Catalyst for grease hydrogenation, preparation method thereof and grease hydrogenation method
By preparing a mesoporous hydroxyapatite-supported nickel-molybdenum catalyst, the problems of high cost and low activity of existing catalysts were solved, realizing low-cost, high-activity oil hydrogenation reaction and extending catalyst life.
Patent Information
- Application Number
- CN202511432607.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-10-09
- Publication Date
- 2026-02-10
AI Technical Summary
Existing catalysts suffer from high cost and limited reactivity in hydrodeoxygenation processes, especially precious metal catalysts which are expensive, while traditional non-precious metal catalysts have slightly poorer catalytic performance.
Hydroxyapatite was prepared using phosphate source, template agent and calcium source as support. By loading nickel salt and molybdate and combining with complexing agent to regulate the coordination state of metal ions, a catalyst with mesoporous structure was prepared, which avoids the sintering, agglomeration and loss of metal components and improves catalytic activity.
The prepared catalyst is low in cost, highly reactive, and exhibits excellent catalytic performance. It can effectively promote the adsorption of oil molecules and the dissociation of hydrogen, extend the catalyst life, and is suitable for industrial applications.
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Figure CN121490796A_ABST
Abstract
Description
Technical Field
[0001] This application relates to the field of oil and fat hydrogenation technology, specifically to catalysts for oil and fat hydrogenation and their preparation methods, and methods for hydrogenating oils and fats. Background Technology
[0002] To promote carbon dioxide emission reduction, the development of renewable and clean alternative energy sources has become particularly important. Compared with fossil fuels, biofuels have high calorific value, are renewable, and organisms such as plants absorb carbon dioxide during their growth, forming a closed carbon cycle. Therefore, biofuels have received widespread attention. Specifically, biofuels refer to energy forms that can replace traditional fossil fuels, produced using biological resources (such as plants, animals, and microorganisms) and their metabolic products as raw materials through biological, chemical, or physical methods.
[0003] Among the raw materials for biofuel production, waste cooking oil and other biological waste oils are not only abundant and widespread but also pose significant hazards. Therefore, utilizing waste oils to produce biofuels has become a key path to achieve waste resource utilization and green energy.
[0004] The main chemical components of waste oils include fatty acid glycerides, free fatty acids, and various impurities. The common method for converting waste oils into biofuels is hydrodeoxygenation, which converts waste oils into hydrocarbon fuels. Hydrodeoxygenation requires a catalyst, and currently, noble metal catalysts such as Pt, Pd, and Ru are widely used. However, noble metal catalysts have the disadvantage of high cost. There are also methods using non-noble metal catalysts, such as Cu, Ni, and Co, but traditional non-noble metal catalysts have limited reactivity and slightly poorer catalytic effects. Summary of the Invention
[0005] Based on this, this application provides a catalyst for the hydrogenation of oils and fats, a method for preparing the catalyst, and a method for hydrogenating oils and fats. The catalyst for the hydrogenation of oils and fats prepared in this application has the advantages of low cost, high reactivity, and excellent catalytic effect.
[0006] The first aspect of this application provides a method for preparing a catalyst for hydrogenating oils and fats, comprising the following steps:
[0007] Phosphoric acid source and template agent are mixed in the first solvent, the pH is adjusted to 10-12, calcium source is added, precipitation reaction and sintering are carried out to prepare hydroxyapatite;
[0008] The hydroxyapatite, nickel salt, molybdate, and complexing agent are mixed in a second solvent, and after loading treatment, the precipitate is collected.
[0009] The precipitate is heated and reduced to prepare the catalyst for hydrogenation of oils and fats.
[0010] In one embodiment, the nickel salt includes one or more of nickel chloride, nickel bromide, nickel sulfate, and nickel nitrate.
[0011] In one embodiment, the molybdate includes one or more of sodium molybdate, potassium molybdate, and ammonium molybdate.
[0012] In one embodiment, the process parameters for the precipitation reaction include: a temperature of 70°C to 90°C and a time of 20h to 48h.
[0013] In one embodiment, the sintering process includes heating to 500°C to 600°C at a heating rate of 3°C / min to 8°C / min.
