containing ligands; (2) Disperse the ligand-containing material with cage-like channels obtained in step (1) in an organic solvent and react it with a metal compound containing M and / or a metal compound containing M'; When the metal compound in the above reaction raw materials is only a metal compound containing M', the reaction in step (2) yields the organic-inorganic composite catalyst; When the metal compound in the above reaction raw materials includes a metal compound containing M, a compound containing X is simultaneously dispersed in the above organic solvent to participate in the reaction; or the reaction may further include the following steps: (3) The reaction product of step (2) is mixed with the compound containing X, filtered, washed and dried to obtain the organic-inorganic composite catalyst.

9. The preparation method according to claim 8, characterized in that: In step (1), The aldehyde compound is selected from at least one of salicylaldehyde, 3-methylsalicylaldehyde, and 3,5-dimethylsalicylaldehyde; and / or, The diamine compound is selected from at least one of cyclohexanediamine, phenylenediamine, ethylenediamine, or substituted cyclohexanediamine, phenylenediamine, or ethylenediamine; and / or, The mass ratio of the material with cage-like channels to the aldehyde compound and the diamine compound is 1:(0.05-0.3):(0.01-0.1); and / or, The reaction temperature is 60-90℃; and / or the reaction time ranges from 3 to 12 h.

10. The preparation method according to claim 8, characterized in that: In step (2), The metal compound containing M is selected from at least one of Co(OAc)₂·4H₂O, Fe(OH)(CH₃COO)₂, Ga(CH₃COO)₃, and Al(CH₃COO)₃; and / or, The M'-containing metal compound is selected from at least one of Cu(CH3COO)2·H2O, Ni(CH3COO)2, and Zn(CH3COO)2; and / or, The compound containing X is selected from at least one of ferrocene hexafluorophosphate, ferrocene tetrafluoroboric acid, silver hexafluoroantimonate, NaCl, NaBr, NaI, acetic acid, benzenesulfonic acid, benzoic acid, substituted acetic acid, substituted benzenesulfonic acid, substituted benzoic acid, substituted ferrocene hexafluorophosphate, and substituted ferrocene tetrafluoroboric acid.

11. The preparation method according to claim 8, characterized in that: In step (2), The reaction temperature is 60-120℃; and / or the reaction time is 2-12 h.

12. The preparation method according to claim 8, characterized in that: In step (3), The mixing temperature is 20-60℃; and / or the mixing time is 10-24 h.

13. A method for hydrating epoxides to produce diols, comprising the step of contacting epoxides and water with the organic-inorganic composite catalyst of any one of claims 1-6 or the organic-inorganic composite catalyst obtained by any one of the preparation methods of claims 7-12.

14. The method as described in claim 13, characterized in that: The epoxide alkane has the following general formula: Among them, R1, R2, R3, and R4 may be the same or different, and each is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

15. The method as described in claim 14, characterized in that: R1, R2, R3, and R4 may be the same or different, and each is independently a hydrogen atom or an alkyl group having 1-2 carbon atoms.

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