Hydrodeoxygenation catalyst and method for preparing the same

Abstract

The present disclosure relates to a hydrodeoxygenation catalyst and a method for preparing the same. Specifically, the hydrodeoxygenation catalyst includes a hydrogenation active component and a catalyst carrier. The hydrogenation active component includes one or more hydrogenation active metals including Pt, Pd, Rh, Ru, Ni, Co, Cu, or a combination thereof. The catalyst carrier is a solid solution composite oxide containing Al, Nb, Si, and O elements, and the catalyst carrier has the chemical formula (Nb2O5) x (Al2O3) y (SiO2) z (0.01 ≦ x ≦ 0.3, 0.01 ≦ y ≦ 0.1 and 0.6 ≦ z ≦ 0.98).

Description

Technical Field

[0001] The present disclosure relates to the technical field of bioenergy, and in particular, to a hydrodeoxygenation catalyst and a method for preparing the same, and a method for preparing a biojet fuel component oil using the hydrodeoxygenation catalyst.

Background Art

[0002] Against the backdrop of the desire to reduce dependence on petroleum-based fuels and cut greenhouse gas emissions, biomass is currently the most promising resource that can be used to prepare hydrocarbon-based liquid fuels as an alternative to petroleum-derived fuels. To continue the transition from a fossil energy economy to a renewable energy economy and convert biomass into high-value-added fuels and chemicals, using furfural, a lignocellulosic hydrolyzate, as a raw material, first extend the carbon chain through an aldol condensation reaction to obtain furfurylacetone (4-(2-furyl)-3-buten-2-one) and difurfurylacetone (1,5-bis-(2-furyl)-1,4-pentadien-3-one), then perform hydrodeoxygenation to obtain C8 linear alkanes and C 13 linear alkanes, and finally isomerize to obtain qualified jet fuel components, thereby achieving the effective utilization of biomass (Science, 308, 1446-1450 (2005)).

[0003] Research on the preparation of difurfurylacetone (1,5-bis-(2-furyl)-1,4-pentadien-3-one) by the Claisen condensation reaction of furfural and acetone catalyzed by inorganic strong alkali has already been relatively mature, and the problem of waste liquid treatment has been solved by a gentle preparation process before. The difurfurylacetone obtained by the reaction can be used not only as an intermediate of jet fuel to obtain C 13 hydrocarbon components added to jet fuel, but also as a high-value-added chemical used as a co-crosslinking agent and co-vulcanizing agent for rubber, and can improve the performance of rubber such as crosslinking degree, heat resistance, and tensile stress.

[0004] It is difficult to directly dehydrate difurfurylacetone using an existing dehydration catalyst. The existing methods employed involve first hydrogenating the carbon-carbon double bond to obtain 1,5-bis(2-tetrahydrofuranyl)-3-pentanone, and then using a dehydration catalyst to dehydrate and hydrogenate it to obtain a C 13 long-chain alkane. Such a stepwise hydrogenation method (two-step hydrogenation) can greatly reduce the difficulty of preparing jet fuel components. In addition, the stepwise hydrogenation method can also improve the yield of the target long-chain alkane. In view of such advantages, many of the existing long-chain alkane preparation methods employed in the prior art are stepwise hydrogenation methods, and the reaction pathway for producing biojet fuel component oil from difurfurylacetone by two-step hydrogenation is as follows. TIFF2025523935000001.tif47170

[0005] However, the existing catalysts for catalyzing the dehydration of difurfurylacetone in the prior art only support the preparation of long-chain alkanes by the above stepwise hydrogenation method, and there is a lack of catalytic efficiency. There is a need for an improved manufacturing method for biomass-based jet fuel components.

[0006] Furthermore, it is known that the bottleneck in the production of biomass-based jet fuel components lies in the development of an inexpensive and efficient hydrodeoxygenation catalyst. Therefore, in this field, there is still a need for an inexpensive and efficient hydrodeoxygenation catalyst.

Summary of the Invention

[0007] The object of the present disclosure is to provide a hydrodeoxygenation catalyst and a method for preparing the same, as well as a method for preparing biojet fuel component oil using the hydrodeoxygenation catalyst, to solve the problems of existing hydrodeoxygenation catalysts for catalyzing the hydrodeoxygenation of biomass for preparing biojet fuel component oil, such as low catalytic efficiency, low raw material conversion rate, low product yield, and low selectivity.

[0008] To achieve the above object, according to one aspect of the present disclosure, a hydrodeoxygenation catalyst is provided. This hydrodeoxygenation catalyst includes a hydrogenation active component and a catalyst support. The hydrogenation active component includes one or more hydrogenation active metals. The catalyst support is a solid solution composite oxide containing Nb, Al, Si, and O elements. The catalyst support has the chemical formula (Nb2O5) x (Al2O3) y (SiO2) z (0.01 ≦ x ≦ 0.3, 0.01 ≦ y ≦ 0.1 and 0.6 ≦ z ≦ 0.98).

[0009] Furthermore, the one or more hydrogenation active metals include Pt, Pd, Rh, Ru, Ni, Co, Cu, or a combination thereof.

[0010] Furthermore, based on the total weight of the hydrodeoxygenation catalyst, the loading amount of the hydrogenation active metal is about 0.4 wt% - 10 wt%.

[0011] Furthermore, Nb2O5, Al2O 3、 and SiO2 in the hydrodeoxygenation catalyst exist in an amorphous form.

[0012] According to another aspect of the present disclosure, a method for preparing a hydrodeoxygenation catalyst is provided. This method includes: a sol-gel step: mixing a hydrogenation active metal source with a niobium source, an aluminum source, and a silicon source having a molar ratio of (0.01 - 0.3):(0.01 - 0.1):(0.6 - 0.98), dissolving in water to obtain a sol of a soluble precursor; a gelation step: stirring the sol at a temperature from room temperature to about 60 °C to obtain a gel; and an aging step: allowing the gel to stand and age to obtain an aged substance; and drying, firing, and reducing the aged substance to obtain a hydrodeoxygenation catalyst.