[0014] In one embodiment, the load processing step includes: performing a first load processing at a temperature of 80°C to 100°C, and performing a second load processing at a temperature of 15°C to 35°C.
[0015] In one embodiment, the heating process parameters include a temperature of 500°C to 600°C.
[0016] In one embodiment, the reduction reaction step includes: carrying out a reduction reaction for 3 to 6 hours in a hydrogen atmosphere at a temperature of 450°C to 550°C.
[0017] In one embodiment, the phosphoric acid source includes one or more of sodium monohydrogen phosphate, ammonium monohydrogen phosphate, and calcium dihydrogen phosphate.
[0018] In one embodiment, the template agent comprises one or more of hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, and dodecyltrimethylammonium chloride.
[0019] In one embodiment, the calcium source includes one or more of calcium chloride, calcium nitrate, calcium acetate, and calcium chlorate.
[0020] In one embodiment, the complexing agent includes one or more of urea and thiourea.
[0021] In one embodiment, the molar ratio of the phosphate source to the template agent is 1:(0.5~3).
[0022] In one embodiment, the molar ratio of the phosphate source to the calcium source is 3:(4.5~5.5).
[0023] In one embodiment, the mass ratio of the hydroxyapatite to the nickel salt is 1:(0.1~2).
[0024] In one embodiment, the mass ratio of the hydroxyapatite to the molybdate is 1:(0.1~2).
[0025] In one embodiment, the mass ratio of the hydroxyapatite to the complexing agent is 1:(0.1~10).
[0026] A second aspect of this application provides a catalyst for the hydrogenation of oils and fats, comprising a support and a nickel-containing component and a molybdenum-containing component supported on the support;
[0027] The carrier includes hydroxyapatite.
[0028] In one embodiment, the mass ratio of the hydroxyapatite to the nickel-containing component is 1:(0.1~2).
[0029] In one embodiment, the mass ratio of the hydroxyapatite to the molybdenum-containing component is 1:(0.1~2).
[0030] A third aspect of this application provides a method for hydrogenating oils and fats, comprising the following steps:
[0031] The oil component to be hydrogenated and the catalyst are subjected to a reduction reaction under a hydrogen atmosphere to prepare the hydrogenated product.
[0032] The catalyst includes the oil hydrogenation catalyst described in the second aspect of this application or the oil hydrogenation catalyst prepared by any of the preparation methods described in the first aspect of this application.
[0033] In one embodiment, the oil component to be hydrogenated includes one or more of fatty acid glycerides, palmitic acid, oleic acid, and stearic acid.
[0034] In one embodiment, the process parameters for the reduction reaction include: a temperature of 300°C to 450°C and a pressure of 3 MPa to 6 MPa.
[0035] The method for preparing the catalyst for hydrogenation of oils and fats provided in this application has at least the following beneficial effects:
[0036] The preparation method provided in this application first utilizes a phosphate source, a template agent, and a calcium source to prepare hydroxyapatite. The template agent guides the orderly growth of the hydroxyapatite, and after precipitation reaction and sintering, a hydroxyapatite with good morphology and a mesoporous structure is obtained. This hydroxyapatite serves as a catalyst support, and the Ca in it... 2+ -PO4 3-The structure can inhibit carbon deposition and extend catalyst lifetime. Further loading of hydroxyapatite involves a complexing agent that regulates the coordination state of metal ions and inhibits agglomeration, effectively dispersing nickel salts and molybdates. Due to the mesoporous structure and surface properties of hydroxyapatite, it can form strong interactions with nickel salts and molybdates through pore confinement effects, achieving loading of nickel- and molybdenum-containing components and effectively avoiding sintering, agglomeration, and loss of these components. Heating and reduction reactions further stabilize the active centers of the nickel- and molybdenum-containing components and enrich the pore structure, giving the catalyst both biocompatibility and catalytic activity.
