CN111036253A

CN111036253A - Hydrogenation catalyst and preparation method thereof and glycerol hydrogenation method

Info

Publication number: CN111036253A
Application number: CN201811197913.1A
Authority: CN
Inventors: 晋超; 郑仁垟; 吴玉; 张荣俊; 王薇; 夏国富; 李明丰
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: 2018-10-15
Filing date: 2018-10-15
Publication date: 2020-04-21

Abstract

The present disclosure relates to a hydrogenation catalyst, a preparation method thereof and a glycerol hydrogenation method, wherein the catalyst comprises an active carrier and an active component loaded on the active carrier, the active component is one or more metal components selected from VIII group metals, the active carrier is a carbide of metal M, and M is one selected from VIB group metals. The catalyst has higher hydrogenation catalytic activity, and can obviously improve the selectivity of a target product 1, 3-propylene glycol when being used for a glycerol hydrogenation reaction.

Description

Hydrogenation catalyst, preparation method thereof and glycerol hydrogenation method

Technical Field

The disclosure relates to a hydrogenation catalyst, a preparation method thereof and a glycerol hydrogenation method.

Background

Glycerol is a major by-product of biodiesel production. Currently, the glycerol on the market comes mainly from the biodiesel and grease industries. With the continuous increase of the yield of the biodiesel, the market of the glycerin is basically saturated at present, the supply amount is obviously surplus, and the price of the glycerin is always stabilized at a low level. Among the derivatives of glycerol, 1,3-propanediol has a wide range of applications and a high market value. 1,3-Propanediol (1,3-Propanediol or 1,3-PDO) is an important organic chemical raw material, and the most important purpose is to be used as a raw material monomer for synthesizing a novel polyester material, namely 1,3-Propanediol terephthalate (PTT). Therefore, the production of 1,3-propanediol by using cheap glycerol as a raw material has important significance for increasing the economic benefit of the biodiesel industry.

At present, there are three main production processes of 1,3-PDO at home and abroad, namely an acrolein hydration and hydrogenation method of Degussa, Germany, an ethylene oxide carbonylation method of American Shell and a biological engineering fermentation method of DuPont. Because the acrolein hydration hydrogenation method and the ethylene oxide carbonyl formylation method have harsh reaction conditions and need high temperature and high pressure, and acrolein and ethylene oxide are respectively flammable, explosive and extremely toxic dangerous chemicals, thereby bringing greater potential safety hazard in production. The bioengineering method uses renewable resources as raw materials, has the advantages of low production cost, environmental protection and the like, gradually becomes the main production method of 1,3-PDO, and the productivity is continuously expanded. Considering that the process for preparing the 1, 3-propylene glycol by directly carrying out hydrogenolysis on the glycerol is simple in process, cheap and easily available in raw materials, free of toxic by-products and in line with the requirements of green chemical development, so that the method has wide application prospect and market value.

The preparation of 1,3-propanediol by the direct hydrogenolysis of glycerol has been widely used by researchers in recent yearsAttention is paid. Literature (Chin.J.Catal.,2012,33:1257-1261) reports that mesoporous tungsten oxide (m-WO) is prepared by adopting an evaporation-induced self-assembly method₃) And the Pt is loaded and then applied to the preparation of 1, 3-propylene glycol by the hydrogenolysis of catalytic glycerol. The results show that the tungsten oxide is compatible with commercial tungsten oxide (c-WO)₃) In contrast, m-WO₃Has the advantages of high specific surface area and easy reduction, thereby enabling Pt nanoparticles to be highly dispersed thereon. At 180 ℃ and 5.5MPaH₂The reaction is carried out for 12h, Pt/m-WO₃The conversion rate of the glycerol and the selectivity of the 1, 3-propylene glycol on the catalyst are respectively 18.0 percent and 39.2 percent, which are obviously higher than that of Pt/c-WO₃A catalyst. The document (Green Chemistry,2017,19(9):2174-2183) reports that a W-doped SBA-15 molecular sieve supported Pt catalyst can be used for the glycerol hydrogenation reaction to achieve the yield of 1,3-PDO of 61.5%, and the authors find that the Pt particle size has volcano-type distribution with the increase of W/Si ratio, and the Pt particle size is the smallest when the W/Si ratio is 1/640, so that the catalyst activity and selectivity are the highest.

