CN107469844B

CN107469844B - Catalyst with deoxidation and hydrogenation functions, preparation method thereof and deoxidation and hydrogenation method of carbonyl compound

Info

Publication number: CN107469844B
Application number: CN201610403020.2A
Authority: CN
Inventors: 郭勇; 刘金胜; 蔺建民; 李宝石; 高岚
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2016-06-08
Filing date: 2016-06-08
Publication date: 2020-08-07
Anticipated expiration: 2036-06-08
Also published as: CN107469844A

Abstract

The invention relates to the field of catalysts, and discloses a catalyst with a deoxidation and hydrogenation function, a preparation method thereof and a deoxidation and hydrogenation method of a carbonyl compound. The catalyst comprises a carrier and palladium loaded on the carrier, wherein the carrier is a niobium phosphate porous material and comprises niobium, phosphorus and oxygen elements, and the pore volume of the carrier is 0.3cm³More than g, the average pore diameter is more than 9nm, the pore diameter distribution is 3-60nm, and the proportion of the pore diameter in the range of 5.6-15.8nm in the total pore diameter distribution is more than or equal to 80 percent. The invention also discloses a method for preparing the catalyst with the deoxidation and hydrogenation functions, which comprises the step of loading palladium on the niobium phosphate porous material. The invention also discloses a method for deoxidizing and hydrogenating the carbonyl compound, which comprises the step of contacting the raw material containing the carbonyl compound with the catalyst and/or the catalyst prepared by the method. The catalyst of the invention can convert carbonyl compounds into liquid oxygen-containing substances through one-step hydrogenation, and has better selectivity of the oxygen-containing compounds.

Description

Catalyst with deoxidation and hydrogenation functions, preparation method thereof and deoxidation and hydrogenation method of carbonyl compound

Technical Field

The invention relates to the field of catalysts, in particular to a catalyst with a deoxidation and hydrogenation function, a preparation method thereof and a deoxidation and hydrogenation method of a carbonyl compound.

Background

With the increasing shortage of fossil resources and the rapid increase of human energy resources, the development and utilization of renewable resources are greatly stimulated. Biomass resources are the only carbon-containing resource among renewable resources, and their main components are cellulose, hemicellulose and lignin. These components can be hydrolyzed and hydrogenated to produce glucose, xylose and corresponding polyol.

In recent years, monosaccharides and their polyols have become important platform compounds for the conversion and utilization of biomass resources. Most of these conversions are carried out under aqueous conditions. American scientists have reported the conversion of sorbitol to alkanes by catalyst hydrogenation under aqueous conditions using aluminum silicate supported platinum catalysts. CN102389832B discloses a catalyst with HZSM-5 and MCM-41 as carriers and nickel supported and application thereof in sorbitol hydrogenation reaction. However, the catalysts in the above reports generally produce linear paraffins when catalyzing glucose, which have a low octane number. Therefore, how to prepare fuel with high octane value by using glucose is important.

Disclosure of Invention

The invention aims to overcome the defect of low activity of the existing catalyst and provide a catalyst with excellent deoxidation and hydrogenation functions, a preparation method thereof and a deoxidation and hydrogenation method of carbonyl compounds.

In order to achieve the above object, in a first aspect, the present invention provides a catalyst with a deoxygenation and hydrogenation function, the catalyst comprising a carrier and palladium supported on the carrier, wherein the carrier is a niobium phosphate porous material, and the niobium phosphate porous material comprises: niobium element, phosphorus element and oxygen element, wherein the pore volume of the niobium phosphate porous material is 0.3cm³More than g, the average pore diameter is more than 9nm, the pore diameter distribution is 3-60nm under the nitrogen isothermal adsorption and desorption test, and the proportion of the pore diameter in the range of 5.6-15.8nm in the total pore diameter distribution is more than or equal to 80 percent.

In a second aspect, the present invention provides a method for preparing a catalyst having a deoxygenating and hydrogenating function, the method comprising: supporting palladium on a carrier, wherein the carrier is a niobium phosphate porous material, and the niobium phosphate porous material comprises: niobium element, phosphorus element and oxygen element, whereinThe pore volume of the niobium phosphate porous material is 0.3cm³More than g, the average pore diameter is more than 9nm, the pore diameter distribution is 3-60nm under the nitrogen isothermal adsorption and desorption test, and the proportion of the pore diameter in the range of 5.6-15.8nm in the total pore diameter distribution is more than or equal to 80 percent.

In a third aspect, the present invention provides a process for the deoxygenation and hydrogenation of a carbonyl compound, the process comprising: contacting a feedstock containing carbonyl compounds with a catalyst, which is a catalyst of the first aspect and/or a catalyst produced by the process of the second aspect, under deoxygenated hydrogenation conditions comprising: the temperature is 100-140 ℃, and the time is 2-120 h.

The catalyst provided by the invention can be used for converting carbonyl compounds into liquid oxygen-containing substances through one-step hydrogenation, and has better selectivity of the oxygen-containing compounds. Moreover, when the glucose is catalyzed, the obtained oxygen-containing compound only retains one oxygen atom, and the oxygen-containing substances containing one oxygen atom have higher octane number and are potential gasoline blending components.

Additional features and advantages of the invention will be set forth in the detailed description which follows.

Drawings

The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:

FIG. 1 is a graph of nitrogen sorption and desorption curves for a niobium phosphate porous material used in accordance with an embodiment of the present invention;

FIG. 2 is a Transmission Electron Microscope (TEM) photograph of a niobium phosphate pore material used in an embodiment according to the present invention;

FIG. 3 is an X-ray diffraction (XRD) spectrum of a niobium phosphate porous material used in accordance with an embodiment of the present invention;

FIG. 4 is a graph of high performance liquid chromatography analysis results of deoxygenated hydrogenated product according to one embodiment of the present invention;

FIG. 5 is a graph of the results of high performance liquid chromatography analysis of deoxygenated hydrogenated product in accordance with another embodiment of the present invention.

Detailed Description

The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

In the present invention, the term "octane number" is used, unless otherwise specified, to refer to the research octane number RON, the higher the value, the better the fuel antiknock property.

In a first aspect, the present invention provides a catalyst with a deoxygenation and hydrogenation function, which comprises a carrier and palladium supported on the carrier, wherein the carrier is a niobium phosphate porous material, and the niobium phosphate porous material comprises: niobium element, phosphorus element and oxygen element, wherein the pore volume of the niobium phosphate porous material is 0.3cm³More than g, the average pore diameter is more than 9nm, the pore diameter distribution is 3-60nm under the nitrogen isothermal adsorption and desorption test, and the proportion of the pore diameter in the range of 5.6-15.8nm in the total pore diameter distribution is more than or equal to 80 percent.

The pore volume of the niobium phosphate pore material refers to the pore volume in the pore material, and the average pore diameter refers to the average pore diameter, which is well known to those skilled in the art and will not be described herein.

