阅读说明：本技术 碳化物基催化剂及其制备方法以及甘油氢解方法 (Carbide-based catalyst, preparation method thereof and glycerol hydrogenolysis method ) 是由 郑仁垟 吴玉 晋超 李明丰 夏国富 李会峰 王薇 徐润 于 2018-09-07 设计创作，主要内容包括：本公开涉及一种碳化物基催化剂及其制备方法以及甘油氢解方法,该催化剂包括载体、第一活性组分、第二活性组分、以及第三活性组分,所述第一活性组分为选自第VIII族金属中的一种的第一活性金属,所述第二活性组分为第二活性金属M的碳化物和氧化物的复合体MC<Sub>x</Sub>-MO<Sub>y</Sub>,所述第三活性组分为第三活性金属N的碳化物和氧化物的复合体NC<Sub>a</Sub>-NO<Sub>b</Sub>,其中M为Mo或Ti,x＝0.5～1,y＝2～3,N为W或Zr,a＝0.5～1,b＝2～3。与现有技术制备的相同活性金属含量的催化剂相比,本公开的碳化物基催化剂表现出优异的催化甘油氢解活性,1,3-丙二醇选择性高。(The present disclosure relates to a carbide-based catalyst, a method for preparing the same, and a method for hydrogenolysis of glycerol, the catalyst comprising a carrier, a first active component, a second active component, and a third active component, the first active component being a first active metal selected from one of group VIII metals, the second active component being a complex MC of a carbide and an oxide of a second active metal M x ‑MO y The third active component is a composite NC of carbide and oxide of a third active metal N a ‑NO b Wherein M is Mo or Ti, x is 0.5-1, y is 2-3, N is W or Zr, a is 0.5-1, and b is 2-3. The carbide-based catalysts of the present disclosure exhibit superior catalytic glycerol hydrogenolysis activity, 1, 3-propanediyl, compared to catalysts of the same active metal content prepared by the prior artThe alcohol selectivity is high.)

1. A carbide-based catalyst comprising a support, a first active component which is a first active metal selected from one of group VIII metals, a second active component which is a composite MC of a carbide and an oxide of a second active metal M, and a third active component_x-MO_yThe third active component is a composite NC of carbide and oxide of a third active metal N_a-NO_bWherein M is Mo or Ti, x is 0.5-1, y is 2-3, N is W or Zr, a is 0.5-1, and b is 2-3.

2. The catalyst of claim 1, wherein the catalyst satisfies (M)_MCx/M_MOy)_XPS＝0.1～20，(M_NCa/M_NOb)_XPS0.1 to 20, preferably, (M)_MCx/M_MOy)_XPS＝1～10，(M_NCa/M_NOb)_XPS1 to 10, wherein (M)_MCx/M_MOy)_XPSMC in terms of metal element M in the catalyst characterized by X-ray photoelectron spectroscopy_xAnd MO_y(M) is_NCa/M_NOb)_XPSNC in terms of metal element N in the catalyst characterized by X-ray photoelectron spectroscopy_aWith NO_bIn a weight ratio of (a).

3. The catalyst of claim 1, wherein the first active metal is Pt or Pd, the second active metal M is Mo, and the third active metal N is W.

4. The catalyst of claim 1, wherein the first active component is present in an amount of 0.01 to 10 wt%, the second active component is present in an amount of 1 to 30 wt%, the third active component is present in an amount of 1 to 70 wt%, and the carrier is present in an amount of 10 to 97 wt%, calculated as the metal element and based on the weight of the catalyst on a dry basis;

preferably, the content of the first active component is 0.1-5 wt%, the content of the second active component is 2-20 wt%, the content of the third active component is 4-50 wt%, and the content of the carrier is 25-93 wt% calculated on the metal element and based on the dry weight of the catalyst;

the weight ratio of the second active component to the third active component is 0.1-1 calculated by metal elements.

5. The catalyst of claim 1 wherein the support is alumina, silica, titania, magnesia, zirconia, thoria, beryllia, clay, molecular sieve or activated carbon, or a combination of two or three thereof.

