Method for Preparing P-Xylene by Biomass Conversion

Abstract

A method for preparing paraxylene by biomass conversion includes the following steps: (1) contacting a biomass starting material with a hydrogenation catalyst for reaction in a multiphase system formed by an organic solvent, an inorganic salt and water, in the presence of hydrogen as a hydrogen source, and separating the resulting product to obtain an organic phase comprising 2,5-hexanedione; and (2) contacting the organic phase comprising 2,5-hexanedione obtained in the step (1) and ethylene with a molecular sieve catalyst for reaction to obtain paraxylene. The molecular sieve catalyst is at least one selected from the group consisting of aluminophosphate molecular sieves and SCM-14 molecular sieves.

Claims

1. A method for preparing a substituted or unsubstituted monocyclic aromatic hydrocarbon from a substituted or unsubstituted furan, comprising the steps of: contacting an organic phase comprising a substituted or unsubstituted furan as starting material with ethylene and a molecular sieve catalyst for reaction to obtain a substituted or unsubstituted monocyclic aromatic hydrocarbon, wherein the molecular sieve catalyst comprises an SCM-X molecular sieve optionally doped with an element A that is at least one selected from the group consisting of Sn, Zr and Al, and X is 14 or 15.

2. The method of claim 1, wherein the SCM-X molecular sieve has a schematic chemical composition as represented by formula mSiO.sub.2.Math.nGeO.sub.2, wherein 1?m/n?30, preferably 0.5?m/n?20, further preferably 2? m/n?10.

3. The method according to claim 1, wherein the organic phase comprises an organic solvent selected from the group consisting of n-hexane, n-heptane, n-octane, tetrahydrofuran, 1,4-dioxane, cyclohexane and methyl isobutyl ketone.

4. The method according to claim 1, wherein the substituted or unsubstituted furan used as starting material has a structure represented by the following formula (I): ##STR00002## wherein R1, R2, R3 and R4 are each independently selected from H and C1-C6 alkyl, preferably each independently selected from H and C1-C4 alkyl, and further preferably at least one of R1, R2, R3 and R4 is not H; with a proviso that the total number of carbon atoms of R1, R2, R3 and R4 is not greater than 8, preferably not greater than 6.

5. The method according to claim 1, wherein the substituted or unsubstituted furan is methylfuran and the substituted or unsubstituted monocyclic aromatic hydrocarbon is toluene.

6. The method according to claim 5, wherein the molecular sieve catalyst is an A-SCM-X molecular sieve, wherein A in the A-SCM-X molecular sieve is at least one selected from the group consisting of Sn, Zr, and Al, and X is 14 or 15.

7. The method according to claim 6, wherein the content of A component, calculated as oxide, in the A-SCM-X molecular sieve is not less than 0.5 wt %, preferably from 0.8 wt % to 3.5 wt %, more preferably from 1.2 wt % to 3.2 wt %; and/or the Lewis acid content of the A-SCM-X molecular sieve is 30-500 ?mol.Math.g.sup.?1, preferably 50-300 ?mol.Math.g.sup.?1, and more preferably 83-292 ?mol.Math.g.sup.?1; and/or the ratio of Lewis/Bronst acid of the A-SCM-X molecular sieve is 0.5-10, preferably 0.6-5, and more preferably 0.6-2.1; and/or the A-SCM-X molecular sieve is SnSCM-14, SnSCM-15, ZrSCM-14, ZrSCM-15, Al-SCM-14 or Al-SCM-15 molecular sieve.

8. The method according to claim 6, wherein: the A-SCM-X molecular sieve has a schematic chemical composition represented by the formula mSiO.sub.2.Math.nGeO.sub.2.Math.pAO.sub.2, wherein 1?m/n?30, preferably 2?m/n?10, more preferably 3.5?m/n?8.7; 20?m/p?200, preferably 30?m/p?150, more preferably 30?m/p?96; and/or the A component is incorporated in the framework of the molecular sieve.

9. The method according to claim 5, wherein: the conditions of the contacting and reaction include: a reaction temperature of 180-300? C., preferably 210-270? C.; and/or a reaction time of 4-72 h, preferably 10-50 h; and/or a reaction pressure of 1-8 MPa, preferably 2-5 MPa.

10. The method according to claim 5, wherein: the contacting is carried out in the presence of an organic solvent that is one or more selected from the group consisting of n-heptane, n-octane, tetrahydrofuran, methyl isobutyl ketone and cyclohexane; and/or the mass ratio of methylfuran to catalyst is 0.2-8:1, preferably 0.5-6:1, and preferably 0.8-2:1; and/or the mass ratio of the organic solvent to methylfuran is 10-80:1, preferably 20-50:1; and/or the ethylene is dilute ethylene, the reaction system is introduced with dilute ethylene, the concentration of the dilute ethylene is 10-25 v %, and other gas in the dilute ethylene is inert gas.

11. The method according to claim 1, wherein the substituted or unsubstituted furan is 2,5-dimethylfuran and the substituted or unsubstituted monocyclic aromatic hydrocarbon is paraxylene.

12. The method according to claim 11, wherein the molecular sieve catalyst is an SCM-X molecular sieve comprising no doping element A; preferably, the SCM-X molecular sieve is an SCM-14 molecular sieve having a schematic chemical composition represented by the formula SiO.sub.2.Math.1/nGeO.sub.2, wherein n?30, preferably 0.5?n?20, more preferably 1?n?10, and further preferably 2?n?8.

13. The method according to claim 11, wherein the conditions of the contacting and reaction include: a pressure of 0.5-8 MPa, preferably 1-5 MPa; a reaction temperature of 160-340? C., preferably 200-300? C.; and/or a reaction time of 6-64 h, preferably 8-48 h.

14. The method according to claim 11, wherein the contacting is carried out in the presence of an organic solvent, and the organic solvent comprises one or more selected from the group consisting of n-hexane, n-heptane, n-octane, tetrahydrofuran, 1,4-dioxane, and cyclohexane; the mass ratio of the starting material to the catalyst is 0.5-20.0:1, preferably 1.0-8.0:1; and/or the mass ratio of the organic solvent to the starting materials is 5-50:1, preferably 10-20:1.

15. A method for preparing para-xylene, comprising the steps of: contacting an organic phase comprising 2,5-hexanedione and ethylene with a molecular sieve catalyst for reaction to produce paraxylene, wherein the molecular sieve catalyst comprises an SCM-X molecular sieve, and X is 14 or 15; preferably, the SCM-X molecular sieve is an SCM-14 molecular sieve having a schematic chemical composition represented by the formula SiO.sub.2.Math.1/nGeO.sub.2, wherein n?30, preferably 0.5?n?20, more preferably 1?n?10, and further preferably 2?n?8, and preferably the conditions for the contacting and reaction include: an ethylene pressure of 0.5-5 MPa, preferably 1-4 MPa; and/or a reaction temperature of 160-340? C., preferably 200-300? C.; and/or a reaction time of 6-64 h, preferably 12-48 h.

16. (canceled)

17. The method according to claim 15, comprising the steps of: (1) contacting a biomass starting material with a hydrophobic hydrogenation catalyst for reaction in a two-phase solvent system comprising an organic solvent phase and an aqueous solution phase, in the presence of hydrogen as a hydrogen source, and separating the resulting product to obtain the organic phase comprising 2,5-hexanedione; wherein the pH of the aqueous solution phase is about 6.5-8.5, preferably 7-8; and (2) contacting the organic phase comprising 2,5-hexanedione and ethylene with a molecular sieve catalyst to produce para-xylene, preferably, in step (1), the aqueous solution phase comprises an inorganic salt dissolved therein, the anion and cation of the inorganic salt being derived from Group VIIA elements and Group IA elements, respectively; preferably, the Group VIIA element is at least one selected from the group consisting of Cl and Br, and/or the Group IA element is at least one selected from the group consisting of Li, Na, and K.

18. (canceled)

19. The method according to claim 17, wherein in step (1), the organic solvent of the organic solvent phase is one of 1,2-dichloroethane, 1,4-dioxane, methyl isobutyl ketone, tetrahydrofuran, ?-valerolactone and toluene, or a mixture of two or more of them, preferably one or two of 1,4-dioxane and tetrahydrofuran; and/or the mass ratio of the organic solvent to the biomass starting material is 4-60, preferably 10-40; and/or the ratio of the mass of organic solvent of the organic solvent phase to the total amount by mass of the inorganic salt and water is 2 to 16, preferably 3 to 10; and/or the ratio of the mass of the inorganic salt to the mass of water is 0.10 to 0.70, preferably 0.20 to 0.70, more preferably 0.40 to 0.70.

20. (canceled)

21. The method according to claim 17, wherein the mass ratio of the biomass starting material to the hydrogenation catalyst used in step (1) is in a range of from 0.2:1 to 4:1, preferably in a range from 0.5:1 to 2:1; and/or in the step (1), the reaction temperature is 160-250? C., preferably 180-230? C.; the reaction time is 4 to 36 hours, preferably 6 to 20 hours; and/or in the reaction system of the step (1), the hydrogen pressure is 0.2-5 MPa, preferably 0.5-3 MPa; and/or in step (1), said hydrophobic hydrogenation catalyst comprises a hydrogenation active component and a carrier; the carrier is one or more selected from the group consisting of activated carbon and graphene having hydrophobicity; the hydrogenation active component is one or more selected from the group consisting of ruthenium, platinum and palladium, and is preferably platinum and/or palladium; preferably, the contact angle of the hydrogenation catalyst used in step (1) with water is greater than than 50?, preferably 55-90?; preferably, the hydrogenation active component is present in an amount of 0.5% to 10%, preferably 2% to 6%, by mass, calculated as metal atom, based on the mass of the hydrogenation catalyst; and/or the biomass starting material used in the step (1) is one or more selected from the group consisting of cellulose, inulin, cellobiose, sucrose, glucose, fructose, corn straw, corncob, pine wood, poplar wood and beech wood, preferably cellulose and/or glucose.

22-23. (canceled)

24. The method according to claim 17, wherein the SCM-14 molecular sieve contained in the molecular sieve catalyst used in the step (2) is fully or partially replaced with an aluminophosphate molecular sieve catalyst, which is M-AlPO molecular sieve catalyst, wherein M is a metal and is at least one selected from the group consisting of Co, Mg, Zn and Sn, and the AlPO molecular sieve is at least one selected from the group consisting of AlPO-17, AlPO-5, AlPO-8, AlPO-11 and AlPO-18, preferably at least one selected from the group consisting of AlPO-17 and AlPO-5; preferably, the metal content of the M-AlPO molecular sieve is not less than 0.2 wt %, preferably 0.2 wt % to 2.0 wt %; preferably, the M-AlPO molecular sieve has a schematic chemical composition represented by the formula mP.sub.2O.sub.5.Math.nAl.sub.2O.sub.3.Math.pMO.sub.x, wherein: 0.5?m/n?2, and 20?m/p?300; preferably 0.8?m/n?1.2, 40?m/p?200, x being the total number of oxygen atoms required to satisfy the valence of M, and further preferably, the M-AlPO molecular sieve has the following properties: a total acid content of 100-500 ?mol.Math.g.sup.?1, preferably 150-400 ?mol.Math.g?1, and further preferably 250-400 ?mol.Math.g?1, wherein the weak acid content is not less than 55%, preferably 60%-80%, further preferably 60%-75%, and the strong acid content is not greater than 35%, preferably 5%-30%, and further preferably 10%-25%.