CN107096564A discloses a SAPO-34 supported Pt and WOx catalyst and a preparation method thereof. The catalyst is used for the reaction of preparing 1,3-PDO by directly hydrogenating glycerol, so that the moderate strength and the large amount of acid B acid in the catalyst are ensured, and the dispersion of WOx and metal Pt is also ensured. CN104667924A discloses a method for impregnating active components Re and Ir in SiO by a co-impregnation method or a step-by-step impregnation method for a carrier₂And HZSM-5 molecular sieve carrier, the catalyst is used for glycerol hydrogenation reaction, and 1,3-PDO can be prepared with high selectivity.

In the fields of chemical synthesis fuel cells and petrochemical industry, metal platinum and noble metal elements adjacent to the periodic table of the elements, such as palladium and ruthenium, are generally used as catalytic active components, but the price of the rare noble metals is high, so that a novel catalyst for replacing platinum and platinum group elements is sought.

At present, the production process for preparing 1,3-propanediol by direct hydrogenolysis of glycerol is not applied to industrial production, mainly because the hydrogenolysis reaction of glycerol has relatively high requirements on energy consumption and equipment, the selectivity of 1,3-PDO is low, the separation difficulty of 1,3-PDO is high, and the like. Meanwhile, the catalyst has poor stability in the reaction process, short service life and relatively poor activity. Therefore, it is very realistic to develop a catalyst for preparing 1,3-PDO with high selectivity.

Disclosure of Invention

The invention aims to provide a hydrogenation catalyst, a preparation method thereof and a glycerol hydrogenation method, wherein the catalyst has high hydrogenation catalytic activity and can obviously improve the selectivity of a target product 1, 3-propylene glycol when being used in a glycerol hydrogenation reaction.

To achieve the above object, a first aspect of the present disclosure: a hydrogenation catalyst is provided, which comprises an active carrier and an active component loaded on the active carrier, wherein the active component is one or more metal components selected from VIII group metals, the active carrier is a carbide of metal M, and M is one selected from VIB group metals.

Optionally, the active carrier is contained in an amount of 80 to 99.9 wt% based on the dry weight of the catalyst, and the active component is contained in an amount of 0.1 to 20 wt% based on the metal element.

Optionally, the active carrier is 85-99.8 wt% based on the dry weight of the catalyst, and the active component is 0.2-15 wt% based on the metal element.

Optionally, the active component is a Ru component, a Pt component, a Co component, a Rh component, a Pd component, or an Ir component, or a combination of two or three thereof; and/or, M is Mo, W or C.

In a second aspect of the present disclosure: there is provided a process for preparing a catalyst according to the first aspect of the present disclosure, the process comprising the steps of:

a. carbonizing the metal M precursor in a carbon-containing compound atmosphere to obtain a carbide of the metal M;

b. and c, contacting the carbide of the metal M obtained in the step a with an impregnation liquid containing an active component precursor for impregnation, and collecting a solid product.

Optionally, in step a, the carbon-containing compound is methane, carbon monoxide, 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 10-40% by volume; preferably, the carbon compound-containing atmosphere comprises methane and hydrogen, wherein the volume ratio of the methane to the hydrogen is (5-50): (30-95), preferably (10-40): (40-90);

the carbonization conditions include: the carbonization temperature is 500-1000 ℃, and preferably 600-900 ℃; the carbonization heating rate is 0.2-30 ℃/min, preferably 0.5-20 ℃/min; the carbonization constant temperature time is 1-12 h, preferably 2-10 h.

Optionally, the method further comprises: cooling the carbide of the metal M obtained in the step a to below 50 ℃ in an inert atmosphere, and carrying out passivation treatment for 1-12 h in a passivation atmosphere and then carrying out the operation of the step b; in the passivation atmosphere, the content of oxygen is 0.05-5 vol%, preferably 0.1-3 vol%.