[0037] Therefore, the catalyst prepared by the method of this application combines mesoporous hydroxyapatite, nickel-containing components, and molybdenum-containing components. This combination promotes the adsorption of oil molecules and the dissociation and overflow of hydrogen, which is beneficial to the hydrodeoxygenation reaction process, ensuring good catalytic activity in the hydrogenation reaction of oils. Simultaneously, it avoids the sintering, agglomeration, and leaching loss of the active sites of the nickel-containing and molybdenum-containing components, inhibiting carbon deposition and effectively extending the catalyst life. Furthermore, the preparation method provided by this application is controllable, low-cost, and operates under mild conditions, making it suitable for industrial applications. Attached Figure Description
[0038] To more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0039] Figure 1 This is a process flow diagram of the preparation method of the catalyst for hydrogenation of oils and fats in this application. Detailed Implementation
[0040] The catalyst for hydrogenation of oils and fats, its preparation method, and the method for hydrogenating oils and fats described in this application are further described in a complete and clear manner with reference to specific embodiments. This application can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the disclosure of this application.
[0041] It should be understood that the terminology used in this application is merely for describing particular embodiments and is not intended to limit the application. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the specification of this application is for the purpose of describing particular embodiments only and is not intended to limit the application.
[0042] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art described herein. While only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this application. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.
[0043] In this article, "one or more" refers to any one, two or more of the listed items.
[0044] In this application, terms such as "first aspect," "second aspect," "third aspect," "fourth aspect," and "fifth aspect" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, terms such as "first," "second," "third," "fourth," and "fifth" serve only as a non-exhaustive enumeration and should be understood not to constitute a closed limitation on quantity.
[0045] In this application, the technical features described in an open-ended manner include both closed technical solutions consisting of the listed features and open technical solutions that include the listed features.
[0046] Furthermore, for numerical ranges in this application, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this application. The upper and lower limits of these smaller ranges may be independently included or excluded from the range. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are incorporated.
[0047] Unless otherwise specified, the percentage content mentioned in this application refers to mass percentage for solid-liquid mixtures and solid-phase-solid mixtures, and volume percentage for liquid-phase-liquid mixtures.
[0048] Unless otherwise specified, all percentage concentrations mentioned in this application refer to the final concentration. The final concentration refers to the proportion of the added component in the system after the addition of that component.
[0049] Unless otherwise specified, the temperature parameters in this application may be either constant temperature processing or processing within a certain temperature range. The constant temperature processing allows temperature fluctuations within the precision range controlled by the instrument.
[0050] The first aspect of this application provides a method for preparing a catalyst for hydrogenating oils and fats, comprising the following steps:
[0051] S10: Phosphoric acid source and template agent are mixed in the first solvent, the pH is adjusted to 10-12, calcium source is added, precipitation reaction and sintering are carried out to prepare hydroxyapatite.
[0052] S20: Hydroxyapatite, nickel salt, molybdate and complexing agent are mixed in a second solvent, and after loading treatment, the precipitate is collected.
[0053] S30: Prepare a catalyst for hydrogenation of oils and fats by heating and reducing the precipitate.
[0054] In some examples, in step S10, the phosphoric acid source includes one or more of sodium monohydrogen phosphate, ammonium monohydrogen phosphate, and calcium dihydrogen phosphate. Further, the phosphoric acid source includes ammonium monohydrogen phosphate. Ammonium monohydrogen phosphate dissociates in water to release hydrogen phosphate ions, which can stably bind with calcium ions under alkaline conditions, promoting the crystallization of hydroxyapatite.
[0055] In some examples, in step S10, the template agent includes one or more of hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, and dodecyltrimethylammonium chloride. The addition of these template agents effectively inhibits disordered aggregation, and the carbon chain length and ion type (such as chloride and bromide ions) of the template agent can regulate the pore size and hydrophobicity of hydroxyapatite, thereby ensuring the mesoporous structure and surface properties of hydroxyapatite. Further, the template agent includes hexadecyltrimethylammonium bromide.
[0056] In some of these examples, in step S10, the first solvent includes one or more of water, ethanol, isopropanol, and acetone.
[0057] In some examples, in step S10, the reagent used to adjust the pH to 10-12 includes one or more of sodium hydroxide solution and potassium hydroxide solution. Understandably, the solvent for both the sodium hydroxide solution and the potassium hydroxide solution is water.
