A method for preparing diisopropyl ether by propylene hydration
By using a supported hierarchical porous Hβ molecular sieve catalyst, the problems of low conversion rate and selectivity in the preparation of diisopropyl ether by propylene hydration in the existing technology have been solved, achieving high efficiency catalyst activity and stability, which is suitable for industrial production.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- DALIAN INSTITUTE OF CHEMICAL PHYSICS CHINESE ACADEMY OF SCIENCES
- Filing Date
- 2024-12-02
- Publication Date
- 2026-06-02
AI Technical Summary
Existing catalysts exhibit low propylene conversion and diisopropyl ether selectivity during the hydration of propylene, and their poor catalyst stability makes it difficult to meet industrial requirements.
The supported hierarchical porous Hβ molecular sieve catalyst was prepared by means of alkaline treatment, drying and calcination, and active components such as CuO, Fe2O3 and CoO were loaded to improve the activity and stability of the catalyst.
It improves the conversion rate of propylene and the selectivity of diisopropyl ether, has good catalyst stability, is suitable for large-scale production, and has high yield and is environmentally friendly.
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Abstract
Description
Technical Field
[0001] This application relates to a method for preparing diisopropyl ether by hydration of propylene, which belongs to the field of chemical engineering. Background Technology
[0002] Diisopropyl ether (DIPE) is an important industrial solvent that can be mixed with other solvents such as alcohol, chloroform, and benzene. Because it is poorly soluble in water, it can be used as an extractant for industrial raw materials. Utilizing its high octane number and good antifreeze properties, DIPE can be used as a gasoline additive. It not only prevents lead from being added to gasoline but also prevents unburned olefins from being present in exhaust gases, thus addressing NOx emissions. x The problems arising from emissions and the evaporation of light olefins. In the environmental protection industry, DIPE can be used to treat wastewater from natural gas plants to reduce water pollution. Due to its wide range of applications, DIPE has long been a research hotspot both domestically and internationally.
[0003] Currently, DIPE is mainly obtained through two routes: ① separation from the byproducts of the propylene to isopropanol production process; ② preparation by isopropanol dehydration, indirect hydration of propylene, direct hydration of propylene, and alcohol-olefin synthesis.
[0004] UOP's patent US5,371,301 discloses a one-step hydration etherification process for propylene to isopropanol and diisopropyl ether using a sulfonated divinylbenzene-styrene copolymer cation exchange resin as a catalyst in the presence of an organic solvent (sulfolane). This patent, using a cation exchange resin as a catalyst, suffers from drawbacks such as poor thermal stability, easy shedding of the active component, and difficulty in regeneration. Mobil's patent US5,231,233 discloses a propylene hydration etherification method using a columnar MCM-36 molecular sieve as a catalyst; however, this catalyst exhibits low hydration activity and low selectivity for diisopropyl ether, for example, at 100 psig, 160°C, and H2O / C320. ＝ =48 / 52 (%), LHSV=0.69h -1 Under these conditions, the propylene conversion rate was only 17.6 wt%, and the diisopropyl ether selectivity was only 10.9 wt%. Patent EP323 268 discloses a propylene hydration process using β-zeolite as a catalyst at 1000 psig, 162°C, propylene / water (mol) = 1:1, and propylene feed space velocity (WHSV) = 0.33 h⁻¹. -1 Under these conditions, the propylene conversion rate was 56%, the DIPE selectivity was 54%, and the propylene hydration etherification activity, especially the diisopropyl ether selectivity, remained low. Summary of the Invention
[0005] To address the aforementioned issues, this application describes the application of a catalyst obtained through a specific preparation method in the hydration reaction of propylene to diisopropyl ether, which can improve the conversion rate of propylene and the selectivity of diisopropyl ether.
[0006] According to one aspect of this application, a method for preparing diisopropyl ether from propylene hydration is provided, wherein a raw material containing propylene and water is contacted with a catalyst and reacted to obtain a product containing diisopropyl ether.