Optionally, in step b, the impregnating comprises: and c, mixing the carbide of the metal M obtained in the step a with an impregnation liquid containing an active component precursor, performing ultrasonic treatment for 0.5-5 h, and then standing for 1-24 h.

Optionally, the active ingredient precursor is nitrate, acetate, sulfate, chloride, acid or complex of the active ingredient, or a combination of two or three of them; and/or the metal M precursor is an oxide, a metal acid or a metal acid salt of the metal M, or a combination of two or three of the metal M and the metal acid.

Optionally, the method further comprises the steps of drying and roasting after collecting the solid product;

the drying conditions include: the temperature is 50-350 ℃, and preferably 80-300 ℃; the time is 1-24 hours, preferably 2-12 hours;

the roasting conditions comprise: the temperature is 200-800 ℃, preferably 300-600 ℃; the time is 1-24 h, preferably 2-12 h.

A third aspect of the disclosure: there is provided a glycerol hydrogenation process comprising contacting glycerol, hydrogen and a catalyst under conditions to catalyze a glycerol hydrogenation reaction, wherein the catalyst is a supported catalyst according to the first aspect of the disclosure.

Optionally, the weight ratio of the glycerol to the catalyst is (10-50): 1;

the conditions for catalyzing the hydrogenation reaction of the glycerol comprise: the hydrogen pressure is 1-15 MPa, 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.

Through the technical scheme, the catalyst disclosed by the invention takes the carbide as the carrier to load the active metal component, is particularly suitable for catalyzing the direct hydrogenation reaction of glycerol, has higher catalytic activity, can obviously improve the selectivity of a target product, has a simple preparation process and low cost, and is beneficial to industrial popularization.

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 hydrogenation catalyst is provided, which comprises an active carrier and an active component loaded on the active carrier, wherein the active component is one or more metal components selected from VIII group metals, the active carrier is a carbide of metal M, and M is one selected from VIB group metals.

In the catalyst disclosed by the invention, because the carbide of the special metal M exists as an active carrier, the catalyst has higher catalytic hydrogenation activity, and can obtain higher selectivity of 1, 3-propylene glycol when being used for hydrogenation reaction of glycerol.

According to the present disclosure, the active carrier may be contained in an amount of 80 to 99.9 wt% based on the dry weight of the catalyst, and the active component may be contained in an amount of 0.1 to 20 wt% based on the metal element. In order to further improve the catalytic activity of the catalyst, preferably, the content of the active carrier is 85-99.8 wt% based on the dry weight of the catalyst, and the content of the active component is 0.2-15 wt% calculated by metal elements.

Further, the active component may be a Ru component, a Pt component, a Co component, a Rh component, a Pd component, or an Ir component, or a combination of two or three of them, further a Ru component and/or a Pt component, and most preferably a Pt component. The metal M may be Mo, W or Cr, further Mo or W, most preferably W.

Thus, the metal M precursor is decomposed at high temperature in the atmosphere of carbon-containing compounds, and carbonized to generate carbide, and then the carbide is used as an active carrier to load active components, so that the hydrogenation catalyst with high catalytic hydrogenation activity can be prepared.

According to the present disclosure, in step a, the carbon-containing compound may be methane, carbon monoxide, 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 40% 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. In a preferred embodiment, the carbon compound-containing atmosphere comprises methane and hydrogen, wherein the volume ratio of methane to hydrogen can be (5-50): (30-95), preferably (10-40): (40-90). The carbonization conditions may include: the carbonization temperature is 500-1000 ℃, and preferably 600-900 ℃; the carbonization heating rate is 0.2-30 ℃/min, preferably 0.5-20 ℃/min; the carbonization constant temperature time is 1-12 h, preferably 2-10 h.

According to the present disclosure, the method may further comprise: and c, cooling the carbide of the metal M obtained in the step a to below 50 ℃ in an inert atmosphere, passivating the carbide of the metal M in a passivation atmosphere for 1-12 h, and then performing the operation in the step b. Wherein, the inert atmosphere can be argon, helium or nitrogen. The passivation atmosphere can be an atmosphere containing a trace amount of oxygen, and further, the content of oxygen in the passivation atmosphere can be 0.05-5% by volume, preferably 0.1-3% by volume; the passivating atmosphere may also include nitrogen, helium, or nitrogen, typically nitrogen.