[0058] In some examples, in step S10, the calcium source includes one or more of calcium chloride, calcium nitrate, calcium acetate, and calcium chlorate. These calcium sources have good solubility, exhibiting high solubility in a primary solvent such as water, thereby enabling the calcium... 2+ It can react with PO4 in the phosphate source 3- The reaction is highly efficient, which improves the nucleation and crystallization rate of hydroxyapatite.
[0059] In some examples, in step S10, the process parameters for the precipitation reaction include: a temperature of 70°C to 90°C and a time of 20 h to 48 h. These precipitation reaction parameters are mild, ensuring that Ca... 2+ - PO4 3-This efficient reaction avoids the disordered growth of hydroxyapatite caused by high temperatures. Furthermore, the precipitation time provides sufficient growth period for hydroxyapatite, resulting in uniform hydroxyapatite size. For example, the temperature for the precipitation reaction includes, but is not limited to, 70°C, 75°C, 78°C, 80°C, 82°C, 85°C, 88°C, or 90°C, or any two of the above values as endpoints.
[0060] In some examples, step S10, the sintering process includes heating to 500°C to 600°C at a heating rate of 3°C / min to 8°C / min. This sintering process effectively removes residual template agent, thereby giving the hydroxyapatite a good morphology and mesoporous structure, which is beneficial for loading nickel-containing and molybdenum-containing components. For example, the heating rate includes, but is not limited to, 3°C / min, 4°C / min, 5°C / min, 6°C / min, 7°C / min, or 8°C / min, or any two of the above values as endpoints. The holding temperature for the sintering process includes, but is not limited to, 500°C, 520°C, 550°C, 580°C, or 600°C, or any two of the above values as endpoints. Further, in step S10, the sintering time is 4h to 10h.
[0061] In some examples, step S10, after the precipitation reaction and before the sintering process, further includes washing and drying. Further, the drying temperature is 95°C to 105°C. The drying apparatus includes, but is not limited to, an oven.
[0062] In some examples, in step S10, the molar ratio of the phosphate source to the template agent is 1:(0.5~3). For example, the molar ratio of the phosphate source to the template agent includes, but is not limited to, 1:0.5, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.5, 1:2, 1:2.5 or 1:3, or any two of the above point values as endpoints.
[0063] In some examples, in step S10, the molar volume ratio of the phosphoric acid source to the first solvent is (0.01~0.2) mol:1L. For example, the molar volume ratio of the phosphoric acid source to the first solvent includes, but is not limited to, 0.01 mol:1L, 0.015 mol:1L, 0.018 mol:1L, 0.02 mol:1L, 0.05 mol:1L, 0.1 mol:1L, 0.15 mol:1L, or 0.2 mol:1L.
[0064] In some examples, in step S10, the molar ratio of the phosphate source to the calcium source is 3:(4.5~5.5). For example, the molar ratio of the phosphate source to the calcium source includes, but is not limited to, 3:4.8, 3:4.9, 3:5, 3:5.1, 3:5.2 or 3:5.5, or any two of the above point values as endpoints.
[0065] In step S10 of this application, hydroxyapatite is prepared using a phosphate source, a template agent, and a calcium source. The template agent guides the orderly growth of the hydroxyapatite, and after precipitation and sintering, a hydroxyapatite with good morphology and a mesoporous structure is obtained. This hydroxyapatite serves as a catalyst support, and the Ca in it... 2+ -PO4 3- The structure can inhibit carbon buildup and extend catalyst life.
[0066] In some examples, in step S20, the nickel salt includes one or more of nickel chloride, nickel bromide, nickel sulfate, and nickel nitrate. The aforementioned nickel salt is selected from soluble nickel salts, which readily dissociate into nickel ions in the second solvent. These ions are easily dispersed on the surface or in the pores of the support through ion exchange, coordination, or uniform dispersion, ensuring that the nickel active component is uniformly distributed and fully integrated with the hydroxyapatite support during loading, thereby improving loading efficiency and catalyst performance stability.
[0067] In some examples, in step S20, the molybdate includes one or more of sodium molybdate, potassium molybdate, and ammonium molybdate. The molybdate readily dissociates into molybdate ions in the second solvent, which can bind to the support surface or pores through ion exchange, coordination adsorption, or uniform dispersion, ensuring uniform distribution and firm anchoring of the molybdenum active component during loading.