6. A method of preparing a carbide-based catalyst, the method comprising the steps of:

a. loading a first active metal, a second active metal and a third active metal on a carrier through impregnation to obtain an impregnated material;

b. carbonizing the impregnated material obtained in the step a in a carbon-containing compound atmosphere to obtain a carbonized material;

c. b, oxidizing the carbonized material obtained in the step b in an oxygen-containing compound atmosphere;

wherein the first active metal is one selected from group VIII metals; the second active metal is Mo or Ti; the third active metal is W or Zr.

7. The method according to claim 6, wherein in step a, the weight ratio of the first active metal, the second active metal, the third active metal to the carrier on a dry basis is (0.0001-1): (0.01-3): (0.01-7): 1, preferably (0.0011-0.2): (0.022-0.8): (0.043-2): 1;

and/or, the impregnation conditions include: the temperature is 10-90 ℃, and preferably 15-40 ℃; the time is 1-10 h, preferably 2-6 h.

8. The method of claim 6, wherein the method further comprises: drying and roasting the impregnated material obtained in the step a, and then performing the operation of the step b; and/or, the drying conditions are as follows: the temperature is 80-150 ℃, and the time is 1-24 h; and/or the roasting conditions are as follows: the temperature is 200-700 ℃, and the time is 1-12 h.

9. The process of claim 6, wherein in step b, the carbon-containing compound is carbon monoxide, methane, ethane, ethylene, acetylene, propane, propylene, or propyne, or a combination of two or three thereof; and/or, in the atmosphere containing the carbon compound, the content of the carbon compound is 5-50% by volume, preferably 10-25% by volume;

and/or, the carbonization conditions comprise: the temperature is 300-1000 ℃, preferably 500-900 ℃; the time is 1-24 h, preferably 2-12 h.

10. The method of claim 6, wherein the method further comprises: and c, cooling the carbonized material obtained in the step b to below 50 ℃ in the atmosphere of the carbon-containing compound, the hydrogen gas or the inert atmosphere, treating the material in the inert atmosphere for 0.2-24 h, and then performing the operation in the step c.

11. The process of claim 6, wherein in step c, the oxygenate is oxygen, carbon dioxide or water vapor, or a combination of two or three thereof; and/or, in the oxygen-containing compound atmosphere, the content of the oxygen-containing compound is 0.01-15% by volume, preferably 0.1-10% by volume;

and/or, the oxidation conditions include: the temperature is 100-800 ℃, and preferably 250-550 ℃; the time is 1-24 h, preferably 2-12 h.

12. The method of claim 6, wherein the first active metal is Pt or Pd, the second active metal is Mo, and the third active metal is W;

and/or the carrier is alumina, silica, titania, magnesia, zirconia, thoria, beryllia, clay, molecular sieve or activated carbon, or the combination of two or three of the above.

13. A carbide-based catalyst prepared by the method of any one of claims 6 to 12.

14. A glycerol hydrogenolysis method comprising contacting a glycerol-containing feedstock, hydrogen, and a catalyst under conditions that catalyze hydrogenolysis of glycerol, wherein the catalyst is the carbide-based catalyst of any one of claims 1-5 and 13.

15. The method of claim 14, wherein the conditions for catalytic glycerol hydrogenolysis comprise: the hydrogen pressure is 1-15MPa, preferably 2-8 MPa; the reaction temperature is 90-300 ℃, and preferably 100-220 ℃; the reaction time is more than 0.5h, preferably 4-36 h.

Technical Field

The disclosure relates to a carbide-based catalyst, a preparation method thereof and a glycerol hydrogenolysis method.