Preferably, the pore volume of the niobium phosphate porous material is 0.3-0.5cm³/g。

Preferably, the average pore diameter of the niobium phosphate porous material is 9-10.6 nm.

Preferably, the ratio of the pore diameter of the niobium phosphate porous material in the range of 5.6-15.8nm to the total pore size distribution under the nitrogen isothermal adsorption and desorption test is 80-95%, and the ratio of the pore diameter in the range of 5.6-15.8nm to the total pore size distribution can be calculated according to the following formula, wherein the number of the pore diameters in the range of 5.6-15.8 nm/the number of the pore diameters in the range of 3-60nm is × 100%.

Preferably, the specific surface area of the niobium phosphate porous material is 140-300m²(ii) in terms of/g. Wherein, the specific surface area of the niobium phosphate porous material refers to the BET total specific surface area, and can be measured according to the ASTM D4222-98 standard method.

According to a preferred embodiment of the present invention, the molar ratio of the niobium element to the phosphorus element in the niobium phosphate porous material is 1: 0.4-2.6, and more preferably, the molar ratio of the niobium element to the phosphorus element in the niobium phosphate porous material is 1: 0.45-1.5 (e.g., 1:0.45, 1:0.6, 1:0.8, 1:1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, or any value therebetween).

The method for preparing the niobium phosphate porous material is not particularly required, and the niobium phosphate porous material with the structure can be prepared.

Therefore, the preparation method of the niobium phosphate porous material used in the invention comprises the following steps: in the presence of a solvent, mixing soluble niobium salt, a phosphorus source and a template agent, then carrying out ultrasonic treatment, and roasting a solid phase obtained after the ultrasonic treatment.

In the method for preparing the niobium phosphate porous material, in the case where no reverse explanation is made, the soluble niobium salt in the present invention is used in terms of niobium element, and the phosphorus source is used in terms of phosphorus element.

In the method for preparing the niobium phosphate porous material, the dosage ratio of the soluble niobium salt and the phosphorus source can be determined according to the content of the niobium element and the phosphorus element in the niobium phosphate porous material. According to a preferred embodiment, the molar ratio of the soluble niobium salt to the phosphorus source is 1: 0.4-2.6, more preferably 1: 0.45-1.5 (e.g., 1:0.45, 1:0.6, 1:0.8, 1:1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, or any value therebetween).

Preferably, the amount of the template is 3 to 120g (e.g., 4g, 15g, 25g, 35g, 45g, 55g, 65g, 75g, 85g, 95g, 105g, 115g, or any value therebetween) per mole of the soluble niobium salt (as niobium element), and more preferably 35 to 75 g.

Preferably, the solvent is used in an amount of 2 to 20L, more preferably 5 to 10L, per mole of soluble niobium salt.

In the method for preparing the niobium phosphate porous material, the soluble niobium salt can be various soluble substances which are commonly used in the field and can provide niobium element, and can be organic soluble niobium salt or inorganic soluble niobium salt. Preferably, the soluble niobium salt is at least one of niobium pentachloride, niobium oxalate (see, e.g., CN1935772A or CN1911892A), niobium malate, niobium tartrate (see, e.g., CN102951683A), and niobium citrate.

According to a preferred embodiment of the method for producing a niobium phosphate porous material, the soluble niobium salt is niobium (water-soluble) citrate and the niobium citrate is produced by the following method (in other words, the method further includes the step of producing niobium citrate by the following method):

the niobium source is contacted with hydrofluoric acid for reaction until the reaction system becomes clear; the obtained clarified solution is brought into contact with an alkaline substance, and the solid phase obtained after the contact is mixed with citric acid in the presence of a solvent until the mixed system becomes clear, wherein the amount of citric acid used is 1.7 to 10mol (1.7mol, 1.8mol, 1.9mol, 2mol, 2.5mol, 3mol, 3.5mol, 4mol, 4.5mol, 5mol, 5.5mol, 6mol, 6.5mol, 7mol, 7.5mol, 8mol, 8.5mol, 9mol, 9.5mol, 10mol or any value therebetween, preferably 1.9 to 5mol) per mol of niobium element.

In the above method for producing niobium citrate, the amount of hydrofluoric acid to be used is not particularly limited as long as it can sufficiently dissolve the niobium source, and the amount of hydrofluoric acid to be used is preferably 5 to 15mol in terms of hydrogen fluoride per mol of niobium element, and the content of hydrogen fluoride in hydrofluoric acid is usually 2 to 15 mol/L.

In the above method for producing niobium citrate, the amount of the basic substance to be used is not particularly limited as long as it can form a precipitate after contacting with the clear liquid, and the amount of the basic substance to be used is preferably 5 to 50mol, more preferably 9 to 25 mol/L, per mol of niobium element.

Preferably, the concentration of niobium element in the mixed system is 0.01 to 3 mol/L (e.g., 0.01 mol/L, 0.05 mol/L0, 0.09 mol/L1, 0.1 mol/L2, 0.15 mol/L3, 0.2 mol/L, 0.25 mol/L, 0.3 mol/L, 0.5 mol/L, 1 mol/L, 2 mol/L, 3 mol/L, or any value therebetween), more preferably 0.05 to 1.5 mol/L.

In the above-mentioned method for preparing Niobium citrate, the Niobium source may be various Niobium sources (i.e., substances capable of providing Niobium element) commonly used in the art, preferably, the Niobium source is at least one of Niobium oxide, niobate, fluoroniobate and niobic acid, more preferably at least one of Niobium pentoxide, potassium niobate, sodium niobate, calcium niobate, potassium fluoroniobate (i.e., potassium heptafluoroniobate) and sodium fluoroniobate, "niobic acid" refers to hydrated Niobium oxide, and the preparation method may be referred to in the document "j.d.a.goncalves, a. L. d.ramos, &. ttttttttttttttt translation = L" &. gttl. l.l.t. &. gtt. g. L. Rocha, a.k.d.domines, r.s.monteiro, j.s.peres, n.c.functional o, c.a.a.tao.2011.2011.g.2011.r.14. niobium.14. d.r.r.s.s.

In the above method for preparing niobium citrate, the basic substance may be an inorganic base or an organic base, for example, a substance having a pH of more than 11 in an aqueous solution of 1 mol/L at 25 ℃.

In the above method for preparing niobium citrate, the conditions for the contact reaction of the niobium source and the hydrofluoric acid may include: the temperature is 50-80 ℃ and the time is 1-20 h.

In the above method for producing niobium citrate, the conditions under which the clarified solution is contacted with the alkaline substance may include: the temperature is 25-80 deg.C, and the time is 5-60 min.

In the above method for preparing niobium citrate, the conditions for mixing the solid phase with citric acid may include: the temperature is 25-100 deg.C, and the time is 5-720min (preferably 30-60 min). Typically, the solid phase is washed and then mixed with citric acid. The washing may be performed using deionized water or dilute ammonia water.

