Method for synthesizing alkane in gasoline or aviation kerosene range by biomass platform compound in one step

Abstract

The invention relates to a method for one-step synthesis of alkane in the range of gasoline or aviation kerosene from a biomass platform compound. Biomass ketone and a mixture of the biomass ketone and biomass alcohol or biomass aldehyde, or the biomass alcohol is used as a raw material, and the biomass ketone and the biomass alcohol are subjected to cascade aldol condensation / hydrodeoxygenation (or cascade dehydrogenation / aldol condensation / hydrodeoxygenation) reaction in a fixed bed continuous reactor under the action of a supported metal multifunctional catalyst, so that the biomass ketone is obtained. And polycycloalkane or branched-chain alkane which can be used as gasoline or aviation kerosene can be synthesized in one step. The method is high in process operability, simple in route, low in cost, low in energy consumption and easy in catalyst preparation, and a brand-new effective way is provided for direct synthesis of gasoline or aviation kerosene from biomass platform compounds.

Description

Technical Field

[0001] The present invention relates to a method for one-step synthesis of alkanes within the range of gasoline or aviation kerosene from biomass platform compounds, and belongs to the technical field of gasoline or aviation kerosene synthesis. Background Art

[0002] With the increasing severity of energy shortage and environmental pollution problems, the development of clean energy to partially replace the current energy supply system has attracted great attention. As the only organic carbon source carrier among renewable energies on the earth, biomass energy is not only cheap, easily available, and rich in reserves, but also a carbon-neutral resource. Therefore, the potential for comprehensive development and utilization of biomass energy is huge. Among them, converting lignocellulosic biomass, which is the main component of agricultural and forestry waste, into gasoline or aviation kerosene is a very attractive option for achieving low-carbon and zero-carbon development goals.

[0003] Lignocellulose is mainly composed of cellulose, hemicellulose, and lignin, and can be highly selectively depolymerized into small molecule platform compounds through biochemical and catalytic conversion methods, including biomass ketones and other biomass-derived aldehydes / alcohols (Chem. Rev. 2018, 118, 2, 505; Green Energy Environ. 2023, 8, 10). Generally, the overall strategy for converting lignocellulose into gasoline or aviation kerosene is to first convert it into platform compounds with low carbon numbers, then obtain high-carbon chain oxygenated fuel precursors through carbon-carbon coupling reactions, and finally completely hydrodeoxygenate to achieve the controllable synthesis of alkanes within the range of gasoline and C8-C 16 aviation kerosene. In short, the key to converting lignocellulose-derived oxygenates into gasoline or aviation kerosene is carbon chain elongation and hydrodeoxygenation reactions. Since there are numerous biomass-derived carbonyl compounds, the use of aldol condensation reactions to increase the carbon chain length has attracted considerable interest.

[0004] A large number of studies have also been devoted to the synthesis of gasoline or aviation kerosene through a two-step method of aldol condensation and hydrodeoxygenation of biomass-derived oxygenates (ACS Sustainable Chem. Eng. 2019, 7, 17354; Chem. Commun. 2014, 50, 2572). However, considering the complexity of multi-step processes and the losses caused by separation, it is highly desirable to develop multifunctional catalysts to upgrade biomass into high-value gasoline or aviation kerosene in one step. A major challenge for the new route is to determine a suitable catalytic system to achieve efficient and continuous aldol condensation and hydrodeoxygenation steps. Summary of the Invention

[0005] The object of the present invention is to provide a method for directly synthesizing alkanes within the range of gasoline or aviation kerosene from biomass platform compounds. Using biomass ketones and their mixtures with biomass alcohols or biomass aldehydes, or biomass alcohols as raw materials, in a fixed-bed continuous reactor, through a cascade aldol condensation / hydrodeoxygenation (or cascade dehydrogenation / aldol condensation / hydrodeoxygenation) reaction on a supported metal multifunctional catalyst, the biomass platform compounds are directly converted into gasoline or aviation kerosene, providing a new, simple, and efficient route for the high-value utilization of biomass ketones / alcohols / aldehydes.