Background

1, 3-propanediol is an important raw material for producing degradable Polyester Trimethylene Terephthalate (PTT) and the like, and the demand is continuously increasing; furthermore, as an important chemical raw material, 1, 3-propanediol is also used in solvents, emulsifiers, medicines, cosmetics and organic synthesis. Currently, the industrial production of 1, 3-propanediol mainly adopts ethylene oxide carbonylation method and acrolein hydration hydrogenation method, and the raw materials of the two process routes are both from petroleum. With the continuous exhaustion of petroleum resources, the search for non-petroleum routes for producing 1, 3-propanediol is of great significance. The glycerol is a metering ratio byproduct (about 10%) in the production process of the biodiesel, and the yield of the byproduct glycerol is greatly increased along with the large demand and large-scale production of the biodiesel. This makes glycerol an ideal feedstock for the production of 1, 3-propanediol and also reduces the production cost of biodiesel.

CN102372602B discloses a method for preparing 1, 3-propylene glycol by glycerol hydrogenation, namely a continuous flow fixed bed reactor and Pt/WO are adopted₃/TiO₂-SiO₂The catalyst, glycerin and solvent are mixed and continuously fed into the reactor, and contact with the catalyst filled in the reactor under flowing hydrogen atmosphere to carry out reaction. Unreacted glycerin and hydrogen from the outlet of the reactorAnd the solvent is recycled after being separated from the product. Compared with the prior art, the method provided by the invention can have higher yield of the 1, 3-propylene glycol.

CN102728380A discloses a catalyst for preparing 1, 3-propanediol by glycerol hydrogenolysis, in particular to preparation and application of a mesoporous tungsten oxide supported platinum-based catalyst. The mesoporous tungsten oxide is used as a carrier, and the active component metal platinum or other noble metals are highly dispersed on the surface of the carrier, wherein the theoretical content of the active component is 0.1-40% of the mass of the carrier. The catalyst has the characteristics of good selectivity and high activity, and can realize the high-selectivity preparation of the 1, 3-propanediol by the hydrogenolysis of the glycerol under the hydrothermal condition of 120-fold-at-300 ℃ and 0.1-15MPa hydrogen pressure.

CN101747150A discloses a method for preparing 1, 3-propanediol by gas phase hydrogenolysis of glycerol using glycerol as raw material, which comprises preparing 1, 3-propanediol by gas phase hydrogenolysis of glycerol in the presence of a metal-acid bifunctional catalyst. The metal-acid bifunctional catalyst comprises the following components loaded on a carrier: (a) a solid acidic active ingredient and (b) a metal component (one of copper, nickel or cobalt) having hydrogenation activity, and optionally (c) a metal promoter component (one or more of iron, zinc, tin, manganese and chromium).

In combination with the research progress of the published literature, the selectivity of the hydrogenolysis of glycerol to 1, 3-propanediol depends mainly on two aspects, namely the intrinsic properties of the selected metal of the catalyst and the auxiliary agent, and the reaction conditions, especially the pH value of the solution and the solvent effect. Although many documents have been reported, the hydrogenolysis activity and selectivity of the glycerol as the catalyst of the reaction still have room for improvement and improvement.

Disclosure of Invention

The purpose of the present disclosure is to provide a carbide-based catalyst, a preparation method thereof, and a glycerol hydrogenolysis method, wherein the catalyst has high glycerol hydrogenolysis activity and 1, 3-propanediol selectivity.

To achieve the above object, a first aspect of the present disclosure: providing a carbide-based catalyst comprising a support, a first active component, a second active component, and a third active component,the first active component is a first active metal selected from one of the group VIII metals, and the second active component is a composite MC of a carbide and an oxide of a second active metal M_x-MO_yThe third active component is a composite NC of carbide and oxide of a third active metal N_a-NO_bWherein M is Mo or Ti, x is 0.5-1, y is 2-3, N is W or Zr, a is 0.5-1, and b is 2-3.

Optionally, the catalyst satisfies (M)_MCx/M_MOy)_XPS＝0.1～20，(M_NCa/M_NOb)_XPS0.1 to 20, preferably, (M)_MCx/M_MOy)_XPS＝1～10，(M_NCa/M_NOb)_XPS1 to 10, wherein (M)_MCx/M_MOy)_XPSMC in terms of metal element M in the catalyst characterized by X-ray photoelectron spectroscopy_xAnd MO_y(M) is_NCa/M_NOb)_XPSNC in terms of metal element N in the catalyst characterized by X-ray photoelectron spectroscopy_aWith NO_bIn a weight ratio of (a).