In step b, 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 20-50 ℃, and the time is 1-12 h. In a preferred embodiment, the impregnation comprises: and c, mixing the carbide of the metal M obtained in the step a with an impregnation liquid containing an active component precursor, then carrying out ultrasonic treatment for 0.5-5 h, preferably 1-3 h, and then standing for 1-24 h. Thus, the dispersion degree of the active component on the active carrier can be further improved, so that the using amount of the active component is reduced, and the catalytic activity of the catalyst is improved.

According to the present disclosure, the active ingredient precursor refers to a compound containing the active ingredient, such as a nitrate, acetate, sulfate, chloride, acid, or complex of the active ingredient, or a combination of two or three thereof; for example, when the first component is Pt, the first active component precursor may be chloroplatinic acid, tetraammineplatinum dichloride, platinum nitrate, or the like. The active component precursor may be in the form of an aqueous solution having a concentration, for example, the concentration of the active component precursor may be 0.5 to 10 wt%, preferably 1 to 5 wt%, based on the metal element. The metal M precursor refers to a compound containing the metal M, such as an oxide, a metal acid or a metal acid salt of the metal M, or a combination of two or three of the metal M and the metal acid; for example, when the metal M is W, the metal M precursor may be ammonium metatungstate, sodium tungstate, silicotungstic acid, phosphotungstic acid, or the like.

According to the present disclosure, the metal M precursor and the active component precursor are used in such amounts that the active carrier is contained in an amount of 80 to 99.9 wt%, preferably 0.1 to 20 wt%, based on the dry weight of the catalyst, and the active component is contained in an amount of 85 to 99.8 wt%, preferably 0.2 to 15 wt%, calculated on the basis of the metal element.

According to the present disclosure, the method may further comprise the steps of drying and calcining after collecting the solid product. The drying and calcining steps are conventional steps in preparing catalysts, and the present disclosure is not particularly limited. For example, the drying conditions may include: the temperature is 50-350 ℃, and preferably 80-300 ℃; the time is 1 to 24 hours, preferably 2 to 12 hours. The conditions for the firing may include: the temperature is 200-800 ℃, preferably 300-600 ℃; the time is 1-24 h, preferably 2-12 h.

The catalyst disclosed by the invention has higher catalytic activity and 1, 3-propylene glycol selectivity when being used for glycerol hydrogenation reaction. Accordingly, the third aspect of the present disclosure: there is provided a glycerol hydrogenation process comprising contacting glycerol, hydrogen and a catalyst under conditions to catalyze a glycerol hydrogenation reaction, wherein the catalyst is a supported catalyst according to the first aspect of the disclosure.

Further, the contacting may be carried out in any reactor sufficient to contact the glycerol-containing feedstock with the catalyst under conditions to catalyze the hydrogenation of glycerol to effect reaction, such as a fixed bed reactor or an autoclave reactor. The glycerin may be in the form of an aqueous solution, and the concentration of the glycerin may be 5 to 95% by weight. The weight ratio of the glycerol to the catalyst can be (10-50): 1. the conditions for the catalytic hydrogenation of glycerol may be carried out according to the prior art, and for example, the conditions for the catalytic hydrogenation of glycerol may include: the hydrogen pressure is 1-15 MPa, 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.

Example 1

CH was added to 1.7g of ammonium metatungstate₄And H₂The volume ratio is 15: 85, raising the temperature to 800 ℃ at a heating rate of 1 ℃/min through a temperature programming program, keeping the temperature for 6 hours for carbonization, then switching to high-purity Ar gas, cooling to room temperature, keeping the temperature for 2 hours, and switching to O with the oxygen content of 0.2 volume percent₂And N₂Passivating for 2 hours in the passivating atmosphere to obtain the C-1 carrier.