[0068] In some examples, in step S20, the complexing agent includes one or more of urea and thiourea. Urea and thiourea, as complexing agents, can form complexes with metal ions such as nickel in the second solvent via amino or thiol groups, thereby regulating the release rate of metal ions in the solution and preventing drawbacks such as poor loading due to excessively high metal ion concentrations.
[0069] In some examples, step S20 includes a loading treatment step comprising: performing a first loading treatment at a temperature of 80°C to 100°C, and a second loading treatment at a temperature of 15°C to 35°C. This application performs the loading treatment in two stages. The high-temperature first loading treatment at 80°C to 100°C promotes the rapid adsorption and diffusion of metal ions on the support surface, followed by a low-temperature second loading treatment at 15°C to 35°C to suppress excessive crystal growth, thereby achieving uniform dispersion and controllable loading of the active component on the support surface. For example, the temperature of the first loading treatment includes, but is not limited to, 80°C, 85°C, 90°C, 95°C, or 100°C, or any two of the above values as endpoints. Further, the duration of the first loading treatment is 1 hour to 5 hours. Even further, the duration of the first loading treatment is 1.5 hours to 2.5 hours. For example, the temperature of the second load treatment includes, but is not limited to, 15°C, 18°C, 20°C, 22°C, 25°C, 28°C, 30°C, 33°C, or 35°C, or any two of the above values as endpoints. Further, the duration of the second load treatment is 10h to 20h. Even further, the duration of the second load treatment is 11h to 13h.
[0070] In some examples, in step S20, the mass ratio of hydroxyapatite to nickel salt is 1:(0.1~2). The mass ratio of hydroxyapatite to nickel salt includes, but is not limited to, 1:0.1, 1:0.2, 1:0.23, 1:0.25, 1:0.26, 1:0.28, 1:0.3, 1:0.5, 1:0.8, 1:1, 1:1.5, or 1:2, or any two of the above values as endpoints. In some examples, in step S20, the mass ratio of hydroxyapatite to molybdate is 1:(0.1~2). The mass ratio of hydroxyapatite to molybdate includes, but is not limited to, 1:0.1, 1:0.2, 1:0.23, 1:0.25, 1:0.26, 1:0.28, 1:0.3, 1:0.5, 1:0.8, 1:1, 1:1.5 or 1:2, or any two of the above point values as endpoints within the range.
[0071] Limiting the mass ratio of hydroxyapatite to nickel salts and molybdates helps to control the metal content in the catalyst, thereby ensuring the catalyst's hydrodeoxygenation catalytic activity.
[0072] In some examples, in step S20, the mass ratio of hydroxyapatite to complexing agent is 1:(0.1~10). The mass ratio of hydroxyapatite to complexing agent includes, but is not limited to, 1:0.1, 1:1, 1:3, 1:4, 1:4.5, 1:4.8, 1:4.9, 1:5, 1:5.1, 1:5.2, 1:5.5, 1:7, 1:9 or 1:10, or any two of the above values as endpoints within a range.
[0073] In step S20, hydroxyapatite is further subjected to a loading treatment. In this step, the complexing agent can regulate the coordination state of metal ions and inhibit agglomeration, thereby effectively dispersing nickel salts and molybdates. Due to the mesoporous structure and surface properties of hydroxyapatite, it can form a strong interaction with nickel salts and molybdates through the pore confinement effect, thereby achieving the loading of nickel-containing and molybdenum-containing components; and effectively avoiding the sintering agglomeration and loss problems of nickel-containing and molybdenum-containing components.
[0074] In some examples, in step S30, the heating process parameters include a temperature of 500°C to 600°C. Further, the heating treatment time is 3 hours to 8 hours. Heating treatment can decompose the supported metal salt or metal ions into metal oxides and enhance the interaction between the nickel-containing and molybdenum-containing components and hydroxyapatite, thereby improving the activity and stability of the catalyst. For example, the heating temperature includes, but is not limited to, 500°C, 520°C, 550°C, 560°C, 580°C, or 600°C, or any two of the above values as endpoints. Further, the heating time includes, but is not limited to, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, or 8 hours, or any two of the above values as endpoints.