Optionally, the first active component is Pt or Pd, the second active metal M is Mo, and the third active metal N is W.

Optionally, the content of the first active component is 0.01-10 wt%, the content of the second active component is 1-30 wt%, the content of the third active component is 1-70 wt%, and the content of the carrier is 10-97 wt% calculated on the metal element and based on the dry weight of the catalyst;

preferably, the content of the first active component is 0.1-5 wt%, the content of the second active component is 2-20 wt%, the content of the third active component is 4-50 wt%, and the content of the carrier is 25-93 wt% calculated on the metal element and based on the dry weight of the catalyst;

the weight ratio of the second active component to the third active component is 0.1-1 calculated by metal elements.

Optionally, the support is alumina, silica, titania, magnesia, zirconia, thoria, beryllia, clay, molecular sieves, or activated carbon, or a combination of two or three thereof.

In a second aspect of the present disclosure: there is provided a method for preparing a carbide-based catalyst, the method comprising the steps of:

a. loading a first active metal, a second active metal and a third active metal on a carrier through impregnation to obtain an impregnated material;

b. carbonizing the impregnated material obtained in the step a in a carbon-containing compound atmosphere to obtain a carbonized material;

c. b, oxidizing the carbonized material obtained in the step b in an oxygen-containing compound atmosphere;

wherein the first active metal is one selected from group VIII metals; the second active metal is Mo or Ti; the third active metal is W or Zr.

Optionally, in the step a, the weight ratio of the first active metal, the second active metal and the third active metal calculated by metal elements to the carrier calculated by dry basis is (0.0001-1): (0.01-3): (0.01-7): 1, preferably (0.0011-0.2): (0.022-0.8): (0.043-2): 1;

the impregnation conditions include: the temperature is 10-90 ℃, and preferably 15-40 ℃; the time is 1-10 h, preferably 2-6 h.

Optionally, the method further comprises: drying and roasting the impregnated material obtained in the step a, and then performing the operation of the step b; the drying conditions are as follows: the temperature is 80-150 ℃, and the time is 1-24 h; the roasting conditions are as follows: the temperature is 200-700 ℃, and the time is 1-12 h.

Optionally, in step b, the carbon-containing compound is carbon monoxide, methane, ethane, ethylene, acetylene, propane, propylene or propyne, or a combination of two or three thereof; in the atmosphere containing the carbon compound, the content of the carbon compound is 5-50% by volume, preferably 10-25% by volume;

the carbonization conditions include: the temperature is 300-1000 ℃, preferably 500-900 ℃; the time is 1-24 h, preferably 2-12 h.

Optionally, the method further comprises: and c, cooling the carbonized material obtained in the step b to below 50 ℃ in hydrogen or inert atmosphere, treating the material in the inert atmosphere for 0.2-24 h, and then performing the operation in the step c.

Optionally, in step c, the oxygenate is oxygen, carbon dioxide or water vapor, or a combination of two or three thereof; in the oxygen-containing compound atmosphere, the content of the oxygen-containing compound is 0.01-15% by volume, preferably 0.1-10% by volume;

the oxidation conditions include: the temperature is 100-800 ℃, and preferably 250-550 ℃; the time is 1-24 h, preferably 2-12 h.

Optionally, the first active metal is Pt or Pd, the second active metal is Mo, and the third active metal is W;

the carrier is alumina, silica, titanium oxide, magnesia, zirconia, thoria, beryllium oxide, clay, molecular sieve or activated carbon, or the combination of two or three of the above.

A third aspect of the disclosure: there is provided a carbide-based catalyst prepared by the method of the second aspect of the disclosure.