25-26. (canceled)

27. The method according to claim 17, wherein: the mass ratio of the molecular sieve catalyst used in the step (2) to the biomass starting material used in the step (1) is from 0.1 to 5, preferably from 0.2 to 3; and/or during step (1), no acid, and preferably no acidic salt, is added to the reaction system.

28. (canceled)

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0124] FIG. 1 shows a diagram showing the measurement results of the contact angle of the 5% Pd/C hydrogenation catalyst obtained in Example 1 with water;

[0125] FIG. 2 shows a diagram showing the measurement results of the contact angle of the 5% Pt/Gr hydrogenation catalyst obtained in Example 2 with water;

[0126] FIG. 3 shows an XRD pattern of the CoAlPO-17 molecular sieve obtained in Example 11;

[0127] FIG. 4 shows an SEM image of the CoAlPO-17 molecular sieve obtained in Example 11;

[0128] FIG. 5 shows a NH.sub.3-TPD diagram of the CoAlPO-17 molecular sieve obtained in Example 11;

[0129] FIG. 6 shows an XRD pattern of the MgAlPO-17 molecular sieve obtained in Example 12;

[0130] FIG. 7 shows an SEM image of the MgAlPO-17 molecular sieve obtained in Example 12;

[0131] FIG. 8 shows a NH.sub.3-TPD diagram of the MgAlPO-17 molecular sieve obtained in Example 12;

[0132] FIG. 9 shows an XRD pattern of the ZnAlPO-17 molecular sieve obtained in Example 14;

[0133] FIG. 10 shows an XRD pattern of the ZnAlPO-5 molecular sieve obtained in Example 19;

[0134] FIG. 11 shows a diagram showing the cycle results of Example 21 in which 5% Pt/Gr was used to catalyze the production of HDO from glucose;

[0135] FIG. 12 shows a diagram showing the cycle results of Example 22 in which a CoAlPO-17 molecular sieve is used to catalyze the production of pX from HDO;

[0136] FIG. 13 shows a diagram showing the measurement results of the contact angle of the catalyst obtained in Comparative Example 2 with water;

[0137] FIG. 14 shows a schematic flow diagram of the production of para-xylene by conversion of biomass according to the present application.

[0138] FIG. 15 shows a ultraviolet-visible absorption spectrum (UV-Vis) of the Sn-SCM-14 molecular sieve obtained in Example II-1;

[0139] FIG. 16 shows an X-ray photoelectron spectrum (XPS) of the SnSCM-14 molecular sieve obtained in Example II-1;

[0140] FIG. 17 shows a pyridine adsorption infrared (Py-FTIR) diagram of the SnSCM-14 molecular sieve obtained in Example II-1;

[0141] FIG. 18 shows an XRD pattern of the SnSCM-14 molecular sieve obtained in Example II-1;

[0142] FIG. 19 shows a ultraviolet-visible absorption spectrum (UV-Vis) of the ZrSCM-14 molecular sieve obtained in Example II-6; and

[0143] FIG. 20 shows an X-ray photoelectron spectrum (XPS) of the ZrSCM-14 molecular sieve obtained in Example II-6.

DETAILED DESCRIPTION OF THE INVENTION

[0144] In the context of the present application, all technical features and preferred features mentioned herein in relation to the various aspects, series and/or embodiments may be combined with each other to form new technical solutions, unless stated otherwise.

[0145] In the context of the present application, unless stated otherwise, the specific steps, specific values and specific materials mentioned in the examples may be combined with other features in other parts of the specification. For example, where the Summary or Detailed Description section of the specification mentions a reaction temperature of 10 to 100? C. and the working examples describe a specific reaction temperature of 20? C., it is to be understood that the range of 10 to 20? C. or the range of 20 to 100? C. has been specifically disclosed herein and may be combined with other features in other sections of the specification to form new embodiments.

[0146] In the context of the present application, unless otherwise indicated, the terms comprising, containing, including, having, and the like are to be construed as open-ended, but should also be construed to cover closed-ended situations as if all such situations were explicitly set forth herein. For example, the term comprising means that other elements not listed may also be comprised, but it should also be construed that the case where only the listed elements are comprised is also explicitly disclosed.

[0147] In the context of the present application, unless stated otherwise, the specific steps, specific values and specific materials mentioned in the examples may be combined with other features in other parts of the specification. For example, where the Summary or Detailed Description section of the specification mentions a reaction temperature of 10 to 100? C. and the working examples describe a specific reaction temperature of 20? C., it is to be understood that the range of 10 to 20? C. or the range of 20 to 100? C. has been specifically disclosed herein and may be combined with other features in other sections of the specification to form new embodiments.

[0148] In the present application, the NH.sub.3 temperature programmed desorption (NH.sub.3-TPD) experiment is carried out on a TPD/TPR Altamira AMI-3300 instrument, the total acid content is calculated by fitting and peak separation on the obtained spectrum, the acid corresponding to the desorption temperature of 100-240? C. is defined as weak acid, the acid corresponding to the desorption temperature of 240-320? C. is defined as medium strong acid, and the acid corresponding to the desorption temperature of 320-510? C. is defined as strong acid, so that the proportion of the weak acid and the strong acid is calculated.

[0149] In the present application, the XRD measurement method of the molecular sieve product is carried out as follows: the sample is analyzed using a Rigaku Ultima IV X-ray powder diffractometer of RIGAKU, Japan, with a CuK? radiation source (?=1.54 ?), a nickel filter, 2? scanning range of 2?-50?, an operating voltage of 35 kV, a current of 25 mA, and a scanning rate of 10?/min.

[0150] In the present application, 2,5-hexanedione (HDO), paraxylene pX are analyzed and characterized by gas chromatography-mass spectrometry (GC-MS), and the yield and conversion of 2,5-hexanedione and the yield of reaction product pX are analyzed by Gas Chromatography (GC). The GC-MS instrument is Agilent 7890A of Agilent, U.S.A., of which the chromatographic column is an HP-5 nonpolar capillary column (30 m, 0.53 mm), the gas chromatograph is Agilent 7890B, of which the detector is a hydrogen flame ionization detector (FID), and the chromatographic column is an SE-54 capillary column (30 m, 0.53 mm).

[0151] The reaction for producing pX from biomass starting material is divided into two steps, the first step is to prepare 2,5-hexanedione (HDO) from the biomass starting material, and the yield of the intermediate product 2,5-hexanedione is calculated according to the following equation:

[0152] Yield of 2,5-hexanedione product, %=(molar amount n.sub.1 of 2,5-hexanedione produced by the reaction)/(molar amount no of hexose unit in the reaction substrate biomass)?100%, wherein the hexose unit is C.sub.6H.sub.10O.sub.5.

[0153] In the second step of reaction, the 2,5-hexanedione (n.sub.1) generated in the first step is used as a starting material, and reacts with high-pressure ethylene to produce pX, and the conversion of 2,5-hexanedione is calculated according to the following equation:

Conversion of 2,5-hexanedione, %=(molar amount n.sub.2 of 2,5-hexanedione remained after the second reaction step)/(molar amount n.sub.1 of 2,5-hexanedione in the starting material of the second reaction step)?100%;

[0154] In the second step, the yield and selectivity of the product pX are calculated according to the following equations:

Yield of the product pX, %=(molar amount n.sub.3 of pX produced by the reaction)/(molar amount n.sub.1 of 2,5-hexanedione in the starting material of the second reaction step)?100%.

Selectivity of the product pX, %=(molar amount n.sub.3 of pX produced by the reaction)/(molar amount n.sub.1 of 2,5-hexanedione in the starting material of the second reaction step?molar amount n.sub.2 of 2,5-hexanedione remained after the second reaction step)?100%.

[0155] In the present application, the contact angle measuring instrument is DSA100 of KRUSS, Germany. A tangent of the gas-liquid interface is taken from the intersection point of the gas, liquid and solid phases, and the included angle ? between the tangent and the solid-liquid boundary line passing through the contact point of the three phases is the contact angle of the liquid on the solid surface. Where the gas is air, the solid is the hydrogenation catalyst, and the liquid is water, the measured contact angle is defined as the contact angle of the hydrogenation catalyst with water, wherein the larger the contact angle, the better the relative hydrophobicity of the hydrogenation catalyst.

[0156] The method for preparing para-xylene by biomass conversion according to the present application is described below with reference to FIG. 14: [0157] (1) contacting a biomass starting material with a hydrogenation catalyst for reaction in a multiphase system formed by an organic solvent, an inorganic salt and water, using hydrogen as a hydrogen source, and subjecting the resulting product to centrifugal separation to obtain an upper organic phase comprising 2,5-hexanedione; [0158] (2) directly contacting the organic phase comprising 2,5-hexanedione obtained in the step (1) with ethylene and an aluminophosphate molecular sieve catalyst for reaction to obtain a reaction product comprising paraxylene. The resulting reaction product comprising paraxylene can be subjected to a subsequent separation process to obtain the paraxylene.

[0159] The present application will be described in more detail with reference to the following examples, which are provided to facilitate understanding of the present application and should not be construed as limiting the present application.

Example 1

[0160] Firstly, 10 g of activated carbon sample was treated in an oven at 80? C. for 4 h, then the sample was transferred to a high-temperature tube furnace, nitrogen was introduced as carrier gas, the gas flow rate was 3 h.sup.?1, the temperature was raised to 700? C. at a heating rate of 5? C., and the temperature was kept for 8 h, so that a hydrophobic activated carbon (represented by C) was obtained.

[0161] Preparation of catalyst 5% Pd/C: palladium nitrate was impregnated onto the hydrophobic active carbon by an isovolumetric impregnation method, wherein the impregnation amount was determined according to a mass ratio of the noble metal Pd:C of 5:100. The resultant was treated in an oven at 80? C. for 8 h, transferred to a high-temperature tube furnace, nitrogen was introduced as a carrier gas at a gas flow rate of 3 h.sup.?1, the temperature was raised to 500? C. at a heating rate of 10? C., kept for 4 h, and cooled to room temperature to obtain PdO/C. The carrier gas was switched to hydrogen at a gas flow rate of 3 h.sup.?1 and the temperature was raised to 400? C. at a heating rate of 10? C., and kept for 4 hours. The carrier gas was switched to nitrogen again and cooled to room temperature to obtain 5% Pd/C. The contact angle measured thereafter was 58?, as shown in FIG. 1, indicating that the material had a good hydrophobicity.

[0162] Cellulose was used as a biomass starting material, 5% Pd/C was used as a hydrogenation catalyst, the mass ratio of the biomass starting material to the hydrogenation catalyst was 1, the mass ratio of NaCl to water was 0.5, 1,4-dioxane was used as an organic solvent, the mass ratio of the organic solvent to NaCl and water was 5, the mass ratio of the organic solvent to the biomass starting material was 20, the hydrogen pressure was 2 MPa, the reaction temperature was 200? C., and the reaction time was 10 hours.

[0163] The detailed operation was as follows: 0.5 g of cellulose, 0.5 g of 5% Pd/C hydrogenation catalyst, 2 g of NaCl and water (the mass ratio of NaCl to water was 0.5), and 10 g of 1,4-dioxane organic solvent were charged into a high-pressure reactor, and 2 MPa of hydrogen was introduced. The reactor was heated to a preset temperature using a temperature programming heating sleeve, then stirred by magnetic stirring. After 10 hours of reaction at 200? C., the reaction solution was centrifuged to obtain an organic phase comprising 2,5-hexanedione, and the HDO yield was 63%, as calculated based on gas phase analysis.

Example 2

[0164] A catalyst was prepared as described in Example 1, except that graphene was used instead of activated carbon and chloroplatinic acid was used instead of palladium nitrate. The catalyst obtained was 5% Pt/Gr. The contact angle of the catalyst with water was measured to be 65?, as shown in FIG. 2, indicating that the material has a good hydrophobicity.

