A method for preparing a supported molecular sieve catalyst, the catalyst prepared therefrom, and its application.
By using Ni and ruthenium nitride in supported molecular sieve catalysts, the problems of high cost and environmental pollution in propanol preparation have been solved, achieving high conversion and selectivity in the efficient preparation of propanol, which is applicable to the chemical, pharmaceutical and food industries.
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
- 2024-11-26
- Publication Date
- 2026-05-26
AI Technical Summary
Existing methods for preparing propanol suffer from high costs, severe environmental pollution, and difficulties in product separation.
Propanol was prepared by supporting a molecular sieve catalyst with Ni and ruthenium nitride as active components via the hydrogenation reaction of propionic acid. The mass content of Ni and ruthenium nitride in the catalyst was 0.5–2 wt%, and the preparation was carried out under specific process conditions.
It achieves high conversion of propionic acid and high selectivity of propanol. The catalyst has high activity and good stability, and the products are easy to separate, making it suitable for large-scale production.
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Abstract
Description
Technical Field
[0001] This application relates to a method for preparing a supported molecular sieve catalyst, the catalyst prepared therefrom, and its application, belonging to the field of catalysts. Background Technology
[0002] Propanol is an important industrial raw material widely used in chemical, pharmaceutical, and food industries. In the chemical industry, propanol can be used as a solvent and a raw material for synthesizing other organic compounds; in the pharmaceutical industry, propanol can be used to prepare drugs and disinfectants; and in the food industry, propanol is commonly used as a food additive. Propanol can also be obtained through bio-fermentation, a green and environmentally friendly production method. Therefore, propanol's renewable and environmentally friendly nature makes it a promising candidate for renewable energy production.
[0003] Propanol can be obtained through the hydration of ethylene or propylene. Additionally, propanol can also be obtained through bio-fermentation. Summary of the Invention
[0004] The advantage of the molecular sieve catalyst prepared in this application, which uses Ni and ruthenium nitride as active components, lies in the fact that ruthenium nitride in this catalyst possesses noble metal-like properties and can replace expensive noble metals. The active components Ni and ruthenium nitride are well dispersed on the molecular sieve surface. When applied to the hydrogenation of propionic acid to propanol, the synthesized catalyst not only exhibits high activity but also good stability and does not pollute the environment; the products are also easily separated.
[0005] According to one aspect of this application, a method for preparing a supported molecular sieve catalyst is provided, characterized in that...
[0006] The supported molecular sieve catalyst is supported on Ni and ruthenium nitride, wherein the mass content of Ni is 0.5-2 wt%, the mass content of ruthenium nitride is 0.5-2 wt%, and the remainder is molecular sieve.
[0007] Optionally, the upper limit of the Ni mass content in the catalyst is selected from 2 wt% and 1.5 wt%, and the lower limit is selected from 0.5 wt% and 1 wt%.
[0008] Optionally, the upper limit of the ruthenium nitride mass content in the catalyst is selected from 2 wt% and 1.5 wt%, and the lower limit is selected from 0.5 wt% and 1 wt%.
[0009] Includes the following steps:
[0010] (1) The molecular sieve was immersed in a solution containing nickel salt, dried, calcined, and reduced with hydrogen to obtain a Ni-loaded molecular sieve.
[0011] (2) The Ni-supported molecular sieve was impregnated with a ruthenium nitride complex solution and evaporated to dryness to obtain the supported molecular sieve catalyst.
[0012] The molecular sieve is selected from at least one of ZSM-5 molecular sieve, MOR molecular sieve, MCM-41 molecular sieve, and Beta molecular sieve.
[0013] The nickel salt is selected from nickel nitrate and / or nickel sulfate;
[0014] The drying temperature is 80–130°C;
[0015] Optionally, the upper limit of the drying temperature is selected from 130°C, 120°C, 110°C, 100°C or 90°C, and the lower limit is selected from 80°C, 90°C, 100°C, 110°C or 120°C.
[0016] The drying time is 6 to 24 hours;
[0017] Optionally, the upper limit of the drying time is selected from 24 hours, 22 hours, 20 hours, 18 hours, and 16 hours, and the lower limit is selected from 6 hours, 8 hours, 10 hours, 12 hours, and 14 hours.
[0018] The calcination temperature is 450–650°C;
[0019] Optionally, the upper limit of the calcination temperature is selected from 650℃, 600℃, and 550℃, and the lower limit is selected from 450℃, 500℃, and 550℃.
[0020] The calcination time is 1 to 6 hours;
[0021] Optionally, the upper limit of the calcination time is selected from 6 hours, 5 hours, and 4 hours, and the lower limit is selected from 1 hour, 2 hours, and 3 hours;
[0022] The temperature for hydrogen reduction is 350–500°C;
[0023] Optionally, the upper limit of the hydrogen reduction temperature is selected from 500°C and 450°C, and the lower limit is selected from 350°C and 400°C.