A fourth aspect of the present disclosure: there is provided a process for the hydrogenolysis of glycerol comprising contacting a feed comprising glycerol, hydrogen and a catalyst under conditions to catalyze the hydrogenolysis of glycerol, wherein the catalyst is a carbide-based catalyst as described in the first or third aspect of the disclosure.

Optionally, the conditions for catalytic hydrogenolysis of glycerol comprise: the hydrogen pressure is 1-15MPa, preferably 2-8 MPa; the reaction temperature is 90-300 ℃, and preferably 100-220 ℃; the reaction time is more than 0.5h, preferably 4-36 h.

The carbide-based catalysts of the present disclosure exhibit excellent catalytic glycerol hydrogenolysis activity with high 1, 3-propanediol selectivity compared to catalysts of the prior art prepared with the same active metal content.

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

Detailed Description

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

The first aspect of the disclosure: a carbide-based catalyst is provided, which comprises a carrier, a first active component which is a first active metal selected from one of group VIII metals, a second active component which is a composite MC of a carbide and an oxide of a second active metal M, and a third active component_x-MO_yThe third active component is a composite NC of carbide and oxide of a third active metal N_a-NO_bWherein M is Mo or Ti, x is 0.5-1, y is 2-3, N is W or Zr, a is 0.5-1, and b is 2-3.

In the catalyst of the present disclosure, the presence of a specific complex MC of a carbide and an oxide of the second active metal M_x-MO_yAs a second active component, and a complex NC of a carbide and an oxide of a third active metal N_a-NO_bAs a third active component, compared with the catalyst with the same metal content prepared by the prior art, the catalyst has obviously higher catalytic glycerol hydrogenolysis activity and 1, 3-propylene glycol selectivity.

According to the present disclosure, the catalyst satisfies (M)_MCx/M_MOy)_XPS＝0.1～20，(M_NCa/M_NOb)_XPS0.1 to 20, wherein (M)_MCx/M_MOy)_XPSMC in terms of metal element M in the catalyst characterized by X-ray photoelectron spectroscopy_xAnd MO_y(M) is_NCa/M_NOb)_XPSNC in terms of metal element N in the catalyst characterized by X-ray photoelectron spectroscopy_aWith NO_bIn a weight ratio of (a). Preferably, (M)_MCx/M_MOy)_XPS＝1～10，(M_NCa/M_NOb)_XPSThe catalyst in the above range has a preferred hydrogen content in glycerinAnd (4) solving the performance.

The above X, y, a, b can be measured according to X-ray Photoelectron Spectroscopy (XPS) tests and their data handbook (Moulder, J.F.; Stickle, W.F.; Sobol, P.E.; Bomben, K.D. handbook of Photoelectron Spectroscopy; Chastatin, J.E.; Perkin-Elmer:1992), X-ray powder diffraction (XRD) tests and corresponding reference samples. The content of the metal element in the catalyst is characterized by X-ray photoelectron spectroscopy, which is well known to those skilled in the art, the weight ratio can be obtained by converting the peak area of the corresponding element characteristic peak of the corresponding compound, and the X-ray photoelectron spectroscopy can be carried out by a conventional method by using a conventional measuring instrument, without special requirements in the present disclosure. For example, the above x, y, a, b and (M)_MCx/M_MOy)_XPSThe XPS measuring instrument is an ESCALB 250 type instrument produced by Thermo Scientific, the excitation source is a monochromator Al K α X-ray with the power of 150W, and the basic vacuum during analysis is about 6.5 multiplied by 10^-8Pa, laser voltage of 50kV and laser current of 50mA, binding energy corrected by C1 s peak (284.8 eV). XRD test was carried out by Philips XPERT series instrument using Cu K α ray (λ 0.154nm), Ni filter, operating voltage of 40kV, operating current of 30mA, and sweep range of 5-75 ° (2 θ). Here, as an example, the third active metal N was tungsten (reference example 1), XPS measured W4 f_7/2Has two peaks of 35.7eV and 31.4eV, respectively, corresponding to WO₃And WC_x(ii) a Can be calculated according to the ratio of the two peak areas (M)_NCa/M_NOb)_XPSThe value is obtained. XRD shows that the peak positions are 31.5, 35.8, 48.4, 64.1-65.7 and 73.2 at 2 theta, and respectively correspond to characteristic signals of (001), (100), (101), (110) and (111) of the WC film of the standard reference sample. Combining the XPS and XRD test results, the third active component is WC-WO₃I.e. a 1 and b 3.