[0006] To achieve the above object, the technical solution of the present invention is as follows:

[0007] The present invention provides a method for directly synthesizing alkanes within the range of gasoline or aviation kerosene from biomass platform compounds. Using biomass platform compounds as raw materials, in a fixed-bed continuous reactor, with a supported metal multifunctional catalyst as the catalyst, under the conditions of a reaction temperature of 150 - 350 °C and a hydrogen pressure of 0.0001 - 0.5 MPa, alkanes within the range of gasoline or aviation kerosene are directly synthesized; the biomass platform compounds are biomass ketones and their mixtures with biomass alcohols or biomass aldehydes, or biomass alcohols.

[0008] In the present invention, biomass ketones and their mixtures with biomass aldehydes, under the action of a metal multifunctional catalyst, directly obtain alkanes within the range of aviation kerosene or gasoline with polycyclic alkanes or branched-chain alkanes as the main components through a cascade aldol condensation / hydrodeoxygenation reaction; biomass alcohols and their mixtures with biomass ketones, under the action of a metal multifunctional catalyst, directly obtain alkanes within the range of gasoline or aviation kerosene through a cascade dehydrogenation / aldol condensation / hydrodeoxygenation reaction. The entire process of the present invention avoids the separation of the catalyst from the product, realizes chemical integration, and is conducive to the continuous production of future gasoline or aviation kerosene.

[0009] Based on the above scheme, preferably, the biomass ketone is one or more of cyclopentanone, cyclohexanone, acetone, butanone, pentanone, methyl isobutyl ketone, mesityl oxide, heptanone, acetophenone; the biomass alcohol is one or more of cyclopentanol, cyclohexanol, isopropanol, butanol, pentanol, methyl isobutyl alcohol, heptanol, phenethyl alcohol; the biomass aldehyde is one of acetaldehyde, propionaldehyde, butyraldehyde, benzaldehyde, methylbenzaldehyde.

[0010] The chemical structural formulas of some raw materials and target products are shown in Table 1.

[0011] Table 1 Structural formulas of compounds

[0012]

[0013]

[0014] Based on the above scheme, preferably, the supported multi-functional metal catalyst comprises an active metal A and a support X, and the catalyst is represented by the formula A / X; the active metal A is one or more of non-precious metals or precious metals, the non-precious metals are Ni, Cu, Co, Mo, Fe, and the precious metals are Pt, Pd, Ru, Rh, Ir; the support X is a metal phosphate, and the metal phosphate is ZrP y , CeP y , LaP y , NbP y , TiP y , AlP y One of them, y = 0.5 - 3, preferably 0.5 - 2.5, more preferably 1 - 2; in the catalyst, the mass fraction of the non-precious metal is 2 - 30%, preferably 3 - 25%, more preferably 4 - 20%, and the mass fraction of the precious metal is 0.1 - 2%, preferably 0.15 - 1.5%, more preferably 0.2 - 1%.

[0015] Based on the above scheme, preferably, the supported multi-functional metal catalyst further comprises an auxiliary agent B, and the catalyst is represented by the formula AB / X. B is one or more of Ca, Mg, Ba, K, Na. In the catalyst, the mass fraction of the auxiliary agent B is 1 - 10%, preferably 1.5 - 9%, more preferably 2 - 8%.

[0016] Based on the above scheme, preferably, the metal phosphate is prepared by the deposition-precipitation method. The deposition-precipitation method comprises the following steps: preparing corresponding solutions M and N of a soluble salt solution of a metal and a precipitating agent respectively according to a stoichiometric ratio, then dropping solution N into solution M, stirring for 4 - 12 h, filtering, washing, drying, and then calcining at 400 - 600 °C for 4 - 6 h to obtain the metal phosphate; the precipitating agent is one of ammonium dihydrogen phosphate and phosphoric acid.

[0017] Based on the above scheme, preferably, the supported metal multi-functional catalyst is prepared by the equal-volume impregnation or deposition-precipitation method;

[0018] The equal-volume impregnation method comprises the following steps: impregnating the soluble salt solution of A onto the support X in an equal volume according to a stoichiometric ratio, standing for more than 8 h, drying, and then calcining at 300 - 700 °C for 2 - 5 h to obtain the A / X catalyst;

[0019] The deposition-precipitation method comprises the following steps: adding the soluble salt solution of A into the suspension of the support X according to a stoichiometric ratio, adding a precipitating agent under stirring, aging for more than 2 h, filtering, drying, and then calcining at 300 - 700 °C for 2 - 5 h to obtain the A / X catalyst; the precipitating agent is one or more of LiOH, NaOH, KOH, ammonia water, and urea.