0.17g of chloroplatinic acid solution with platinum content of 2.375 wt% is dissolved in 10g of deionized water and fully stirred, 1.0g of the C-1 carrier is added into the diluted chloroplatinic acid solution, the solution is placed in an ultrasonic instrument for ultrasonic treatment for 2 hours after being fully stirred at room temperature, then the solution is placed for 12 hours, then the solution is evaporated to dryness at 80 ℃, a solid product is roasted for 3 hours at 400 ℃, and the catalyst A1 prepared in the embodiment is obtained, wherein the composition of the catalyst A1 is 0.5 wt% of Pt/C-1 based on the metal element and the dry basis weight of the catalyst.

Example 2

CH was added to 1.7g of ammonium metatungstate₄And H₂The volume ratio is 15: 85, raising the temperature to 800 ℃ at a heating rate of 1 ℃/min through a temperature programming program, keeping the temperature for 6 hours for carbonization, then switching to high-purity Ar gas, cooling to room temperature, keeping the temperature for 2 hours, and switching to O with the oxygen content of 0.2 volume percent₂And N₂Passivating for 2 hours in the passivating atmosphere to obtain the C-2 carrier.

0.35g of chloroplatinic acid solution with platinum content of 2.375 wt% is dissolved in 10g of deionized water and fully stirred, 1.0g of the C-2 carrier is added into the diluted chloroplatinic acid solution, the solution is placed in an ultrasonic instrument for ultrasonic treatment for 2 hours after being fully stirred at room temperature, then the solution is placed for 12 hours, then the solution is evaporated to dryness at 80 ℃, a solid product is roasted for 3 hours at 400 ℃, and the catalyst A2 prepared in the embodiment is obtained, wherein the catalyst A2 has the composition of 1.0 wt% Pt/C-2 based on the metal element and the dry basis weight of the catalyst.

Example 3

Introducing CH into 5g of molybdenum trioxide₄And H₂The volume ratio is 15: 85, raising the temperature to 900 ℃ at the temperature rise rate of 2 ℃/min through the temperature programming program, keeping the temperature for 5 hours for carbonization, then switching to high-purity Ar gas, reducing the temperature to room temperature, keeping the temperature for 2 hours, and switching to O with the oxygen content of 0.2 volume percent₂And N₂Passivating for 2 hours in the passivation atmosphere to obtain the molybdenum carbide C-3 carrier.

0.19g of ruthenium nitrosyl nitrate solution with the ruthenium content of 3.15 wt% is dissolved in 10g of deionized water and fully stirred, 1.0g of the C-3 carrier is added into the diluted ruthenium nitrosyl nitrate solution, the mixed solution is placed in an ultrasonic instrument for ultrasonic treatment for 2 hours after being fully stirred at room temperature, then the mixed solution is placed for standing for 12 hours, then the solution is evaporated to dryness at 80 ℃, a solid product is roasted for 3 hours at 400 ℃, and the catalyst A3 prepared in the embodiment is obtained, wherein the composition of the catalyst A3 is 0.5 wt% Ru/C-3 based on metal elements and the dry basis weight of the catalyst.

Example 4

CH was added to 1.7g of ammonium metatungstate₄And H₂The volume ratio is 15: 85, raising the temperature to 800 ℃ at a heating rate of 1 ℃/min through a temperature programming program, keeping the temperature for 6 hours for carbonization, then switching to high-purity Ar gas, cooling to room temperature, keeping the temperature for 2 hours, and switching to O with the oxygen content of 0.2 volume percent₂And N₂Passivating for 2 hours in the passivating atmosphere to obtain the C-4 carrier.

Dissolving 0.06g of chloroplatinic acid solution with platinum content of 2.375 wt% in 10g of deionized water, fully stirring, adding 1.0g of the C-4 carrier into the diluted chloroplatinic acid solution, fully stirring at room temperature, placing in an ultrasonic instrument for ultrasonic treatment for 2 hours, standing for 12 hours, evaporating the solution at 80 ℃, roasting a solid product at 400 ℃ for 3 hours to obtain the catalyst A4 prepared in the embodiment, wherein the catalyst A4 is 0.15 wt% of Pt/C-4 calculated by metal elements and based on the dry weight of the catalyst.