[0007] The catalyst is composed of a support and an active component loaded on the surface of the support;
[0008] The carrier is an Hβ molecular sieve;
[0009] The active component is selected from at least one of CuO, Fe2O3, and CoO;
[0010] The supported multi-level porous molecular sieve has an active component loading of 1-4 wt%.
[0011] Optionally, in the supported multi-level porous molecular sieve, the loading of the active component is any value among 1wt%, 2wt%, 3wt%, and 4wt%, or a range between any two.
[0012] The catalyst is obtained through the following steps:
[0013] The Hβ molecular sieve was treated with an alkaline solution, heated, filtered and washed until neutral, dried and calcined to obtain a hierarchical porous molecular sieve; the hierarchical porous molecular sieve was immersed in an aqueous solution containing an active component precursor, dried and calcined to obtain the supported hierarchical porous molecular sieve.
[0014] The supported multi-level porous molecular sieve has micropores and mesopores;
[0015] The micropores have a pore size of 1.5–2.0 nm and a pore volume of 0.20–0.25 cm³. 3 / g;
[0016] The mesopores have a pore size of 3.0–3.5 nm and a pore volume of 0.15–0.20 cm³. 3 / g;
[0017] The specific surface area of the supported multi-level porous molecular sieve is 250–280 m². 2 / g.
[0018] The alkaline solution is selected from at least one of NaAlO2 aqueous solution and NaHCO3 aqueous solution;
[0019] The concentration of the alkaline solution is 0.2–0.6 mol / L;
[0020] Optionally, the concentration of the alkaline solution is any value among 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, 0.5 mol / L, and 0.6 mol / L, or a range between any two.
[0021] The solid-liquid ratio of the Hβ molecular sieve to the alkaline solution is 1:(5~10)g / ml.
[0022] Optionally, the solid-liquid ratio of the Hβ molecular sieve to the alkaline solution is any value among 1:5 g / ml, 1:6 g / ml, 1:7 g / ml, 1:8 g / ml, 1:9 g / ml, and 1:10 g / ml, or any range between two of these values.
[0023] The heating temperature is 65–90°C;
[0024] Optionally, the heating temperature is any value among 65°C, 70°C, 80°C, and 90°C, or a range between any two.
[0025] The heating time is 1 to 5 hours;
[0026] Optionally, the heating time is any value among 1h, 2h, 3h, 4h, and 5h, or a range between any two.
[0027] The number of times the filter is washed is 2 to 4.
[0028] The drying temperature is 80–130°C;
[0029] Optionally, the drying temperature is any value among 80°C, 90°C, 100°C, 110°C, 120°C, and 130°C, or a range between any two.
[0030] The drying time is 8–24 hours;
[0031] Optionally, the drying time is any value among 8h, 16h, and 24h, or a range between any two.
[0032] The calcination temperature is 450–650°C;
[0033] Optionally, the calcination temperature is any value among 450°C, 500°C, 550°C, 600°C, and 650°C, or a range between any two.
[0034] The calcination time is 1 to 6 hours.
[0035] Optionally, the calcination time is any value among 1h, 2h, 3h, 4h, 5h, and 6h, or a range between any two.
[0036] The active component precursor is selected from at least one of ferric sulfate, ferric chloride, copper sulfate, copper nitrate, and cobalt sulfate.
[0037] The drying temperature is 80–130°C;
[0038] Optionally, the drying temperature is any value among 80°C, 90°C, 100°C, 110°C, 120°C, and 130°C, or a range between any two.
[0039] The drying time is 6–24 hours;
[0040] Optionally, the drying time is any value among 6h, 12h, 18h, and 24h, or a range between any two.
[0041] The roasting temperature is 450–650°C;
[0042] Optionally, the roasting temperature is any value among 450°C, 500°C, 550°C, 600°C, and 650°C, or a range between any two.
[0043] The roasting time is 1 to 6 hours.
[0044] Optionally, the roasting time is any value among 1h, 2h, 3h, 4h, 5h, and 6h, or a range between any two.