In the above method for preparing niobium citrate, the method may further include: the mixed product (with citric acid) was contacted with a source of ammonium ions and stirred until the mixed system became clear. By using the ammonium ion source, the mixed system can be further promoted to be clarified, and the obtained niobium citrate is more suitable for preparing the niobium-containing catalyst with better performance. The ammonium ion source is used in an amount of 0.01 to 30mol (0.01mol, 0.05mol, 0.08mol, 0.1mol, 0.2mol, 0.5mol, 1mol, 2mol, 5mol, 10mol, 15mol, 20mol, 25mol, 30mol or any value therebetween, preferably 0.01 to 0.1mol) in terms of ammonium ion per mol of niobium element. The ammonium ion source may be any conventional material capable of providing ammonium ions, and preferably the ammonium ion source is aqueous ammonia and/or an ammonium salt, more preferably aqueous ammonia and/or ammonium nitrate.

In the above-mentioned method for preparing niobium citrate, the solvent used is not particularly limited, and may be a conventional solvent such as water.

In the above method for preparing niobium citrate, in order to obtain niobium citrate in a solid form, the method of the present invention may further comprise: the product after the mixed system became clear was crystallized. The specific method of crystallization is not particularly limited, and for example, cooling crystallization or evaporative crystallization may be employed. The selection of the crystallization conditions can be made by the person skilled in the art and will not be described in detail here.

In order to obtain niobium citrate which is easier to store, the process of the invention may further comprise a step of drying the crystallized product. The drying conditions may be conventional conditions, such as drying at 50-150 deg.C for 10-20 h.

In the method of preparing the niobium phosphate porous material, the phosphorus source may be various soluble substances capable of providing phosphorus element, for example, at least one of phosphate, dihydrogen phosphate, and hydrogen phosphate. Preferably, the phosphorus source is at least one of sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium dihydrogen phosphate, sodium phosphate, potassium phosphate, ammonium phosphate, diammonium hydrogen phosphate, disodium hydrogen phosphate, and dipotassium hydrogen phosphate.

In the method for preparing the niobium phosphate porous material, the template may be various templates conventionally used in the art, such as a surfactant. Preferably, the template agent is at least one of a cationic surfactant (e.g., cetyltrimethylammonium bromide, CTAB), a nonionic surfactant (e.g., polyoxypropylene polyoxyethylene copolymer (P123)), and a fluorocarbon surfactant (e.g., FS-3100).

In the method for preparing the niobium phosphate porous material, the object of the present invention can be achieved by subjecting a mixture of the soluble niobium salt, the phosphorus source and the template to ultrasonic treatment in the presence of a solvent, and the mixing manner of the soluble niobium salt, the phosphorus source and the template is not particularly required, but preferably, the method for mixing the soluble niobium salt, the phosphorus source and the template is: and dropwise adding the solution of the soluble niobium salt into a mixed solution containing a phosphorus source and a template agent, wherein the pH value of the mixed solution containing the phosphorus source and the template agent is 1-10 (preferably 2-7).

In the method of preparing the niobium phosphate porous material, the solvent may be at least one of water, methanol, and ethanol. The solvent used in the preparation of the niobium phosphate porous material in the present invention may be the same as or different from the solvent used in the preparation of the niobium citrate.

In a preferred embodiment of the preparation of the niobium phosphate porous material, the ultrasonic treatment conditions comprise: the frequency is 25-130KHz, more preferably 25-45 KHz.

In a preferred embodiment of the preparation of the niobium phosphate porous material, the ultrasonic treatment conditions further comprise: the power density is 80-1200w/cm²More preferably 100-300w/cm²。

In a preferred embodiment of the preparation of the niobium phosphate porous material, the ultrasonic treatment conditions further comprise: the temperature is 20 to 100 deg.C, more preferably 20 to 50 deg.C.

In a preferred embodiment of the preparation of the niobium phosphate porous material, the ultrasonic treatment conditions further comprise: the pH value is 1-7.

In a preferred embodiment of the preparation of the niobium phosphate porous material, the ultrasonic treatment conditions further comprise: the time is 0.5 to 4 hours, more preferably 1.5 to 3 hours.

In the method of preparing the niobium phosphate porous material, the calcination may be performed using conditions conventional in the art. Preferably, the conditions of the calcination include: the temperature is 360-550 ℃. Preferably, the roasting conditions further include: the time is 3-5 h. The atmosphere for firing includes an air atmosphere. More preferably, the material to be roasted is first heated to roasting temperature in inert atmosphere and then turned to air atmosphere for roasting, so that the roasting conditions include: firstly, roasting at 360-550 ℃ in an inert atmosphere for 0.5-2h, and then roasting at 360-550 ℃ in an air atmosphere for 0.5-5 h. It is well known to those skilled in the art that the solid phase obtained after sonication can be washed and dried before calcination, and will not be described further herein.

The catalyst according to the present invention has no particular requirement for the supported amount of palladium, and preferably, the palladium content is 0.05 to 10 parts by weight per 100 parts by weight of the carrier. The catalyst of the present invention is mainly composed of the above-mentioned carrier and palladium, and the content of palladium may be 0.05 to 10% by weight based on the total weight of the catalyst, and the content of the carrier may be 20 to 90% by weight based on the niobium element.

The form in which palladium is present on the support according to the catalyst of the present invention is not particularly limited, and may be a conventional choice in the art (such as a salt form, an oxide form, or a reduced form (e.g., elemental)). From the viewpoint of further improving the catalytic activity of the catalyst according to the present invention, palladium is supported on the carrier substantially (i.e., mainly or substantially) in a reduced form when used. That is, palladium is preferably supported on the carrier in the reduced form of palladium.

In a second aspect, the present invention provides a method for preparing a catalyst having a deoxygenating and hydrogenating function, comprising: and (3) palladium is loaded on a carrier, wherein the carrier is the niobium phosphate porous material and/or the niobium phosphate porous material prepared by the method (the niobium phosphate porous material and the preparation method thereof are not repeated herein). In other words, the method for preparing the catalyst with the deoxidation and hydrogenation functions provided by the invention can comprise the following steps: the niobium phosphate porous material is prepared by the method, and palladium is loaded on the niobium phosphate porous material.

In the present invention, the method for supporting palladium on a carrier is not particularly limited, and various methods commonly used in the art can be used. For example, palladium may be supported on the carrier by impregnation. The impregnation may be a saturated impregnation or an excess impregnation. In one embodiment of the present invention, the mode of supporting palladium on the support may be an impregnation reduction method, and may include, for example: the support is impregnated with a solution containing at least one palladium-containing salt in the presence of a reducing agent, such as sodium borohydride and/or potassium borohydride, to reduce the metallic element to the surface of the support.

In another embodiment of the present invention, the manner of supporting palladium on the carrier includes: impregnating the support with a solution containing at least one palladium-containing salt, and optionally drying the impregnated support. The concentration of the solution in the present invention is not particularly limited as long as the palladium content in the finally prepared catalyst can satisfy the use requirements (for example, the aforementioned requirements).