Example 5

A catalyst was prepared by the method of example 1 except that, without the ultrasonic treatment, the carrier was added to the diluted chloroplatinic acid solution, sufficiently stirred at room temperature, directly left to stand for 12 hours, then the solution was evaporated to dryness at 80 ℃, and the solid product was calcined at 400 ℃ for 3 hours to obtain catalyst a5 prepared in this example.

Example 6

CH was added to 1.7g of ammonium metatungstate₄And H₂The volume ratio is 50: heating 50 carbon-containing compound atmosphere to 800 deg.C at a heating rate of 1 deg.C/min by programmed heating program, maintaining the temperature for 6 hr for carbonization, switching to high-purity Ar gas, cooling to room temperature, maintaining the temperature for 2 hr, and switching to O with oxygen content of 0.2 vol%₂And N₂Passivating for 2 hours in the passivating atmosphere to obtain the C-6 carrier.

0.17g of chloroplatinic acid solution with platinum content of 2.375 wt% is dissolved in 10g of deionized water and fully stirred, 1.0g of the C-6 carrier is added into the diluted chloroplatinic acid solution, the solution is placed in an ultrasonic instrument for ultrasonic treatment for 2 hours after being fully stirred at room temperature, then the solution is placed for 12 hours, then the solution is evaporated to dryness at 80 ℃, a solid product is roasted for 3 hours at 400 ℃, and the catalyst A6 prepared in the embodiment is obtained, wherein the composition of the catalyst A6 is 0.5 wt% Pt/C-6 based on the metal element and the dry basis weight of the catalyst.

Example 7

CH was added to 1.7g of ammonium metatungstate₄And H₂The volume ratio is 15: 85, raising the temperature to 1000 ℃ at a heating rate of 25 ℃/min through a temperature programming program, keeping the temperature for 12h for carbonization, then switching to high-purity Ar gas, cooling to room temperature, keeping the temperature for 2h, and switching to O with the oxygen content of 0.2 volume percent₂And N₂Passivating for 2 hours in the passivating atmosphere to obtain the C-7 carrier.

0.17g of chloroplatinic acid solution with platinum content of 2.375 wt% is dissolved in 10g of deionized water and fully stirred, 1.0g of the C-7 carrier is added into the diluted chloroplatinic acid solution, the solution is placed in an ultrasonic instrument for ultrasonic treatment for 2 hours after being fully stirred at room temperature, then the solution is placed for 12 hours, then the solution is evaporated to dryness at 80 ℃, a solid product is roasted for 3 hours at 400 ℃, and the catalyst A7 prepared in the embodiment is obtained, wherein the composition of the catalyst A7 is 0.5 wt% Pt/C-7 based on the metal element and the dry basis weight of the catalyst.

Comparative example 1

The catalyst was prepared as in example 1, with the difference that an equal amount of WO was used₃For the support replacement C-1, a catalyst composition D1 of composition 0.5 wt.% Pt/WO was prepared₃。

Test examples

The catalysts prepared in examples 1 to 7 and comparative example 1 were tested for catalytic activity for catalyzing hydrogenation reaction of glycerol.

Weighing 0.5g of catalyst, placing the catalyst in a 50mL high-pressure reaction kettle, adding 20g of glycerol aqueous solution with the mass concentration of 10 wt% of glycerol, reacting for 24h under the conditions that the reaction temperature is 180 ℃, the magnetic stirring rotating speed is 700r/min and the hydrogen pressure is 4.0MPa, cooling to room temperature after the reaction is finished, sampling and analyzing by adopting gas chromatography, calculating the conversion rate and the selectivity according to the following formula, and obtaining the reaction results shown in Table 1.

Conversion ratio (%) of glycerin (molar amount of glycerin before reaction-molar amount of glycerin after reaction)/molar amount of glycerin before reaction × 100%

1,3-propanediol selectivity (%): the molar amount of 1, 3-propanediol/total molar amount of carbon-forming substances × 100%

TABLE 1

As can be seen from table 1, the catalysts of the present disclosure have higher catalytic activity and 1,3-propanediol selectivity when used in the glycerol hydrogenation reaction.

