A catalyst support, a hydrogenation catalyst, its preparation method and application
By preparing a titanium-silicon composite oxide support and loading it with active components, the deactivation problem of existing catalysts under high oxygen and high acid conditions was solved, and a highly efficient hydrogenation catalytic effect was achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- BEIJING XIANGPENG NEW ENERGY TECH CO LTD
- Filing Date
- 2023-11-08
- Publication Date
- 2026-06-30
AI Technical Summary
Existing hydrogenation catalysts are insufficient in strength and catalytic performance when processing materials with high oxygen content and high acid value. They are easily deactivated by acid corrosion, resulting in a decrease in hydrogenation efficiency.
A titanium-silicon composite oxide was prepared by mixing a solid inorganic silicon source, a liquid inorganic silicon source, and a solid inorganic titanium source with an organic binder and water, extruding and molding the mixture, and then drying and calcining it. This mixture served as a catalyst support and loaded the active components to form a hydrogenation catalyst with high acid resistance and hydrothermal resistance.
The strength and specific surface area of the catalyst support were improved, enhancing the catalytic performance and enabling the structure to remain stable even under high oxygen content conditions, with deoxygenation and denitrification rates both exceeding 95%.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of catalytic hydrogenation technology, specifically relating to a catalyst support, a hydrogenation catalyst, its preparation method, and its application. Background Technology
[0002] Hydrogenation catalysts typically use alumina, silica, silicon carbide, boron oxide, and their complexes as catalyst supports, prepared through an impregnation process to create catalysts carrying the active components. The hydrogenation process removes harmful impurities such as sulfur, nitrogen, and oxygen from oil products and hydrogenates and saturates olefins and dienes, while partially saturating aromatics, thereby improving oil quality and producing hydrocarbons with a hydrocarbon composition.
[0003] Oils rich in fatty acids generally refer to leftover cooking oil, swill oil, acidified oil, and rancid oil. They are characterized by high oxygen content and high acid value. Hydrogenation requires catalysts with high hydrothermal resistance and high acid resistance. Current hydrogenation catalyst supports generally cannot simultaneously meet these requirements. For example, a support with alumina as the main component is easily corroded by acid under high acid value conditions, leading to deactivation and pulverization, thus reducing the hydrogenation effect.
[0004] Therefore, it is essential to develop a hydrogenation catalyst suitable for materials with high oxygen content and high acid value, which also possesses excellent strength, specific surface area, pore volume, and catalytic performance. Summary of the Invention
[0005] Therefore, the technical problem to be solved by the present invention is to overcome the shortcomings of existing hydrogenation catalysts, which are generally suitable for hydrogenation treatment of materials with high oxygen content and high acid value, and whose strength and catalytic performance need to be further improved. Thus, the present invention provides a catalyst support, a hydrogenation catalyst, its preparation method and application.
[0006] Therefore, the present invention provides the following technical solution:
[0007] This invention provides a method for preparing a catalyst support, comprising the following steps:
[0008] S1, a solid inorganic silicon source, a liquid inorganic silicon source, and a solid inorganic titanium source are mixed under the action of an organic binder and water, and then extruded to obtain a precursor;
[0009] S2, the obtained precursor is dried and calcined to obtain the catalyst support.
[0010] Optionally, in step S1, the mass ratio of the solid inorganic silicon source, the liquid inorganic silicon source, and the solid inorganic titanium source is 1:1-4:0.7-2.
[0011] Optionally, the solid inorganic silicon source has an average particle size of 30-300 nm and a specific surface area of 150-300 m².2 / g, apparent density is 0.1-0.5g / ml;
[0012] And / or, the content of silicon dioxide in the liquid inorganic silicon source is 20-45 wt%, and the average particle size of silicon dioxide is 5-30 nm;
[0013] And / or, the average particle size of the solid inorganic titanium source is 10-200 nm.