According to the present disclosure, preferably, the first active metal is Pt or Pd, more preferably Pt; the second active metal M is preferably Mo, and the third active metal N is preferably W.

According to the present disclosure, the first active component may be contained in an amount of 0.01 to 10 wt%, the second active component may be contained in an amount of 1 to 30 wt%, the third active component may be contained in an amount of 1 to 70 wt%, and the carrier may be contained in an amount of 10 to 97 wt%, based on the metal element and based on the dry weight of the catalyst. Preferably, the content of the first active component is 0.1-5 wt%, the content of the second active component is 2-20 wt%, the content of the third active component is 4-50 wt%, and the content of the carrier is 25-93 wt%, calculated by metal elements and based on the dry weight of the catalyst, and the catalyst in the above range has higher catalytic glycerol hydrogenolysis activity. Further, the weight ratio of the second active component to the third active component can be 0.1-1 calculated by metal elements.

According to the present disclosure, the support may be alumina, silica, titania, magnesia, zirconia, thoria, beryllia, clay, molecular sieves or activated carbon, or a combination of two or three of them. Preferably, the support is silica, alumina or silica-alumina. The carrier can also be obtained by modifying the substances by one or more of phosphorus, silicon, fluorine and boron, and can be obtained by commercial products or modification by the existing method.

In a second aspect of the present disclosure: there is provided a method for preparing a carbide-based catalyst, the method comprising the steps of:

a. loading a first active metal, a second active metal and a third active metal on a carrier through impregnation to obtain an impregnated material;

b. carbonizing the impregnated material obtained in the step a in a carbon-containing compound atmosphere to obtain a carbonized material;

c. b, oxidizing the carbonized material obtained in the step b in an oxygen-containing compound atmosphere;

wherein the first active metal is one selected from group VIII metals; the second active metal is Mo or Ti; the third active metal is W or Zr.

The carbide-based catalysts of the present disclosure have significantly higher catalytic glycerol than catalysts of the same metal content prepared by the prior artHydrogenolysis activity and 1, 3-propanediol selectivity. The chemical states of the second active component and the third active component of the catalyst are represented by X-ray photoelectron spectroscopy, and the finding shows that the carbide MC with lower binding energy exists in the characteristic electron binding energy interval of the second active metal M/the third active metal N_x/NC_aAnd higher binding energy oxide MO_y/NO_b(ii) a Further, the catalyst satisfies (M)_MCx/M_MOy)_XPS＝0.1～20，(M_NCa/M_NOb)_XPS0.1 to 20, preferably, (M)_MCx/M_MOy)_XPS＝1～10，(M_NCa/M_NOb)_XPS1 to 10, wherein (M)_MCx/M_MOy)_XPSMC in terms of metal element M in the catalyst characterized by X-ray photoelectron spectroscopy_xAnd MO_y(M) is_NCa/M_NOb)_XPSNC in terms of metal element N in the catalyst characterized by X-ray photoelectron spectroscopy_aWith NO_bIn a weight ratio of (a).

According to the present disclosure, the "supporting the first active metal, the second active metal and the third active metal on the carrier by impregnation" in the step a may be performed by one or more of the following manners:

1) respectively impregnating the carrier with a first impregnation liquid containing a first active metal precursor, a second impregnation liquid containing a second active metal precursor and a third impregnation liquid containing a third active metal precursor (the impregnation order is not limited);

2) impregnating the carrier with impregnation liquid containing two active metal precursors, and then impregnating the carrier with impregnation liquid containing a third active metal precursor;

3) impregnating the carrier with an impregnation liquid containing one active metal precursor, and then impregnating the carrier with an impregnation liquid containing the other two active metal precursors;

4) simultaneously impregnating the carrier with a first impregnation liquid containing a first active metal precursor, a second impregnation liquid containing a second active metal precursor and a third impregnation liquid containing a third active metal precursor;

5) preparing the first active metal precursor, the second active metal precursor and the third active metal precursor into an impregnation liquid, and then impregnating the carrier with the impregnation liquid.