[0165] Glucose was used as a biomass starting material, 5% Pt/Gr was used as a hydrogenation catalyst, the mass ratio of the biomass starting material to the hydrogenation catalyst was 1, the mass ratio of NaCl to water was 0.40, tetrahydrofuran was used as an organic solvent, the mass ratio of the organic solvent to NaCl and water was 8, the mass ratio of the organic solvent to the biomass starting material was 30, the hydrogen pressure was 2.5 MPa, the reaction temperature was 210? C., and the reaction time was 15 hours.

[0166] The detailed operation was as follows: 0.5 g of glucose, 0.5 g of 5% Pt/Gr hydrogenation catalyst, 1.9 g of NaCl and water (the mass ratio of NaCl to water was 0.40), and 15 g of tetrahydrofuran organic solvent were charged into a high-pressure reactor, and 2.5 MPa hydrogen was introduced. The reactor was heated to a preset temperature using a temperature programming heating sleeve, then stirred by magnetic stirring. After 15 hours of reaction at 210? C., the reaction solution was centrifuged to obtain an organic phase comprising 2,5-hexanedione, and the HDO yield was 61%, as calculated based on gas phase analysis.

Example 3

[0167] A catalyst was prepared as described in Example 1, except that the palladium nitrate was replaced with chloroplatinic acid and the impregnation amount was changed in accordance with a mass ratio of the noble metal Pt:C of 3:100. The catalyst obtained was 3% Pt/C. The contact angle of the catalyst with water was measured to be 63?, similar to that shown in FIG. 1, indicating that the material has a good hydrophobicity.

[0168] Fructose was used as a biomass starting material, 3% Pt/C was used as a hydrogenation catalyst, the mass ratio of the biomass starting material to the hydrogenation catalyst was 1.7, the mass ratio of NaCl to water was 0.30, methyl isobutyl ketone was used as an organic solvent, the mass ratio of the organic solvent to NaCl and water was 7, the mass ratio of the organic solvent to the biomass starting material was 18, the hydrogen pressure was 1 MPa, the reaction temperature was 180? C., and the reaction time was 12 hours.

[0169] The detailed operation was as follows: 0.5 g of fructose, 0.3 g of 3% Pt/C hydrogenation catalyst, 1.3 g of NaCl and water (the mass ratio of NaCl to water was 0.30), and 9 g of methyl isobutyl ketone organic solvent were charged into a high-pressure reactor, and 1 MPa hydrogen was introduced. The reactor was heated to a preset temperature using a temperature programming heating sleeve, then stirred by magnetic stirring. After 12 hours of reaction at 180? C., the reaction solution was centrifuged to obtain an organic phase comprising 2,5-hexanedione, and the HDO yield was 53%, as calculated based on gas phase analysis.

Example 4

[0170] A catalyst was prepared as described in Example 3, except that palladium nitrate was used in place of chloroplatinic acid and graphene was used in place of activated carbon. The catalyst obtained was 3% Pd/Gr. The contact angle of the catalyst with water was measured to be 67?, similar to that shown in FIG. 1, indicating that the material has a good hydrophobicity.

[0171] Cellobiose was used as a biomass starting material, 3% Pd/Gr was used as a hydrogenation catalyst, the mass ratio of the biomass starting material to the hydrogenation catalyst was 0.5, the mass ratio of KCl to water was 0.25, ?-valerolactone was used as an organic solvent, the mass ratio of the organic solvent to KCl and water was 5, the mass ratio of the organic solvent to the biomass starting material was 40, the hydrogen pressure was 3 MPa, the reaction temperature was 200? C., and the reaction time was 8 hours.

[0172] The detailed operation was as follows: 0.5 g of cellobiose, 1.0 g of 3% Pd/Gr hydrogenation catalyst, 4 g of KCl and water (the mass ratio of KCl to water was 0.25), and 20 g of ?-valerolactone organic solvent were charged into a high-pressure reactor, and 3 MPa hydrogen was introduced. The reactor was heated to a preset temperature using a temperature programming heating sleeve, then stirred by magnetic stirring. After 8 hours of reaction at 200? C., the reaction solution was separated to obtain an organic phase comprising 2,5-hexanedione, and the HDO yield was 54%, as calculated based on gas phase analysis.

Example 5

[0173] A 5% Pt/Gr hydrogenation catalyst was prepared as described in Example 2.

[0174] Inulin was used as a biomass starting material, 5% Pt/Gr was used as a hydrogenation catalyst, the mass ratio of the biomass starting material to the hydrogenation catalyst was 1.7, the mass ratio of KBr to water was 0.34, 1,2-dichloroethane was used as an organic solvent, the mass ratio of the organic solvent to the KBr and water was 6, the mass ratio of the organic solvent to the biomass starting material was 20, the hydrogen pressure was 1.5 MPa, the reaction temperature was 190? C., and the reaction time was 10 hours.

[0175] The detailed operation was as follows: 0.5 g of inulin, 0.3 g of 5% Pt/Gr hydrogenation catalyst, 1.7 g of KBr and water (the mass ratio of the KBr to water was 0.34), 10 g of 1,2-dichloroethane organic solvent were charged into a high-pressure reactor, and 1.5 MPa of hydrogen was introduced. The reactor was heated to a preset temperature using a temperature programming heating sleeve, then stirred by magnetic stirring. After 10 hours of reaction at 190? C., the reaction solution was centrifuged to obtain an organic phase comprising 2,5-hexanedione, and the HDO yield was 58%, as calculated based on gas phase analysis.

Example 6

[0176] A 3% Pd/C catalyst was prepared as described in Example 1, except that the impregnation amount was determined in accordance with a mass ratio of the noble metal Pd:C of 3:100. The contact angle of the catalyst with water was measured to be 61?, similar to that shown in FIG. 1, indicating that the material has a good hydrophobicity.

[0177] Corn straw was used as a biomass starting material, 3% Pd/C was used as a hydrogenation catalyst, the mass ratio of the biomass starting material to the hydrogenation catalyst was 0.5, the mass ratio of NaCl to water was 0.20, 1,2-dichloroethane was used as an organic solvent, the mass ratio of the organic solvent to NaCl and water was 10, the mass ratio of the organic solvent to the biomass starting material was 30, the hydrogen pressure was 2 MPa, the reaction temperature was 210? C., and the reaction time was 13 hours.

[0178] The detailed operation was as follows: 0.5 g of corn straw, 1.0 g of 3% Pd/C hydrogenation catalyst, 1.5 g of NaCl and water (the mass ratio of NaCl to water was 0.20), 15 g of 1,2-dichloroethane organic solvent were charged into a high-pressure reactor, and 2 MPa of hydrogen was introduced. The reactor was heated to a preset temperature using a temperature programming heating sleeve, then stirred by magnetic stirring. After reacting at 210? C. for 13 hours, the reaction solution was centrifuged to obtain an organic phase comprising 2,5-hexanedione, and the HDO yield was 52%, as calculated based on gas phase analysis.

Example 7

[0179] A 3% Pd/Gr hydrogenation catalyst was prepared as described in Example 4.

[0180] Corncob was used as a biomass starting material, 3% Pd/Gr was used as a hydrogenation catalyst, the mass ratio of the biomass starting material to the hydrogenation catalyst was 0.8, the mass ratio of NaCl to water was 0.65, methyl isobutyl ketone was used as an organic solvent, the mass ratio of the organic solvent to NaCl and water was 8, the mass ratio of the organic solvent to the biomass starting material was 36, the hydrogen pressure was 3 MPa, the reaction temperature was 200? C., and the reaction time was 18 hours.

[0181] The detailed operation was as follows: 0.5 g of corncob, 0.6 g of 3% Pd/Gr hydrogenation catalyst, 2.3 g of NaCl and water (the mass ratio of NaCl to water was 0.65), 18 g of methyl isobutyl ketone organic solvent were charged into a high-pressure reactor, and 3 MPa of hydrogen was introduced. The reactor was heated to a preset temperature using a temperature programming heating sleeve, then stirred by magnetic stirring. After reacting at 200? C. for 18 hours, the reaction solution was centrifuged to obtain an organic phase comprising 2,5-hexanedione, and the HDO yield was 65%, as calculated based on gas phase analysis.

Example 8

[0182] A 3% Pt/C hydrogenation catalyst was prepared as described in Example 3.

[0183] Pine wood was used as a biomass starting material, 3% Pt/C was used as a hydrogenation catalyst, the mass ratio of the biomass starting material to the hydrogenation catalyst was 1.3, the mass ratio of NaCl to water was 0.28, tetrahydrofuran was used as an organic solvent, the mass ratio of the organic solvent to NaCl and water was 10, the mass ratio of the organic solvent to the biomass starting material was 18, the hydrogen pressure was 1 MPa, the reaction temperature was 220? C., and the reaction time was 16 hours.

[0184] The detailed operation was as follows: 0.5 g of pine wood, 0.4 g of 3% Pt/C hydrogenation catalyst, 0.9 g of 28 wt % of salinity NaCl and water (the mass ratio of NaCl to water was 0.28) and 9 g of tetrahydrofuran organic solvent were charged into a high-pressure reactor, and 1 MPa of hydrogen was introduced. The reactor was heated to a preset temperature using a temperature programming heating sleeve, then stirred by magnetic stirring. After 16 hours of reaction at 220? C., the reaction solution was centrifuged to obtain an organic phase comprising 2,5-hexanedione, and the HDO yield was 55%, as calculated based on gas phase analysis.

Example 9

[0185] A 3% Pd/Gr hydrogenation catalyst was prepared as described in Example 4.

[0186] Poplar wood was used as a biomass starting material, 3% Pd/Gr was used as a hydrogenation catalyst, the mass ratio of the biomass starting material to the hydrogenation catalyst was 1, the mass ratio of NaCl to water was 0.30, methyl isobutyl ketone was used as an organic solvent, the mass ratio of the organic solvent to NaCl and water was 5, the mass ratio of the organic solvent to the biomass starting material was 20, the hydrogen pressure was 2 MPa, the reaction temperature was 190? C., and the reaction time was 14 hours.

[0187] The detailed operation was as follows: 0.5 g of poplar wood, 0.5 g of 3% Pd/Gr hydrogenation catalyst, 2 g of 30 wt % salinity NaCl, water (the mass ratio of NaCl to water was 0.30) and 10 g of methyl isobutyl ketone organic solvent were charged into a high-pressure reactor, and 2 MPa of hydrogen was introduced. The reactor was heated to a preset temperature using a temperature programming heating sleeve, then stirred by magnetic stirring. After 14 hours of reaction at 190? C., the reaction solution was centrifuged to obtain an organic phase comprising 2,5-hexanedione, and the HDO yield was 56%, as calculated based on gas phase analysis.

Example 10

[0188] A 5% Pd/C hydrogenation catalyst was prepared as described in Example 1.

[0189] Beech wood was used as a biomass starting material, 5% Pd/C was used as a hydrogenation catalyst, the mass ratio of the biomass starting material to the hydrogenation catalyst was 0.7, the mass ratio of NaCl to water was 0.54, tetrahydrofuran was used as an organic solvent, the mass ratio of the organic solvent to NaCl and water was 6, the mass ratio of the organic solvent to the biomass starting material was 30, the hydrogen pressure was 1.5 MPa, the reaction temperature was 200? C., and the reaction time was 8 hours.