[0013] Furthermore, in the sol-gel step, the mixing of the niobium source, the aluminum source, the silicon source, and the hydrogenation active metal source is carried out in the presence of a hydrolysis agent.

[0014] Furthermore, in the gelation step, the stirring time is about 1 - 12 hours.

[0015] Furthermore, in the aging step, the aging time is about 1 to 3 hours.

[0016] Furthermore, the reduction is carried out at a temperature of about 200 to 500 °C in the presence of hydrogen for about 2 to 6 hours.

[0017] Furthermore, the niobium source is selected from the group consisting of niobium tartrate, niobium citrate, niobium malate, niobium nitrate, niobium chloride, niobium sulfate, and combinations thereof, and preferably, the niobium source is niobium tartrate.

[0018] Furthermore, the hydrolyzing agent is selected from the group consisting of acids and alkalis; the aluminum source is selected from the group consisting of aluminum nitrate, aluminum chloride, aluminum acetate, and combinations thereof, and preferably, the aluminum source is aluminum nitrate; the silicon source is selected from the group consisting of silica sol, water glass, ethyl orthosilicate, and combinations thereof, and preferably, the silicon source is silica sol; the hydrogenated active metal source is selected from the group consisting of nitrates, sulfates, chlorides, acetates, and combinations thereof, and preferably, the hydrogenated active metal source is selected from the group consisting of palladium nitrate, palladium sulfate, palladium chloride, palladium acetate, platinum nitrate, platinum sulfate, platinum chloride, platinum acetate, ruthenium nitrate, nickel nitrate, cobalt nitrate, and combinations thereof.

[0019] According to another aspect of the present disclosure, a method for preparing isoalkane using a hydrodeoxygenation catalyst is provided, the method including performing a hydrogenation reaction on difurfurylacetone of the following formula in the presence of a hydrodeoxygenation catalyst and an organic solvent to obtain an isoalkane. TIFF2025523935000002.tif17170

[0020] Furthermore, the hydrodeoxygenation reaction is carried out at a temperature of about 150 °C to 280 °C under a hydrogen pressure of about 0.5 MPa to 8 MPa with stirring for about 1 hour to 36 hours.

[0021] Furthermore, the organic solvent is cyclohexane, and based on the total weight of difurfuryl acetone and the organic solvent, the weight percentage of difurfuryl acetone is about 10 wt% to 30 wt%.

[0022] Furthermore, the weight ratio of difurfuryl acetone to the hydrodeoxygenation catalyst is (2 to 20):1.

[0023] According to the technical scheme of the present disclosure, a hydrodeoxygenation catalyst, a method for preparing the same, and a method for preparing a biojet fuel component oil using the hydrodeoxygenation catalyst are provided. The hydrodeoxygenation catalyst of the present disclosure has the chemical formula (Nb2O5) x (Al2O3) y (SiO2) z (0.01 ≦ x ≦ 0.3, 0.01 ≦ y ≦ 0.1 and 0.6 ≦ z ≦ 0.98) is adopted to solve the problems of existing hydrodeoxygenation catalysts for catalyzing biomass hydrodeoxygenation to prepare biojet fuel component oil, such as low catalyst efficiency, low raw material conversion rate, low product yield and low selectivity. In the present disclosure, the above problems are solved by adopting a hydrodeoxygenation catalyst containing a catalyst support with a specific chemical composition of the present disclosure. Therefore, the conversion rate of the raw material, the product yield, and the selectivity of the hydrodeoxygenation catalyst are improved.

Embodiments for Carrying Out the Invention

[0024] It should be noted that the embodiments of the present application and the features of the embodiments can be combined with each other according to the examples without contradiction. The present disclosure will be described in detail below with reference to the examples.

[0025] In the existing technology, the hydrodeoxygenation product prepared by catalyzing the hydrodeoxygenation of biomass is n-alkane, and its freezing point is relatively high. The ideal component of biojet fuel component oil is isoalkane, because the freezing point of isoalkane is lower than that of n-alkane (for example, the freezing point of isotridecane is about -30 °C). In addition, the hydrodeoxygenation catalyst for catalyzing the hydrodeoxygenation of biomass to prepare biojet fuel component oil in the existing technology has problems such as low catalyst efficiency, low raw material conversion rate, low product yield, and low selectivity. In view of the above defects in the existing technology, the present application provides a hydrodeoxygenation catalyst, which includes a hydrodeoxygenation active component and a catalyst support. The hydrodeoxygenation active component includes one or more hydrodeoxygenation active metals, and the catalyst support is a solid solution composite oxide containing Al, Nb, Si, and O elements. The catalyst support has the chemical formula (Nb2O5) x (Al2O3) y (SiO2) z (0.01 ≦ x ≦ 0.3, 0.01 ≦ y ≦ 0.1).

[0026] According to the present disclosure, the hydrodeoxygenation catalyst for catalyzing the hydrodeoxygenation of biomass to prepare long-chain alkanes in the existing technology has low efficiency, excessive raw material consumption, low raw material conversion efficiency, and low product selectivity. Based on the above problems, the present disclosure prepares a hydrodeoxygenation catalyst for catalyzing the hydrogenation of difurfurylacetone to prepare biojet fuel component oil. This specific catalyst has a catalyst support (chemical formula (Nb2O5) x (Al2O3) y (SiO2) z(0.01 ≦ x ≦ 0.3, 0.01 ≦ y ≦ 0.1 and 0.6 ≦ z ≦ 0.98)) is used to solve the above problem. The catalyst support of the present disclosure is a Nb2O5-Al2O3-SiO2 ternary composite material having a specific ratio. The Nb2O5 portion in the composite material has excellent C-O bond activation ability, efficiently catalyzes the hydrodeoxygenation reaction of difurfurylacetone to obtain alkanes, and at the same time provides acid sites to catalyze the isomerization reaction of the alkanes produced by the hydrodeoxygenation reaction, thereby obtaining isoalkane products; the Al2O3 portion and the SiO2 portion in the composite material are used as components of the molecular sieve, thereby providing acid sites and promoting the alkanes produced by the hydrodeoxygenation reaction to carry out the isomerization reaction. Furthermore, the chemical formula (Nb2O5) x (Al2O3) y (SiO2) z In the catalyst support of, x, y, and z are within the scope of the present disclosure, which means that each part in the composite material effectively exerts its catalytic function, improves the conversion rate of biofuel oxygen-containing compound raw materials such as difurfurylacetone in the hydrodeoxygenation reaction, and C 10+ long-chain alkanes (e.g., C 13 alkanes), and compensates for the selectivity of isoalkanes (the main component of sustainable aviation fuel (SAF)) to be excellent.