The impregnated support may be dried under conditions commonly used in the art. Generally, the drying conditions include: the temperature can be 90-120 ℃; the time can be 5-15 h.

According to a more preferred embodiment of the invention, said impregnation is carried out under ultrasonic conditions. The conditions of the ultrasound preferably include: the frequency is 25-130KHz, more preferably 25-45 KHz. The conditions of the ultrasound preferably further comprise: the power density is 80-1200w/cm²More preferably 100-300w/cm². The conditions of the ultrasound preferably further comprise: the temperature is 20 to 100 deg.C, more preferably 20 to 50 deg.C. The conditions of the ultrasound preferably further comprise: the pH value is 1-7. The conditions of the ultrasound preferably further comprise: the time is 0.5 to 4 hours, more preferably 1.5 to 3 hours. The ultrasonic conditions during the impregnation can be the same as or different from the ultrasonic treatment conditions during the preparation of the niobium phosphate porous material.

In order to further increase the catalytic activity of the resulting catalyst, according to a more preferred embodiment of the invention, the solution comprising at least one palladium-containing salt further comprises a promoter which is an organic complexing agent and/or an organic solvent having a boiling point below 80 ℃. The promoter is preferably used in an amount of 3 to 25 parts by weight per part by weight of the palladium-containing salt. More preferably, the accelerator is an organic complexing agent and an organic solvent having a boiling point of 80 ℃ or lower, and further preferably, the organic complexing agent is used in an amount of 0.05 to 3 parts by weight and the organic solvent having a boiling point of 80 ℃ or lower is used in an amount of 3 to 20 parts by weight per part by weight of the group VIII metal element-containing salt.

The organic complexing agent can be various conventional substances with dispersing performance, preferably C2-C10 organic acid, and more preferably citric acid and/or ethylene diamine tetraacetic acid. The organic solvent may be any of various volatile water-miscible organic solvents, such as at least one of ethanol, acetone, and chloroform.

Most preferably, the accelerator is citric acid and ethanol, and the citric acid is preferably used in an amount of 0.05 to 3 parts by weight (e.g., 0.8 to 1.2 parts by weight) and the ethanol is preferably used in an amount of 3 to 20 parts by weight (e.g., 4 to 6 parts by weight) per part by weight of the salt containing the group VIII metal element.

Thus, according to a most preferred embodiment of the present invention, the manner of supporting palladium on the carrier comprises: the support is impregnated under sonication conditions (as described above) with a solution containing at least one palladium-containing salt, and which also contains citric acid and ethanol (as described above).

According to the present invention, the palladium-loaded support (or the method) may or may not be calcined (after impregnation and drying) (i.e., the catalyst is prepared in which each palladium is supported on the support in the form of an oxide), i.e., the catalyst is prepared in which palladium is supported on the support substantially in the form of a salt; i.e., the catalyst is prepared in which palladium is supported on the support substantially in the form of a non-oxide). The method of the invention can also further comprise reducing the roasted product (the reducing conditions can comprise the temperature of 150 ℃ C. and 400 ℃ C., the hydrogen partial pressure of 0.1-4MPa and the time of 2-6h) so that the palladium is loaded on the carrier in a reduced state. From the viewpoint of further improving the catalytic activity of the catalyst according to the present invention, palladium is preferably supported on the carrier substantially in a reduced state, that is, the carrier on which palladium is supported is preferably subjected to calcination and reduction. Since the raw material for the deoxygenation and hydrogenation reaction includes hydrogen, the reduction step may be performed again at the time of use.

According to the present invention, the palladium-containing salt may be various water-soluble palladium-containing salts commonly used in the art, for example: the palladium-containing salt may be selected from water-soluble palladium salts of inorganic acids, water-soluble palladium salts of organic acids, water-soluble salts of water-insoluble palladium-containing salts formed by contacting an acid (e.g., phosphoric acid) and/or a base (e.g., aqueous ammonia) in water, and the like.

In particular, the palladium-containing salt may be selected from, but is not limited to: palladium chloride and/or palladium nitrate.

In a third aspect, the present invention provides a method for deoxygenating and hydrogenating a carbonyl compound, comprising: contacting a feedstock containing carbonyl compounds with a catalyst, which is the aforementioned catalyst and/or a catalyst produced by the aforementioned method, under deoxygenated hydrogenation conditions comprising: the temperature is 100-140 ℃ (preferably 110-140 ℃), and the time is 2-120h (preferably 48-72 h).

The deoxygenation and hydrogenation method according to the present invention, wherein the amount of the catalyst used is not particularly limited, preferably, the amount of the catalyst used is 0.05 to 1 part by weight per part by weight of the carbonyl compound.

The catalyst of the present invention has good acid properties and good hydrothermal stability, and is therefore particularly suitable for aqueous phase reactions. Thus, in a preferred embodiment, the carbonyl compound-containing feedstock is contacted with the catalyst in the form of a solution. The content of the carbonyl compound in the solution may be 1 to 30% by weight, preferably 5 to 15% by weight.

According to the deoxygenation and hydrogenation method of the present invention, the carbonyl compound may be various carbonyl group-containing compounds, for example, aldehydes, ketones, carboxylic acids, derivatives thereof, and the like. Preferably, the carbonyl compound is a C6 monosaccharide. More preferably, the carbonyl compound is at least one of glucose, fructose, galactose and mannose. The inventors of the present invention found that the catalyst of the present invention is capable of catalyzing glucose to produce a product with a higher octane number, which is a potential gasoline blending component.

The deoxygenation and hydrogenation method according to the present invention, wherein the deoxygenation and hydrogenation conditions preferably further comprise: the hydrogen partial pressure is from 1 to 8MPa, more preferably from 4 to 6 MPa.

The present invention will be described in detail below by way of examples.

In the following examples, "room temperature" means 25 ℃, the pore volume, pore size distribution and specific surface area of the sample were measured on an ASAP2405 static nitrogen adsorption apparatus from Micromeritics, inductively coupled plasma analysis was performed on an inductively coupled plasma spectrometer model Optima8300 from Perkin Elmer, and total carbon analysis was performed on a Total carbon Analyzer model Shimadzu-L.

Preparation example 1

This preparation was used to prepare the soluble niobium salts used in the examples.

Weighing 4g of niobium pentoxide, adding the niobium pentoxide into 40m L hydrofluoric acid (with the concentration of 7 mol/L), heating and stirring until the niobium pentoxide is dissolved and clarified (50 ℃ for 3h), adding 150m L ammonia water (with the concentration of 2 mol/L) to obtain white precipitate (30 ℃ for 1h), washing and filtering the white precipitate, adding the white precipitate into 120m L citric acid aqueous solution with the concentration of 0.5 mol/L, stirring at 25 ℃ for 0.5h to obtain clarified solution, namely niobium citrate solution, analyzing by Inductive Coupling Plasma (ICP) and total carbon (TOC) to obtain the molar ratio of citric acid to niobium of 1.98, and evaporating the obtained niobium citrate solution at 60 ℃ for 12h to obtain transparent jelly-like solid (niobium citrate).