[0190] The detailed operation was as follows: 0.5 g of beech wood, 0.7 g of 5% Pd/C hydrogenation catalyst, 2.5 g of NaCl and water (the mass ratio of NaCl to water was 0.54), and 15 g of tetrahydrofuran organic solvent were charged into a high-pressure reactor, and 1.5 MPa of hydrogen was introduced. The reactor was heated to a preset temperature using a temperature programming heating sleeve, then stirred by magnetic stirring. After 8 hours of reaction at 200? C., the reaction solution was centrifuged to obtain an organic phase comprising 2,5-hexanedione, and the HDO yield was 64%, as calculated based on gas phase analysis.

[0191] To more intuitively describe the reaction conditions and results of Examples 1 to 10 above, the operation parameters and reaction results are listed in Table 1.

TABLE-US-00006 TABLE 1 Reaction conditions and results for Examples 1-10 Mass ratio Mass ratio Mass ratio of biomass of organic Mass of organic starting solvent ratio of solvent to Yield Biomass Hydro- material to to biomass inorganic inorganic Hydrogen Reaction Reaction of starting genation hydrogenation starting salt to salt to pressure temperature time HDO x. material catalyst catalyst material water Organic solvent water (MPa) (? C.) (h) (%) 1 Cellulose 5% Pd/C 1 20 0.50 1,4-dioxane 5 2 200 10 63 2 Glucose 5% Pt/Gr 1 30 0.40 Tetrahydrofuran 8 2.5 210 15 61 3 Fructose 3% Pt/C 1.7 18 0.30 Methyl isobutyl 7 1 180 12 53 ketone 4 Cellobiose 3% Pd/Gr 0.5 40 0.25 ?-valerolactone 5 3 200 8 54 5 Inulin 5% Pt/Gr 1.7 20 0.34 1,2-dichloroethane 6 1.5 190 10 58 6 Corn straw 3% Pd/C 0.5 30 0.20 1,2-dichloroethane 10 2 210 13 52 7 Corncob 3% Pd/Gr 0.8 36 0.65 Methyl isobutyl 8 3 200 18 65 ketone 8 Pine wood 3% Pt/C 1.3 18 0.28 Tetrahydrofuran 10 1 220 16 55 9 Poplar wood 3% Pd/Gr 1 20 0.30 Methyl isobutyl 5 2 190 14 56 ketone 10 Beech wood 5% Pd/C 0.7 30 0.54 Tetrahydrofuran 6 1.5 200 8 64

Example 11

[0192] Preparation of CoAlPO-17 molecular sieve: phosphoric acid, aluminum isopropoxide, cobalt phosphate, cyclohexylamine and deionized water were uniformly mixed at a molar ratio of 1 P.sub.2O.sub.5: 1 Al.sub.2O.sub.3: 0.01 COO: 1 CHA (cyclohexylamine): 50 H.sub.2O, to form a gel, then subjected to hydrothermal crystallization at 180? C. for 120 hours, washed, dried, and calcined at 550? C. for 5 hours in the presence of air to obtain the CoAlPO-17 molecular sieve.

[0193] The XRD pattern of the sample is shown in FIG. 3, and its SEM image is shown in FIG. 4. The CoAlPO-17 molecular sieve has a cobalt content of 0.7 wt % and an exemplary chemical composition of P.sub.2O.sub.5.Math.0.91Al.sub.2O.sub.3.Math.0.009CoO, as measured by inductively coupled plasma atomic emission spectroscopy (ICP). NH.sub.3-TPD diagram of the CoAlPO-17 molecular sieve is shown in FIG. 5, the total acid content is 311 ?mol.Math.g.sup.?1, the weak acid content is 72.3%, and the strong acid content is 11.4%.

[0194] The organic phase comprising 2,5-hexanedione obtained in Example 1 was used as a starting material, CoAlPO-17 molecular sieve was used as an aluminophosphate molecular sieve catalyst, the mass ratio of the aluminophosphate molecular sieve catalyst to the biomass starting material used in Example 1 was 1, the ethylene pressure was 3 MPa, the reaction temperature was 260? C., and the reaction time was 30 hours.

[0195] The detailed operation was as follows: the organic phase comprising 2,5-hexanedione obtained in Example 1, and 0.5 g of CoAlPO-17 molecular sieve were charged into a high-pressure reactor, and 3 MPa ethylene was introduced. The reactor was heated to a preset temperature using a temperature programming heating sleeve, then stirred by magnetic stirring. After 30 hours of reaction at 260? C., the reaction solution was centrifuged, and HDO conversion was 92% and pX selectivity was 97%, as calculated based on gas phase analysis.

Example 12

[0196] Preparation of MgAlPO-17 molecular sieve: phosphoric acid, aluminum isopropoxide, magnesium nitrate, cyclohexylamine and deionized water were uniformly mixed, at a molar ratio of 1 P.sub.2O.sub.5:1.2 Al.sub.2O.sub.3: 0.02 MgO:1 CHA (cyclohexylamine): 50 H.sub.2O, to form a gel, then subjected to hydrothermal crystallization at 200? C. for 70 hours, washed, dried, and calcined at 550? C. for 5 hours in the presence of oxygen to obtain the MgAlPO-17 molecular sieve. The XRD pattern of the MgAlPO-17 molecular sieve is shown in FIG. 6, and its SEM image is shown in FIG. 7. The MgAlPO-17 molecular sieve has an Mg content of 1.0 wt % and a schematic chemical composition of P.sub.2O.sub.5.Math.1.12Al.sub.2O.sub.3.Math.0.015MgO, as measured by inductively coupled plasma atomic emission spectroscopy (ICP). NH.sub.3-TPD diagram of the MgAlPO-17 molecular sieve is shown in FIG. 8, the total acid content is 325 ?mol.Math.g.sup.?1, the weak acid content is 67.2%, and the strong acid content is 19.5%.

[0197] The organic phase comprising 2,5-hexanedione obtained in Example 1 was used as a starting material, the MgAlPO-17 molecular sieve was used as an aluminophosphate molecular sieve catalyst, the mass ratio of the aluminophosphate molecular sieve catalyst to the biomass starting material used in Example 1 was 0.6, the ethylene pressure was 2.5 MPa, the reaction temperature was 230? C., and the reaction time was 36 hours.

[0198] The detailed operation was as follows: the organic phase comprising 2,5-hexanedione obtained in Example 1, and 0.3 g of MgAlPO-17 molecular sieve were charged into a high-pressure reactor, and 2.5 MPa of ethylene was introduced. The reactor was heated to a preset temperature using a temperature programming heating sleeve, then stirred by magnetic stirring. After 36 hours of reaction at 230? C., the reaction solution was centrifuged, and the HDO conversion was 96% and the pX selectivity was 96%, as calculated based on gas phase analysis.

Example 13

[0199] A MgAlPO-17 molecular sieve was prepared as described in Example 12.

[0200] The organic phase comprising 2,5-hexanedione obtained in Example 3 was used as a starting material, the MgAlPO-17 molecular sieve was used as an aluminophosphate molecular sieve catalyst, the mass ratio of the aluminophosphate molecular sieve catalyst to the biomass starting material used in Example 3 was 1.5, the ethylene pressure was 3 MPa, the reaction temperature was 270? C., and the reaction time was 24 hours.

[0201] The detailed operation was as follows: the organic phase comprising 2,5-hexanedione obtained in Example 3, and 0.75 g of MgAlPO-17 molecular sieve were charged into a high-pressure reactor and 3 MPa of ethylene was introduced. The reactor was heated to a preset temperature using a temperature programming heating sleeve, then stirred by magnetic stirring. After 24 hours of reaction at 270? C., the reaction solution was centrifuged, and HDO conversion was 90% and pX selectivity was 97%, as calculated based on gas phase analysis.

Example 14

[0202] Preparation of ZnAlPO-17 molecular sieve: phosphoric acid, aluminum isopropoxide, zinc nitrate, cyclohexylamine and deionized water were uniformly mixed, at a molar ratio of 1 P.sub.2O.sub.5: 1.1 Al.sub.2O.sub.3: 0.01 ZnO: 1 CHA (cyclohexylamine): 50 H.sub.2O, to form a gel, subjected to hydrothermal crystallization for 96 hours at 200? C., washed, dried, and calcined for 5 hours at 550? C. in the presence of oxygen to obtain the ZnAlPO-17 molecular sieve. The SEM image of the sample is similar to that shown in FIG. 4 and shows a rod-like shape; the XRD pattern of the ZnAlPO-17 molecular sieve is shown in FIG. 9. The ZnAlPO-17 molecular sieve has a zinc content of 0.7 wt % and a schematic chemical composition of P.sub.2O.sub.5.Math.1.03Al.sub.2O.sub.3.Math.0.008ZnO, as measured by inductively coupled plasma atomic emission spectroscopy (ICP). NH.sub.3-TPD diagram of the sample is similar to that shown in FIG. 5, the total acid content is 254 ?mol.Math.g.sup.?1, the weak acid content is 71.2% and the strong acid content is 12.1%.

[0203] The organic phase comprising 2,5-hexanedione obtained in Example 4 was used as a starting material, the ZnAlPO-17 molecular sieve was used as an aluminophosphate molecular sieve catalyst, the mass ratio of the aluminophosphate molecular sieve catalyst to the biomass starting material used in Example 4 was 2, the ethylene pressure was 3.5 MPa, the reaction temperature was 240? C., and the reaction time was 40 hours.

[0204] The detailed operation was as follows: the organic phase comprising 2,5-hexanedione obtained in Example 4, and 1 g ZnAlPO-17 molecular sieve were charged into a high-pressure reactor, and 3.5 MPa ethylene was introduced. The reactor was heated to a preset temperature using a temperature programming heating sleeve, then stirred by magnetic stirring. After 40 hours of reaction at 240? C., the reaction solution was centrifuged, and the HDO conversion was 95% and the pX selectivity was 95%, as calculated based on gas phase analysis.

Example 15

[0205] A ZnAlPO-17 molecular sieve was prepared as described in Example 14.

[0206] The organic phase comprising 2,5-hexanedione obtained in Example 5 was used as a starting material, the ZnAlPO-17 molecular sieve was used as an aluminophosphate molecular sieve catalyst, the mass ratio of the aluminophosphate molecular sieve catalyst to the biomass starting material used in Example 5 was 0.8, the ethylene pressure was 1.8 MPa, the reaction temperature was 250? C., and the reaction time was 48 hours.

[0207] The detailed operation was as follows: the organic phase comprising 2,5-hexanedione obtained in Example 5, and 0.4 g of ZnAlPO-17 molecular sieve were charged into a high-pressure reactor, and 1.8 MPa of ethylene was introduced. The reactor was heated to a preset temperature using a temperature programming heating sleeve, then stirred by magnetic stirring. After 48 hours of reaction at 250? C., the reaction solution was centrifuged, and the HDO conversion was 99% and the pX selectivity was 98%, as calculated based on gas phase analysis.

Example 16

[0208] A CoAlPO-17 molecular sieve was prepared as described in Example 11.

[0209] The organic phase comprising 2,5-hexanedione obtained in Example 6 was used as a starting material, the CoAlPO-17 molecular sieve was used as an aluminophosphate molecular sieve catalyst, the mass ratio of the aluminophosphate molecular sieve catalyst to the biomass starting material used in Example 6 was 1.4, the ethylene pressure was 2 MPa, the reaction temperature was 250? C., and the reaction time was 32 hours.

[0210] The detailed operation was as follows: the organic phase comprising 2,5-hexanedione obtained in Example 6, and 0.7 g of CoAlPO-17 molecular sieve were charged into a high-pressure reactor, and 2 MPa ethylene was introduced. The reactor was heated to a preset temperature using a temperature programming heating sleeve, then stirred by magnetic stirring. After reacting at 250? C. for 32 hours, the reaction solution was centrifuged, and the HDO conversion was 95% and the pX selectivity was 96%, as calculated based on gas phase analysis.