[0020] Based on the above scheme, preferably, the supported metal multifunctional catalyst is prepared by incipient wetness impregnation or deposition-precipitation method;

[0021] The incipient wetness impregnation method includes the following steps:

[0022] The soluble salt solution of A is impregnated onto the support X in an equal volume according to the stoichiometric ratio, left standing for more than 8 h, dried, and then calcined at 300 - 700 °C for 2 - 5 h to obtain the A / X catalyst; the soluble salt solution of B is impregnated onto the A / X catalyst in an equal volume according to the stoichiometric ratio, left standing for more than 8 h, dried, and then calcined at 300 - 700 °C for 2 - 5 h to obtain the AB / X catalyst;

[0023] Or the soluble salt solutions of A and B are impregnated onto the support X in an equal volume according to the stoichiometric ratio, left standing for more than 8 h, dried, and then calcined at 300 - 700 °C for 2 - 5 h to obtain the AB / X catalyst;

[0024] The deposition-precipitation method includes the following steps:

[0025] The soluble salt solution of A is added to the suspension of the support X according to the stoichiometric ratio, a precipitant is added under stirring, aged for more than 2 h, filtered, dried, and then calcined at 300 - 700 °C for 2 - 5 h to obtain the A / X catalyst; the soluble salt solution of B is added to the suspension of the A / X catalyst according to the stoichiometric ratio, a precipitant is added under stirring, aged for more than 2 h, filtered, dried, and then calcined at 300 - 700 °C for 2 - 5 h to obtain the AB / X catalyst;

[0026] Or the soluble salt solutions of A and B are added to the suspension of the support X according to the stoichiometric ratio, a precipitant is added under stirring, aged for more than 2 h, filtered, dried, and then calcined at 300 - 700 °C for 2 - 5 h to obtain the AB / X catalyst;

[0027] The precipitant is one or more of LiOH, NaOH, KOH, ammonia water, and urea.

[0028] Based on the above scheme, preferably, before use, the supported metal multifunctional catalyst is reduced with hydrogen at 300 - 700 °C for 1 - 4 h.

[0029] Based on the above scheme, preferably, the reaction temperature is 155 - 340 °C, preferably 160 - 320 °C, the hydrogen pressure is 0.0001 - 0.45 MPa, preferably 0.0001 - 0.4 MPa, the molar ratio of hydrogen to the biomass platform compound is 5 - 400:1, preferably 10 - 350:1, further preferably 20 - 300:1, and the space velocity of the biomass platform compound is 0.01 - 10 h -1 , preferably 0.05 - 9 h -1 , further preferably 0.1 - 8 h-1 。

[0030] The beneficial effects of the present invention are as follows:

[0031] The process route of the present invention is simple, and it can convert biomass platform compounds into aviation kerosene or gasoline mainly composed of polycyclic alkanes or branched-chain alkanes in one step through a cascade aldol condensation / hydrodeoxygenation (or cascade dehydrogenation / aldol condensation / hydrodeoxygenation) reaction.

[0032] The catalyst of the present invention is simple to prepare, can be synthesized in large quantities, has good catalytic performance, can achieve a conversion rate of biomass platform compounds above 95% under mild reaction conditions, and the yield of aviation kerosene or gasoline mainly composed of polycyclic alkanes or branched-chain alkanes is above 80%. Moreover, the catalyst has good stability.

[0033] The present invention adopts a fixed-bed continuous flow reactor, and under the action of a supported metal multifunctional catalyst, it can convert biomass platform compounds into gasoline or aviation kerosene in one step, with the advantages of a wide application range, high operability, low energy consumption, and environmental friendliness, and can be used for actual industrial production. Brief Description of the Drawings

[0034] Figure 1 It is the gas chromatogram of the product of synthesizing polycyclic alkanes from cyclopentanone in Example 53;

[0035] Figure 2 It is the mass spectrum control chart of the product of synthesizing polycyclic alkanes from cyclopentanone in Example 53. Detailed Description of the Invention

[0036] The technical solution of the present invention will be further described in detail below in combination with specific examples, but the protection scope of the present invention is not limited to these examples.