[0024] The hydrogen reduction time is 3 to 6 hours;
[0025] Optionally, the upper limit of the hydrogen reduction time is selected from 6 hours and 5 hours, and the lower limit is selected from 3 hours and 4 hours;
[0026] The hydrogen flow rate for hydrogen reduction is 20–60 ml / min;
[0027] Optionally, the upper limit of the hydrogen flow rate for hydrogen reduction is selected from 60 ml / min, 50 ml / min, and 40 ml / min, and the lower limit is selected from 20 ml / min, 30 ml / min, and 40 ml / min;
[0028] The heating rate for hydrogen reduction is 0.5–2 °C / min.
[0029] Optionally, the upper limit of the heating rate for hydrogen reduction is selected from 2℃ / min and 1.5℃ / min, and the lower limit is selected from 0.5℃ / min and 1℃ / min;
[0030] The temperature for evaporation is 60–100°C;
[0031] Optionally, the upper limit of the evaporation temperature is selected from 100°C and 80°C, and the lower limit is selected from 60°C and 80°C;
[0032] The evaporation time is 0.5 to 2 hours.
[0033] Optionally, the upper limit of the evaporation time is selected from 2 hours and 1.5 hours, and the lower limit is selected from 0.5 hours and 1 hour.
[0034] The ruthenium nitride complex solution was obtained through the following steps:
[0035] Aminothiourea, 1,2-dihydroxybenzene, dilute hydrochloric acid, and ruthenium chloride trihydrate were mixed and heated to obtain the ruthenium nitride complex solution.
[0036] Optionally, the ruthenium nitride complex solution is obtained through the following steps:
[0037] Aminothiourea, 1,2-dihydroxybenzene, and dilute hydrochloric acid were mixed and stirred to obtain dimercaptobenzene. Ruthenium chloride trihydrate was then added and heated to obtain the ruthenium nitride complex solution.
[0038] The total mass of aminothiourea, 1,2-dihydroxybenzene, dilute hydrochloric acid, and ruthenium chloride trihydrate is 100 wt%, wherein aminothiourea accounts for 3-4.6 wt%, 1,2-dihydroxybenzene accounts for 8.6-13.8 wt%, ruthenium chloride trihydrate accounts for 2.9-7.3 wt%, and the remainder is dilute hydrochloric acid.
[0039] Optionally, the upper limit of the mass content of aminothiourea is selected from 4.6 wt% and 4 wt%, and the lower limit is selected from 3 wt% and 3.5 wt%; the upper limit of the mass content of 1,2-dihydroxybenzene is selected from 13.8 wt%, 13 wt%, 12.5 wt%, 12 wt%, 11.5 wt%, and 11 wt%, and the lower limit is selected from 8.6 wt%, 9 wt%, 9.5 wt%, 10 wt%, 10.5 wt%, and 11 wt%; the upper limit of the mass content of ruthenium chloride trihydrate is selected from 7.3 wt%, 7 wt%, 6.5 wt%, 6 wt%, and 5.5 wt%, and the lower limit is selected from 2.9 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, and 5 wt%.
[0040] The heating temperature is 120–200°C;
[0041] Optionally, the upper limit of the heating temperature is selected from 200℃, 190℃, 180℃, 170℃, and 160℃, and the lower limit is selected from 120℃, 130℃, 140℃, 150℃, and 160℃;
[0042] The heating time is 2 to 5 hours.
[0043] Optionally, the upper limit of the heating time is selected from 5 hours and 4 hours, and the lower limit is selected from 2 hours and 3 hours;
[0044] Optionally, the method includes the following steps:
[0045] (1) Molecular sieves are impregnated in nickel salt solutions to obtain catalyst precursors, and the obtained catalyst precursors are dried and calcined to obtain molecular sieves loaded with NiO.
[0046] (2) The molecular sieve loaded with NiO is reduced in a hydrogen atmosphere to obtain Ni / molecular sieve;
[0047] (3) Synthesize ruthenium nitride complex by impregnating the above Ni / molecular sieve in ruthenium nitride complex solution and evaporating the solution to obtain Ni, ruthenium nitride / molecular sieve catalyst.
[0048] According to another aspect of this application, a supported molecular sieve catalyst prepared by the above-described preparation method is provided.
[0049] According to another aspect of this application, a method for preparing propanol from propionic acid by hydrogenation is provided, comprising the following steps:
[0050] Propionic acid is reacted with a catalyst under a hydrogen atmosphere to produce propanol.