[0075] In some examples, step S30 includes a reduction reaction carried out in a hydrogen atmosphere at a temperature of 450°C to 550°C for 3 to 6 hours. Further reduction enhances the activity of the metal component, ensuring the catalyst's activity and selectivity in the hydrodeoxygenation catalytic reaction. Furthermore, the reduction reaction temperature includes, but is not limited to, 450°C, 480°C, 500°C, 520°C, 530°C, 540°C, or 550°C, or any two of these values as endpoints. The reduction reaction temperature includes, but is not limited to, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, or 6 hours, or any two of these values as endpoints.
[0076] Heating and reduction reactions can further stabilize the active centers of nickel-containing and molybdenum-containing components and enrich the pore structure, giving the catalyst both biocompatibility and catalytic activity.
[0077] A second aspect of this application provides a catalyst for the hydrogenation of oils and fats, comprising a support and a nickel-containing component and a molybdenum-containing component supported on the support.
[0078] The carrier includes hydroxyapatite.
[0079] The catalyst of this application combines hydroxyapatite, a nickel-containing component, and a molybdenum-containing component. The mesoporous structure of the hydroxyapatite promotes the adsorption of oil molecules and the dissociation and overflow of hydrogen, which is beneficial to the hydrodeoxygenation reaction process. The nickel-containing and molybdenum-containing components supported on the hydroxyapatite support exhibit good catalytic activity in the hydrogenation reaction of oils. Furthermore, the strong interaction between the hydroxyapatite support, the nickel-containing component, and the molybdenum-containing component prevents sintering, agglomeration, and leaching loss of the active sites of the nickel-containing and molybdenum-containing components, inhibits carbon deposition, and thus effectively extends the catalyst lifetime.
[0080] In some examples, the mass ratio of hydroxyapatite to the nickel-containing component is 1:(0.1~2). This mass ratio includes, but is not limited to, 1:0.1, 1:0.2, 1:0.23, 1:0.25, 1:0.26, 1:0.28, 1:0.3, 1:0.5, 1:0.8, 1:1, 1:1.5, or 1:2, or any two of the above values as endpoints. In some examples, the mass ratio of hydroxyapatite to the molybdenum-containing component is 1:(0.1~2). This mass ratio includes, but is not limited to, 1:0.1, 1:0.2, 1:0.23, 1:0.25, 1:0.26, 1:0.28, 1:0.3, 1:0.5, 1:0.8, 1:1, 1:1.5, or 1:2, or any two of the above values as endpoints.
[0081] A third aspect of this application provides a method for hydrogenating oils and fats, comprising the following steps:
[0082] Hydrogenated products are prepared by reducing the oil components to be hydrogenated and the catalyst under a hydrogen atmosphere.
[0083] The catalyst includes the catalyst for hydrogenation of oils and fats according to the second aspect of this application or the catalyst for hydrogenation of oils and fats prepared by any of the preparation methods according to the first aspect of this application.
[0084] In some of these examples, the oil components to be hydrogenated include one or more of fatty acid glycerides, palmitic acid, oleic acid, and fatty acids.
[0085] In some examples, the process parameters for the reduction reaction include: a temperature of 300℃ to 450℃ and a pressure of 3MPa to 6MPa. The temperature of the reduction reaction includes, but is not limited to, 300℃, 330℃, 350℃, 370℃, 400℃, 420℃, 430℃, or 450℃, or any two of the above values as endpoints. The pressure of the reduction reaction includes, but is not limited to, 3MPa, 3.5MPa, 4MPa, 4.5MPa, 5MPa, 5.2MPa, 5.5MPa, 5.8MPa, or 6MPa, or any two of the above values as endpoints.
[0086] In some examples, the mass ratio of the oil component to be hydrogenated to the catalyst is 1:(0.02~0.2). For example, the mass ratio of the oil component to be hydrogenated to the catalyst includes, but is not limited to, 1:0.02, 1:0.024, 1:0.025, 1:0.026, 1:0.03, 1:0.05, 1:0.08, 1:0.1, 1:0.15, or 1:0.2, or any two of the above values as endpoints within a range.