[0037] Unless otherwise specified, the materials used in the examples of the present invention can be obtained through commercial channels or prepared according to the conventional methods well-known to those skilled in the art.

[0038] Example 1

[0039] (1) Preparation method of the catalyst:

[0040] a. Prepare corresponding solutions M and N of zirconium oxychloride and ammonium dihydrogen phosphate according to the stoichiometric ratio, then drop solution N into solution M, stir vigorously for 4 h, filter, wash, and dry, and then calcine at 400 °C for 5 h to obtain the support ZrP1;

[0041] b. Impregnate nickel nitrate on the support ZrP1 in an equal volume according to the stoichiometric ratio, let it stand for more than 8 h and then dry, and then calcine at 500 °C for 4 h to obtain the 10% Ni / ZrP1 catalyst;

[0042] (2) Mix 1 g of the catalyst evenly with 2 g of quartz sand (40 - 70 mesh), and fill it into a fixed - bed continuous reactor. Heat it to 200 °C at a rate of 10 °C / min, and then carry out the reaction under a hydrogen pressure of 0.001 MPa, a molar ratio of hydrogen to cyclopentanone of 60:1, and a cyclopentanone space velocity of 0.5 h -1 The experimental results are shown in Table 2.

[0043] Example 2 - 10

[0044] The difference from Example 1 is that the active components of the catalyst are different, and the other conditions are the same as those in Example 1. The catalysts and experimental results are shown in Table 2.

[0045] Table 2 Effects of different A / ZrP1 - type catalysts on the synthesis of dicyclopentane and tricyclopentane from cyclopentanone

[0046]

[0047] It can be seen from the data results in Table 2 that although there are slight differences in the conversion rate and the yield of the target product, biomass cyclopentanone can be efficiently converted into dicyclopentane and tricyclopentane on different A / ZrP1 - type catalysts, which can be used as high - density aviation kerosene.

[0048] Example 11

[0049] (1) Preparation method of the catalyst:

[0050] a. Prepare the corresponding solutions M and N of zirconium oxychloride and phosphoric acid according to the stoichiometric ratio, then drop solution N into solution M, stir vigorously for 6 h, filter, wash, dry, and then calcine at 400 °C for 4 h to obtain the support ZrP1;

[0051] b. Add the nickel acetate solution to the suspension of the support ZrP1 according to the stoichiometric ratio, add the precipitant ammonia water under stirring, age for more than 2 h, filter, dry, and then calcine at 500 °C for 6 h to obtain the 10% Ni / ZrP1 catalyst;

[0052] (2) Mix 1 g of the catalyst evenly with 2 g of quartz sand (40 - 70 mesh), and fill it into a fixed - bed continuous reactor. Heat it to 200 °C at a rate of 10 °C / min, and then carry out the reaction under a hydrogen pressure of 0.001 MPa, a molar ratio of hydrogen to cyclopentanone of 60:1, and a cyclopentanone space velocity of 0.5 h -1 The experimental results are shown in Table 3.

[0053] Examples 12 - 16

[0054] The difference from Example 11 is that the metal in the supported metal phosphate is different, and the other conditions are the same as those in Example 11. The catalysts and experimental results are shown in Table 3.

[0055] Table 3 Effects of different Ni / X type catalysts on the synthesis of dicyclopentane and tricyclopentane from cyclopentanone

[0056]

[0057] As can be seen from the data results in Table 3, the different Ni / X type catalysts listed in the table all have good effects on the direct conversion of biomass cyclopentanone into dicyclopentane and tricyclopentane. However, different carriers have a certain influence on the conversion rate of cyclopentanone and the yields of dicyclopentane and tricyclopentane.

[0058] Example 17

[0059] (1) Preparation method of catalyst:

[0060] a. Prepare corresponding solutions M and N of zirconium oxychloride and phosphoric acid according to the stoichiometric ratio. Then, add solution N dropwise to solution M, stir vigorously for 5 h, filter, wash, and dry. Subsequently, calcine at 450 °C for 5 h to obtain the support ZrP1.