[0045] In the raw materials, the molar ratio of propylene to water is 1:3 to 8;
[0046] Optionally, the molar ratio of propylene to water in the raw material is any value from 1:3, 1:4, 1:5, 1:6, 1:7, 1:8 or any range between the two.
[0047] The mass hourly space velocity (MSV) of the propylene is 0.2–10 h⁻¹. -1 .
[0048] Optionally, the mass hourly space velocity (MSV) of the propylene is 0.2 h⁻¹. -1 0.5h -1 1h -1 2h -1 3h -1 4h -1 5h -1 6h -1 7h -1 8h -1 9h -1 10h -1 Any value in the range or any value between the two.
[0049] The reaction temperature is 140–180°C;
[0050] Optionally, the temperature of the reaction is any value of 140°C, 150°C, 160°C, 170°C, or 180°C, or a range between any two.
[0051] The reaction is carried out at a pressure of 4–10 MPa.
[0052] Optionally, the pressure of the reaction is any value of 4 MPa, 5 MPa, 6 MPa, 7 MPa, 8 MPa, 9 MPa, 10 MPa, or a range between any two.
[0053] The beneficial effects that this application can produce include:
[0054] 1) The catalyst provided in this application can be applied to the reaction of propylene hydration to prepare diisopropyl ether, and can improve the conversion rate of propylene and the selectivity of diisopropyl ether. The prepared alkali-modified hierarchical porous molecular sieve with transition metal loading has excellent catalyst activity and stability.
[0055] 2) The preparation method of the catalyst provided in this application is stable, controllable, and reproducible.
[0056] 3) The method for preparing diisopropyl ether by propylene hydration provided in this application uses the catalyst provided in this application, which has a fast reaction rate and high yield, and can be applied to large-scale production.
[0057] 4) Compared to the severe desilication caused by NaOH, the NaAlO2 solution used in this application for alkaline treatment is relatively mild. Slight etching preserves the molecular sieve structure and increases its mesopores and active sites. The transition metal loading increases the L-acid centers in the β-zeolite, making the catalyst more conducive to the formation of diisopropyl ether during the reaction. Furthermore, it exhibits good dispersion on the surface of the hierarchical porous molecular sieve. The synthesized catalyst not only has high activity but also good stability and does not pollute the environment; the products are also easily separated. While removing framework aluminum, some Al replenishes silicon vacancies. Attached Figure Description
[0058] Figure 1 The nitrogen physisorption-desorption curves of the hierarchical porous molecular sieve in catalyst 1 of Example 1 of this application are shown. Detailed Implementation
[0059] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.
[0060] The endpoints and any values of the ranges disclosed in this application are not limited to the precise ranges or values, but should be understood to include those approximations of such ranges or values. For numerical ranges, the endpoint values of the various ranges and individual point values can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.
[0061] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.
[0062] Unless otherwise specified, the raw materials used in the embodiments of this application were purchased commercially or prepared by known methods. Unless otherwise specified, the analytical methods used in the embodiments employed conventional instrument settings and conventional analytical methods.
[0063] In this embodiment, the initial Hβ molecular sieve was produced by the catalyst factory of Nankai University.
[0064] Characterization of specific surface area and pore size distribution
[0065] Specific surface area and pore volume were analyzed, and pore size distribution was characterized using a Quanta QuadraSorb SI4 physical adsorption analyzer.
[0066] Specific surface area and pore volume analysis were performed under the following conditions: 0.1 g of catalyst was loaded into a quartz adsorption tube and vacuum-treated at 350 °C for 12 h to remove moisture and impurities adsorbed by the molecular sieve. Nitrogen adsorption / desorption experiments were conducted at 77.4 K. The Brunauer-Emmett-Teller (BET) equation was used to calculate the microporous specific surface area of the sample, and the t-plot method was used to calculate the microporous specific surface area, microporous pore volume, mesoporous specific surface area, and mesoporous pore volume of the molecular sieve sample. The BJH method was used to obtain the pore size distribution of the sample.
[0067] Gas chromatography characterization
[0068] The composition of the products from the hydration of propylene to diisopropyl ether was analyzed using an Agilent 7890B gas chromatograph (FID detector, HP-1 column).