Weighing 4g of potassium fluoroniobate, adding the potassium fluoroniobate into 40m of L hydrofluoric acid (the concentration is 3.5 mol/L), heating and stirring until the potassium fluoroniobate is dissolved and clarified (80 ℃ and 5 hours), adding 150m of L ammonia water (the concentration is 1 mol/L) into the solution to obtain white precipitate (80 ℃ and 5 minutes), washing and filtering the white precipitate, adding 130m of citric acid aqueous solution with the concentration of L of 0.5 mol/L and 10m of L ammonia water (the concentration is 0.1 mol/L), stirring at 60 ℃ for 0.5 hours to obtain a clarified solution, namely a niobium citrate solution-1, and analyzing by ICP and TOC, wherein the molar ratio of ammonium ions, citric acid and niobium in the solution is 0.08:4.89: 1.

Weighing 4g of sodium niobate, adding the sodium niobate into 40m of L hydrofluoric acid (with the concentration of 9 mol/L), heating and stirring until the sodium niobate is dissolved and clarified (80 ℃ for 3h), adding 300m of L ammonia water (with the concentration of 2 mol/L) into the solution to obtain white precipitate (30 ℃ for 1h), washing and filtering the white precipitate, adding 150m of citric acid aqueous solution with the concentration of L of 0.5 mol/L and 10m of L ammonia water (with the concentration of 0.1 mol/L), stirring at 80 ℃ for 1h to obtain a clarified solution, namely a niobium citrate solution-2, and analyzing by ICP and TOC, wherein the molar ratio of ammonium ions, citric acid and niobium in the solution is 0.03:3.12: 1.

Niobium oxalate was prepared according to CN1935772A example 1.

Example 1

(1) Preparation of the support

Weighing 1.2g of hexadecyl trimethyl ammonium bromide (CTAB) and 3.64g of disodium hydrogen phosphate, dissolving in 70m L deionized water, fully stirring and dissolving, adjusting the pH value to 2 by hydrochloric acid to obtain a solution A, weighing 8g of niobium citrate (containing 1.84g of niobium) and dissolving in 42.6m L deionized water, fully stirring and dissolving to obtain a solution B, dropwise adding the solution B into the solution A, and performing ultrasonic treatment on the mixed solution at 20 ℃ (the frequency is 40KHz, the power density is 300w/cm²) After 2h, filtering and washing, drying the obtained solid at 100 ℃ for 10h, and then roasting at 550 ℃ for 5h to obtain a niobium phosphate porous material sample, wherein the sample has a porous structure under a nitrogen isothermal adsorption and desorption test (a nitrogen adsorption and desorption curve chart is shown in figure 1) and has a pore size distribution of 3-60nm, and other parameters are determined as shown in table 1.

The sample was observed by placing it under TEM, and from the TEM photograph (fig. 2), it was found that the sample had a worm-like pore structure with a pore diameter of about 9nm, and the sample was subjected to XRD analysis (the same applies below) on a Siemens D5005 type X-ray diffractometer using a Cu target K α (λ 0.154056nm) source with a test voltage of 40kV, a test current of 40mA, a scanning range of 10 to 80 °, and a scanning speed of 6 °/min, and it was judged that the sample had a long-range disordered mesoporous structure from the XRD spectrum (see fig. 3).

(2) Preparation of the catalyst

Weighing 1g of the niobium phosphate porous material obtained in the step (1), and mixing the prepared PdCl₂Mixed solution of citric acid, ethanol and water (PdCl)₂Has a concentration of 10mg/m L₂The weight ratio of the citric acid to the ethanol is 1: 1: 5) adding 1ml of the mixture into a niobium phosphate porous material, carrying out ultrasonic treatment for 0.5h at room temperature, then carrying out magnetic stirring until no flowing water exists, then carrying out forced air drying for 12h at 100 ℃, roasting for 5h at 550 ℃ in a muffle furnace after drying to obtain an initial catalyst, and reducing for 2h at 160 ℃ by hydrogen (the hydrogen partial pressure is 0.1MPa) before use to obtain a catalyst 1, wherein the Pd content is 1 percent/NbPO_x。

The composition of the catalyst was measured using Inductively Coupled Plasma (ICP) and the results are listed in table 2.

Comparative example 1

This comparative example illustrates a conventional hydrothermal method for preparing a catalyst using a niobium phosphate porous material as a support.

(1) Preparation of the support

Weighing 1.2g of hexadecyl trimethyl ammonium bromide (CTAB) and 3.64g of disodium hydrogen phosphate, dissolving in 70m L deionized water, fully stirring and dissolving, adjusting the pH value to 2 by hydrochloric acid to obtain a solution A, weighing 8g of niobium citrate (containing 1.84g of niobium) and dissolving in 42.6m L deionized water, fully stirring and dissolving to obtain a solution B, dropwise adding the solution B into the solution A, stirring and aging the mixed solution at 90 ℃ for 24 hours, transferring into a stainless steel pressure bomb with a polytetrafluoroethylene lining, crystallizing at 170 ℃ for 72 hours, filtering and washing, drying the obtained solid at 100 ℃ for 10 hours, roasting at 550 ℃ for 5 hours to obtain a niobium phosphate porous material sample, displaying that the sample has a pore size distribution of 3-60nm under a nitrogen isothermal adsorption and desorption test, and determining other parameters as shown in Table 1.

According to the results of nitrogen isothermal adsorption and desorption tests and TEM observation, the obtained sample has a worm-like pore structure, and the pore diameter is about 3 nm; from the XRD spectrogram, the sample has a long-range disordered mesoporous structure.

(2) Preparation of the catalyst

The procedure is as in example 1 to give catalyst D1. The composition of the catalyst was determined by ICP and the results are listed in table 2.

Example 2

(1) Preparation of the support

Weighing 1.2g of hexadecyl trimethyl ammonium bromide (CTAB) and 3.64g of disodium hydrogen phosphate, dissolving in 70m L deionized water, fully stirring and dissolving, adjusting the pH value to 2 by hydrochloric acid to obtain a solution A, weighing 8g of niobium citrate (containing 1.84g of niobium) and dissolving in 42.6m L deionized water, fully stirring and dissolving to obtain a solution B, dropwise adding the solution B into the solution A, and performing ultrasonic treatment on the mixed solution at 20 ℃ (the frequency is 40KHz, the power density is 100w/cm²)2h, then filtered and washed,and drying the obtained solid at 100 ℃ for 10h, heating to 550 ℃ at the speed of 5 ℃/min under the nitrogen atmosphere, switching to the air atmosphere, and roasting for 5h to obtain a niobium phosphate porous material sample, wherein the sample has the pore size distribution of 3-60nm under the nitrogen isothermal adsorption and desorption test, and the measurement results of other parameters are shown in table 1.