[0061] b. Impregnate nickel nitrate on the support ZrP1 in an equal volume according to the stoichiometric ratio. After standing for more than 8 h, dry it, and then calcine at 450 °C for 6 h to obtain the 10% Ni / ZrP1 catalyst.

[0062] (2) Uniformly mix 1 g of the catalyst with 2 g of quartz sand (40 - 70 mesh), fill it into a fixed-bed continuous reactor, heat it to 200 °C at a rate of 10 °C / min, and then react under a hydrogen pressure of 0.001 MPa, a molar ratio of hydrogen to biomass platform compound of 60:1, and a space velocity of biomass platform compound of 0.5 h -1 for the reaction. The experimental results are shown in Table 4.

[0063] Table 4 Synthesis of polycyclic alkanes or branched alkanes from biomass platform compounds over 10% Ni / ZrP1 catalyst

[0064]

[0065] As can be seen from the data results in Table 4, different biomass ketone raw materials can directly synthesize polycyclic alkanes or branched alkanes on the supported metal multifunctional catalyst. Among them, the C6 alkane in the product obtained from acetone can be used as gasoline, and the C9 and C 12 alkanes can be used as aviation kerosene; the polycyclic alkanes or branched alkanes obtained from the remaining biomass ketone raw materials are all high-density aviation kerosene.

[0066] Examples 24 - 28

[0067] (1) Preparation method of catalyst:

[0068] a. Prepare the corresponding solutions M and N with zirconium oxychloride and ammonium dihydrogen phosphate in stoichiometric ratio. Then, add solution N dropwise to solution M, stir vigorously for 4 h, filter, wash, and dry. Subsequently, calcine at 400 °C for 5 h to obtain the support ZrP1.

[0069] b. Add the nickel nitrate solution to the suspension of the support ZrP1 in a stoichiometric ratio. Add the precipitant sodium hydroxide under stirring, age for more than 2 h, filter and dry, and then calcine at 500 °C for 4 h to obtain the 10% Ni / ZrP1 catalyst.

[0070] (2) Uniformly mix 1 g of the catalyst with 2 g of quartz sand (40 - 70 mesh), and fill it into a fixed-bed continuous reactor. Heat it to 200 °C at a rate of 10 °C / min, and then carry out the reaction under a hydrogen pressure of 0.001 MPa, a molar ratio of hydrogen to biomass raw material of 60:1, and a space velocity of biomass platform compounds of 0.5 h -1 The experimental results are shown in Table 5.

[0071] Table 5 Synthesis of cycloalkanes or branched alkanes from different biomass platform compounds over 10% Ni / ZrP1 catalyst

[0072]

[0073] It can be seen from the data results in Table 5 that different biomass ketones and their mixtures with biomass alcohols or biomass aldehydes can all be directly synthesized into alkane fuels over the supported metal multifunctional catalyst. Among them, the C7 alkanes in the products obtained from cyclopentanone and acetaldehyde or ethanol can be used as gasoline, and the C9 alkanes can be used as aviation kerosene; the alkanes obtained from the remaining biomass platform compounds are all high-density aviation kerosene.

[0074] Examples 29 - 36

[0075] Synthesis of polycycloalkanes or branched alkanes from different biomass alcohols over the supported metal multifunctional Ni / ZrP1 catalyst: Uniformly mix 1 g of the catalyst prepared in Example 1 with 2 g of quartz sand (40 - 70 mesh), and fill it into a fixed-bed continuous reactor. Heat it to 200 °C at a rate of 10 °C / min, and then carry out the reaction under a hydrogen pressure of 0.001 MPa, a molar ratio of hydrogen to biomass alcohol of 60:1, and a space velocity of biomass alcohol of 0.5 h -1 The experimental results are shown in Table 6.