The preferred embodiments of the present disclosure have been described in detail above, however, the present disclosure 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 disclosure within the technical idea of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.

It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.

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

Claims

1. A hydrogenation catalyst, characterized in that the catalyst comprises an active carrier and an active component supported on the active carrier, and the active component is a metal component selected from Group VIII metals or A variety of, the active carrier is a carbide of metal M, wherein M is one selected from the group VIB metals.

2 . The catalyst according to claim 1 , wherein, based on the dry weight of the catalyst, the content of the active carrier is 80-99.9% by weight, and the content of the active component is 0.1-99.9% by weight in terms of metal elements. 3 . 20% by weight.

3. The catalyst according to claim 2, wherein, based on the dry weight of the catalyst, the content of the active carrier is 85-99.8% by weight, and the content of the active component is 0.2-99.8% by weight in terms of metal elements 15% by weight.

4. The catalyst according to claim 1, wherein the active component is a Ru component, a Pt component, a Co component, a Rh component, a Pd component or an Ir component, or two of them or A combination of three; and/or, M is Mo, W, or C.

5. A method for preparing the catalyst according to any one of claims 1 to 4, wherein the method comprises the following steps:

a. Carbonizing the metal M precursor in a carbon-containing compound atmosphere to obtain a metal M carbide;

b. The carbide of the metal M obtained in step a is contacted with an impregnation solution containing an active component precursor for impregnation, and a solid product is collected.

6. The method according to claim 5, wherein, in step a, the carbon-containing compound is methane, carbon monoxide, ethane, ethylene, acetylene, propane, propylene or propyne, or two or three of them a combination of; and/or,

In the carbon-containing compound atmosphere, the content of the carbon-containing compound is 5-50% by volume, preferably 10-40% by volume; preferably, the carbon-containing compound atmosphere includes methane and hydrogen, wherein the volume ratio of methane and hydrogen is (5-50): (50-95), preferably (10-40): (60-90); and/or,

The carbonization conditions include: the carbonization temperature is 500-1000°C, preferably 600-900°C; the carbonization heating rate is 0.2-30°C/min, preferably 0.5-20°C/min; the carbonization constant temperature time is 1-12h, Preferably 2～10h.

7 . The method according to claim 5 , wherein the method further comprises: cooling the carbide of the metal M obtained in step a to below 50° C. under an inert atmosphere, and performing a passivation treatment for 1 under a passivation atmosphere. 8 . After ~12h, the operation of step b is performed; and/or,

In the passivation atmosphere, the content of oxygen is 0.05-5% by volume, preferably 0.1-3% by volume.

8 . The method according to claim 5 , wherein, in step b, the impregnation comprises: mixing the carbide of the metal M obtained in step a with an impregnation solution containing an active component precursor and then performing ultrasonic treatment for 0.5 ~5h, then let stand for 1~24h.

9. The method according to claim 5, wherein the active component precursor is nitrate, acetate, sulfate, chloride, acid or complex of the active component, or two of them. one or a combination of three; and/or, the metal M precursor is an oxide, a metal acid or a metal salt of the metal M, or a combination of two or three of them.

10. The method according to claim 6, wherein the method further comprises the steps of drying and roasting after collecting the solid product; and/or,

The drying conditions include: the temperature is 50-350°C, preferably 80-300°C; the time is 1-24 hours, preferably 2-12 hours; and/or,

The roasting conditions include: the temperature is 200-800° C., preferably 300-600° C.; and the time is 1-24 h, preferably 2-12 h.

11. A method for hydrogenation of glycerol, comprising contacting glycerol and hydrogen with a catalyst under the condition of catalyzing the hydrogenation of glycerol, wherein the catalyst is the supported type according to any one of claims 1 to 4 catalyst.

12. The method according to claim 11, wherein the weight ratio of the glycerol to the catalyst is (10-50): 1; and/or,

The conditions for the catalytic glycerol hydrogenation reaction include: the hydrogen pressure is 1-15MPa, preferably 2-8MPa; the reaction temperature is 90-300°C, preferably 100-220°C; the reaction time is more than 0.5h, preferably 4- 36h.