[0014] Optionally, the solid inorganic silicon source is silicon dioxide powder;
[0015] And / or, the liquid inorganic silicon source is a silica sol;
[0016] And / or, the solid inorganic titanium source is at least one of metatitanic acid, titanium dioxide, titanium tetrachloride, titanium phosphate, and titanium tetrabromide;
[0017] And / or, the organic binder is selected from at least one of polysaccharides and proteins; optionally, the polysaccharide is selected from at least one of guar gum and guar gum, and the protein is selected from at least one of wheat gluten and soy protein isolate.
[0018] Optionally, in step S1, the amount of the organic binder accounts for 20%-35% of the sum of the mass of the solid inorganic silicon source and the solid inorganic titanium source;
[0019] And / or, the amount of water used accounts for 60%-100% of the sum of the masses of the solid inorganic silicon source and the solid inorganic titanium source.
[0020] Optionally, in step S2, the calcination is carried out in an oxygen-containing atmosphere, the calcination temperature is 400℃-800℃, and the calcination time is ≥4h; optionally, the calcination time is 4-12h.
[0021] And / or, the drying temperature is 60℃-120℃, and the drying time is 2h-24h.
[0022] The present invention also provides a catalyst support, which is prepared by the above-described preparation method;
[0023] Optionally, the catalyst support contains 46 wt%-76 wt% silica and 24-54 wt% titanium dioxide.
[0024] And / or, the specific surface area of the catalyst support is not less than 100 m². 2 / g, optionally 100–300m 2 / g, with an average pore volume of 0.4-0.6cm³. 3 / g, with an average pore size of 14-25nm.
[0025] The present invention also provides a hydrogenation catalyst, comprising the above-described catalyst support and active component;
[0026] Optionally, the active component exists in the form of a metal oxide, including at least one oxide of cobalt, nickel, palladium, platinum, chromium, molybdenum, and tungsten.
[0027] Optionally, the active component in the hydrogenation catalyst is 15-25 wt%.
[0028] This invention also provides the application of a hydrogenation catalyst in the hydrogenation and deoxygenation of fatty acid-containing oils to prepare white oil or hydrocarbon-based biodiesel;
[0029] Optionally, the fatty acid-containing oils contain 8-13 wt% oxygen and 10-100 wt% free fatty acids.
[0030] Optionally, the hydrodeoxygenation reaction conditions are: reaction temperature 260-400℃, hydrogen pressure 6.0-18.0 MPa, and liquid hourly space velocity 0.25-2 h⁻¹. -1 The hydrogen-to-oil volume ratio is 800-2000:1.
[0031] In this invention, the preparation method of the hydrogenation catalyst is conventional in the art. Typically, and non-limitingly, it includes the following steps: impregnating a support in an active component precursor solution, and then drying and calcining the impregnated support to obtain the hydrogenation catalyst. The active component precursor solution is a saturated solution prepared from a soluble salt of the active metal component and deionized water. For example, the molybdenum salt can be ammonium molybdate; the cobalt salt can be selected from cobalt nitrate, cobalt oxalate, cobalt carbonate, etc.; and the nickel salt can be selected from basic nickel carbonate, etc.
[0032] The technical solution of this invention has the following advantages:
[0033] The catalyst support preparation method provided by this invention includes the following steps: S1, mixing a solid inorganic silicon source, a liquid inorganic silicon source, and a solid inorganic titanium source under the action of an organic binder and water, and extruding them to obtain a precursor; S2, drying and calcining the obtained precursor to obtain the catalyst support. The obtained catalyst support uses titanium-silicon composite oxide as the support component, wherein the silicon oxide component is derived from both the solid and liquid inorganic silicon sources. The combination of the solid and liquid silicon sources, along with the addition of the solid inorganic titanium source, helps to improve the specific surface area and pore volume of the support while simultaneously increasing its strength, average pore size, acid resistance, and hydrothermal resistance.
[0034] The hydrogenation catalyst provided by this invention, using a catalyst support obtained through a specific preparation method provided by this invention, not only possesses strong acid resistance and resistance to water formation, but also exhibits strong hydrogenation activity. Even with an oxygen content as high as 13% and complete water formation, the catalyst structure remains intact. When combined with a specific active metal support, the hydrogenation activity is further enhanced, with both deoxygenation and denitrification rates exceeding 95%. Detailed Implementation
[0035] The following embodiments are provided to better understand the present invention and are not limited to the preferred embodiments described. They do not constitute a limitation on the content and scope of protection of the present invention. Any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the protection scope of the present invention.