Example 17

[0211] A CoAlPO-17 molecular sieve was prepared as described in Example 11.

[0212] The organic phase comprising 2,5-hexanedione obtained in Example 7 was used as a starting material, the CoAlPO-17 molecular sieve was used as an aluminophosphate molecular sieve catalyst, the mass ratio of the aluminophosphate molecular sieve catalyst to the biomass starting material used in Example 7 was 1.6, the ethylene pressure was 1.5 MPa, the reaction temperature was 230? C., and the reaction time was 24 hours.

[0213] The detailed operation was as follows: the organic phase comprising 2,5-hexanedione obtained in Example 7, and 0.8 g of CoAlPO-17 molecular sieve were charged into a high-pressure reactor, and 1.5 MPa of ethylene was introduced. The reactor was heated to a preset temperature using a temperature programming heating sleeve, then stirred by magnetic stirring. After 24 hours of reaction at 230? C., the reaction solution was centrifuged, and the HDO conversion was 91% and the pX selectivity was 98%, as calculated based on gas phase analysis.

Example 18

[0214] A MgAlPO-17 molecular sieve was prepared as described in Example 12.

[0215] The organic phase comprising 2,5-hexanedione obtained in Example 9 was used as a starting material, the MgAlPO-17 molecular sieve was used as an aluminophosphate molecular sieve catalyst, the mass ratio of the aluminophosphate molecular sieve catalyst to the biomass starting material used in Example 9 was 2.5, the ethylene pressure was 3 MPa, the reaction temperature was 260? C., and the reaction time was 28 hours.

[0216] The detailed operation was as follows: the organic phase comprising 2,5-hexanedione obtained in Example 9, and 1.25 g of MgAlPO-17 molecular sieve were charged into a high-pressure reactor and 3 MPa of ethylene was introduced. The reactor was heated to a preset temperature using a temperature programming heating sleeve, then stirred by magnetic stirring. After reacting at 260? C. for 28 hours, the reaction solution was centrifuged, and the HDO conversion was 94% and the pX selectivity was 97%, as calculated based on gas phase analysis.

Example 19

[0217] Preparation of ZnAlPO-5 molecular sieve: phosphoric acid, aluminum isopropoxide, zinc nitrate, ethylenediamine and deionized water were uniformly mixed, at a molar ratio of according to 1.0 P.sub.2O.sub.5: 1.0 Al.sub.2O.sub.3: 0.01 ZnO: 1.0 ethylene diamine: 50 H.sub.2O, to form a gel, then subjected to hydrothermal crystallization for 4 hours at 190? C., washed, dried, and calcined for 5 hours at 550? C. in the presence of oxygen to obtain the ZnAlPO-5 molecular sieve. The SEM image of the sample is similar to that shown in FIG. 4, and shows a rod-like shape; the XRD pattern of the sample is shown in FIG. 10. The sample has a zinc content of 0.7 wt % and a schematic chemical composition of P.sub.2O.sub.5.Math.0.92Al.sub.2O.sub.3.Math.0.009ZnO, as measured by inductively coupled plasma atomic emission spectroscopy (ICP). NH.sub.3-TPD diagram of the sample is similar to that shown in FIG. 3, the total acid content is 235 ?mol.Math.g.sup.?1, the weak acid content is 67.3% and the strong acid content is 16.5%.

[0218] The organic phase comprising 2,5-hexanedione obtained in Example 1 was used as a starting material, the ZnAlPO-5 molecular sieve was used as an aluminophosphate molecular sieve catalyst, the mass ratio of the aluminophosphate molecular sieve catalyst to the biomass starting material used in Example 1 was 1, the ethylene pressure was 2 MPa, the reaction temperature was 260? C., and the reaction time was 26 hours.

[0219] The detailed operation was as follows: the organic phase comprising 2,5-hexanedione obtained in Example 1, and 0.5 g of ZnAlPO-5 molecular sieve were charged into a high-pressure reactor, and 2 MPa of ethylene was introduced. The reactor was heated to a preset temperature using a temperature programming heating sleeve, then stirred by magnetic stirring. After reaction at 260? C. for 26 hours, the reaction solution was centrifuged, and the HDO conversion was 91% and the pX selectivity was 96%, as calculated based on gas phase analysis.

[0220] To more intuitively describe the reaction conditions and results of Examples 11-19 above, the operation parameters and results are listed in Table 2.

TABLE-US-00007 TABLE 2 Reaction conditions and results for Examples 11-19 Mass ratio of aluminophosphate Aluminophosphate molecular sieve Ethylene Reaction Reaction HDO pX Source of molecular sieve catalyst to biomass pressure temperature time conversion selectivity Examples HDO catalyst starting material (MPa) (? C.) (h) (%) (%) 11 Example 1 CoAlPO-17 1 3 260 30 92 97 12 Example 1 MgAlPO-17 0.6 2.5 230 36 96 96 13 Example 3 MgAlPO-17 1.5 3 270 24 90 97 14 Example 4 ZnAlPO-17 2 3.5 240 40 95 95 15 Example 5 ZnAlPO-17 0.8 1.8 250 48 99 98 16 Example 6 CoAlPO-17 1.4 2 250 32 95 96 17 Example 7 CoAlPO-17 1.6 1.5 230 24 91 98 18 Example 9 MgAlPO-17 2.5 3 260 28 94 97 19 Example 1 ZnAlPO-5 1 2 260 26 91 96

Example 20

[0221] In this example, the SCM-14 molecular sieve obtained in Example 1 of CN109081360B was used as a catalyst.

[0222] The organic phase comprising 2,5-hexanedione obtained in Example 9 was used as a starting material, the SCM-14 molecular sieve was used as a catalyst, the mass ratio of the catalyst to the biomass starting material used in Example 9 was 2.5, the ethylene pressure was 3 MPa, the reaction temperature was 250? C., and the reaction time was 24 hours.

[0223] The detailed operation was as follows: the organic phase comprising 2,5-hexanedione obtained in Example 9, and 1.25 g of SCM-14 molecular sieve were charged into a high-pressure reactor, and 3 MPa of ethylene was introduced. The reactor was heated to a preset temperature using a temperature programming heating sleeve, then stirred by magnetic stirring. After 24 hours of reaction at 250? C., the reaction solution was centrifuged, and the HDO conversion was 91% and the pX selectivity was 96%, as calculated based on gas phase analysis.

Example 21

[0224] The operation procedures of the cycling stability experiment were as follows: to NaCl and water obtained after the completion of the reaction in Example 2 and the 5% Pt/Gr catalyst in Example 2, 0.5 g of glucose and 15 g of tetrahydrofuran were added directly to conduct a new reaction, and 2.5 MPa of hydrogen was introduced. The reactor was heated to a preset temperature using a temperature programming heating sleeve, then stirred by magnetic stirring. After 15 hours of reaction at 210? C., the reaction solution was centrifuged to obtain an organic phase comprising 2,5-hexanedione, and the HDO yield was calculated based on gas phase analysis. Total 4 cycles of reactions were conducted in this way, and the HDO yield remained above 60% after 4 cycles of reactions as shown in FIG. 11, indicating that the hydrogenation catalyst added in the reaction system in the first reaction step had good cycling stability.

Example 22

[0225] The organic phases comprising 2,5-hexanedione obtained in the cycling test of Example 21 were used as a starting material, and the organic phases were used in the order obtained in the cycling test, the CoAlPO-17 molecular sieve obtained in Example 11 was used as an aluminophosphate molecular sieve catalyst, the mass ratio of the aluminophosphate molecular sieve catalyst to the biomass starting material used in Example 20 was 1, the ethylene pressure was 3 MPa, the reaction temperature was 260? C., and the reaction time was 30 hours.

[0226] The detailed operation was as follows: the organic phase comprising 2,5-hexanedione obtained in each cycle of Example 20 and 0.5 g of CoAlPO-17 molecular sieve were charged into a high-pressure reactor, and 3 MPa ethylene was introduced. The reactor was heated to a preset temperature using a temperature programming heating sleeve, then stirred by magnetic stirring. After 30 hours of reaction at 260? C., the reaction solution was separated, and the HDO conversion and pX selectivity were calculated based on gas phase analysis. After the completing of each reaction, the CoAlPO-17 molecular sieve was separated, and was directly used for the next reaction after being ultrasonically washed with tetrahydrofuran solution, and 4 cycles of reaction were conducted. The results are shown in FIG. 12. The HDO conversion remained above 90% and the pX selectivity remained above 95% after 4 cycles of reactions, indicating that the M-AlPO molecular sieve catalyst used in the reaction system in the second step had good cycling stability.

Comparative Example 1

[0227] A 3% Pd/Gr hydrogenation catalyst was prepared as described in Example 4.

[0228] Cellobiose was used as a biomass starting material, 3% Pd/Gr was used as a hydrogenation catalyst, the mass ratio of the biomass starting material to the hydrogenation catalyst was 0.5, deionized water was used as aqueous phase, ?-valerolactone was used as an organic solvent, the mass ratio of the organic solvent to water was 5, the mass ratio of the organic solvent to the biomass starting material was 40, the hydrogen pressure was 3 MPa, the reaction temperature was 200? C., and the reaction time was 8 hours.

[0229] The detailed operation was as follows: 0.5 g of cellobiose, 1.0 g of 3% Pd/Gr hydrogenation catalyst, 4 g of deionized water and 20 g of ?-valerolactone organic solvent were charged into a high-pressure reactor, and 3 MPa hydrogen was introduced. The reactor was heated to a preset temperature using a temperature programming heating sleeve, then stirred by magnetic stirring. After 8 hours of reaction at 200? C., the reaction solution was separated and the HDO yield was only 7%, as calculated based on gas phase analysis.

Comparative Example 2

[0230] Preparation of catalyst 5% Pd/DC: palladium nitrate was impregnated on untreated activated carbon (expressed as DC) of Example 1 in an isovolumetric impregnation method at a mass ratio of the noble metal Pd: DC of 5:100. The resultant was treated in an oven at 80? C. for 8 h, transferred to a high-temperature tube furnace, nitrogen was introduced as a carrier gas at a gas flow rate of 3 h.sup.?1, the temperature was raised to 500? C. at a heating rate of 10? C., kept for 4 h, and cooled to room temperature. The carrier gas was switched to hydrogen at a gas flow rate of 3 h.sup.?1 and the temperature was raised to 400? C. at a heating rate of 10? C., and kept for 4 hours. The carrier gas was switched to nitrogen again and cooled to room temperature to obtain 5% Pd/DC. Contact angle was then measured to be about 30?, as shown in FIG. 13, indicating that the material had a poor hydrophobicity.

[0231] Cellulose was used as a biomass starting material, 5% Pd/DC was used as a hydrogenation catalyst, the mass ratio of the biomass starting material to the hydrogenation catalyst was 1, the mass ratio of NaCl to water was 0.5, 1,4-dioxane was used as an organic solvent, the mass ratio of the organic solvent to NaCl and water was 5, the mass ratio of the organic solvent to the biomass starting material was 20, the hydrogen pressure was 2 MPa, the reaction temperature was 200? C., and the reaction time was 10 hours.