According to the results of nitrogen isothermal adsorption and desorption tests and TEM observation, the obtained sample has a worm-like pore structure, and the pore diameter is about 9 nm; from the XRD spectrogram, the sample has a long-range disordered mesoporous structure.

(2) Preparation of the catalyst

The procedure is as in example 1 to give catalyst 2. The composition of the catalyst was determined by ICP and the results are listed in table 2.

Example 3

(1) Preparation of the support

Weighing 1.2g of hexadecyl trimethyl ammonium bromide (CTAB) and 1.82g of disodium hydrogen phosphate, dissolving in 70m L deionized water, fully stirring and dissolving, adjusting the pH value to 5 by hydrochloric acid to obtain a solution A, weighing 5.3g of niobium pentachloride, dissolving in 42.6m L deionized water, fully stirring and dissolving to obtain a solution B, dropwise adding the solution B into the solution A, and performing ultrasonic treatment on the mixed solution at 30 ℃ (the frequency is 25KHz, and the power density is 300w/cm²) After 3 hours, filtering and washing, drying the obtained solid at 100 ℃ for 10 hours, and then roasting at 550 ℃ for 5 hours to obtain a niobium phosphate porous material sample, wherein the sample has a pore size distribution of 3-60nm under a nitrogen isothermal adsorption and desorption test, and the measurement results of other parameters are shown in table 1.

(2) Preparation of the catalyst

The procedure is as in example 1 to give catalyst 3. The composition of the catalyst was determined by ICP and the results are listed in table 2.

Example 4

(1) Preparation of the support

3g of cetyltrimethylammonium bromide (CTAB) and 3.64g were weighed outDissolving disodium hydrogen phosphate in 70m L deionized water, stirring thoroughly to dissolve, adjusting pH to 5 with hydrochloric acid to obtain solution A, weighing niobium oxalate 23g (containing niobium 3.96g) and dissolving in 100m L deionized water, stirring thoroughly to dissolve to obtain solution B, adding solution B dropwise into solution A, subjecting the above mixed solution to ultrasonic treatment at 50 deg.C (frequency of 45KHz, power density of 200w/cm²)1.5h, then filtering and washing, drying the obtained solid at 100 ℃ for 10h, then roasting at 550 ℃ for 5h to obtain a niobium phosphate porous material sample, wherein the sample has a pore size distribution of 3-60nm under a nitrogen isothermal adsorption and desorption test, and other parameters are determined as shown in Table 1.

(2) Preparation of the catalyst

The procedure is as in example 1 to give catalyst 4. The composition of the catalyst was determined by ICP and the results are listed in table 2.

Example 5

(1) Preparation of the support

A niobium phosphate porous material was prepared by following the procedure of example 1 except that "niobium citrate solution-1" was used in place of "niobium citrate", the amount of niobium citrate solution-1 was such that the amount of niobium was 1.84g, and the sample showed a pore size distribution of 3 to 60nm under the nitrogen isothermal adsorption and desorption test, and the results of the other parameters were as shown in Table 1. According to the results of nitrogen isothermal adsorption and desorption tests and TEM observation, the obtained sample has a worm-like pore structure, and the pore diameter is about 9 nm; from the XRD spectrogram, the sample has a long-range disordered mesoporous structure.

(2) Preparation of the catalyst

The procedure is as in example 1 to give catalyst 5. The composition of the catalyst was determined by ICP and the results are listed in table 2.

Example 6

(1) Preparation of the support

A niobium phosphate porous material was prepared by following the procedure of example 1 except that "niobium citrate solution-2" was used in place of "niobium citrate", the amount of niobium citrate solution-2 was such that the amount of niobium was 1.84g, and the sample showed a pore size distribution of 3 to 60nm under the nitrogen isothermal adsorption and desorption test, and the results of the other parameters were as shown in Table 1. According to the results of nitrogen isothermal adsorption and desorption tests and TEM observation, the obtained sample has a worm-like pore structure, and the pore diameter is about 9 nm; from the XRD spectrogram, the sample has a long-range disordered mesoporous structure.

(2) Preparation of the catalyst

The procedure is as in example 1 to give catalyst 6. The composition of the catalyst was determined by ICP and the results are listed in table 2.

Example 7

(1) Preparation of the support

A niobium phosphate porous material was prepared as in example 1, except that "P123 (available from Beijing Yinaoka technologies, Ltd.) was used in place of" cetyltrimethylammonium bromide ", and that the sample was shown to have a pore size distribution of 3 to 60nm under the nitrogen desorption isothermal adsorption test, and the results of the other parameters are shown in Table 1.

According to the results of nitrogen isothermal adsorption and desorption tests and TEM observation, the obtained sample has a worm-like pore structure, and the pore diameter is about 12 nm; from the XRD spectrogram, the sample has a long-range disordered mesoporous structure.

(2) Preparation of the catalyst

The procedure is as in example 1 to give catalyst 7. The composition of the catalyst was determined by ICP and the results are listed in table 2.

Example 8

(1) Preparation of the support

A niobium phosphate porous material was prepared as in example 1, except that "FS-3100 (available from Kyoto Kopu Seiki laboratories, Inc.)" was used in place of "cetyltrimethylammonium bromide", and the samples were shown to have a pore size distribution of 3 to 60nm under nitrogen desorption isothermal adsorption test, and the results of other parameters are shown in Table 1. According to the results of nitrogen isothermal adsorption and desorption tests and TEM observation, the obtained sample has a worm-like pore structure, and the pore diameter is about 11 nm; from the XRD spectrogram, the sample has a long-range disordered mesoporous structure.

(2) Preparation of the catalyst

The procedure is as in example 1 to give catalyst 8. The composition of the catalyst was determined by ICP and the results are listed in table 2.

Example 9

(1) Preparation of the support

Weighing 1.8g of hexadecyl trimethyl ammonium bromide (CTAB) and 4.6g of disodium hydrogen phosphate, dissolving in 70m L deionized water, fully stirring and dissolving, adjusting the pH value to 2 by hydrochloric acid to obtain a solution A, weighing 12g of niobium citrate (containing 2.64g of niobium) and dissolving in 60m L deionized water, fully stirring and dissolving to obtain a solution B, dropwise adding the solution B into the solution A, and performing ultrasonic treatment on the mixed solution at 20 ℃ (the frequency is 40KHz, and the power density is 300w/cm²) And 2h, filtering and washing, drying the obtained solid at 100 ℃ for 10h, heating to 550 ℃ at the speed of 5 ℃/min under the nitrogen atmosphere, switching to the air atmosphere, and roasting for 5h to obtain a niobium phosphate porous material sample, wherein the sample has the pore size distribution of 3-60nm under the nitrogen isothermal adsorption and desorption test, and the measurement results of other parameters are shown in table 1.

According to the results of the nitrogen isothermal adsorption and desorption test and the TEM observation, the obtained sample has a worm-like pore structure; from the XRD spectrogram, the sample has a long-range disordered mesoporous structure.