[0036] For experiments not specifically described in the examples, the procedures or conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.
[0037] Example 1
[0038] This embodiment provides a catalyst support, the composition of which and its preparation method are as follows:
[0039] Take 500g of silica powder, 1690g of silica sol, 500g of metatitanic acid, 170g of guar gum, 130g of wheat gluten, and 700g of deionized water. The silica powder has a particle size of 150nm and a specific surface area of 200m². 2 / g, apparent density is 0.35g / ml, metatitanic acid particle size is 50nm, silica content in silica sol is 40wt%, silica particle size is 10nm.
[0040] Prepare according to the following steps:
[0041] 1) Mix silica powder, metatitanic acid, guar gum and gluten powder thoroughly to obtain a mixed solid powder;
[0042] 2) Stir the silica sol and deionized water to mix thoroughly to obtain a suspension;
[0043] 3) The suspension is added dropwise to the mixed solid powder and kneaded thoroughly for 30 minutes. The kneaded mixture is then extruded using a single-screw extruder to obtain short strips with a diameter of 2-3 mm and a length of 15-20 mm. Finally, the short strips are placed in a ventilated drying oven for drying at 120°C for 3 hours. The dried short strips are then placed in a muffle furnace and calcined in air at 500°C for 6 hours. The calcined short strips are then removed and cooled to room temperature to obtain the catalyst support A.
[0044] The catalyst support prepared in the above embodiments, based on the total weight of the support (100%), consists of 74.2 wt% silica and 25.8 wt% titanium dioxide, and the measured specific surface area of the support is 150 m². 2 / g, with an average pore volume of 0.51cm³. 3 / g, with an average pore size of 16nm.
[0045] Example 2
[0046] This embodiment provides a catalyst support, the composition of which and its preparation method are as follows:
[0047] Take 500g of silica powder, 520g of silica sol, 850g of metatitanic acid, 345g of guar gum, 120g of wheat gluten, and 1282g of deionized water. The silica powder has a particle size of 280nm and a specific surface area of 160m². 2 / g, apparent density is 0.23g / ml, metatitanic acid particle size is 100nm, silica sol contains 30wt% silica and silica particle size is 15nm.
[0048] Prepare according to the following steps:
[0049] 1) Mix silica powder, metatitanic acid, guar gum and gluten powder thoroughly to obtain a mixed solid powder;
[0050] 2) Stir the silica sol and deionized water to mix thoroughly to obtain a suspension;
[0051] 3) The suspension is added dropwise to the mixed solid powder and kneaded thoroughly for 60 minutes. The kneaded mixture is then extruded using a single-screw extruder to obtain short strips with a diameter of 3-5 mm and a length of 15-20 mm. Finally, the short strips are placed in a ventilated drying oven for drying at 100°C for 8 hours. The dried short strips are then placed in a muffle furnace and calcined in air at 750°C for 5 hours. The calcined short strips are then removed and cooled to room temperature to obtain the catalyst support B.
[0052] The catalyst support prepared in the above embodiments, based on the total weight of the support (100%), consists of 48.6 wt% silica and 51.4 wt% titanium dioxide, and the measured specific surface area of the support is 110 m². 2 / g, with an average pore volume of 0.42cm³. 3 / g, with an average pore size of 18nm.
[0053] Example 3
[0054] This embodiment provides a catalyst support, the composition of which and its preparation method are as follows:
[0055] Take 500g of silica powder, 1500g of silica sol, 360g of titanium dioxide, 170g of guar gum, 106g of soy protein isolate powder, and 774g of deionized water. The silica powder has a particle size of 50nm and a specific surface area of 260m². 2 / g, apparent density is 0.45g / ml, titanium dioxide particle size is 180nm, silica sol contains 25wt% silica and silica particle size is 26nm.