[0069] The propylene conversion rate and diisopropyl ether selectivity in the embodiments of this application are calculated as follows:
[0070] Propylene conversion rate = (mass of propylene consumed) * 100% / (mass of propylene feed)
[0071] Diisopropyl ether selectivity = mass of diisopropyl ether product * 100% / mass of propylene reacted.
[0072] Example 1: Preparation of Catalyst
[0073] Maintaining the solution temperature at 80℃, Hβ molecular sieve with a solid-liquid ratio (g / ml) of 1:8 was treated with a 0.5 mol / L NaAlO2 solution for 3 h, washed three times until neutral, dried at 120℃ for 12 h, and calcined at 500℃ for 6 h to obtain a hierarchical porous molecular sieve material. The hierarchical porous molecular sieve material was impregnated in a copper sulfate solution that resulted in a CuO content of 3 wt% in the catalyst, dried at 120℃ for 12 h, and calcined at 500℃ for 6 h to obtain a CuO-supported hierarchical porous molecular sieve catalyst, denoted as Catalyst 1. # .
[0074] Example 2 Preparation of Catalyst
[0075] Maintaining the solution temperature at 65℃, Hβ molecular sieve with a solid-liquid ratio (g / ml) of 1:7 was treated with a 0.3 mol / L NaAlO2 solution for 2 h, washed twice until neutral, dried at 100℃ for 16 h, and calcined at 550℃ for 4 h to obtain a hierarchical porous molecular sieve material. The hierarchical porous molecular sieve material was impregnated in a ferric chloride solution that resulted in a Fe2O3 content of 2 wt% in the catalyst, dried at 100℃ for 16 h, and calcined at 550℃ for 4 h to obtain a Fe2O3-supported hierarchical porous molecular sieve catalyst, denoted as catalyst 2. # .
[0076] Example 3: Preparation of Catalyst
[0077] Maintaining the solution temperature at 70℃, Hβ molecular sieve with a solid-liquid ratio (g / ml) of 1:9 was treated with a 0.4 mol / L NaHCO3 solution for 1 h, washed 5 times until neutral, dried at 90℃ for 18 h, and calcined at 600℃ for 3 h to obtain a hierarchical porous molecular sieve material. The hierarchical porous molecular sieve material was impregnated in a ferric sulfate solution that resulted in a Fe2O3 content of 1 wt% in the catalyst, dried at 90℃ for 18 h, and calcined at 600℃ for 3 h to obtain a Fe2O3-supported hierarchical porous molecular sieve catalyst, denoted as catalyst 3. # .
[0078] Example 4: Preparation of Catalyst
[0079] Maintaining the solution temperature at 90℃, Hβ molecular sieve with a solid-liquid ratio (g / ml) of 1:6 was treated with a 0.2 mol / L NaAlO2 solution for 4 h, washed four times until neutral, dried at 110℃ for 22 h, and calcined at 450℃ for 1 h to obtain a hierarchical porous molecular sieve material. The hierarchical porous molecular sieve material was impregnated in a cobalt sulfate-copper nitrate solution that could achieve a CoO content of 4 wt% in the catalyst, dried at 110℃ for 22 h, and calcined at 450℃ for 1 h to obtain a CoO-supported hierarchical porous molecular sieve catalyst, denoted as catalyst 4. # .
[0080] Example 5: Preparation of Catalyst
[0081] Maintaining the solution temperature at 85℃, Hβ molecular sieve with a solid-liquid ratio (g / ml) of 1:10 was treated with a 0.6 mol / L NaHCO3 solution for 5 h, washed three times until neutral, dried at 80℃ for 8 h, and calcined at 650℃ for 2 h to obtain a hierarchical porous molecular sieve material. The hierarchical porous molecular sieve material was impregnated in a copper nitrate solution that resulted in a CuO content of 3 wt% in the catalyst, dried at 80℃ for 8 h, and calcined at 650℃ for 2 h to obtain a CuO-supported hierarchical porous molecular sieve catalyst, denoted as catalyst 5. # .