[0027] In addition, the hydrodeoxygenation catalyst of the present disclosure contains a hydrogenation active component. The hydrogenation active component contains a metal as a hydrogenation active substance. The hydrogenation active metal catalyzes the hydrogen molecules adsorbed on the catalyst to form hydrogen atoms so as to participate in the addition reaction with the carbon-oxygen double bond in difurfurylacetone, ensuring the hydrogenation reaction of difurfurylacetone.

[0028] Preferably, x is 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2, 0.25, 0.28, 0.3, or any value therebetween. y is 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, or any value therebetween. z is 0.61, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 0.98, or any value therebetween. The values of x, y, and z are within the scope of the present disclosure, and Nb2O5 in the composite material can provide excellent carbon-oxygen bond activation ability and sufficient acid sites. The Al2O3 part and the SiO2 part as components of the molecular sieve further provide acid sites, whereby the conversion rate of difurfurylacetone and the 10+ long-chain alkane yield and the selectivity of isoalkane are improved more favorably.

[0029] Preferably, the one or more hydrogenation active metals include Pt, Pd, Rh, Ru, Ni, Co, Cu, or a combination thereof. More preferably, the one or more hydrogenation active metals are Pt, Pd, or a combination of Pt and Pd. The hydrogenation active metals within the scope of the present disclosure can promote the adsorption of hydrogen molecules, thereby promoting the conversion of hydrogen molecules into hydrogen atoms and further promoting the hydrogenation reaction of difurfurylacetone.

[0030] Preferably, the ratios of x, y, and z in the chemical formula of the catalyst support are (0.01 to 0.3):(0.01 to 0.1):(0.6 to 0.98). For example, the ratios of x, y, and z are 0.01:0.01:0.6, 0.05:0.01:0.6, 0.08:0.01:0.6, 0.1:0.01:0.6, 0.15:0.01:0.6, 0.2:0.01:0.6, 0.25:0.01:0.6, 0.3:0.01:0.6, 0.01:0.03:0.6, 0.01:0.05:0.6, 0.01:0.07:0.6, 0.01:0.1:0.6, 0.01:0.05:0.65, 0.01:0.05:0.7, 0.01:0.05:0.75, 0.01:0.05:0.8, 0.01:0.05:0.85, 0.01:0.05:0.9, 0.01:0.05:0.95, and 0.01:0.05:0.98, etc. According to the present disclosure, the ratios of x, y, and z are within the scope of the present disclosure, but can further provide excellent carbon-oxygen bond activation ability and more acid sites, whereby the conversion rate of difurfurylacetone and C 10+ The yield of long-chain alkanes can be further improved, and the selectivity of isoalkanes can be further improved.

[0031] In some embodiments, based on the total weight of the hydrodeoxygenation catalyst, the loading amount of the hydrogenation active metal is about 0.4 wt% to 10 wt%. For example, the loading amounts of the hydrogenation active metal are 0.4 wt%, 0.42 wt%, 0.44 wt%, 0.46 wt%, 0.48 wt%, 0.5 wt%, 0.8 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 7 wt%, 8 wt%, and 10 wt%, etc. If the loading amount is too high, the cost may increase. If the loading amount is too low, the number of active metal catalyst centers will decrease, which is not beneficial for exerting the hydrogenation catalyst activity. Compared with existing hydrodeoxygenation catalysts, the catalyst of the present disclosure has a low loading amount of the active metal component (noble metal) and excellent catalyst performance, so that a catalyst with excellent performance can be prepared at low cost.

[0032] In some embodiments, Nb2O5, Al2O3, and SiO2 in the hydrodeoxygenation catalyst exist in an amorphous form. The hydrodeoxygenation catalyst synthesized according to the present disclosure is a solid solution composite oxide. In this specification, Nb2O5, Al2O3, and SiO2 exist in an amorphous form and have more unsaturated coordination active centers compared with existing hydrodeoxygenation catalysts. As a result, the catalytic activity of the carbon-oxygen bond is further improved, the cleavage of the carbon-oxygen bond is promoted, thereby improving the catalytic activity of the catalyst, the conversion rate of the reactants, C 10+ The yield of long-chain alkanes and the selectivity of isoalkanes are further improved.

[0033] In some embodiments, the method for preparing a hydrodeoxygenation catalyst comprises: a sol-gel step of mixing a hydrogenation active metal source with a niobium source, an aluminum source, and a silicon source having a molar ratio of (0.01 to 0.3):(0.01 to 0.1):(0.6 to 0.98), dissolving them in water to obtain a sol of a soluble precursor; a gelation step of stirring the sol at a temperature from room temperature to about 60 °C to obtain a gel; and an aging step of allowing the gel to stand and age to obtain an aged substance; and a step of drying, firing, and reducing the aged substance to obtain a hydrodeoxygenation catalyst. According to the method of the present disclosure, in the sol-gel step, the hydrogenation active metal source is mixed with a niobium source, an aluminum source, and a silicon source in a specific molar ratio, dissolved in water at a general temperature, and the niobium source, aluminum source, and silicon source undergo a hydrolysis reaction in water to form a stable and transparent sol system. In the gelation step, the sol system is stirred at a temperature from room temperature to about 60 °C to cause a cross-linking reaction between the colloidal particles of the sol over time, forming a gel system having a three-dimensional network structure. In the aging step, aging occurs while the gel system is allowed to stand for a certain period of time. During the aging process, the cross-linking of the gel is more thoroughly performed, and the three-dimensional network structure becomes more stable. The aged substance is dried to remove the moisture therein by volatilization; the firing process decomposes each component in the dried aged substance; and then, by reducing the fired aged substance, the hydrogenation active metal in the form of an oxide is reduced, oxygen vacancies are generated, and finally, a metal active center having activated hydrogen and an oxygen vacancy center for improving the C-O bond activation ability are obtained. In this way, a catalyst support having a specific chemical composition of the present disclosure is obtained (chemical formula (Nb2O5) x (Al2O3) y (SiO2) z (represented by 0.01 ≦ x ≦ 0.3, 0.01 ≦ y ≦ 0.1 and 0.6 ≦ z ≦ 0.98)).