[0232] The detailed operation was as follows: 0.5 g of cellulose, 0.5 g of 5% Pd/DC hydrogenation catalyst, 2 g of NaCl and water (the mass ratio of NaCl to water was 0.5), and 10 g of 1,4-dioxane organic solvent were charged into a high-pressure reactor, and 2 MPa of hydrogen was introduced. The reactor was heated to a preset temperature using a temperature programming heating sleeve, then stirred by magnetic stirring. After 10 hours of reaction at 200? C., the reaction solution was centrifuged to obtain an organic phase comprising 2,5-hexanedione, and the HDO yield was only 37%, as calculated based on gas phase analysis.

[0233] In the following examples of Series II, the procedure for producing SCM-14 molecular sieve in accordance with the method described in Example 1 of CN109081360A was as follows:

[0234] 10.08 g of deionized water, 3.045 g of organic template 4-pyrrolidinylpyridine (98 wt %), 1.674 g of germanium oxide (99 wt %), 1.0 g of hydrofluoric acid (40 wt %) and 6.0 g of silica sol (SiO.sub.2, 40 wt %) were uniformly mixed to obtain a reaction mixture, wherein the material ratio (molar ratio) of the reaction mixture was as follows: SiO.sub.2/GeO.sub.2=2.5; template/SiO.sub.2=0.50; H.sub.2O/SiO.sub.2=20; after being mixed evenly, the mixture was put into a stainless steel reaction kettle, aged for 4 hours in water bath at a temperature of 80? C., then crystallized for 2 days at a temperature of 100? C. under stirring, and further crystallized for 5 days at a temperature of 170? C. After crystallization was completed, the resultant was filtered, washed and dried for 8 hours at 150? C., to obtain a molecular sieve precursor with a schematic chemical composition of 0.21F.Math.0.06Q.Math.SiO.sub.2.Math.1/3.7GeO.sub.2.Math.0.02H.sub.2O. The precursor was calcined in air at 550? C. for 6 hours to obtain the SCM-14 molecular sieve.

[0235] In the following examples, the procedure for producing SCM-14 molecular sieve in accordance with the method described in Example 2 of CN109081360A was as follows: the starting materials were fed as described in Example 1 of CN109081360A, and the material ratio (molar ratio) of the reaction mixture was changed as follows: SiO.sub.2/GeO.sub.2=3; template/SiO.sub.2=0.30; F/SiO.sub.2=0.30; H.sub.2O/SiO.sub.2=18; after being mixed evenly, the mixture was put into a stainless steel reaction kettle, aged for 1 hour in water bath at a temperature of 80? C., then crystallized for 1 day at a temperature of 110? C. under stirring, and further crystallized for 4 days at a temperature of 165? C. to obtain the SCM-14 molecular sieve.

[0236] In the following examples, the procedure for producing SCM-15 molecular sieve in accordance with the method described in Example 1 of CN109081359A was as follows:

[0237] 43.2 g of deionized water, 42.63 g of organic template 4-pyrrolidinylpyridine (98 wt %), 8.37 g of germanium oxide (99 wt %), 14.0 g of hydrofluoric acid (40 wt %), and 60.0 g of silica sol (SiO.sub.2, 40 wt %) were mixed uniformly to obtain a reaction mixture, wherein the material ratio (molar ratio) of the reaction mixture was: SiO.sub.2/GeO.sub.2=5; template/SiO.sub.2=0.70; F/SiO.sub.2=0.70; H.sub.2O/SiO.sub.2=12; after being mixed evenly, the mixture was put into a stainless steel reaction kettle, aged for 2 hours in water bath at a temperature of 80? C., and then crystallized for 5 days at a temperature of 170? C. under stirring. After the crystallization was completed, the resultant was filtered, washed and dried at 120? C. for 12 hours to obtain the SCM-15 molecular sieve.

Example II-1

[0238] An SCM-14 molecular sieve was synthesized in accordance with the method described in Example 1 of CN109081360A, and added to a dimethyl sulfoxide solution with a concentration of 0.01 mol/L hydrochloric acid (hydrochloric acid concentration of 30 wt %), with a solid-liquid mass ratio of 1:20, and the mixture was pretreated for 3 hours under stirring in a water bath at 60? C. The product was centrifuged and washed till the resulting solution had a pH of 7, dried overnight at 110? C., and then Sn-containing organometallic precursor (CH.sub.3).sub.2SnCl.sub.2 was added, the mass ratio of Sn (the theoretical amount of Sn in the organometallic precursor) to SCM-14 molecular sieve was 1:49, and the mixture was ground thoroughly in a mortar to obtain a uniformly dispersed mixture.

[0239] The product was dried in a drying oven at 110? C., and then calcined at 550? C. in air atmosphere for 5 hours to obtain an SnSCM-14 molecular sieve, of which the Uv-vis spectrum is shown in FIG. 15, which shows that heteroatom tin species is present in the molecular sieve framework in a four-coordination form, and the XPS spectrum is shown in FIG. 16, which indicates that Sn has successfully entered the framework of the SCM-14 molecular sieve; the pyridine desorption infrared diagram of the sample is shown in FIG. 17, and it can be seen from FIG. 17 that the molecular sieve has two acidic species, i.e. Bronst and Lewis acids. The sample has an atomic ratio Si/Ge=5.2 and an atomic ratio of Si/Sn=57, as measured by inductively coupled plasma atomic emission spectroscopy (ICP). The Lewis acid content is 210 ?mol.Math.g.sup.?1, and the ratio of Lewis/Bronst acid is 0.8, as calculated based on the pyridine desorption infrared diagramand, and the content of tin is 2.0 wt %, calculated as oxide. The XRD pattern of the resulted SnSCM-14 molecular sieve is shown in FIG. 18, and the uniform dispersion of tin species in the molecular sieve can be seen from FIG. 18.

Example II-2

[0240] An SCM-14 molecular sieve was synthesized in accordance with the method described in Example 1 of CN109081360A, and added to a dimethyl sulfoxide solution with a concentration of 0.02 mol/L hydrochloric acid (hydrochloric acid concentration of 30 wt %), with a solid-liquid mass ratio of 1:20, and the mixture was pretreated for 1 hour under stirring in a water bath at 70? C. The product was centrifuged and washed till the resulting solution had a pH of 7, dried overnight at 110? C., and then Sn-containing organometallic precursor (CH.sub.3).sub.2SnCl.sub.2 was added, the mass ratio of Sn (the theoretical amount of Sn in the organometallic precursor) to SCM-14 molecular sieve was 1:33, and the mixture was ground thoroughly in a mortar to obtain a uniformly dispersed mixture.

[0241] The product was dried in a drying oven at 110? C., and then calcined at 550? C. for 5 hours to obtain an SnSCM-14 molecular sieve, of which the Uv-vis spectrum is similar to that shown in FIG. 15, and the XPS spectrum is similar to that shown in FIG. 16, which indicates that Sn has successfully entered the framework of the SCM-14 molecular sieve; the pyridine desorption infrared diagram of the sample is similar to that shown in FIG. 17. The sample has a ratio of Si/Ge=6.1 (atomic ratio) and a ratio of Si/Sn=39 (atomic ratio), as measured by inductively coupled plasma atomic emission spectroscopy (ICP). The Lewis acid content is 284 ?mol.Math.g.sup.?1, and the Lewis/Bronst acid ratio is 1.0, as calculated based on the pyridine desorption infrared diagram, and the content of tin is 2.9 wt %, calculated as oxide.

Example II-3

[0242] An SCM-14 molecular sieve was synthesized in accordance with the method described in Example 1 of CN109081360A, the SCM-14 molecular sieve was added into a dimethyl sulfoxide solution with a concentration of 0.01 mol/L nitric acid, the solid-liquid mass ratio was 1:15, and the mixture was pretreated for 2 hours under stirring in a water bath at 40? C. The product was centrifuged and washed till the resulting solution had a pH of 7, dried overnight at 110? C., and then Sn-containing organometallic precursor (CH.sub.3).sub.2SnCl.sub.2 was added, the mass ratio of Sn (the theoretical amount of Sn in the organometallic precursor) to SCM-14 molecular sieve was 1:83, and the mixture was ground thoroughly in a mortar to obtain a uniformly dispersed mixture.

[0243] The product was dried in a drying oven at 110? C., and then calcined at 550? C. for 5 hours to obtain an SnSCM-14 molecular sieve, of which the Uv-vis spectrum is similar to that shown in FIG. 15, and the XPS spectrum is similar to that shown in FIG. 16, which indicates that Sn has successfully entered the framework of the SCM-14 molecular sieve; the pyridine desorption infrared diagram of the sample is similar to that shown in FIG. 17. The sample has a ratio of Si/Ge=5.4 (atomic ratio) and a ratio of Si/Sn=96 (atomic ratio), as measured by inductively coupled plasma atomic emission spectroscopy (ICP). The Lewis acid content is 124 ?mol.Math.g.sup.?1, the ratio of Lewis/Bronst acid is 0.6, as calculated based on the pyridine desorption infrared diagram, and the content of tin is 1.2 wt %, calculated as oxide.

Example II-4

[0244] An SCM-14 molecular sieve was synthesized in accordance with the method described in Example 2 of CN109081360A, the SCM-14 molecular sieve was added into a dimethyl sulfoxide solution with a concentration of 0.008 mol/L oxalic acid, the solid-liquid mass ratio was 1:15, and the mixture was pretreated for 5 hours under stirring in a water bath at 60? C. The product was centrifuged and washed till the resulting solution had a pH of 7, dried overnight at 110? C., and then Sn-containing organometallic precursor (CH.sub.3).sub.2SnCl.sub.2 was added, the mass ratio of Sn (the theoretical amount of Sn in the organometallic precursor) to SCM-14 molecular sieve was 1:49, and the mixture was ground thoroughly in a mortar to obtain a uniformly dispersed mixture.

[0245] The product was dried in a drying oven at 110? C., and then calcined at 550? C. for 5 hours to obtain an SnSCM-14 molecular sieve, of which the Uv-vis spectrum is similar to that shown in FIG. 15, and the XPS spectrum is similar to that shown in FIG. 16, which indicates that Sn has successfully entered the framework of the SCM-14 molecular sieve; the pyridine desorption infrared diagram of the sample is similar to that shown in FIG. 17. The sample has a ratio of Si/Ge=3.5 (atomic ratio) and a ratio of Si/Sn=61 (atomic ratio), as measured by inductively coupled plasma atomic emission spectroscopy (ICP). The Lewis acid content is 187 ?mol.Math.g.sup.?1, and the ratio of Lewis/Bronst acid is 0.8, as calculated based on the pyridine desorption infrared diagram, and the content of tin is 2.0 wt %, calculated as oxide.

Example II-5

[0246] An SCM-14 molecular sieve was synthesized in accordance with the method described in Example 2 of CN109081360A, the SCM-14 molecular sieve was added into a dimethyl sulfoxide solution with a concentration of 0.02 mol/L oxalic acid, the solid-liquid mass ratio was 1:20, and the mixture was pretreated for 3 hours under stirring in a water bath at 70? C. The product was centrifuged and washed till the resulting solution had a pH of 7, dried overnight at 110? C., and then Sn-containing organometallic precursor (CH.sub.3).sub.2SnCl.sub.2 was added, the mass ratio of Sn (the theoretical amount of Sn in the organometallic precursor) to SCM-14 molecular sieve was 1:60, and the mixture was ground thoroughly in a mortar to obtain a uniformly dispersed mixture.