(2) Preparation of the catalyst

Weighing 1g of the niobium phosphate porous material obtained in the step (1), and mixing the prepared PdCl₂Mixed solution of citric acid, ethanol and water (PdCl)₂Has a concentration of 10mg/m L₂The weight ratio of the citric acid to the ethanol is 1: 1: 5) adding 2ml of the mixture into a niobium phosphate porous material, carrying out ultrasonic treatment for 0.5h at room temperature, then carrying out magnetic stirring until no flowing water exists, then carrying out forced air drying for 12h at 100 ℃, roasting for 5h at 550 ℃ in a muffle furnace after drying to obtain an initial catalyst, and reducing for 2h at 160 ℃ by hydrogen (the hydrogen partial pressure is 0.1MPa) before use to obtain a catalyst 9, wherein the catalyst is expressed as 1% Pd/NbPO_x. The composition of the catalyst was determined by ICP and the results are listed in table 2.

Comparative example 2

Catalyst D2 was prepared according to the procedure (2) of example 9, except that "hydrogen type aluminosilicate molecular sieve (available from Kagaku chemical Co., Ltd.)" was used in place of "niobium phosphate pore material", and the composition of the catalyst was measured by ICP, and the results are shown in Table 2.

Example 10

(1) Preparation of the support

Same as in step (1) of example 9.

(2) Preparation of the catalyst

Weighing 1g of the niobium phosphate porous material obtained in the step (1), and preparing PdCl with the concentration of 10mg/m L₂Adding 1ml of the aqueous solution into a niobium phosphate porous material, magnetically stirring the mixture until the surface is dried, then drying the mixture by blowing at 100 ℃ for 12 hours, roasting the dried mixture in a muffle furnace at 550 ℃ for 5 hours to obtain an initial catalyst, and reducing the initial catalyst by hydrogen (with hydrogen partial pressure of 0.1MPa) at 160 ℃ for 2 hours before use to obtain a catalyst 10, wherein the c-Pd/NbPO is 1 percent_xThe composition of the catalyst was measured by ICP and the results are shown in Table 2.

TABLE 1

TABLE 2

Test example 1

This test example is intended to illustrate the deoxygenation and hydrogenation process of the present invention.

(1) 0.1g of the catalyst prepared in the above example or comparative example and a 10 wt% aqueous solution of glucose 5m L were charged into a 100m L compact autoclave, and reacted at 140 ℃ under 6MPa of hydrogen partial pressure for 72 hours to analyze the reaction product (liquid fuel) by high performance liquid chromatography and gas chromatography-mass spectrometry (GC-MS), wherein the analysis of the aqueous phase product was performed on Agilent1200 type HP L C, the column was XDB-C18 column (4.5 μm, 250mm, Eclipse USA), the column was thermostated at 35 ℃, the analysis of the oil phase product was performed by gas chromatography-mass spectrometry (GC-MS (Agilent 7890A-5975C), HP-5 column, 30-150 ℃ temperature programming, FID detector temperature 270 ℃ and He carrier gas), and the remaining glucose after the reaction was analyzed by Agilent1200 type HP L C color carrier gasSpectral allocation Agilent G1362A type differential refraction detector (RID) and Bio-Rad Aminex HPX-87H sugar column for detection, wherein the chromatographic column is kept at 80 deg.C, the mobile phase is pure water, and the flow rate is 0.8m L min^-1The results of the analysis are shown in table 3, in which the conversion rate is × 100% by mole (the molar amount of glucose before the reaction-the molar amount of glucose after the reaction)/the molar amount of glucose before the reaction), the oxygenate selectivity is × 100% by mole of total carbon in the oxygenate in the liquid fuel/(the molar amount of total carbon in the oxygenate in the liquid fuel + the molar amount of saturated hydrocarbon in the liquid fuel), the saturated hydrocarbon selectivity is ×% by mole of total carbon in the saturated hydrocarbon in the liquid fuel/(the molar amount of total carbon in the oxygenate in the liquid fuel + the molar amount of saturated hydrocarbon in the liquid fuel) × 100% by mole of total carbon in the liquid fuel, and the total liquid fuel carbon yield is × 100% by mole (the molar amount of total carbon in the oxygenate in the liquid fuel + the molar amount of saturated hydrocarbon in the liquid fuel)/(the molar amount of total carbon in glucose before the reaction-the molar amount of total carbon in glucose after the reaction), the total carbon yield is ×% (when calculated, the total carbon, the oxygenate, the saturated hydrocarbon and the total carbon are based on the 9 compounds shown below, the same as follows).

TABLE 3

The results of high performance liquid chromatography analysis of the product obtained using catalyst 9 are shown in fig. 4, in which fig. 4, the compounds represented by the respective peaks and their structural formulae are as follows:

1: the reaction product of isohexane,

2: n-hexane,

3: the preparation method of the methyl cyclopentane is shown in the specification,

4: 2, 5-dimethyltetrahydrofuran,

5: 2, 5-dimethylfuran, in the presence of a catalyst,

6: 2-methyl-tetrahydrofuran,

7: 2-butyl tetrahydrofuran, and the solvent is a solvent,

8: 2-hexanone, and the synthesis of the 2-hexanone,

9: 2-methyl-cyclopentanone and a solvent, wherein,

the results of high performance liquid chromatography analyses of the products obtained using catalysts 1 to 10 were similar (for example, the results of high performance liquid chromatography analyses of the products obtained using catalyst 1 are shown in fig. 5, and the compounds represented by the respective peaks in fig. 5 and the structural formulae thereof are shown above), indicating that the above-mentioned compounds were all obtained.

As can be seen from the data in the above Table 3, the catalyst of the present invention has the dual functions of catalytic deoxygenation and catalytic hydrogenation, and has high activity, and can convert carbonyl compounds into liquid oxygen-containing substances through one-step hydrogenation, and has good selectivity for oxygen-containing compounds. When the catalyst disclosed by the invention is used for catalyzing glucose, the obtained oxygen-containing compound only retains one oxygen atom, and the product has a higher octane number and can be used as a potential gasoline blending component.

In particular, comparing the test results of catalyst 1, catalyst D1 and catalyst D2, it can be seen that the catalysts prepared by using other niobium phosphate porous materials (including the existing silicoaluminophosphate molecular sieves) as the carrier have lower catalytic activity; as can be seen from the results of the test comparing catalyst 9A with catalyst 10, a catalyst having more excellent performance can be obtained by supporting palladium on a carrier using a promoter.

Test example 2

Glucose was subjected to deoxygenation hydrogenation according to the method of test example 1 (using catalyst 9) except that the reaction temperature was controlled to 240 ℃ and the analysis results of the reaction products were shown in Table 4.

Test example 3

Glucose was subjected to deoxygenation hydrogenation according to the method of test example 1 (using catalyst 9) except that the reaction time was controlled to 24 hours, and the analysis results of the reaction products are shown in Table 4.