[0034] In some embodiments, in the sol-gel step, the mixing of the niobium source, aluminum source, silicon source, and hydrogenated active metal source is carried out in the presence of a hydrolyzing agent. The presence of the hydrolyzing agent may further promote the hydrolysis process of the aluminum source, niobium source, and silicon source, thereby further promoting the formation of the sol system. On the other hand, the addition of the hydrolyzing agent may promote the polymerization reaction process between the colloidal particles of the sol and the formation of a three-dimensional network structure, which is beneficial for shortening the conversion time of the sol to the gel. Those skilled in the art can adjust it as needed to achieve the sol-gel process and gelation process.

[0035] In some embodiments, in the gelation step, the stirring time is about 1 to 12 hours. For example, the duration of stirring is 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, and 12 hours, etc. After the sol of the soluble precursor is obtained, when the sol is stirred at a selected temperature for a period within the above range, the polymerization reaction process between the colloidal particles of the sol and the formation of a three-dimensional network structure can be further promoted. Those skilled in the art can adjust it as needed to achieve the conversion process from the sol to the gel.

[0036] In some embodiments, in the aging step, the aging time is about 1 to 3 hours. For example, the aging time is 1 hour, 2 hours, and 3 hours, etc. During the aging time within the above range, sufficient cross-linking of the gel can be further promoted, and the three-dimensional network structure can be further stabilized. Those skilled in the art can adjust it as needed to achieve the sufficient cross-linking process and stabilization process of the gel.

[0037] In some embodiments, the reduction of the catalyst support is carried out at a temperature of 200 to 500 °C, in the presence of hydrogen, for about 2 to 6 hours. For example, the reduction temperatures are 200 °C, 300 °C, 350 °C, 400 °C, 450 °C, and 500 °C, etc. For example, the reduction times are 2 hours, 3 hours, 4 hours, 5 hours, and 6 hours, etc. The catalyst support is reduced using hydrogen, and when the reduction temperature and time are within the above ranges, the hydrogenation active metal in the oxide form can be more fully reduced, and the hydrogen molecule activation ability of the hydrogenation active metal can be further improved.

[0038] In some embodiments, the niobium source is selected from the group consisting of niobium tartrate, niobium citrate, niobium malate, niobium nitrate, niobium hydrochloride, niobium sulfate, and combinations thereof. Preferably, the niobium source is niobium tartrate. The niobium source within the scope of the present disclosure has a higher solubility compared to commercially available soluble niobium sources. For example, the solubility of niobium tartrate prepared in the present disclosure is 1.0 mol / L, while the solubility of niobium oxalate or ammonium niobium oxalate, which are commercially available soluble niobium sources, is only 0.25 mol / L. The higher the solubility, the better the solubility of the niobium source in water, and the more likely the occurrence of the hydrolysis reaction is to be promoted, which is beneficial for the preparation of the hydrogenation deoxygenation catalyst having the chemical formula of the present disclosure by the sol-gel method. On the other hand, the niobium source within the scope of the present disclosure can be left standing for a period exceeding 3 weeks without precipitation after being dissolved in water. Compared with niobium oxalate or ammonium niobium oxalate, which are commercially available soluble niobium sources in the prior art and can form apparent precipitates within 1 week, the niobium source within the scope of the present disclosure has good stability, thereby further improving the stability of the sol prepared therefrom. In addition, the cost of the niobium source used in the present disclosure is low, whereby the manufacturing cost of preparing the hydrogenation deoxygenation catalyst can be reduced.

[0039] The hydrolyzing agent is selected from the group consisting of acids and alkalis, and the concentration of the hydrolyzing agent is about 0.1 mol / L to 2.0 mol / L, for example, 0.1 mol / L, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, 0.5 mol / L, 1.0 mol / L, 1.5 mol / L, and 2.0 mol / L. The acid is selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid, oxalic acid, citric acid, and combinations thereof, and the alkali is selected from the group consisting of aqueous ammonia, triethylamine, ethylenediamine, tetramethylethylenediamine, and combinations thereof. The type and concentration of the hydrolyzing agent are within the scope of the present disclosure, whereby the hydrolysis process of each reactant in the sol-gel process and the polymerization and cross-linking between colloidal particles in the gelation process are further promoted, and the conversion time from sol to gel can be further shortened. Those skilled in the art can adjust it as necessary to achieve the sol-gel process.

[0040] In some embodiments, the aluminum source is selected from the group consisting of aluminum nitrate, aluminum chloride, aluminum acetate, and combinations thereof, and preferably, the aluminum source is aluminum nitrate. The use of an aluminum source within the scope of the present disclosure can further increase the number of acid sites provided, thereby further promoting the isomerization reaction of alkanes. Those skilled in the art can adjust it as necessary to achieve the isomerization reaction of alkanes.

[0041] In some embodiments, the silicon source is selected from the group consisting of silica sol, water glass, ethyl orthosilicate, and combinations thereof, and preferably, the silicon source is silica sol. The use of a silicon source within the scope of the present disclosure can further increase the number of acid sites provided, thereby further promoting the isomerization reaction of alkanes. Those skilled in the art can adjust it as necessary to achieve the isomerization reaction of alkanes.