[0247] The product was dried in a drying oven at 110? C., and then calcined at 550? C. for 5 hours to obtain an SnSCM-14 molecular sieve, of which the Uv-vis spectrum is similar to that shown in FIG. 15, and the XPS spectrum is similar to that shown in FIG. 16, which indicates that Sn has successfully entered the framework of the SCM-14 molecular sieve; the pyridine desorption infrared diagram of the sample is similar to that shown in FIG. 17. The sample has a ratio of Si/Ge=7.4 (atomic ratio) and a ratio of Si/Sn=85 (atomic ratio), as measured by inductively coupled plasma atomic emission spectroscopy (ICP). The Lewis acid content is 153 ?mol.Math.g.sup.?1, and the ratio of Lewis/Bronst acid is 0.7, as calculated based on the pyridine desorption infrared diagram, and the content of tin is 1.6 wt %, calculated as oxide.

Example II-6

[0248] An SCM-14 molecular sieve was synthesized in accordance with the method described in Example 1 of CN109081360A, the SCM-14 molecular sieve was added into a dimethyl sulfoxide solution with a concentration of 0.01 mol/L acetic acid, the solid-liquid mass ratio was 1:20, and the mixture was pretreated for 6 hours under stirring in a water bath at 60? C. The product was centrifuged and washed the resulting solution had a pH of 7, dried overnight at 110? C., then Zr-containing organometallic precursor Cp.sub.2ZrCl.sub.2 was added, the mass ratio of Zr (theoretical amount of Zr in the organometallic precursor) to SCM-14 molecular sieve was 1:49, and the mixture was ground thoroughly in a mortar to obtain a uniformly dispersed mixture.

[0249] The product was dried in a drying oven at 110? C., and then calcined at 550? C. for 5 hours to obtain the ZrSCM-14 molecular sieve, wherein the Uv-vis spectrum of the sample is shown in FIG. 19, which shows that the heteroatom zirconium species is present in the molecular sieve framework in a four-coordination form, and its XPS spectrum is shown in FIG. 20, which indicates that Zr has successfully entered the framework of the SCM-14 molecular sieve; the pyridine desorption infrared diagram of the sample is similar to that shown in FIG. 17. The sample has a ratio of Si/Ge=4.3 (atomic ratio) and a ratio of Si/Zr=44 (atomic ratio), as measured by inductively coupled plasma atomic emission spectroscopy (ICP). The Lewis acid content is 237 ?mol.Math.g.sup.?1, the ratio of Lewis/Bronst acid is 0.9, as calculated based on the pyridine desorption infrared diagram, and the content of zirconium was 2.0 wt %, calculated as oxide.

Example II-7

[0250] An SCM-14 molecular sieve was synthesized in accordance with the method described in Example 2 of CN109081360A, the SCM-14 molecular sieve was added into a dimethyl sulfoxide solution with a concentration of 0.04 mol/L acetic acid, the solid-liquid mass ratio was 1:20, and the mixture was pretreated for 3 hours under stirring in a water bath at 50? C. The product was centrifuged and washed till the resulting solution had a pH of 7, dried overnight at 110? C., then Zr-containing organometallic precursor Cp.sub.2ZrCl.sub.2 was added, the mass ratio of Zr (the theoretical amount of Zr in the organometallic precursor) to the SCM-14 molecular sieve was 1:35, and the mixture was ground thoroughly in a mortar to obtain a uniformly dispersed mixture.

[0251] The product was dried in a drying oven at 110? C., and then calcined at 550? C. for 5 hours to obtain the ZrSCM-14 molecular sieve, of which the Uv-vis spectrum is similar to that shown in FIG. 19, and the XPS spectrum is similar to that shown in FIG. 20, which indicates that Zr has successfully entered the framework of the SCM-14 molecular sieve; the pyridine desorption infrared diagram of the sample is similar to that shown in FIG. 17. The sample has a ratio of Si/Ge=7.9 (atomic ratio) and a ratio of Si/Zr=33 (atomic ratio), as measured by inductively coupled plasma atomic emission spectroscopy (ICP). The Lewis acid content was 292 ?mol.Math.g.sup.?1, and the ratio of Lewis/Bronst acid is 1.1, as calculated based on the pyridine desorption infrared diagramand, and the content of zirconium was 2.8 wt %, calculated as oxide.

Example II-8

[0252] An SCM-15 molecular sieve was synthesized in accordance with the method described in Example 1 of CN109081359A, the SCM-15 molecular sieve was added into a dimethyl sulfoxide solution with a concentration of 0.01 mol/L hydrochloric acid, the solid-liquid mass ratio was 1:15, and the mixture was pretreated for 3 hours under stirring in a water bath at 70? C. The product was centrifuged and washed till the resulting solution had a pH of 7, dried overnight at 110? C., and then Sn-containing organometallic precursor (CH.sub.3).sub.2SnCl.sub.2 was added, the mass ratio of Sn (the theoretical amount of Sn in the organometallic precursor) to SCM-15 molecular sieve was 1:30, and the mixture was ground thoroughly in a mortar to obtain a uniformly dispersed mixture.

[0253] The product was dried in a drying oven at 110? C., and then calcined at 550? C. for 5 hours to obtain an SnSCM-15 molecular sieve, of which the Uv-vis spectrum is similar to that shown in FIG. 15, and the XPS spectrum is similar to that shown in FIG. 16, which indicates that Sn has successfully entered the framework of the SCM-15 molecular sieve; the pyridine desorption infrared diagram of the sample is similar to that shown in FIG. 17. The sample has a ratio of Si/Ge=8.7 (atomic ratio) and a ratio of Si/Sn=34 (atomic ratio), as measured by inductively coupled plasma atomic emission spectroscopy (ICP). The Lewis acid content was 277 ?mol.Math.g.sup.?1, and the ratio of Lewis/Bronst acid is 2.1, as calculated based on the pyridine desorption infrared diagram, and the content of tin is 3.2 wt %, calculated as oxide.

Example II-9

[0254] An SCM-15 molecular sieve was synthesized in accordance with the method described in Example 1 of CN109081359A, the SCM-15 molecular sieve was added into a dimethyl sulfoxide solution with a concentration of 0.02 mol/L oxalic acid, the solid-liquid mass ratio was 1:20, and the mixture was pretreated for 2 hours under stirring in a water bath at 80? C. The product was centrifuged and washed till the resulting solution had a pH of 7, dried overnight at 110? C., then Zr-containing organometallic precursor Cp.sub.2ZrCl.sub.2 was added, the mass ratio of Zr (the theoretical amount of Zr in the organometallic precursor) to the SCM-15 molecular sieve was 1:30, and the mixture was ground thoroughly in a mortar to obtain a uniformly dispersed mixture.

[0255] The product was dried in a drying oven at 110? C., and then calcined at 550? C. for 5 hours to obtain a ZrSCM-15 molecular sieve, of which the Uv-vis spectrum is similar to that shown in FIG. 19, and the XPS spectrum is similar to that shown in FIG. 20, which indicates that Zr has successfully entered the framework of the SCM-15 molecular sieve; the pyridine desorption infrared diagram of the sample is similar to that shown in FIG. 17. The sample has a ratio of Si/Ge=7.7 (atomic ratio) and a ratio of Si/Zr=30 (atomic ratio), as measured by inductively coupled plasma atomic emission spectroscopy (ICP). The Lewis acid content was 284 ?molog?1, and the ratio of Lewis/Bronst acid is 1.8, as calculated based on the pyridine desorption infrared diagram, and the content of zirconium was 3.1%, calculated as oxide.

Example II-10

[0256] An SCM-14 molecular sieve was synthesized in accordance with the method described in Example 1 of CN109081360A, and added to a dimethylsulfoxide solution with a concentration of 0.02 mol/L hydrochloric acid (hydrochloric acid concentration 30 wt %), the solid-liquid mass ratio was 1:20, and the mixture was pretreated for 1 hour under stirring in a water bath at 70? C. The product was centrifuged and washed till the resulting solution had a pH of 7, dried overnight at 110? ? C., and then Sn-containing organometallic precursor (CH.sub.3).sub.2SnCl.sub.2 was added, the mass ratio of Sn (the theoretical amount of Sn in the organometallic precursor) to SCM-14 molecular sieve was 1:160, and the mixture was ground thoroughly in a mortar to obtain a uniformly dispersed mixture.

[0257] The product was dried in a drying oven at 110? C., and then calcined at 550? C. for 5 hours to obtain an SnSCM-14 molecular sieve, of which the Uv-vis spectrum is similar to that shown in FIG. 15, and the XPS spectrum is similar to that shown in FIG. 16, which indicates that Sn has successfully entered the framework of the SCM-14 molecular sieve; the pyridine desorption infrared diagram of the sample is similar to that shown in FIG. 17. The sample has a ratio of Si/Ge=5.9 (atomic ratio) and a ratio of Si/Sn=190 (atomic ratio), as measured by inductively coupled plasma atomic emission spectroscopy (ICP). The Lewis acid content is 83 ?mol.Math.g.sup.?1, the ratio of Lewis/Bronst acid is 0.4, as calculated based on the pyridine desorption infrared diagram, and the content of tin is 0.6 wt %, calculated as oxide.

Examples II-11 to II-20

[0258] Methylfuran was used as a substrate and n-heptane was used as a reaction solvent, 1.0 g of the A-SCM-X molecular sieves of Examples II-1 to II-10, 1.0 g of methylfuran, and 30 g of n-heptane were charged into a high-pressure reactor equipped with a stirrer, and 4.0 MPa of dilute ethylene (15 (v) %, the remainder being nitrogen) was introduced. The reactor was heated to a preset temperature using a temperature programming heating sleeve, then stirred by magnetic stirring. The reaction was carried out for 24 hours at a temperature of 260? C., and the reaction solution was analyzed to obtain the conversion rate of methylfuran and the selectivity of the target product toluene, which are shown in Table 1.

TABLE-US-00008 TABLE 1 Evaluation results of catalysts of Examples II-1 to II-10 Atomic Atomic ratio Content Lewis acid Ratio of Methylfuran Toluene Example Source of ratio of of Si/A of A content Lewis/Bronst conversion Selectivity II- catalyst Si/Ge (Sn or Zr) (wt %) (?mol/g) acid (%) (%) 11 Example 5.2 57 2.0 210 0.8 90 96 II-1 12 Example 6.1 39 2.9 284 1.0 91 95 II-2 13 Example 5.4 96 1.2 104 0.6 88 96 II-3 14 Example 3.5 61 2.0 187 0.8 90 95 II-4 15 Example 7.4 85 1.6 153 0.7 86 94 II-5 16 Example 4.3 44 2.0 237 0.9 88 94 II-6 17 Example 7.9 33 2.8 292 1.1 93 97 II-7 18 Example 8.7 34 3.2 277 2.1 95 95 II-8 19 Example 7.7 30 3.1 284 1.8 92 93 II-9 20 Example 5.9 190 0.6 83 0.4 80 92 II-10

[0259] If the data in the table was inconsistent with the examples, the examples shall control. The same applies below.

Example II-21

[0260] In this example, n-heptane was used as a reaction solvent, the mass ratio of n-heptane to methylfuran was 20, the mass ratio of methylfuran to catalyst was 0.8, the reaction temperature was 240? C., and the reaction time was 20 h. 1.0 g of the SnSCM-14 molecular sieve of the above Example II-1, 0.8 g of methylfuran and 16 g of n-heptane were charged into a high-pressure reactor equipped with a stirrer, and 2.0 MPa of dilute ethylene (15 (v) %, the remainder being nitrogen) was introduced. The reactor was heated to a preset temperature using a temperature programming heating sleeve, then stirred by magnetic stirring. The reaction was carried out for 20 hours at a temperature of 240? C., and the conversion rate of methylfuran was 91% and the selectivity of toluene was 94%, as calculated based on gas phase analysis of the reaction solution.