TABLE 4

Numbering	Conversion rate	Oxygenate selectivity	Selectivity for saturated hydrocarbon	Total liquid fuel yield
					Test example 2	99％	<1％	>99％	60.8％
Test example 3	36％	4.7％	0.3％	1.4％

Comparing the test results of test example 1 using the catalyst 9 with the results of test examples 2 to 3, it can be seen that the deoxygenation hydrogenation can be effectively achieved only by controlling the temperature and time of the deoxygenation hydrogenation within the range of the present invention.

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.

In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims

1. A catalyst with a deoxidation and hydrogenation function, which comprises a carrier and palladium supported on the carrier, and is characterized in that the carrier is a niobium phosphate porous material, and the niobium phosphate porous material comprises: niobium element, phosphorus element and oxygen element, wherein the pore volume of the niobium phosphate porous material is 0.3cm³More than g, the average pore diameter is more than 9nm, the pore diameter distribution is 3-60nm under the nitrogen isothermal adsorption and desorption test, and the proportion of the pore diameter in the range of 5.6-15.8nm in the total pore diameter distribution is more than or equal to 80 percent.

2. The catalyst of claim 1, wherein the niobium phosphate porous material has a pore volume of 0.3-0.5cm³The proportion of the pore diameter of 5.6-15.8nm in the total pore diameter distribution amount under nitrogen isothermal adsorption and desorption test is 80-95 percent; and/or

The niobium phosphate poresThe specific surface area of the material is 140-300m²/g。

3. The catalyst of claim 1, wherein the molar ratio of niobium to phosphorus is 1: 0.4-2.6.

4. The catalyst according to any one of claims 1 to 3, wherein the palladium is contained in an amount of 0.05 to 10 parts by weight per 100 parts by weight of the carrier; and/or

The palladium is supported on the carrier in a reduced form.

5. A method of preparing a catalyst having deoxygenating and hydrogenating functions, the method comprising: supporting palladium on a carrier, wherein the carrier is a niobium phosphate porous material, and the niobium phosphate porous material comprises: niobium element, phosphorus element and oxygen element, wherein the pore volume of the niobium phosphate porous material is 0.3cm³More than g, the average pore diameter is more than 9nm, the pore diameter distribution is 3-60nm under the nitrogen isothermal adsorption and desorption test, and the proportion of the pore diameter in the range of 5.6-15.8nm in the total pore diameter distribution is more than or equal to 80 percent.

6. The method of claim 5, wherein the niobium phosphate porous material has a pore volume of 0.3-0.5cm³The proportion of the pore diameter of 5.6-15.8nm in the total pore diameter distribution amount under nitrogen isothermal adsorption and desorption test is 80-95 percent; and/or the presence of a gas in the gas,

the specific surface area of the niobium phosphate porous material is 140-300m²/g。

7. The method of claim 5, wherein the molar ratio of niobium to phosphorus is 1: 0.4-2.6.

8. The method of any one of claims 5-7, wherein the method comprises preparing the niobium phosphate porous material by: in the presence of a solvent, mixing soluble niobium salt, a phosphorus source and a template agent, then carrying out ultrasonic treatment, and roasting a solid phase obtained after the ultrasonic treatment.

9. The method of claim 8, wherein the template is used in an amount of 3 to 120g per mole of soluble niobium salt calculated as niobium.

10. The method of claim 8, wherein the soluble niobium salt is at least one of niobium pentachloride, niobium oxalate, niobium malate, niobium tartrate, and niobium citrate; and/or

The solvent is at least one of water, methanol and ethanol.

11. The method of claim 8, wherein the soluble niobium salt is niobium citrate and the niobium citrate is made by:

the niobium source is contacted with hydrofluoric acid for reaction until the reaction system becomes clear; and (2) contacting the obtained clarified liquid with an alkaline substance, and mixing a solid phase obtained after the contact with citric acid in the presence of a solvent until a mixed system becomes clear, wherein the dosage of the citric acid is 1.7-10mol relative to each mol of niobium element.

12. The method of claim 8, wherein the phosphorus source is at least one of a phosphate salt, a dihydrogen phosphate salt, and a hydrogen phosphate salt.

13. The method of claim 8, wherein the templating agent is a cationic surfactant and/or a nonionic surfactant; or

The template agent is a hydrocarbon surfactant and/or a fluorocarbon surfactant.

14. The method of claim 8, wherein the method of mixing the soluble niobium salt, the phosphorus source, and the templating agent is: and dropwise adding the soluble niobium salt solution into a mixed solution containing a phosphorus source and a template agent, wherein the pH value of the mixed solution containing the phosphorus source and the template agent is 1-10.

15. The method of claim 8, wherein the sonication conditions include: the frequency is 25-130kHz, and the power density is 80-1200W/cm²The temperature is 20-100 ℃, the pH value is 1-7, and the time is 0.5-4 h; and/or

The roasting conditions comprise: the temperature is 360-550 ℃, and the time is 3-5 h.

16. The method according to claim 5, wherein the palladium is used in an amount of 0.05 to 10 parts by weight per 100 parts by weight of the carrier; and/or

The palladium is supported on the carrier in a reduced form.

17. The method according to claim 5 or 16, wherein the manner of supporting palladium on the carrier comprises: impregnating the support with a solution containing at least one palladium-containing salt under ultrasonic conditions; or

The manner of supporting palladium on the carrier includes: impregnating the support with a solution comprising at least one palladium-containing salt, and which solution also contains a promoter; or

The manner of supporting palladium on the carrier includes: impregnating the support with a solution containing at least one palladium-containing salt under ultrasonication conditions, and which solution also contains a promoter;

wherein the promoter is an organic complexing agent and/or an organic solvent with a boiling point below 80 ℃.

18. The method of claim 17, wherein the organic complexing agent is C₂-C₁₀The organic acid of (1).

19. The method of claim 17, wherein the organic complexing agent is citric acid and/or ethylenediaminetetraacetic acid.

20. The method of claim 17, wherein the organic solvent is at least one of ethanol, acetone, and chloroform.

21. A process for the deoxygenation and hydrogenation of a carbonyl compound, the process comprising: contacting a feedstock containing carbonyl compounds with a catalyst according to any one of claims 1 to 4 and/or a catalyst produced by the process of any one of claims 5 to 20 under deoxygenated hydrogenation conditions comprising: the temperature is 100-140 ℃, and the time is 2-120 h.

22. The deoxygenation hydrogenation process of claim 21, wherein the catalyst is used in an amount of 0.05 to 1 part by weight per part by weight of the carbonyl compound; and/or

Contacting a feedstock containing a carbonyl compound in solution with a catalyst; and/or

The carbonyl compound is at least one of glucose, fructose, galactose and mannose.

23. The deoxygenation hydrogenation process of claim 21 or 22, wherein the deoxygenation hydrogenation conditions comprise: the temperature is 110-140 ℃, the hydrogen partial pressure is 1-8MPa, and the time is 48-72 h.