[0082] Example 6 Preparation of Catalyst
[0083] Maintaining the solution temperature at 75℃, Hβ molecular sieve with a solid-liquid ratio (g / ml) of 1:5 was treated with a 0.5 mol / L NaHCO3 solution for 3 h, washed twice until neutral, dried at 130℃ for 14 h, and calcined at 500℃ for 5 h to obtain a hierarchical porous molecular sieve material. The hierarchical porous molecular sieve material was impregnated in a copper sulfate solution that resulted in a CuO content of 2 wt% in the catalyst, dried at 130℃ for 14 h, and calcined at 500℃ for 5 h to obtain a CuO-supported hierarchical porous molecular sieve catalyst, denoted as Catalyst 6. # .
[0084] Example 7 Preparation of Catalyst
[0085] Maintaining the solution temperature at 80℃, Hβ molecular sieve with a solid-liquid ratio (g / ml) of 1:8 was treated with a 0.4 mol / L NaAlO2 solution for 4 h, washed 5 times until neutral, dried at 120℃ for 20 h, and calcined at 550℃ for 6 h to obtain a hierarchical porous molecular sieve material. The hierarchical porous molecular sieve material was impregnated in a cobalt sulfate solution that could achieve a CoO content of 4 wt% in the catalyst, dried at 120℃ for 20 h, and calcined at 550℃ for 6 h to obtain a CoO-supported hierarchical porous molecular sieve catalyst, denoted as Catalyst 7. # .
[0086] Example 8: Preparation of Catalyst
[0087] Maintaining the solution temperature at 90℃, Hβ molecular sieve with a solid-liquid ratio (g / ml) of 1:5 was treated with a 0.2 mol / L NaHCO3 solution for 2 h, washed four times until neutral, dried at 110℃ for 10 h, and calcined at 600℃ for 4 h to obtain a hierarchical porous molecular sieve material. The hierarchical porous molecular sieve material was then impregnated in a ferric chloride solution that resulted in a Fe2O3 content of 1 wt% in the catalyst, dried at 110℃ for 10 h, and calcined at 600℃ for 4 h to obtain a Fe2O3-supported hierarchical porous molecular sieve catalyst, denoted as Catalyst 8. # .
[0088] Example 9 Preparation of Catalyst
[0089] Maintaining the solution temperature at 85℃, Hβ molecular sieve with a solid-liquid ratio (g / ml) of 1:7 was treated with a 0.3 mol / L NaAlO2 solution for 5 h, washed three times until neutral, dried at 90℃ for 24 h, and calcined at 450℃ for 2 h to obtain a hierarchical porous molecular sieve material. The hierarchical porous molecular sieve material was then impregnated in a copper nitrate solution that resulted in a CuO content of 1 wt% in the catalyst, dried at 90℃ for 24 h, and calcined at 450℃ for 2 h to obtain a CuO-supported hierarchical porous molecular sieve catalyst, denoted as Catalyst 9. # .
[0090] Example 10 Preparation of Catalyst
[0091] Maintaining the solution temperature at 70℃, Hβ molecular sieve with a solid-liquid ratio (g / ml) of 1:9 was treated with a 0.6 mol / L NaHCO3 solution for 1 h, washed four times until neutral, dried at 80℃ for 12 h, and calcined at 650℃ for 3 h to obtain a hierarchical porous molecular sieve material. The hierarchical porous molecular sieve material was impregnated in a ferric sulfate solution that resulted in a Fe2O3 content of 3 wt% in the catalyst, dried at 80℃ for 12 h, and calcined at 650℃ for 3 h to obtain a Fe2O3-supported hierarchical porous molecular sieve catalyst, denoted as Catalyst 10. # .