[0076] Table 6 Synthesis of polycycloalkanes or branched alkanes from biomass alcohols over 10% Ni / ZrP1 catalyst

[0077]

[0078] As can be seen from the data results in Table 6, different biomass alcohol raw materials can directly synthesize alkane fuels on the supported metal multifunctional catalyst. Among them, the C7 alkanes in the products obtained from ABE fermentation broth can be used as gasoline, and the C9 and C 11 alkanes can be used as aviation kerosene; the alkanes obtained from the remaining biomass platform compounds are all high-density aviation kerosene.

[0079] Examples 37 - 39

[0080] The difference from Example 1 is that the P / Zr ratio is different, and the other conditions are the same as those in Example 1. The catalysts and experimental results are shown in Table 7.

[0081] Table 7 Effects of catalysts with different P / Zr ratios on the synthesis of dicyclopentane and tricyclopentane from cyclopentanone

[0082]

[0083] As can be seen from the data results in Table 7, the P / Zr ratio of the supported metal multifunctional catalyst has a certain influence on the conversion rate of biomass ketone and the total yield of dicyclopentane and tricyclopentane. However, generally speaking, the supported metal multifunctional catalysts with different P / Zr ratios all have good effects on the direct synthesis of high-density polycyclic alkane aviation kerosene from cyclopentanone.

[0084] Examples 40 - 42

[0085] The difference from Example 1 is that the mass fraction of Ni is different, and the other conditions are the same as those in Example 1. The catalysts and experimental results are shown in Table 8.

[0086] Table 8 Effects of catalysts with different Ni mass fractions on the synthesis of dicyclopentane and tricyclopentane from cyclopentanone

[0087]

[0088]

[0089] As can be seen from the data results in Table 8, when the mass fraction of Ni in the supported metal multifunctional catalyst is in the range of 5 - 20%, the direct catalytic conversion of biomass ketone to high-density polycyclic alkane aviation kerosene shows relatively high conversion rates and target product yields.

[0090] Examples 43 - 55

[0091] 1 g of the catalyst prepared in Example 1 was uniformly mixed with 2 g of quartz sand (40 - 70 mesh), filled into a fixed-bed continuous reactor, heated to the reaction temperature at a rate of 10 °C / min, and then reacted under a certain hydrogen pressure, a certain molar ratio of hydrogen to cyclopentanone, and a certain cyclopentanone space velocity. The reaction conditions and experimental results are shown in Table 9.

[0092] Table 9 Influence of Different Reaction Conditions on the Synthesis of Bicyclopentane and Tricyclopentane from Cyclopentanone

[0093]

[0094]

[0095] It can be seen from the data results in Table 9 that under the condition of the same other conditions, the reaction temperature has a significant influence on the total yield of polycyclic alkanes. To a certain extent, the increase in reaction temperature will improve the reaction activity, but too high a temperature will instead reduce the total yield of the target product. With the increase of hydrogen pressure, the conversion rate of biomass ketone is not affected, but the total yield of polycyclic alkanes first remains unchanged and then gradually decreases. With the increase of the hydrogen / cyclopentanone molar ratio, the conversion rate of biomass ketone remains unchanged, but the total yield of polycyclic alkanes first increases and then gradually decreases. In addition, with the increase of the space velocity of biomass ketone, the conversion rate is completely converted within the range of 0.1 - 5 h -1 range, and further increase will cause the conversion rate to decrease; and the total yield of polycyclic alkanes will also be affected, but generally remains in a relatively high range.

[0096] Example 56

[0097] (1) Preparation of catalyst:

[0098] a. Prepare the corresponding solutions M and N of zirconium oxychloride and ammonium dihydrogen phosphate according to the stoichiometric ratio, then drop solution N into solution M, stir vigorously for 6 h, filter, wash, dry, and then calcine at 400 °C for 5 h to obtain the support ZrP1;

[0099] b. Impregnate nickel nitrate and calcium nitrate on the support ZrP1 in equal volume according to the stoichiometric ratio, let it stand for more than 8 h, dry, and then calcine at 500 °C for 4 h to obtain the NiCa / ZrP1 catalyst, where the mass fraction of Ni is 10% and the mass fraction of Ca is 2%;

[0100] (2) Uniformly mix 1 g of the catalyst with 2 g of quartz sand (40 - 70 mesh), fill it into a fixed-bed continuous reactor, heat it to 240 °C at a rate of 10 °C / min, and then carry out the reaction under a hydrogen pressure of 0.001 MPa, a hydrogen / cyclopentanone molar ratio of 60:1, and a cyclopentanone space velocity of 0.5 h -1 The experimental results are shown in Table 10.