[0051] The catalyst is the one described above. When applied in the hydrogenation of propionic acid to propanol, this catalyst achieves a high conversion rate of propionic acid and a high selectivity for propanol.
[0052] The propionic acid mass hourly space velocity (HHSV) is 0.5–2 h⁻¹. -1 ;
[0053] Optionally, the upper limit of the propionic acid mass hourly space velocity is selected from 2 hours. -1 1.5h -1 The lower limit is selected from 0.5h. -1 1h -1 .
[0054] The hydrogen flow rate in the hydrogen atmosphere is 100–140 ml / min;
[0055] Optionally, the upper limit of the hydrogen flow rate in the hydrogen atmosphere is selected from 140 ml / min, 130 ml / min, and 120 ml / min, and the lower limit is selected from 100 ml / min, 110 ml / min, and 120 ml / min;
[0056] The reaction temperature is 130–160°C;
[0057] Optionally, the upper limit of the reaction temperature is selected from 160°C and 150°C, and the lower limit is selected from 130°C and 140°C.
[0058] The reaction is carried out at a pressure of 5–7 MPa.
[0059] Optionally, the upper limit of the reaction pressure is selected from 7 MPa and 6 MPa, and the lower limit is selected from 5 MPa and 6 MPa;
[0060] Optionally, the propionic acid is a 5 wt% aqueous solution of propionic acid.
[0061] The beneficial effects that this application can produce include:
[0062] 1) The catalyst provided in this application can be applied to the reaction of propionic acid hydrogenation to prepare propanol, and can achieve high conversion of propionic acid and high selectivity of propanol. The molecular sieve supported on active components Ni and ruthenium nitride has excellent catalyst activity and stability.
[0063] 2) The preparation method of the catalyst provided in this application is stable, controllable, and reproducible.
[0064] 3) The method for preparing propanol by hydrogenation of propionic acid 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. Detailed Implementation
[0065] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.
[0066] 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.
[0067] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.
[0068] 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.
[0069] In the embodiments of this application, ZSM-5, MOR, MCM-41, and Beta molecular sieves were produced by the catalyst factory of Nankai University.
[0070] Gas chromatography characterization
[0071] The composition of the products from the hydrogenation of propionic acid to propanol was analyzed using an Agilent 7890B gas chromatograph (FID detector, FFAP column).
[0072] The propionic acid conversion rate and propanol selectivity in the embodiments of this application are calculated as follows:
[0073] Propionic acid conversion rate = (mass of propionic acid consumed) * 100% / (mass of propionic acid feed)
[0074] Propanol selectivity = mass of propanol product * 100% / mass of propionic acid reacted.
[0075] Example 1: Preparation of Catalyst
[0076] ZSM-5 molecular sieve was impregnated in a nickel nitrate solution with a NiO content of 1 wt%, dried in an oven at 120 °C for 20 hours, and calcined at 550 °C for 4 hours to obtain a molecular sieve material loaded with NiO. This material was then subjected to reduction treatment in a hydrogen atmosphere (hydrogen flow rate of 40 ml / min), with the temperature increased to 500 °C at a rate of 1 °C / min and reduced for 4 hours to obtain a catalyst of molecular sieve loaded with the active component Ni. 3.5 wt% aminothiourea and 10 wt% 1,2-dihydroxybenzene were then used. 4 wt% ruthenium chloride trihydrate, with the balance being dilute hydrochloric acid, was mixed with aminothiourea and 1,2-dihydroxybenzene. Dilute hydrochloric acid was added, and the mixture was stirred at high speed to obtain dimercaptobenzene. Ruthenium chloride trihydrate was then added, and the mixture was placed in a hydrothermal reactor. The temperature was raised to 160°C, and the reaction was carried out for 3 hours to obtain a ruthenium nitride complex solution. The synthesized Ni / ZSM-5 molecular sieve was impregnated in the ruthenium nitride complex solution (ruthenium nitride content 1.5 wt%), and the solution was evaporated to dryness at 80°C for 1 hour to obtain a Ni, ruthenium nitride / ZSM-5 molecular sieve catalyst, denoted as Catalyst 1. # .
[0077] Comparative Example 1: Comparative Catalyst
[0078] This embodiment, compared to Example 1, does not include the loading process for Ni and ruthenium nitride. ZSM-5 molecular sieve was selected, crushed, and sieved to a 20-mesh material, designated as catalyst 17. # .