[0056] Prepare according to the following steps:
[0057] 1) Stir the silica powder, titanium dioxide, silica sol, guar gum, gluten powder, and deionized water until fully mixed;
[0058] 2) Knead the mixture in a kneader for 120 minutes, then extrude the kneaded mixture using a single-screw extruder to obtain short strips with a diameter of 5-7 mm and a length of 25-30 mm. Finally, place the short strips in a ventilated drying oven for drying at 110°C for 5 hours. Place the dried short strips in a muffle furnace and calcine them in an air atmosphere at 550°C for 8 hours. Remove the calcined short strips and cool them to room temperature to obtain the catalyst support C.
[0059] The catalyst support prepared in the above embodiments, based on the total weight of the support (100%), consists of 70.9 wt% silica and 29.1 wt% titanium dioxide, and the measured specific surface area of the support is 135 m². 2 / g, with an average pore volume of 0.54cm³. 3 / g, with an average pore size of 23nm.
[0060] Example 4
[0061] This embodiment provides a hydrogenation catalyst, the composition of which and its preparation method are as follows:
[0062] Weigh 486.19g of ammonium heptamolybdate, 116.5g of basic nickel carbonate, and 380g of citric acid monohydrate. Mix with deionized water at 80°C and stir thoroughly for 30 minutes to prepare a saturated solution. Immerse 1584g of support A prepared in Example 1 in the solution for 2 hours. After filtration, dry at 100°C for 4 hours and calcine at 550°C for 4 hours to obtain catalyst A1, which is a silicon-titanium support supporting molybdenum-nickel active metal with a MoO3 content of 20.3% by weight and a NiO content of 3.3% by weight.
[0063] Example 5
[0064] This embodiment provides a hydrogenation catalyst, the composition of which and its preparation method are as follows:
[0065] Weigh 430.2g of ammonium heptamolybdate, 103.5g of basic nickel carbonate, and 344g of citric acid monohydrate. Mix with deionized water at 80°C and stir thoroughly for 30 minutes to prepare a saturated solution. Immerse 1350g of support B prepared in Example 2 in the solution for 3 hours. After filtration, dry at 110°C for 4 hours and calcine at 550°C for 4 hours to obtain catalyst B1, a silicon-titanium support supporting molybdenum-nickel active metal catalyst with a MoO3 content of 20.9% by weight and a NiO content of 3.5%.
[0066] Example 6
[0067] This embodiment provides a hydrogenation catalyst, the composition of which and its preparation method are as follows:
[0068] Weigh 381.3g of ammonium heptamolybdate, 91.4g of basic nickel carbonate, and 305g of citric acid monohydrate. Prepare a saturated solution by stirring thoroughly in deionized water at 80°C for 30 minutes. Immerse 1235g of support C prepared in Example 3 in the solution for 3.5 hours. After filtration, dry at 110°C for 2 hours and calcine at 550°C for 4 hours to obtain catalyst C1, a silicon-titanium support supporting molybdenum-nickel active metal catalyst with a MoO3 content of 20.4% by weight and a NiO content of 3.4% by weight.
[0069] Example 7
[0070] This embodiment provides a hydrogenation catalyst, the composition of which and its preparation method are as follows:
[0071] 1) Weigh 152.7g of cobalt nitrate, prepare a saturated solution with deionized water at room temperature, impregnate 1584g of carrier A prepared in Example 1 at room temperature for 2h, filter, dry at 110℃ for 4h, and calcine at 550℃ for 4h.
[0072] 2) Weigh 401.5g of ammonium heptamolybdate, prepare a saturated aqueous solution, impregnate the product from step 1 for 2 hours, filter, dry at 110℃ for 6 hours, and calcine at 500℃ for 4 hours.
[0073] 3) Weigh 59.8g of basic nickel carbonate, prepare a saturated aqueous solution, impregnate the product from step 2 for 2 hours, filter, dry at 110℃ for 6 hours, and calcine at 550℃ for 4 hours.
[0074] Catalyst A2, consisting of molybdenum-nickel-cobalt active metals supported on a silicon-titanium carrier, was prepared with a MoO3 content of 17.1% by weight, a NiO content of 1.8% by weight, and a CoO content of 3.1% by weight.