[0087] The following detailed embodiments illustrate this application in more detail. It should also be understood that the following embodiments are for further explanation only and should not be construed as limiting the scope of protection of this application. Any non-essential improvements and adjustments made by those skilled in the art based on the above description of this application fall within the scope of protection of this application. The specific process parameters, etc., in the following embodiments are merely examples within a suitable range; that is, those skilled in the art can make appropriate selections within the range based on the description herein, and are not necessarily limited to the specific values in the embodiments below.
[0088] Example 1
[0089] Example 1 provides a method for preparing a catalyst for hydrogenation of oils and fats, comprising the following steps:
[0090] (1) Preparation of mesoporous hydroxyapatite:
[0091] 0.03 mol of ammonium hydrogen phosphate ((NH4)2HPO4, phosphate source) and 0.03 mol of hexadecyltrimethylammonium bromide (CTAB, template agent) were dissolved in 500 mL of water and stirred. Sodium hydroxide (NaOH) solution was added to bring the pH to 12. Then, 200 mL of 0.25 mol / L calcium nitrate (calcium salt) solution was added dropwise, and the solution was heated to 80 °C and maintained for 24 h to carry out the precipitation reaction. The mixture was then filtered, the precipitate was washed and dried in an oven at 100 °C, and then heated in a muffle furnace at a heating rate of 5 °C / min at 550 °C for 6 h to obtain a mesoporous hydroxyapatite support.
[0092] (2) Preparation of catalysts for hydrogenation of oils and fats:
[0093] 2 g of mesoporous hydroxyapatite support, 0.5 g of nickel nitrate (nickel salt), and 0.5 g of ammonium molybdate (molybdate) were dispersed in 100 mL of water and stirred at room temperature for 2 h. Then, 10 g of urea (complexing agent) was added, and the mixture was heated to 90 °C and maintained for 2 h. The mixture was then allowed to stand at room temperature for 12 h to age, allowing for the loading reaction. After filtration, washing, and drying, a precipitate was obtained. The precipitate was calcined at 550 °C for 4 h, followed by reduction at 500 °C for 4 h in a tube furnace under a hydrogen atmosphere to obtain the catalyst.
[0094] Example 2
[0095] Example 2 is basically the same as Example 1, the main difference being that the nickel salt used in Example 2 is nickel sulfate.
[0096] Example 3
[0097] Example 3 is basically the same as Example 1, the main difference being that the molybdate used in Example 3 is sodium molybdate.
[0098] Example 4
[0099] Example 4 is basically the same as Example 1, the main difference being that the amount of nickel salt added in Example 4 is 3g.
[0100] Example 5
[0101] Example 5 is basically the same as Example 1, the main difference being that the amount of molybdate added in Example 5 is 3g.
[0102] Comparative Example 1
[0103] Comparative Example 1 is basically the same as Example 1, the main difference being that molybdate was not added in Comparative Example 1.
[0104] Comparative Example 2
[0105] Comparative Example 2 is basically the same as Example 1, the main difference being that no nickel salt was added to Comparative Example 2.
[0106] Comparative Example 3
[0107] Comparative Example 3 is basically the same as Example 1, except that Comparative Example 3 does not include step (1), and step (2) uses a silica carrier instead of a mesoporous hydroxyapatite carrier.
[0108] Test case
[0109] 0.5g of the catalyst from the above examples and comparative examples was mixed with 20g of oleic acid and placed in a batch reactor. Hydrogen gas was introduced, and the reaction was carried out at 350℃ and 4MPa for 2 hours. After the reaction was completed, the conversion rate of the reactants was tested. The corresponding test results are shown in Table 1.
[0110] Table 1
[0111]
[0112] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.
[0113] The embodiments described above are merely illustrative of several implementation methods of this application, intended to facilitate a detailed understanding of the technical solutions of this application, but should not be construed as limiting the scope of protection of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the scope of protection of this application. It should be understood that technical solutions obtained by those skilled in the art based on the technical solutions provided in this application through logical analysis, reasoning, or limited experimentation are all within the scope of protection of the appended claims. Therefore, the scope of protection of this patent application should be determined by the content of the appended claims, and the specification can be used to interpret the content of the claims.