[0079] Following these steps, adjust the type, amount, and reaction parameters of each raw material to obtain sequence number 1. # ~17 # A series of catalysts, denoted as Catalyst 1 # Catalyst 17 # As shown in Tables 1 and 2 below:
[0080] Table 1 Catalyst 1 # Catalyst 17 # Raw material selection and parameters
[0081]
[0082]
[0083] The explanations for each column in Table 1 above are as follows:
[0084] Aluminum sources: aluminum nitrate (Al1), aluminum sulfate (Al2);
[0085] Molecular sieves: ZSM-5 molecular sieve (part 1), MOR molecular sieve (part 2), MCM-41 molecular sieve (part 3), Beta molecular sieve (part 4).
[0086] Table 2 Catalyst 1 # Catalyst 17 # Raw material selection and parameters
[0087]
[0088]
[0089] Example 17: Evaluation of the Catalyst's Reaction
[0090] The catalyst 1 obtained above # ~17 # It is applied to the hydrogenation of propionic acid to prepare propanol, and the reaction conditions are shown in Table 3.
[0091] Catalyst 1, which has been tableted, pulverized, and sieved, # Up to 17 # The feedstock is loaded into a fixed-bed reactor, heated to the reaction temperature, and then pumped in.
[0092] The composition of the products was analyzed using an Agilent 7890B gas chromatograph (FID detector, FFAP column), and the results are shown in Table 3.
[0093] Table 3 Catalyst 1 # ~16 # Catalyst and Comparative Example 17 # Reaction conditions and results of catalyst used in the hydrogenation of propionic acid to propanol
[0094]
[0095]
[0096] 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 a supported molecular sieve catalyst, characterized in that, The supported molecular sieve catalyst is supported on Ni and ruthenium nitride, wherein the mass content of Ni is 0.5-2 wt%, the mass content of ruthenium nitride is 0.5-2 wt%, and the remainder is molecular sieve. Includes the following steps: (1) The molecular sieve was immersed in a solution containing nickel salt, dried, calcined, and reduced with hydrogen to obtain a Ni-loaded molecular sieve. (2) The Ni-supported molecular sieve was impregnated with a ruthenium nitride complex solution and evaporated to dryness to obtain the supported molecular sieve catalyst. The molecular sieve is selected from at least one of ZSM-5 molecular sieve, MOR molecular sieve, MCM-41 molecular sieve, and Beta molecular sieve.
2. The preparation method according to claim 1, characterized in that, The nickel salt is selected from nickel nitrate and / or nickel sulfate; The drying temperature is 80–130°C; The drying time is 6 to 24 hours; The calcination temperature is 450–650°C; The calcination time is 1 to 6 hours; The temperature for hydrogen reduction is 350–500°C; The hydrogen reduction time is 3 to 6 hours; The hydrogen flow rate for hydrogen reduction is 20–60 ml / min; The heating rate for hydrogen reduction is 0.5–2 °C / min.
3. The preparation method according to claim 1, characterized in that, The temperature for evaporation is 60–100°C; The evaporation time is 0.5 to 2 hours.
4. The preparation method according to claim 1, characterized in that, The ruthenium nitride complex solution was obtained through the following steps: Aminothiourea, 1,2-dihydroxybenzene, dilute hydrochloric acid, and ruthenium chloride trihydrate were mixed and heated to obtain the ruthenium nitride complex solution.
5. The preparation method according to claim 4, characterized in that, The ruthenium nitride complex solution was obtained through the following steps: Aminothiourea, 1,2-dihydroxybenzene, and dilute hydrochloric acid were mixed and stirred to obtain dimercaptobenzene. Ruthenium chloride trihydrate was then added and heated to obtain the ruthenium nitride complex solution.
6. The preparation method according to claim 5, characterized in that, The total mass of aminothiourea, 1,2-dihydroxybenzene, dilute hydrochloric acid, and ruthenium chloride trihydrate is 100 wt%, wherein aminothiourea accounts for 3-4.6 wt%, 1,2-dihydroxybenzene accounts for 8.6-13.8 wt%, ruthenium chloride trihydrate accounts for 2.9-7.3 wt%, and the remainder is dilute hydrochloric acid.
7. The preparation method according to claim 5, characterized in that, The heating temperature is 120–200°C; The heating time is 2 to 5 hours.
8. A supported molecular sieve catalyst prepared by the preparation method according to any one of claims 1 to 7.
9. A method for preparing propanol by hydrogenation of propionic acid, characterized in that, Includes the following steps: Propionic acid is reacted with a catalyst under a hydrogen atmosphere to produce propanol. The catalyst is the catalyst according to claim 8.
10. The method according to claim 9, characterized in that, The propionic acid mass hourly space velocity (HHSV) is 0.5–2 h⁻¹. -1 ; The hydrogen flow rate in the hydrogen atmosphere is 100–140 ml / min; The reaction temperature is 130–160°C; The reaction is carried out at a pressure of 5–7 MPa.