[0075] Example 8
[0076] This embodiment provides a hydrogenation catalyst, the composition of which and its preparation method are as follows:
[0077] 1) Weigh 91.4g of cobalt nitrate, prepare a saturated solution with deionized water at room temperature, impregnate 1350g of carrier B prepared in Example 2 at room temperature for 2h, filter, dry at 110℃ for 4h, and calcine at 550℃ for 4h.
[0078] 2) Weigh 275.0g of ammonium heptamolybdate, prepare a saturated aqueous solution, impregnate the product from step one for 2 hours, filter, dry at 110℃ for 6 hours, and calcine at 550℃ for 4 hours.
[0079] 3) Weigh 99.3g of basic nickel carbonate, prepare a saturated aqueous solution, impregnate the product from step 2 for 2 hours, filter, dry at 110℃ for 6 hours, and calcine at 550℃ for 4 hours.
[0080] Catalyst B2, consisting of molybdenum-nickel-cobalt active metals supported on a silicon-titanium carrier, was prepared with a MoO3 content of 14.1% by weight, a NiO content of 3.5% by weight, and a CoO content of 2.2% by weight.
[0081] Example 9
[0082] This embodiment provides a hydrogenation catalyst, the composition of which and its preparation method are as follows:
[0083] 1) Weigh 336.4g of ammonium heptamolybdate and prepare a saturated aqueous solution. Impregnate 1235g of carrier C prepared in Example 3 at room temperature for 2 hours. After filtration, dry at 110°C for 6 hours and calcine at 550°C for 4 hours.
[0084] 2) Weigh 109.7g of basic nickel carbonate, prepare a saturated aqueous solution, impregnate the product from step 1 for 2 hours, filter, dry at 110℃ for 4 hours, and calcine at 500℃ for 4 hours.
[0085] A catalyst C2 with a MoO3 content of 18.3% by weight and a NiO content of 4.1% by weight was prepared on a silicon-titanium support supporting molybdenum-nickel active metal.
[0086] Comparative Example 1
[0087] This comparative example provides a hydrogenation catalyst, the composition of which and its preparation method are as follows:
[0088] Take 500g of silica powder, 0g of silica sol, 300g of metatitanic acid, 170g of guar gum, 130g of wheat gluten, and 700g of deionized water. The silica powder has a particle size of 150nm and a specific surface area of 200m². 2 / g, with an apparent density of 0.35g / ml and a metatitanic acid particle size of 50nm.
[0089] Prepare according to the following steps:
[0090] 1) Mix silica powder, metatitanic acid, guar gum and gluten powder thoroughly to obtain a mixed solid powder;
[0091] 2) Add deionized water to the mixed solid powder and knead thoroughly for 30 minutes. Then, extrude the kneaded mixture using a single-screw extruder to obtain short strips with a diameter of 2-3 mm and a length of 15-20 mm. Finally, place the short strips in a ventilated drying oven for drying at 120°C for 3 hours. Place the dried short strips in a muffle furnace and calcine them in an air atmosphere at 500°C for 6 hours. Remove the calcined short strips and cool them to room temperature to obtain the catalyst support D.
[0092] The catalyst support prepared in the above embodiments, based on the total weight of the support (100%), consists of 67.1 wt% silica and 32.9 wt% titanium dioxide, and the measured specific surface area of the support is 83 m². 2 / g, with an average pore volume of 0.18cm³. 3 / g, with an average pore size of 29nm.
[0093] 229.0g of ammonium heptamolybdate, 54.2g of basic nickel carbonate, and 181g of citric acid monohydrate were weighed and mixed thoroughly with deionized water at 80℃ for 30 minutes to prepare a saturated solution. 744g of support D was immersed in the solution for 2 hours, filtered, dried at 110℃ for 4 hours, and calcined at 550℃ for 4 hours to obtain catalyst D1, a silicon-titanium support supporting molybdenum-nickel active metal catalyst with a MoO3 content of 20.3% by weight and a NiO content of 3.3% by weight.