[0101] Examples 57 - 60

[0102] The difference from Example 56 is that the modified components are different, and the other conditions are the same as those in Example 56. The catalysts and experimental results are shown in Table 10.

[0103] Table 10 Effects of Different 10% Ni2%B / ZrP1 Catalysts on the Synthesis of Bicyclopentane and Tricyclopentane from Cyclopentanone

[0104]

[0105] As can be seen from the data results in Table 10, NiB / ZrP1 catalysts modified with different promoters can all efficiently and directly catalyze the conversion of biomass cyclopentanone into high-density polycyclic alkane aviation kerosene. The biomass ketone is completely converted, and the total yield of bicyclopentane and tricyclopentane is as high as over 95%.

[0106] Example 61

[0107] (1) Preparation of the catalyst:

[0108] Calcium nitrate was impregnated onto the 10% Ni / ZrP1 catalyst obtained in Example 1 in an equal volume according to the stoichiometric ratio, left standing for more than 8 h, dried, and then calcined at 500 °C for 4 h to obtain the 10% Ni2%Ca / ZrP1 catalyst.

[0109] (2) 1 g of the catalyst was uniformly mixed with 2 g of quartz sand (40 - 70 mesh), filled into a fixed-bed continuous reactor, heated to 240 °C at a rate of 10 °C / min, and then reacted under a hydrogen pressure of 0.001 MPa, a molar ratio of hydrogen to cyclopentanone of 60:1, and a cyclopentanone space velocity of 0.5 h -1 The experimental results are shown in Table 11.

[0110] Table 11 Stability Test Results of Supported Metal Multifunctional Catalysts

[0111]

[0112] As can be seen from Table 11, the 10% Ni / ZrP1 catalyst has good stability for 24 h, but shows a certain degree of deactivation after 48 h; while the 10% Ni2%Ca / ZrP1 catalyst still maintains good stability after 48 h of the experiment.

[0113] The above examples are only the preferred examples of the present invention and are not intended to limit the implementation manner. The protection scope of the present invention should be subject to the scope defined by the claims. Based on the above description, other different forms of changes or variations can be made. The obvious changes or variations derived therefrom are still within the protection scope of the present invention.

Claims

1. A method for one-step synthesis of alkanes within the range of gasoline or aviation kerosene from biomass platform compounds, characterized in that, Using biomass platform compounds as raw materials, in a fixed-bed continuous reactor, with a supported metal multifunctional catalyst as the catalyst, under the conditions of a reaction temperature of 150 - 350 °C and a hydrogen pressure of 0.0001 - 0.5 MPa, alkanes within the range of gasoline or aviation kerosene are synthesized in one step; the biomass platform compounds are biomass ketones and their mixtures with biomass alcohols or biomass aldehydes, or biomass alcohols.

2. The method according to claim 1, characterized in that, The biomass ketones are one or more of cyclopentanone, cyclohexanone, acetone, butanone, pentanone, methyl isobutyl ketone, mesityl oxide, heptanone, acetophenone; the biomass alcohols are one or more of cyclopentanol, cyclohexanol, isopropanol, butanol, pentanol, methyl isobutyl alcohol, heptanol, phenylethyl alcohol; the biomass aldehyde is one of acetaldehyde, propionaldehyde, butyraldehyde, benzaldehyde, methylbenzaldehyde.

3. The method according to claim 1, characterized in that, The supported multi-functional metal catalyst comprises an active metal A and a support X, and the catalyst is represented by the formula A / X; the active metal A is one or more of non-noble metals or noble metals, the non-noble metals are Ni, Cu, Co, Mo, Fe, and the noble metals are Pt, Pd, Ru, Rh, Ir; the support X is a metal phosphate, and the metal phosphate is ZrP y , CeP y , LaP y , NbP y , TiP y , AlP y or one of them, where y = 0.5 - 3; in the catalyst, the mass fraction of the non-noble metal is 2 - 30%, and the mass fraction of the noble metal is 0.1 - 2%.