[0042] In some embodiments, the hydrogenation active metal source is selected from the group consisting of nitrates, sulfates, chlorides, acetates, and combinations thereof. Preferably, the hydrogenation active metal source is selected from the group consisting of palladium nitrate, palladium sulfate, palladium chloride, palladium acetate, platinum nitrate, platinum sulfate, platinum chloride, platinum acetate, ruthenium nitrate, nickel nitrate, cobalt nitrate, and combinations thereof. Most preferably, the hydrogenation active metal source is palladium nitrate. Those skilled in the art can adjust it as needed to achieve the hydrodeoxygenation reaction of difurfurylacetone.

[0043] In some embodiments, during the preparation process of the hydrodeoxygenation catalyst, the prepared hydrodeoxygenation catalyst is subjected to further shaping treatment to improve the mechanical strength of the hydrodeoxygenation catalyst. Here, the shaping treatment includes, but is not limited to, extrusion, ball rolling, tableting, pelletization, and combinations thereof. Those skilled in the art can adjust it as needed to achieve the improvement of the mechanical strength of the hydrodeoxygenation catalyst.

[0044] In some embodiments, a method for catalyzing biomass hydrodeoxygenation to prepare isoalkanes using a hydrodeoxygenation catalyst includes performing a hydrogenation reaction on difurfurylacetone of the following formula in the presence of a hydrodeoxygenation catalyst and an organic solvent to obtain isoalkanes. TIFF2025523935000003.tif17170

[0045] Preferably, the reaction of difurfurylacetone, the organic solvent, and the hydrodeoxygenation catalyst is carried out in a stainless-steel high-pressure reactor containing a polytetrafluoroethylene liner.

[0046] In some embodiments, the hydrodeoxygenation reaction is carried out at a temperature of about 150°C to about 280°C, under a hydrogen pressure of about 0.5 MPa to about 8 MPa, and with stirring for about 1 to 36 hours. For example, the temperature of the hydrogenation reaction is 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, and 280°C, etc. For example, the hydrogen pressure is 0.5 MPa, 0.6 MPa, 0.7 MPa, 0.8 MPa, 0.9 MPa, 1.0 MPa, 2.0 MPa, 3.0 MPa, 4.0 MPa, 5.0 MPa, 6.0 MPa, 7.0 MPa, and 8.0 MPa, etc. For example, the reaction is carried out over 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 15 hours, 20 hours, 25 hours, 30 hours, 32 hours, 34 hours, and 36 hours, etc. Those skilled in the art can adjust it as necessary to achieve the hydrodeoxygenation reaction of difurfuryl acetone catalyzed by the hydrodeoxygenation catalyst.

[0047] In some embodiments, the organic solvent for the hydrogenation reaction is selected from the group consisting of cyclohexane, biojet fuel, and other common jet fuels, and preferably, the organic solvent is cyclohexane. Based on the total weight of difurfuryl acetone and the organic solvent in the hydrogenation reaction, the weight percentage of difurfuryl acetone is about 10 wt% to 30 wt%, for example, 10 wt%, 15 wt%, 20 wt%, 25 wt%, and 30 wt%, etc. The weight ratio of difurfuryl acetone to the hydrodeoxygenation catalyst (the ratio of the weight of difurfuryl acetone to the weight of the hydrodeoxygenation catalyst) is (2 - 20):1, for example, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 12:1, 14:1, 16:1, 18:1, and 20:1, etc. Those skilled in the art can adjust it as necessary to achieve the hydrodeoxygenation of difurfuryl acetone catalyzed by the hydrodeoxygenation catalyst.

[0048] This application will be described in further detail below with reference to specific embodiments, which should not be construed as limiting the scope of protection claimed by this application.

[0049] In the following examples and comparative examples, the selectivity of isoalkane means the proportion of isoalkane in all alkanes in the product and can be calculated by the following formula: Selectivity of isoalkane (%) = weight of isoalkane in the product / weight of all alkanes in the product.

Example

[0050] Preparation Example 1: Weighed 0.5 g of aluminum nitrate and 4 g of silica sol (silicon dioxide concentration was 11% w / w), weighed 0.5 mL of palladium nitrate solution (0.01 g / mL), added 0.5 g of citric acid to 20 mL of deionized water, and mixed them uniformly. Weighed 10 mL of niobium tartrate solution (0.7 mol / L) and added it to the above solution to form a sol. Stirring was continued at a constant temperature of 35 °C in a water tank for 2 hours until a gel was formed. The gel was allowed to stand for 1 hour. The gel was dehydrated and dried under the condition of 100 °C, and the dried sample was heated to 500 °C at a heating rate of 1 °C / min in a muffle furnace, calcined for 300 minutes, then naturally cooled to room temperature, and reduced with hydrogen at 200 °C for 2 hours before use, and finally Catalyst 1 was obtained. According to the fluorescence X-ray (XRF) measurement, the chemical formula of the carrier of Catalyst 1 is ((Nb2O5) x (Al2O3) y (SiO2) z (where x:y:z was 0.28:0.07:0.65), and the content of the active metal Pd was 0.4 wt%.

[0051] Preparation Example 2: The preparation method was as follows: the addition amount of aluminum nitrate was 0.1 g, the addition amount of silica sol (silicon dioxide concentration was 11% w / w) was 6 g, 0.3 mL (0.01 g / mL) of palladium nitrate solution (0.01 g / mL) was weighed, the addition amount of niobium tartrate solution (0.7 mol / L) was 2 mL, the conversion from sol to gel was carried out in a water bath under the condition of 60 °C, and it was the same as Preparation Example 1 except that the gel was allowed to stand for 3 hours. Finally, Catalyst 2 was obtained. According to XRF measurement, the chemical formula of the carrier in Catalyst 2 was ((Nb2O5) x (Al2O3) y (SiO2) z (where x:y:z was 0.05:0.02:0.93), and the content of active metal Pd was 0.48 wt%.