[0092] Example 11 Preparation of Catalyst
[0093] Maintaining the solution temperature at 75℃, Hβ molecular sieve with a solid-liquid ratio (g / ml) of 1:6 was treated with a 0.5 mol / L NaAlO2 solution for 3 h, washed 5 times until neutral, dried at 100℃ for 16 h, and calcined at 500℃ for 5 h to obtain a hierarchical porous molecular sieve material. The hierarchical porous molecular sieve material was impregnated in a copper sulfate solution that could achieve a CuO content of 4 wt% in the catalyst, dried at 100℃ for 16 h, and calcined at 500℃ for 5 h to obtain a CuO-supported hierarchical porous molecular sieve catalyst, denoted as Catalyst 11. # .
[0094] Example 12 Preparation of Catalyst
[0095] Maintaining the solution temperature at 65℃, Hβ molecular sieve with a solid-liquid ratio (g / ml) of 1:10 was treated with a 0.4 mol / L NaHCO3 solution for 2 h, washed twice until neutral, dried at 130℃ for 14 h, and calcined at 550℃ for 1 h to obtain a hierarchical porous molecular sieve material. The hierarchical porous molecular sieve material was impregnated in a copper sulfate solution that resulted in a CuO content of 2 wt% in the catalyst, dried at 130℃ for 14 h, and calcined at 550℃ for 1 h to obtain a CuO-supported hierarchical porous molecular sieve catalyst, denoted as Catalyst 12.# .
[0096] Example 13 Preparation of Catalyst
[0097] Maintaining the solution temperature at 80℃, Hβ molecular sieve with a solid-liquid ratio (g / ml) of 1:8 was treated with a 0.3 mol / L NaHCO3 solution for 4 h, washed four times until neutral, dried at 120℃ for 18 h, and calcined at 600℃ for 6 h to obtain a hierarchical porous molecular sieve material. The hierarchical porous molecular sieve material was impregnated in a ferric sulfate solution that resulted in a Fe2O3 content of 3 wt% in the catalyst, dried at 120℃ for 18 h, and calcined at 600℃ for 6 h to obtain a Fe2O3-supported hierarchical porous molecular sieve catalyst, designated as catalyst 13. # .
[0098] Example 14 Preparation of Catalyst
[0099] Maintaining the solution temperature at 85℃, Hβ molecular sieve with a solid-liquid ratio (g / ml) of 1:8 was treated with a 0.6 mol / L NaAlO2 solution for 3 h, washed three times until neutral, dried at 110℃ for 20 h, and calcined at 450℃ for 5 h to obtain a hierarchical porous molecular sieve material. The hierarchical porous molecular sieve material was impregnated in a cobalt sulfate solution that could achieve a CoO content of 2 wt% in the catalyst, dried at 110℃ for 20 h, and calcined at 450℃ for 5 h to obtain a CoO-supported hierarchical porous molecular sieve catalyst, designated as catalyst 14. # .
[0100] Example 15 Preparation of Catalyst
[0101] Maintaining the solution temperature at 75℃, Hβ molecular sieve with a solid-liquid ratio (g / ml) of 1:7 was treated with a 0.2 mol / L NaAlO2 solution for 5 h, washed twice until neutral, dried at 100℃ for 10 h, and calcined at 650℃ for 4 h to obtain a hierarchical porous molecular sieve material. The hierarchical porous molecular sieve material was impregnated in a copper sulfate solution that resulted in a CuO content of 1 wt% in the catalyst, dried at 100℃ for 10 h, and calcined at 650℃ for 4 h to obtain a CuO-supported hierarchical porous molecular sieve catalyst, denoted as Catalyst 15. # .
[0102] Example 16 Preparation of Catalyst
[0103] Maintaining the solution temperature at 80℃, Hβ molecular sieve with a solid-liquid ratio (g / ml) of 1:9 was treated with a 0.5 mol / L NaHCO3 solution for 3 h, washed 5 times until neutral, dried at 130℃ for 12 h, and calcined at 500℃ for 6 h to obtain a hierarchical porous molecular sieve material. The hierarchical porous molecular sieve material was impregnated in a copper sulfate solution that could achieve a CuO content of 4 wt% in the catalyst, dried at 130℃ for 12 h, and calcined at 500℃ for 6 h to obtain a CuO-supported hierarchical porous molecular sieve catalyst, denoted as Catalyst 16. # .