4. The method according to claim 3, wherein The supported multifunctional metal catalyst further includes promoter B, and the catalyst is represented by the formula AB / X, where B is one or more of Ca, Mg, Ba, K, Na, and in the catalyst, the mass fraction of promoter B is 1 - 10%.

5. The method according to claim 3, characterized in that, The metal phosphate is prepared by the deposition precipitation method, and the deposition precipitation method includes the following steps: preparing corresponding solutions M and N of the soluble salt solution of the metal and the precipitant respectively according to the stoichiometric ratio, then dropping solution N into solution M, stirring for 4 - 12 h, filtering, washing, drying, and then calcining at 400 - 600 °C for 4 - 6 h to obtain the metal phosphate; the precipitant is one of ammonium dihydrogen phosphate and phosphoric acid.

6. The method according to claim 3, characterized in that, The supported metal multifunctional catalyst is prepared by the equal-volume impregnation or deposition precipitation method; The equal-volume impregnation method includes the following steps: impregnating the soluble salt solution of A onto the support X in an equal volume according to the stoichiometric ratio, standing for more than 8 h, drying, and then calcining at 300 - 700 °C for 2 - 5 h to obtain the A / X catalyst; The deposition precipitation method includes the following steps: adding the soluble salt solution of A into the suspension of the support X according to the stoichiometric ratio, adding the precipitant under stirring, aging for more than 2 h, filtering, drying, and then calcining at 300 - 700 °C for 2 - 5 h to obtain the A / X catalyst; the precipitant is one or more of LiOH, NaOH, KOH, ammonia water, and urea.

7. The method according to claim 4, wherein The supported metal multifunctional catalyst is prepared by the equal-volume impregnation or deposition precipitation method; The equal-volume impregnation method includes the following steps: Impregnating the soluble salt solution of A onto the support X in an equal volume according to the stoichiometric ratio, standing for more than 8 h, drying, and then calcining at 300 - 700 °C for 2 - 5 h to obtain the A / X catalyst; impregnating the soluble salt solution of B onto the A / X catalyst in an equal volume according to the stoichiometric ratio, standing for more than 8 h, drying, and then calcining at 300 - 700 °C for 2 - 5 h to obtain the AB / X catalyst; Or impregnating the soluble salt solutions of A and B onto the support X in an equal volume according to the stoichiometric ratio, standing for more than 8 h, drying, and then calcining at 300 - 700 °C for 2 - 5 h to obtain the AB / X catalyst; The deposition precipitation method includes the following steps: Add the soluble salt solution of A to the suspension of carrier X according to the stoichiometric ratio. Add the precipitant under stirring, age for more than 2 h, filter and dry, and then calcine at 300 - 700 °C for 2 - 5 h to obtain the A / X catalyst; add the soluble salt solution of B to the suspension of the A / X catalyst according to the stoichiometric ratio. Add the precipitant under stirring, age for more than 2 h, filter and dry, and then calcine at 300 - 700 °C for 2 - 5 h to obtain the AB / X catalyst; Or add the soluble salt solutions of A and B to the suspension of carrier X according to the stoichiometric ratio. Add the precipitant under stirring, age for more than 2 h, filter and dry, and then calcine at 300 - 700 °C for 2 - 5 h to obtain the AB / X catalyst; The precipitant is one or more of LiOH, NaOH, KOH, ammonia water, and urea.

8. The method according to claim 1, wherein Before use, the supported metal multifunctional catalyst is reduced with hydrogen at 300 - 700 °C for 1 - 4 h.

9. The method according to claim 1, wherein The reaction temperature is 155 - 340 °C, the hydrogen pressure is 0.0001 - 0.45 MPa, the molar ratio of hydrogen to the biomass platform compound is 5 - 400:1, and the space velocity of the biomass platform compound is 0.01 - 10 h -1 .

10. The method according to claim 1, characterized in that, The reaction temperature is 160 - 320 °C, the hydrogen pressure is 0.0001 - 0.4 MPa, the molar ratio of hydrogen to the biomass platform compound is 10 - 350:1, and the space velocity of the biomass platform compound is 0.05 - 9 h -1 .

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