[0052] Preparation Example 3: The preparation method was as follows: the addition amount of aluminum nitrate was 0.25 g, the addition amount of silica sol (silicon dioxide concentration was 11% w / w) was 5 g, 0.42 mL of palladium nitrate solution (0.01 g / mL) was weighed, the addition amount of niobium tartrate solution (0.7 mol / L) was 6.7 mL, the conversion from sol to gel was carried out at room temperature, and it was the same as Preparation Example 1 except that the gel was allowed to stand for 3 hours. Finally, Catalyst 3 was obtained. According to XRF measurement, the chemical formula of the carrier in Catalyst 3 was ((Nb2O5) x (Al2O3) y (SiO2) z (where x:y:z was 0.21:0.05:0.74), and the content of active metal Pd was 0.4 wt%.

[0053] Preparation Comparative Example 1: The preparation method was the same as Preparation Example 1 except that no aluminum nitrate was added. Finally, Catalyst A (without Al) was obtained. According to XRF measurement, the chemical formula of Catalyst A was ((Nb2O5) x (SiO2) z (where x:z was 0.28:0.65), and the content of active metal Pd was 0.44 wt%.

[0054] Preparation Comparative Example 2: The preparation method was the same as that of Preparation Example 1 except that no silica sol was added. Finally, Catalyst B (without Si) was obtained. According to XRF measurement, the chemical formula of Catalyst B was ((Nb2O5) x (Al2O3) y ) x:y was 0.28:0.07), and the content of active metal Pd was 0.57 wt%.

[0055] Preparation Comparative Example 3: The preparation method was the same as that of Preparation Example 1 except that niobium tartrate was not added. Finally, Catalyst C (without Nb) was obtained. According to XRF measurement, the chemical formula of Catalyst C was ((Al2O3) y (SiO2) z (y:z was 0.07:0.65), and the content of active metal Pd was 1.1 wt%.

[0056] Preparation Comparative Example 4: The preparation method was the same as that of Preparation Example 1 except that 3.0 g of aluminum nitrate was added and 0.7 mL of palladium nitrate solution (0.01 g / mL) was weighed. Finally, Catalyst D was obtained. According to XRF measurement, the chemical formula of Catalyst D was ((Nb2O5) x (Al2O3) y (SiO2) z (x:y:z was 0.19:0.36:0.45), and the content of active metal Pd was 0.4 wt%.

[0057] Preparation Comparative Example 5: The preparation method was the same as that of Preparation Example 1 except that 2.2 g of silica sol was added. Finally, Catalyst E was obtained. According to XRF measurement, the chemical formula of Catalyst E was ((Nb2O5) x (Al2O3) y (SiO2) z (x:y:z was 0.55:0.13:0.32), and the content of active metal Pd was 0.41 wt%.

[0058] Preparation Comparative Example 6: The preparation method was the same as that of Preparation Example 1, except that 40 mL of niobium tartrate solution (0.5 mol / L) was added and 0.8 mL of palladium nitrate solution (0.01 g / mL) was weighed. Finally, Catalyst F was obtained. According to XRF measurement, the chemical formula of the obtained Catalyst F was ((Nb2O5) x (Al2O3) y (SiO2) z (where x:y:z was 0.61:0.03:0.36), and the content of active metal Pd was 0.42 wt%. TIFF2025523935000004.tif81170

[0059] Test Example 4: 0.1 g of Catalyst 1, 1.0 g of difurfurylacetone, and 4 g of cyclohexane were taken and placed in a 30 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner. After detecting leakage, hydrogen was supplied and maintained at 3.5 MPa. Then, high-speed stirring was carried out at a reaction temperature of 180 °C for 12 hours to obtain long-chain alkanes. The content of long-chain alkanes in the reaction product was measured by gas chromatography (GC). As a result, the conversion rate of difurfurylacetone was 100%, and the yield of C 10+ alkanes (C 10 -C 13 total alkanes) was 91%, and the selectivity of isoalkanes was 40%.

[0060] Test Example 5: The test method was the same as that of Test Example 4, except that Catalyst 1 was replaced with Catalyst 2. The content of long-chain alkanes in the reaction product was measured by GC. As a result, the conversion rate of difurfurylacetone was 99%, and the yield of C 10+ alkanes (C 10 -C 13 total alkanes) was 89%, and the selectivity of isoalkanes was 38%.

[0061] Test Example 6: The test method was the same as that of Test Example 4, except that Catalyst 1 was replaced with Catalyst 3. The content of long-chain alkanes in the reaction product was measured by GC. As a result, the conversion rate of difurfurylacetone was 100%, and the yield of C10+ Alkane (C 11 -C 13 alkane) had a yield of 90% and a selectivity for isoalkane of 39%.

[0062] Test control example 7: The test method was the same as that of Test Example 4 except that Catalyst 1 was replaced with Catalyst A. The content of long-chain alkane in the reaction product was measured by GC. As a result, the conversion rate of difurfurylacetone was 100%, and the yield of C 10+ alkane (C 11 -C 13 alkane) was 88% and the selectivity for isoalkane was 12%.

[0063] Test control example 8: The test method was the same as that of Test Example 4 except that Catalyst 1 was replaced with Catalyst B. The content of long-chain alkane in the reaction product was measured by GC. As a result, the conversion rate of difurfurylacetone was 100%, and the yield of C 10+ alkane (alkane with carbon number greater than 10) was 80% and the selectivity for isoalkane was 35%.

[0064] Test control example 9: The test method was the same as that of Test Example 4 except that Catalyst 1 was replaced with Catalyst C. The content of long-chain alkane in the reaction product was measured by GC. As a result, the conversion rate of difurfurylacetone was 100%, and the yield of C 10+ alkane (alkane with carbon number greater than 10) was 56% and the selectivity for isoalkane was 8%.

[0065] Test control example 10: The test method was the same as that of Test Example 4 except that Catalyst 1 was replaced with Catalyst D. The content of long-chain alkane in the reaction product was measured by GC. As a result, the conversion rate of difurfurylacetone was 100%, and the yield of C 10+ alkane (alkane with carbon number greater than 10) was 81% and the selectivity for isoalkane was 35%.

[0066] Test control example 11: The test method was the same as that of Test Example 4 except that Catalyst 1 was replaced with Catalyst E. The content of long-chain alkanes in the reaction product was measured by GC. As a result, the conversion rate of difurfurylacetone was 100%, and the C 10+ alkane (C 11 -C 13 alkane) yield was 81%, and the selectivity for isoalkanes was 33%.