[0104] Example 17 Comparative Catalyst
[0105] This embodiment differs from Example 1 in that it does not include the loading process of transition metal oxides; otherwise, it is the same as Example 1. Specifically, the solution temperature is maintained at 80°C, and the Hβ molecular sieve with a solid-liquid ratio (g / ml) of 1:8 is treated with a 0.5 mol / L NaAlO2 solution for 3 hours, washed three times until neutral, dried at 120°C for 12 hours, and calcined at 500°C for 6 hours to obtain a hierarchical porous molecular sieve material, denoted as Catalyst 17. # .
[0106] Example 17: Evaluation of the Catalyst's Reaction
[0107] The catalyst 1 obtained above # ~17 # It is used in the reaction of propylene hydration to produce diisopropyl ether, and the reaction conditions are shown in Table 1.
[0108] Catalyst 1, which has been tableted, pulverized, and sieved, # Up to 17 # The mixture is loaded into a fixed-bed reactor, and the temperature is raised to the reaction temperature. Propylene and water are then pumped into the reactor separately.
[0109] The composition of the products was analyzed using an Agilent 7890B gas chromatograph (FID detector, HP-1 column), and the results are shown in Table 1.
[0110] Table 1
[0111] Example 1 Catalyst # ~16 # Comparative catalyst 17 # Reaction conditions and results for the preparation of diisopropyl ether by propylene hydration.
[0112]
[0113]
[0114]
[0115] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.
Claims
1. A method for preparing diisopropyl ether by propylene hydration, characterized in that, The raw materials containing propylene and water are contacted with a catalyst and reacted to obtain a product containing diisopropyl ether. The catalyst is a supported hierarchical porous molecular sieve, which consists of a support and an active component supported on the surface of the support; The carrier is an Hβ molecular sieve; The active component is selected from at least one of CuO, Fe2O3, and CoO; The loading of the active ingredient is 1–4 wt%.
2. The method according to claim 1, characterized in that, The supported multi-level porous molecular sieve has micropores and mesopores; The micropores have a pore size of 1.5–2.0 nm and a pore volume of 0.20–0.25 cm³. 3 / g; The mesopores have a pore size of 3.0–3.5 nm and a pore volume of 0.15–0.20 cm³. 3 / g; The specific surface area of the supported multi-level porous molecular sieve is 250–280 m². 2 / g.
3. The method according to claim 1, characterized in that, The supported multi-level porous molecular sieve is obtained through the following steps: The Hβ molecular sieve was treated with alkaline solution, heated, filtered and washed until neutral, dried and calcined to obtain a hierarchical porous molecular sieve; the hierarchical porous molecular sieve was immersed in an aqueous solution containing an active component precursor, dried and calcined to obtain the supported hierarchical porous molecular sieve. Preferably, the alkaline solution is selected from at least one of NaAlO2 aqueous solution and NaHCO3 aqueous solution; The concentration of the alkaline solution is 0.2–0.6 mol / L; The solid-liquid ratio of the Hβ molecular sieve to the alkaline solution is 1:(5~10)g / ml.
4. The method according to claim 3, characterized in that, The heating temperature is 65–90°C; The heating time is 1 to 5 hours; The drying temperature is 80–130°C; The drying time is 8–24 hours; The calcination temperature is 450–650°C; The calcination time is 1 to 6 hours.
5. The method according to claim 3, characterized in that, The active component precursor is selected from at least one of ferric sulfate, ferric chloride, copper sulfate, copper nitrate, and cobalt sulfate.
6. The method according to claim 3, characterized in that, The drying temperature is 80–130°C; The drying time is 6–24 hours; The roasting temperature is 450–650°C; The roasting time is 1 to 6 hours.
7. The method according to claim 3, characterized in that, In the raw materials, the molar ratio of propylene to water is 1:3 to 8; The mass hourly space velocity (MSV) of the propylene is 0.2–10 h⁻¹. -1 .
8. The method according to claim 3, characterized in that, The reaction temperature is 140–180°C; The reaction is carried out at a pressure of 4–10 MPa.