[0094] Comparative Example 2
[0095] This comparative example provides a hydrogenation catalyst, the composition of which and its preparation method are as follows:
[0096] Take 0g of silica powder, 3800g of silica sol, 500g of metatitanic acid, 100g of guar gum, 75g of gluten, and 475g of deionized water. The metatitanic acid has a particle size of 100nm, the silica sol has a silica content of 30wt%, and the silica has a particle size of 15nm.
[0097] Prepare according to the following steps:
[0098] 1) Mix metatitanic acid, guar gum and gluten powder thoroughly to obtain a mixed solid powder;
[0099] 2) Stir the silica sol and deionized water to mix thoroughly to obtain a suspension;
[0100] 3) The suspension is added dropwise to the mixed solid powder and kneaded thoroughly for 60 minutes. The kneaded mixture is then extruded using a single-screw extruder to obtain short strips with a diameter of 3-5 mm and a length of 15-20 mm. Finally, the short strips are placed in a ventilated drying oven for drying at 100°C for 8 hours. The dried short strips are then placed in a muffle furnace and calcined in air at 750°C for 5 hours. The calcined short strips are then removed and cooled to room temperature to obtain the catalyst support E.
[0101] The catalyst support prepared in the above embodiments, based on the total weight of the support (100%), consists of 73.6 wt% silica and 26.4 wt% titanium dioxide, and the measured specific surface area of the support is 74 m². 2 / g, with an average pore volume of 0.24cm³. 3 / g, with an average pore size of 12nm.
[0102] 4) Weigh 102g of cobalt nitrate, prepare a saturated solution with deionized water at room temperature, impregnate 1548g of carrier E prepared in Comparative Example 2 at room temperature for 2h, filter, dry at 110℃ for 4h, and calcine at 550℃ for 4h.
[0103] 5) Weigh 311g of ammonium heptamolybdate, prepare a saturated aqueous solution, impregnate the product from step one for 2 hours, filter, dry at 110℃ for 6 hours, and calcine at 550℃ for 4 hours.
[0104] 6) Weigh 109g of basic nickel carbonate, prepare a saturated aqueous solution, impregnate the product from step 2 for 2 hours, filter, dry at 110℃ for 6 hours, and calcine at 550℃ for 4 hours.
[0105] A catalyst E1, consisting of molybdenum-nickel-cobalt active metals supported on a silicon-titanium support, was prepared, with a MoO3 content of 14.0% by weight, a NiO content of 3.4% by weight, and a CoO content of 2.2% by weight.
[0106] Comparative Example 3
[0107] This comparative example provides a hydrogenation catalyst, the composition of which and its preparation method are as follows:
[0108] 1) Weigh 10,000 g of aluminum hydroxide powder (70% by weight, dry basis) and 4,000 g of silica sol (containing 25% by weight of silica), mix them, and extrude them into clover-shaped strips with an outer circumscribed circle diameter of 1.4 mm using an extruder. Then dry them at 120 °C for 10 h and calcine them at 600 °C for 3 h to obtain carrier S. The silica content in carrier S is 12.5% by weight, and the alumina content is 87.5% by weight.
[0109] 2) Take 200g of carrier S, soak it in 170ml of aqueous solution containing 17.5g of ammonium fluoride for 2h, then dry it at 120℃ for 4h, and calcine it at 480℃ for 3h to obtain fluorine-containing carrier S1.
[0110] 3) The above-mentioned S1 support was impregnated with 167 mL of an aqueous solution containing 76.69 g of phosphomolybdic acid and 12.11 g of urea for 2 h, then dried at 140 °C for 4 h, and then impregnated with 163 mL of an aqueous solution containing 8.81 g of ammonium citrate and 17.92 g of nickel nitrate hexahydrate (nickel content 20% by weight, elemental basis) for 2 h, then dried at 180 °C for 5 h, and calcined at 550 °C for 4 h to obtain catalyst S2. The content of MoO3 was 25.29% by weight, and the content of NiO was 1.57% by weight.
[0111] Comparative Example 4
[0112] This comparative example provides a hydrogenation catalyst, the composition of which and its preparation method are as follows:
[0113] 1) Mix MgAl2O4 powder with a crystal size of 10nm, aluminum hydroxide dry glue, and guar gum powder in a mass ratio of 6:4:0.3. Add 5% dilute nitric acid dropwise at a ratio of 0.6mL / g MgAl2O4 powder. Then extrude the mixture into strips and calcine at 700℃ for 3h to obtain catalyst support X.