[0067] Test control example 12: The test method was the same as that of Test Example 4 except that Catalyst 1 was replaced with Catalyst F. The content of long-chain alkanes in the reaction product was measured by GC. As a result, the conversion rate of difurfurylacetone was 100%, and the C 10+ alkane (C 11 -C 13 alkane) yield was 89%, and the selectivity for isoalkanes was 5%. TIFF2025523935000005.tif106170

[0068] From the above description, it can be recognized that the above embodiments of the present disclosure achieve the following technical effects.

[0069] The present disclosure significantly improves the yield and selectivity of long-chain alkanes in the process of preparing biojet fuel component oil from biomass. Compared with Test control examples 7 to 12, the C 10+ alkane yield and isoalkane selectivity of Test examples 4 to 6 are significantly higher. That is, the C 10+ alkane yield of the hydrodeoxygenation catalyst of the present disclosure may reach about 90%, and the isoalkane selectivity may reach nearly 40%. Biomass was effectively converted into biojet fuel component oil with lower industrial costs and milder reaction conditions.

[0070] Furthermore, the present disclosure includes embodiments according to the following clauses.

[0071] Clause 1. A hydrodeoxygenation catalyst comprising a hydrogenation active component and a catalyst support, wherein the hydrogenation active component contains one or more hydrogenation active metals, and the catalyst support is a solid solution composite oxide containing Nb, Al, Si, and O elements, and the catalyst support has the chemical formula (Nb2O5) x (Al2O3) y (SiO2) z (0.01 ≦ x ≦ 0.3, 0.01 ≦ y ≦ 0.1, and 0.6 ≦ z ≦ 0.98), a hydrodeoxygenation catalyst.

[0072] Clause 2. The hydrodeoxygenation catalyst according to Clause 1, wherein the one or more hydrogenation active metals contain Pt, Pd, Rh, Ru, Ni, Co, Cu, or a combination thereof.

[0073] Clause 3. The hydrodeoxygenation catalyst according to Clause 1 or 2, wherein the loading amount of the hydrogenation active metal is about 0.4 wt% to 10 wt% based on the total weight of the hydrodeoxygenation catalyst.

[0074] Clause 4. The hydrodeoxygenation catalyst according to any one of Clauses 1 to 3, wherein Nb2O5, Al2O3, and SiO2 in the hydrodeoxygenation catalyst are present in an amorphous form.

[0075] Clause 5. A method for preparing the hydrodeoxygenation catalyst according to any one of Clauses 1 to 4, comprising a sol-gel step: mixing a hydrogenation active metal source with a niobium source, an aluminum source, and a silicon source having a molar ratio of (0.01 to 0.3):(0.01 to 0.1):(0.6 to 0.98), dissolving in water to obtain a sol of a soluble precursor; a gelation step: stirring the sol at a temperature from room temperature to about 60 °C to obtain a gel; and an aging step: allowing the gel to stand and age to obtain an aged substance; and drying, firing, and reducing the aged substance to obtain a hydrodeoxygenation catalyst.

[0076] Clause 6. The method according to Clause 5, wherein the mixing of the niobium source, the aluminum source, the silicon source, and the hydrogenation active metal source in the sol-gel step is carried out in the presence of a hydrolyzing agent.

[0077] Clause 7. The method according to clause 6, wherein the hydrolyzing agent is selected from the group consisting of an acid and an alkali.

[0078] Clause 8. The method according to clause 7, wherein the concentration of the hydrolyzing agent is from about 0.1 mol / L to about 2.0 mol / L.

[0079] Clause 9. The method according to any one of clauses 5 to 8, wherein in the gelling step, the stirring time is from about 1 to 12 hours.

[0080] Clause 10. The method according to any one of clauses 5 to 9, wherein in the aging step, the aging time is from about 1 to 3 hours.

[0081] Clause 11. The method according to any one of clauses 5 to 10, wherein the reduction is carried out at a temperature of about 200 to 500 °C in the presence of hydrogen for about 2 to 6 hours.

[0082] Clause 12. The method according to any one of clauses 5 to 11, wherein the niobium source is selected from the group consisting of niobium tartrate, niobium citrate, niobium malate, niobium nitrate, niobium chloride, niobium sulfate, and combinations thereof.

[0083] Clause 13. The method according to any one of clauses 5 to 12, wherein the aluminum source is selected from the group consisting of aluminum nitrate, aluminum chloride, aluminum acetate, and combinations thereof; the silicon source is selected from the group consisting of silica sol, water glass, ethyl orthosilicate, and combinations thereof, preferably the silicon source is silica sol; the hydrogenated active metal source is selected from the group consisting of nitrates, sulfates, chlorides, acetates, and combinations thereof, preferably the hydrogenated active metal source is selected from the group consisting of palladium nitrate, palladium sulfate, palladium chloride, palladium acetate, platinum nitrate, platinum sulfate, platinum chloride, platinum acetate, ruthenium nitrate, nickel nitrate, cobalt nitrate, and combinations thereof.

[0084] Clause 14. A method for preparing isoalkane using the hydrodeoxygenation catalyst according to any one of claims 1 to 4, comprising performing a hydrogenation reaction on difurfurylacetone of the following formula in the presence of a hydrodeoxygenation catalyst and an organic solvent to obtain an isoalkane. TIFF2025523935000006.tif17170

[0085] Clause 15. The method according to clause 14, wherein the hydrodeoxygenation reaction is carried out at a temperature of about 150°C to 280°C, under a hydrogen pressure of about 0.5 MPa to 8 MPa, and with stirring for about 1 hour to 36 hours.

[0086] Clause 16. The method according to clause 14 or 15, wherein the organic solvent is cyclohexane, and the weight percentage of difurfurylacetone is about 10 wt% to 30 wt% based on the total weight of difurfurylacetone and the organic solvent.

[0087] Clause 17. The method according to any one of clauses 14 to 16, wherein the weight ratio of difurfurylacetone to the hydrodeoxygenation catalyst is (2 to 20):1.