Example II-22

[0261] In this example, n-heptane was used as a reaction solvent, the mass ratio of n-heptane to methylfuran was 20, the mass ratio of methylfuran to catalyst was 2.0, the reaction temperature was 260? C., and the reaction time was 30 h. 1.0 g of the SnSCM-14 molecular sieve of the above Example II-1, 2.0 g of methylfuran and 40 g of n-heptane were charged into a high-pressure reactor equipped with a stirrer, and 5.0 MPa of dilute ethylene (15 (v) %, the remainder being nitrogen) was introduced. The reactor was heated to a preset temperature using a temperature programming heating sleeve, then stirred by magnetic stirring. The reaction was carried out for 30 hours at a temperature of 260? C., and the conversion rate of methylfuran was 87% and the selectivity of toluene was 96%, as calculated based on gas phase analysis of the reaction solution.

Example II-23

[0262] In this example, n-octane was used as a reaction solvent, the mass ratio of n-octane to methylfuran was 30, the mass ratio of methylfuran to catalyst was 1.0, the reaction temperature was 250? C., and the reaction time was 18 h. 1.0 g of the SnSCM-14 molecular sieve of the above Example II-1, 1.0 g of methylfuran and 30 g of n-octane were charged into a high-pressure reactor equipped with a stirrer, and 4.0 MPa of dilute ethylene (15 (v) %, the remainder being nitrogen) was introduced. The reactor was heated to a preset temperature using a temperature programming heating sleeve, then stirred by magnetic stirring. The reaction was carried out for 18 hours at a temperature of 250? C., and the conversion rate of methylfuran was 89% and the selectivity of toluene was 94%, as calculated based on gas phase analysis of the reaction solution.

Example II-24

[0263] In this example, n-octane was used as a reaction solvent, the mass ratio of n-octane to methylfuran was 40, the mass ratio of methylfuran to catalyst was 1.2, the reaction temperature was 240? C., and the reaction time was 25 hours. 1.0 g of the SnSCM-14 molecular sieve of the above Example II-1, 1.2 g of methylfuran and 48 g of n-octane were charged into a high-pressure reactor equipped with a stirrer, and 3.0 MPa of dilute ethylene (15 (v) %, the remainder being nitrogen) was introduced. The reactor was heated to a preset temperature using a temperature programming heating sleeve, then stirred by magnetic stirring. The reaction was carried out for 25 hours at a temperature of 240? C., and the conversion rate of methylfuran is 86% and the selectivity of toluene is 95%, as calculated based on gas phase analysis of the reaction solution.

Example II-25

[0264] In this example, tetrahydrofuran was used as a reaction solvent, the mass ratio of tetrahydrofuran to methylfuran was 20, the mass ratio of methylfuran to catalyst was 2, the reaction temperature was 260? C., and the reaction time was 24 hours. 1.0 g of the SnSCM-14 molecular sieve of the above Example II-1, 2.0 g of methylfuran and 40 g of tetrahydrofuran were charged into a high-pressure reactor equipped with a stirrer, and 3.0 MPa of dilute ethylene (15 (v) %, the remainder being nitrogen) was introduced. The reactor was heated to a preset temperature using a temperature programming heating sleeve, then stirred by magnetic stirring. The reaction was carried out for 24 hours at a temperature of 260? C., and the conversion rate of methylfuran was 90% and the selectivity of toluene was 93%, as calculated based on gas phase analysis of the reaction solution.

Example II-26

[0265] In this example, tetrahydrofuran was used as a reaction solvent, the mass ratio of tetrahydrofuran to methylfuran was 25, the mass ratio of methylfuran to catalyst was 1.5, the reaction temperature was 250? C., and the reaction time was 28 hours. 1.0 g of the SnSCM-14 molecular sieve of the above Example II-1, 1.5 g of methylfuran and 37.5 g of tetrahydrofuran were charged into a high-pressure reactor equipped with a stirrer, and 2.0 MPa of dilute ethylene (15 (v) %, the remainder being nitrogen) was introduced. The reactor was heated to a preset temperature using a temperature programming heating sleeve, then stirred by magnetic stirring. The reaction was carried out for 28 h at a temperature of 250? C., and the conversion rate of methylfuran was 86% and the selectivity of toluene was 94%, as calculated based on gas phase analysis of the reaction solution.

Example II-27

[0266] In this example, methyl isobutyl ketone was used as a reaction solvent, the mass ratio of methyl isobutyl ketone to methylfuran was 20, the mass ratio of methylfuran to catalyst was 3, the reaction temperature was 260? C., and the reaction time was 48 hours. 1.0 g of the SnSCM-14 molecular sieve of the above Example II-1, 3.0 g of methylfuran and 60.0 g of methyl isobutyl ketone were charged into a high-pressure reactor equipped with a stirrer, and 5.0 MPa of dilute ethylene (15 (v) %, the remainder being nitrogen) was introduced. The reactor was heated to a preset temperature using a temperature programming heating sleeve, then stirred by magnetic stirring. The reaction was carried out for 48 hours at a temperature of 260? C., and the conversion rate of methylfuran was 85% and the selectivity of toluene was 95%, as calculated based on gas phase analysis of the reaction solution.

Example II-28

[0267] In this example, methyl isobutyl ketone was used as a reaction solvent, the mass ratio of methyl isobutyl ketone to methylfuran was 40, the mass ratio of methylfuran to catalyst was 1, the reaction temperature was 250? C., and the reaction time was 20 hours. 1.0 g of the SnSCM-14 molecular sieve of the above Example II-1, 1.0 g of methylfuran and 40.0 g of methyl isobutyl ketone were charged into a high-pressure reactor equipped with a stirrer, and 2.0 MPa of dilute ethylene (15 (v) %, the remainder being nitrogen) was introduced. The reactor was heated to a preset temperature using a temperature programming heating sleeve, then stirred by magnetic stirring. The reaction was carried out for 20 hours at a temperature of 250? C., and the conversion rate of methylfuran was 89% and the selectivity of toluene was 94%, as calculated based on gas phase analysis of the reaction solution.

Example II-29

[0268] In this example, cyclohexane was used as a reaction solvent, the mass ratio of cyclohexane to methylfuran was 30, the mass ratio of methylfuran to catalyst was 2, the reaction temperature was 260? C., and the reaction time was 30 hours. 1.0 g of the SnSCM-14 molecular sieve of the above Example II-1, 2.0 g of methylfuran and 60.0 g of cyclohexane were charged into a high-pressure reactor equipped with a stirrer, and 4.0 MPa of dilute ethylene (15 (v) %, the remainder being nitrogen) was introduced. The reactor was heated to a preset temperature using a temperature programming heating sleeve, then stirred by magnetic stirring. The reaction was carried out for 30 hours at a temperature of 260? C., and the conversion rate of methylfuran was 92% and the selectivity of toluene was 95%, as calculated based on gas phase analysis of the reaction solution.

Example II-30

[0269] In this example, cyclohexane was used as a reaction solvent, the mass ratio of cyclohexane to methylfuran was 30, the mass ratio of methylfuran to catalyst was 1.4, the reaction temperature was 250? C., and the reaction time was 48 hours. 1.0 g of the SnSCM-14 molecular sieve of the above Example II-1, 1.4 g of methylfuran and 42.0 g of cyclohexane were charged into a high-pressure reactor equipped with a stirrer, and 3.0 MPa of dilute ethylene (15 (v) %, the remainder being nitrogen) was introduced. The reactor was heated to a preset temperature using a temperature programming heating sleeve, then stirred by magnetic stirring. The reaction was carried out for 48 hours at a temperature of 250? C., and the conversion rate of methylfuran was 93% and the selectivity of toluene was 95%, as calculated based on gas phase analysis of the reaction solution.

Example II-31

[0270] In this example, n-heptane was used as a reaction solvent, the mass ratio of n-heptane to methylfuran was 20, the mass ratio of methylfuran to catalyst was 0.25, the reaction temperature was 240? C., and the reaction time was 20 h. 3.2 g of the SnSCM-14 molecular sieve of the above Example II-1, 0.8 g of methylfuran and 16 g of n-heptane were charged into a high-pressure reactor equipped with a stirrer, and 2.0 MPa of dilute ethylene (15 (v) %, the remainder being nitrogen) was introduced. The reactor was heated to a preset temperature using a temperature programming heating sleeve, then stirred by magnetic stirring. The reaction was carried out for 20 hours at a temperature of 240? C., and the conversion rate of methylfuran was 95% and the selectivity of toluene was 90%, as calculated based on gas phase analysis of the reaction solution.

[0271] To more intuitively describe the reaction conditions and results of Examples II-21 to II-31 above, the operation parameters and results are listed in Table 2.

TABLE-US-00009 TABLE 2 Catalysis results of Examples II-21 to II-31 Mass ratio Pressure Mass ratio to MF to Reaction Reaction of dilute MF Toluene Example of MF to organic temperature time ethylene conversion Selectivity II- Reaction solvent catalyst solvent (? C.) (h) (MPa) (%) (%) 21 N-heptane 0.8 20 240 20 2 91 94 22 N-heptane 2.0 20 260 30 5 87 96 23 N-octane 1 30 250 18 4 89 94 24 N-octane 1.2 40 240 25 3 86 95 25 Tetrahydrofuran 2 20 260 24 3 90 93 (THF) 26 Tetrahydrofuran 1.5 25 250 28 2 86 94 (THF) 27 Methyl isobutyl 3 20 260 48 5 85 95 ketone 28 Methyl isobutyl 1 40 250 20 2 89 94 ketone 29 Cyclohexane 2 30 260 30 4 92 95 30 Cyclohexane 1.4 30 250 48 3 93 95 31 N-heptane 0.25 20 240 20 2 95 90

Example II-32

[0272] Methylfuran was used as a substrate and n-heptane was used as a reaction solvent, 1.0 g of the SnSCM-14 molecular sieve of the above Example II-1, 1.0 g of methylfuran and 30 g of n-heptane were charged into a high-pressure reactor equipped with a stirrer, and 4.0 MPa of dilute ethylene (15 (v) %, the remainder being nitrogen) was introduced. The reactor was heated to a preset temperature using a temperature programming heating sleeve, then stirred by magnetic stirring. The reaction was carried out for 24 hours at a temperature of 260? C., and the reaction solution was analyzed to determine the conversion rate of methylfuran and the selectivity of the target product toluene. The spent catalyst was washed, dried and then used in the next reaction, and 4 cycles of reactions were conducted, and the results are shown in Table 3. The results show that the DMF conversion rate remained above 86% after 4 cycles of reactions, and the pX selectivity remained at 94%, indicating that the catalyst of the present application has good cycling stability.

TABLE-US-00010 TABLE 3 Methylfuran conversion and toluene selectivity obtained using Sn-SCM-14 molecular sieve under cycling conditions Number of cycles Methylfuran conversion/% Toluene selectivity/% 1 90 96 2 89 96 3 88 95 4 86 94

Comparative Example II-1

[0273] An SCM-14 molecular sieve was synthesized in accordance with the method described in Example II-1 of CN109081360A, methylfuran was used as a substrate, n-heptane was used as a reaction solvent, 1.0 g of the above SCM-14 molecular sieve, 1.0 g of methylfuran and 30 g of n-heptane were charged into a high-pressure reactor equipped with a stirrer, and 4.0 MPa of dilute ethylene (15 (v) %, the remainder being nitrogen) was introduced. The reactor was heated to a preset temperature using a temperature programming heating sleeve, then stirred by magnetic stirring. The reaction was carried out for 24 hours at a temperature of 260? C., and the reaction solution was analyzed, giving a conversion rate of methylfuran of 52% and a selectivity of target product toluene of 83%.