Wherein the first active metal precursor is a compound containing a first active metal, and the first active metal is one selected from VIII group metals; the second active metal precursor is a compound containing a second active metal, and the second active metal is Mo or Ti; the third active metal precursor is a compound containing a third active metal, and the third active metal is W or Zr. Further, the first active metal is Pt or Pd, more preferably Pt; the second active metal is preferably Mo, and the third active metal is preferably W. The first active metal precursor may be various soluble compounds of the first active metal, preferably a nitrate, acetate, sulfate, chloride or acid of the first active metal, or a combination of two or three thereof; for example, when the first active metal is Pt, the first metal precursor may be tetraammineplatinum dichloride, tetraammineplatinum dinitrate, chloroplatinic acid, or the like. The second active metal precursor may be various soluble compounds of the second active metal, preferably a nitrate, acetate, sulfate, chloride or acid of the second active metal, or a combination of two or three thereof; for example, when the second active metal is Mo, the second metal precursor may be a molybdate and/or a paramolybdate. The third active metal precursor may be various soluble compounds of the third active metal, preferably a nitrate, acetate, sulfate, chloride or acid of the third active metal, or a combination of two or three thereof; for example, when the third active metal is W, the third metal precursor may be tungstate and/or metatungstate. The first impregnation liquid/the second impregnation liquid/the third impregnation liquid is a solution obtained by mixing a first metal precursor/a second metal precursor/a third metal precursor with a suitable solvent (the preparation of the first active metal precursor, the second active metal precursor and the third metal precursor into one impregnation liquid means that the first active metal precursor, the second active metal precursor and the third metal precursor are mixed with a suitable solvent to obtain the impregnation liquid containing the first active metal precursor, the second active metal precursor and the third metal precursor), and the used solvent may be water, ethanol, ethylene glycol, n-propanol, isopropanol, propylene glycol, n-hexane, cyclohexane or n-heptane, preferably water.

According to the present disclosure, the support may be alumina, silica, titania, magnesia, zirconia, thoria, beryllia, clay, molecular sieves or activated carbon, or a combination of two or three of them. Preferably, the support is silica, alumina or silica-alumina. The carrier can also be obtained by modifying the substances by one or more of phosphorus, silicon, fluorine and boron, and can be obtained by commercial products or modification by the existing method.

According to the present disclosure, in step a, the weight ratio of the first, second, third active metals, calculated as metal elements, to the support, calculated on a dry basis, may be (0.0001 to 1): (0.01-3): (0.01-7): 1. in order to further improve the catalytic glycerol hydrogenolysis activity of the catalyst, the weight ratio of the first active metal, the second active metal and the third active metal calculated by metal elements to the carrier calculated by dry basis is preferably (0.0011-0.2): (0.022-0.8): (0.043-2): 1.

in step a, the impregnation method is not particularly limited, and various methods known to those skilled in the art, for example, an equal volume impregnation method, a supersaturation impregnation method, and the like, may be used according to the present disclosure. Specifically, the impregnation conditions may include: the impregnation conditions include: the temperature is 10-90 ℃, and preferably 15-40 ℃; the time is 1-10 h, preferably 2-6 h.

According to the present disclosure, to further improve the catalytic glycerol hydrogenolysis activity and 1, 3-propanediol selectivity of the catalyst, the method may further comprise: and c, drying and roasting the impregnated material obtained in the step a, and then performing the operation of the step b. Wherein, the drying conditions can be as follows: the temperature is 80-150 ℃, and the time is 1-24 h; the roasting conditions can be as follows: the temperature is 200-700 ℃, and the time is 1-12 h.