[0088] The terms used in this specification are for the purpose of describing particular embodiments and are not intended to limit the embodiments. As used in this specification, the singular forms with "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly dictates otherwise. Further, the terms "comprises", "comprising", "includes" and / or "including" as used in this specification, when used, specify the presence of the described features, integers, steps, operations, elements and / or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components and / or groups thereof.

[0089] It should be noted that terms such as "first" and "second" in the description and claims of this application are used to distinguish similar objects and are not necessarily used to describe a specific order or priority. Terms used in this way are interchangeable under appropriate circumstances. For example, it should be understood that the embodiments of this application described in this specification can be implemented in an order other than the order described in this specification, for example.

[0090] The terms "consisting of" and "including" in this specification are intended to be optionally replaceable with the terms "consisting essentially of", "consisting of", and their grammatical variations in all cases, respectively.

[0091] Unless otherwise indicated, approximate terms such as "generally", "substantially", and "about" used in this specification indicate that the terms so modified can be applied only to an approximate degree that will be recognized by those skilled in the art, rather than an absolute or complete degree. Therefore, values modified by terms such as "about", "approximately", and "substantially" are not limited to the specified exact values. For example, the approximate terms can correspond to the accuracy of the instrument used to measure the value.

[0092] The above are only preferred embodiments of the present disclosure and do not limit the present disclosure. Various modifications and changes to the present disclosure are possible for those skilled in the art. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle scope of the present disclosure are included in the protection scope of the present disclosure.

Claims

1. A hydrogenation deoxygenation catalyst comprising a hydrogenation active component and a catalyst support, wherein the hydrogenation active component comprises one or more hydrogenation active metals, the catalyst support is a solid solution composite oxide containing elements Nb, Al, Si and O, and the catalyst support is a catalyst with chemical formula (Nb ２ O ５ ) ｘ ? (Al ２ O ３ ) ｙ ?(SiO ２ ) ｚ A hydrogenation deoxygenation catalyst represented by (0.01 ≤ x ≤ 0.3, 0.01 ≤ y ≤ 0.1, and 0.6 ≤ z ≤ 0.98).

2. The hydrogenation deoxygenation catalyst according to Claim 1, wherein the one or more hydrogenation active metals include Pt, Pd, Rh, Ru, Ni, Co, Cu, or a combination thereof.

3. The hydrogenation deoxygenation catalyst according to claim 1 or 2, wherein the amount of hydrogenation active metal supported is about 0.4 wt% to 10 wt% based on the total weight of the hydrogenation deoxygenation catalyst.

4. Nb in the hydrodeoxygenation catalyst ２ O ５ , Al ２ O ３ and SiO ２ which is present in an amorphous form, the hydrodeoxygenation catalyst according to claim 1.

5. A method for preparing a hydrogenation deoxygenation catalyst according to claim 1, Solification step: Mix a hydrogenation-active metal source with a niobium source, an aluminum source, and a silicon source in a molar ratio of (0.01-0.3):(0.01-0.1):(0.6-0.98), dissolve in water, and obtain a sol of a soluble precursor; Gelation step: A step of stirring the sol at a temperature from room temperature to 60°C to obtain a gel; and Aging step: Allow the gel to stand and mature to obtain a matured substance; Dry the matured substance, calcine it, and reduce it to obtain the hydrogenation deoxygenation catalyst. A method that includes this.

6. The method according to claim 5, wherein in the solification step, the mixing of the niobium source, the aluminum source, the silicon source and the hydrogenated active metal source is carried out in the presence of a hydrolyzing agent.

7. The method according to claim 6, wherein the hydrolyzing agent is selected from the group consisting of acids and alkalis.

8. The method according to claim 7, wherein the concentration of the hydrolyzing agent is about 0.1 mol / L to about 2.0 mol / L.

9. The method according to claim 5, wherein the stirring time in the gelation step is about 1 to 12 hours.

10. The method according to claim 5, wherein the maturation time in the maturation step is approximately 1 to 3 hours.

11. The method according to claim 5, wherein the reduction is carried out at a temperature of about 200 to 500°C in the presence of hydrogen for about 2 to 6 hours.

12. The method according to claim 5, wherein the niobium source is selected from the group consisting of niobium tartrate, niobium citrate, niobium malate, niobium nitrate, niobium hydrochloride, niobium sulfate, and combinations thereof.

13. The aluminum source is selected from the group consisting of aluminum nitrate, aluminum chloride, aluminum acetate, and combinations thereof. The silicon source is selected from the group consisting of silica sol, water glass, ethyl orthosilicate, and combinations thereof. The hydrogenation-active metal source is selected from the group consisting of nitrates, sulfates, chlorides, acetates, and combinations thereof. The method according to claim 5.

14. The method according to claim 13, wherein the silicon source is silica sol.

15. The method according to claim 13, wherein the hydrogenation-active metal source is selected from the group consisting of palladium nitrate, palladium sulfate, palladium chloride, palladium acetate, platinum nitrate, platinum sulfate, platinum chloride, platinum acetate, ruthenium nitrate, nickel nitrate, cobalt nitrate, and combinations thereof.

16. A method for preparing an isoalkane using the hydrogenation deoxygenation catalyst described in claim 1, In the presence of the aforementioned hydrogenation deoxygenation catalyst and organic solvent, a hydrogenation deoxygenation reaction is carried out on diflufurylacetone of the following formula to obtain an isoalkane: To obtain A method that includes this.

17. The method according to claim 16, wherein the hydrogenation deoxygenation reaction is carried out at a temperature of about 150°C to 280°C, under a hydrogen pressure of about 0.5 MPa to 8 MPa, and with stirring for about 1 hour to 36 hours.

18. The method according to claim 16, wherein the organic solvent is cyclohexane, and the weight percentage of diflufrurylacetone is about 10 wt% to 30 wt% based on the total weight of diflufrurylacetone and the organic solvent.

19. The method according to claim 16, wherein the weight ratio of diflufrylacetone to the hydrogenation deoxygenation catalyst is (2 to 20):1.

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