Claims
1. A method for preparing a catalyst for the hydrogenation of oils and fats, characterized in that, Includes the following steps: Phosphoric acid source and template agent are mixed in the first solvent, the pH is adjusted to 10-12, calcium source is added, precipitation reaction and sintering are carried out to prepare hydroxyapatite; The hydroxyapatite, nickel salt, molybdate, and complexing agent are mixed in a second solvent, and after loading treatment, the precipitate is collected. The precipitate is heated and reduced to prepare the catalyst for hydrogenation of oils and fats.
2. The method for preparing the catalyst for hydrogenation of oils and fats according to claim 1, characterized in that, The nickel salt includes one or more of nickel chloride, nickel bromide, nickel sulfate, and nickel nitrate; And / or, the molybdate includes one or more of sodium molybdate, potassium molybdate, and ammonium molybdate.
3. The method for preparing the catalyst for hydrogenation of oils and fats according to claim 1, characterized in that, The process parameters for the precipitation reaction include: temperature of 70℃~90℃ and time of 20h~48h; And / or, the sintering process includes heating to 500°C to 600°C at a heating rate of 3°C / min to 8°C / min.
4. The method for preparing the catalyst for hydrogenation of oils and fats according to claim 1, characterized in that, The load processing steps include: performing a first load processing at a temperature of 80℃~100℃, and performing a second load processing at a temperature of 15℃~35℃. And / or, the heating process parameters include: a temperature of 500℃~600℃; And / or, the reduction reaction steps include: carrying out a reduction reaction for 3 to 6 hours in a hydrogen atmosphere at a temperature of 450°C to 550°C.
5. The method for preparing the catalyst for hydrogenation of oils and fats according to claim 1, characterized in that, The preparation method has one or more of the following characteristics: (1) The phosphoric acid source includes one or more of sodium monohydrogen phosphate, ammonium monohydrogen phosphate and calcium dihydrogen phosphate; (2) The template agent includes one or more of hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, and dodecyltrimethylammonium chloride; (3) The calcium source includes one or more of calcium chloride, calcium nitrate, calcium acetate and calcium chlorate; (4) The complexing agent includes one or more of urea and thiourea.
6. The method for preparing the catalyst for hydrogenation of oils and fats according to any one of claims 1 to 5, characterized in that, The preparation method has one or more of the following characteristics: (1) The molar ratio of the phosphate source to the template agent is 1:(0.5~3); (2) The molar ratio of the phosphate source to the calcium source is 3:(4.5~5.5); (3) The mass ratio of the hydroxyapatite to the nickel salt is 1:(0.1~2); (4) The mass ratio of the hydroxyapatite to the molybdate is 1:(0.1~2); (5) The mass ratio of the hydroxyapatite to the complexing agent is 1: (0.1~10).
7. A catalyst for the hydrogenation of oils and fats, characterized in that, Includes a carrier and a nickel-containing component and a molybdenum-containing component loaded on the carrier; The carrier includes hydroxyapatite.
8. The catalyst for hydrogenation of oils and fats according to claim 7, characterized in that, The mass ratio of the hydroxyapatite to the nickel-containing component is 1:(0.1~2). And / or, the mass ratio of the hydroxyapatite to the molybdenum-containing component is 1:(0.1~2).
9. A method for hydrogenating oils and fats, characterized in that, Includes the following steps: The oil component to be hydrogenated and the catalyst are subjected to a reduction reaction under a hydrogen atmosphere to prepare the hydrogenated product. The catalyst includes the catalyst for hydrogenation of oils and fats as described in claim 7 or 8, or the catalyst for hydrogenation of oils and fats prepared by the preparation method described in any one of claims 1 to 6.
10. The method for hydrogenating oils and fats according to claim 9, characterized in that, The hydrogenated oil components include one or more of fatty acid glycerides, palmitoleic acid, oleic acid, and stearic acid; And / or, the process parameters for the reduction reaction include: temperature of 300℃~450℃ and pressure of 3MPa~6MPa.