According to the present disclosure, in step b, the carbon-containing compound may be carbon monoxide, methane, ethane, ethylene, acetylene, propane, propylene or propyne, or a combination of two or three thereof. The purpose of the disclosure can be achieved when the content of the carbon-containing compound in the carbon-containing compound atmosphere is small, for example, the content of the carbon-containing compound in the carbon-containing compound atmosphere can be 5 to 50% by volume, preferably 10 to 25% by volume; in this case, the carbon compound-containing atmosphere may further include hydrogen, nitrogen, argon, or helium, or a combination of two or three thereof. The carbonization conditions may include: the temperature is 300-1000 ℃, preferably 500-900 ℃; the time is 1-24 h, preferably 2-12 h.

According to the present disclosure, in order to facilitate the performing of step c, the method may further include: and c, cooling the carbonized material obtained in the step b to below 50 ℃ in the atmosphere of the carbon-containing compound, the hydrogen atmosphere or the inert atmosphere, treating the material in the inert atmosphere for 0.2-24 h, and then performing the operation in the step c. Wherein, the inert atmosphere can be nitrogen, argon or helium.

According to the present disclosure, in step c, the oxygenate is oxygen, carbon dioxide or water vapor, or a combination of two or three thereof. The purpose of the present disclosure can be achieved when the content of the oxygen-containing compound in the oxygen-containing compound atmosphere is small, for example, the content of the oxygen-containing compound in the oxygen-containing compound atmosphere may be 0.01 to 15 vol%, preferably 0.1 to 10 vol%; in this case, the oxygen-containing compound atmosphere may further include nitrogen, argon, or helium, or a combination of two or three thereof. The oxidation conditions may include: the temperature is 100-800 ℃, and preferably 250-550 ℃; the time is 1-24 h, preferably 2-12 h.

In the carbide-based catalyst prepared by the method provided by the disclosure, the first active metal is formed into a first active component, the second active metal is formed into a second active component after carbonization and oxidation, and the third active metal is formed into a third active component after carbonization and oxidation; the content of the first active component can be 0.01-10 wt%, the content of the second active component can be 1-30 wt%, the content of the third active component can be 1-70 wt%, and the content of the carrier can be 10-97 wt% calculated on the metal element and based on the dry weight of the catalyst. Preferably, the content of the first active component is 0.1-5 wt%, the content of the second active component is 2-20 wt%, the content of the third active component is 4-50 wt%, and the content of the carrier is 25-93 wt%, calculated on the metal element and based on the dry weight of the catalyst.

A third aspect of the disclosure: there is provided a carbide-based catalyst prepared by the method of the second aspect of the disclosure.

The catalyst provided by the present disclosure has high catalytic glycerol hydrogenolysis activity and 1, 3-propanediol selectivity when used in a glycerol hydrogenolysis reaction. Accordingly, the fourth aspect of the present disclosure: there is provided a process for the hydrogenolysis of glycerol comprising contacting a feed comprising glycerol, hydrogen and a catalyst under conditions to catalyze the hydrogenolysis of glycerol, wherein the catalyst is a carbide-based catalyst as described in the first or third aspect of the disclosure.

Further, the reaction may be carried out in any reactor sufficient to contact the glycerol-containing feedstock with the carbide-based catalyst under conditions to catalyze hydrogenolysis of glycerol to effect reaction, such as a fixed bed reactor or an autoclave reactor. The raw material containing glycerol may be a mixture of glycerol and a solvent, the concentration of the glycerol may be 5-95 wt%, and the solvent may be water, methanol, ethanol or propanol. The conditions for the catalytic glycerol hydrogenolysis may be performed with reference to the prior art, and may include, for example, the following, as evaluated in an autoclave reactor: the hydrogen pressure is 1-15MPa, preferably 2-8 MPa; the reaction temperature is 90-300 ℃, and preferably 100-220 ℃; the reaction time is more than 0.5h, preferably 4-36 h.

The following examples are presented to facilitate a better understanding of the present disclosure, but are not intended to limit the same.