[0114] 2) Weigh out a certain amount of Ni(NO3)2·6H2O and (NH4)6Mo7O according to the proportion. 24 H2O and citric acid were used to prepare catalyst X1, wherein the active component (Mo+Ni) was added at 30% of the support mass based on the mass of MoO3+NiO, the molar ratio of Mo to Ni was 0.4, and the molar ratio of (Mo+Ni) to citric acid was 3:1. The active component was loaded by an equal volume impregnation method, and the catalyst was prepared by standing at 20℃ for 11 h, drying at 105℃ for 5 h, and calcining at 650℃ for 3 h.
[0115] Test case
[0116] (1) The performance of the catalyst supports prepared in Examples 1-3 and Comparative Examples 1-4 was tested. The corrosion of the supports after acid boiling was tested. 100g of the above supports were soaked in 200g of 20% acetic acid aqueous solution. The solutions were kept at a constant temperature of 180℃ and 1.0MPa in a reaction pressure vessel for 168 hours. After the constant temperature was maintained, the filtered solution was removed, washed with deionized water, and dried at 110℃ for 4 hours. The mass of the supports was weighed and the difference was calculated with the added starting supports to test whether the catalyst supports were corroded and lost weight under organic acid conditions. ICP analysis was performed on the filtered solution to measure whether any metal elements were precipitated. The test results are shown in Table 1.
[0117] Table 1
[0118] sample Carrier name Weight loss (g) Ti (ppm) Al (ppm) Mg (ppm) Example 1 A 0.08 238 0 0 Example 2 B 0.13 387 0 0 Example 3 C 0.10 299 0 0 Comparative Example 1 D 0.21 630 0 0 Comparative Example 2 E 0.19 561 0 0 Comparative Example 3 S 3.62 0 9831 0 Comparative Example 4 X 5.49 0 11296 2107
[0119] (2) The hydrogenation catalysts prepared in Examples 4-9 and Comparative Examples 1-5 were tested for their catalytic hydrogenation performance.
[0120] Test conditions:
[0121] 1) Using rancid palm oil containing 50% fatty acids by mass as feedstock, the hydrodeoxygenation and denitrification activity of the catalyst was investigated in a continuous fixed-bed reactor. The reactor was run continuously for 50 days, and the pressure drop of the catalyst was observed. The feedstock parameters are shown in Table 2 below.
[0122] Table 2
[0123]
[0124]
[0125] 2) The oxidized catalyst was first sulfided for 48 hours in a continuous fixed-bed reactor under a hydrogen atmosphere of 350℃, 10.0MPa and 2000ppm hydrogen sulfide content.
[0126] 3) Raw materials are introduced into the reactor, and under the conditions of inlet reaction temperature of 280℃, pressure of 10.0MPa, volume hourly space velocity of 0.5h-1, and hydrogen-to-oil volume ratio of 1200:1, hydrogenation, deoxygenation, and saturation reactions are carried out.
[0127] 4) The evaluation results are shown in Table 3:
[0128] Evaluation of reactor pressure drop change = initial reactor inlet / outlet pressure difference - final reactor inlet / outlet pressure difference;
[0129] Deoxygenation rate of reaction = 1 - Oxygen content of product after reaction / Oxygen content of raw material before reaction;
[0130] Reaction denitrification rate = 1 - nitrogen content of product after reaction / nitrogen content of raw material before reaction;
[0131] Table 3
[0132] sample Sample Name Pressure drop change (MPa) Deoxygenation rate % Denitrification rate % Example 4 A1 -0.21 98.67％ 96.21％ Example 5 B1 -0.18 99.03％ 96.48％ Example 6 C1 -0.10 97.78％ 97.00％ Example 7 A2 -0.22 98.13％ 98.61％ Example 8 B2 -0.17 98.35％ 98.08％ Example 9 C2 -0.09 97.23％ 95.98％ Comparative Example 1 D1 -0.26 91.55％ 90.40％ Comparative Example 2 E1 -0.25 92.34％ 91.18％ Comparative Example 3 S2 -0.33 91.25％ 87.78％ Comparative Example 4 X1 -0.45 90.36％ 89.52％
[0133] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.
Claims
1. A method for preparing a catalyst support, characterized in that, It is prepared by the following steps: S1, a solid inorganic silicon source, a liquid inorganic silicon source, and a solid inorganic titanium source are mixed under the action of an organic binder and water, and then extruded to obtain a precursor; S2, the obtained precursor is dried and calcined to obtain the catalyst support; In step S1, the mass ratio of the solid inorganic silicon source, the liquid inorganic silicon source, and the solid inorganic titanium source is 1:1-4:0.7-2; The solid inorganic silicon source is silicon dioxide powder; The liquid inorganic silicon source is silica sol; The solid inorganic titanium source is at least one of metatitanic acid, titanium dioxide, and titanium phosphate.
2. The method for preparing the catalyst support according to claim 1, characterized in that, The solid inorganic silicon source has an average particle size of 30-300 nm and a specific surface area of 150-300 nm. 2 / g, with an apparent density of 0.1-0.5g / ml.
3. The method for preparing the catalyst support according to claim 1, characterized in that, The liquid inorganic silicon source contains 20-45 wt% silica, and the average particle size of the silica is 5-30 nm. And / or, the average particle size of the solid inorganic titanium source is 10-200 nm.
4. The method for preparing the catalyst support according to claim 1, characterized in that, The organic binder is selected from at least one of polysaccharides and proteins.
5. The method for preparing the catalyst support according to claim 4, characterized in that, The polysaccharide is selected from at least one of guar gum and guar gum, and the protein is selected from at least one of wheat gluten and soy protein isolate.
6. The method for preparing the catalyst support according to claim 1, characterized in that, In step S1, the amount of the organic binder accounts for 20%-35% of the sum of the mass of the solid inorganic silicon source and the solid inorganic titanium source; And / or, the amount of water used accounts for 60%-100% of the sum of the masses of the solid inorganic silicon source and the solid inorganic titanium source.
7. The method for preparing the catalyst support according to any one of claims 1-6, characterized in that, In step S2, the calcination is carried out in an oxygen-containing atmosphere, the calcination temperature is 400℃-800℃, and the calcination time is ≥4h; And / or, the drying temperature is 60℃-120℃, and the drying time is 2h-24h.
8. The method for preparing the catalyst support according to claim 7, characterized in that, The roasting time is 4-12 hours.
9. A catalyst support, characterized in that, Prepared by the preparation method according to any one of claims 1-8, wherein the content of silicon oxide in the catalyst support is 46wt%-76wt%, the content of titanium oxide is 24-54wt%, and the specific surface area of the catalyst support is not less than 100m². 2 / g.
10. The catalyst support according to claim 9, characterized in that, The specific surface area of the catalyst support is 100~300m². 2 / g, with an average pore volume of 0.4-0.6cm³. 3 / g, with an average pore size of 14-25nm.
11. A hydrogenation catalyst, characterized in that, It includes the catalyst support and active component as described in claim 9 or 10; the active component exists in the form of a metal oxide, including at least one oxide of cobalt, nickel, palladium, platinum, molybdenum, and tungsten.
12. The hydrogenation catalyst according to claim 11, characterized in that, The active component in the hydrogenation catalyst is 15-25 wt%.
13. The application of the hydrogenation catalyst according to claim 11 or 12 in the hydrogenation and deoxygenation of fatty acid-containing oils to prepare white oil or hydrocarbon-based biodiesel, characterized in that, The fatty acid-containing oil has an oxygen content of 8-13 wt% and a free fatty acid content of 10-100 wt%.
14. The application according to claim 13, characterized in that, The conditions for the hydrodeoxygenation reaction are: reaction temperature 260-400℃, hydrogen pressure 6.0-18.0 MPa, and liquid hourly space velocity 0.25-2 h⁻¹. -1 The hydrogen-to-oil volume ratio is 800-2000:1.