CN111036287A

CN111036287A - Supported catalyst, preparation method thereof and glycerol hydrogenation method

Info

Publication number: CN111036287A
Application number: CN201811197900.4A
Authority: CN
Inventors: 晋超; 吴玉; 郑仁垟; 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 supported catalyst, a preparation method thereof and a glycerol hydrogenation method, wherein the catalyst comprises a carrier, a first active component and a second active component, wherein the carrier contains a manganese oxide molecular sieve OMS-2, the first active component is one or more metal components selected from VIII group metals, and the second active component is one or more metal components selected from VIB group metals; the carrier comprises 75-98 wt% of a carrier, and the first metal component comprises 0.1-10 wt% and the second metal component comprises 0.1-15 wt% of a metal element. The catalyst can obtain higher selectivity of 1, 2-propylene glycol when used in the hydrogenation reaction of glycerol.

Description

Supported catalyst, preparation method thereof and glycerol hydrogenation method

Technical Field

The disclosure relates to a supported catalyst, a preparation method and application 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. Propylene Glycol (PG) is mainly used for the production of coatings and Unsaturated Polyester Resins (UPR), and is additionally used as an antifreeze, as an alternative to ethylene glycol for the deicing of aircraft, as a coolant in food, and the like. In addition, a large amount of propylene glycol is used for producing a plasticizer and hydraulic brake fluid, the propylene glycol can also be used for a nonionic detergent and used as a humectant in the industries of medicines, cosmetics, animal foods and tobacco, and the propylene glycol is also a good solvent and can be used for the aspects of printing ink, epoxy resin and the like.

There are about 5 common propylene glycol production technologies: propylene oxide direct hydration method, propylene oxide indirect hydration method, propylene direct catalytic oxidation method, biochemical process method, and dimethyl carbonate (DMC) -propylene glycol co-production method.

At present, in the research on the hydrogenolysis of glycerol, the catalyst mainly comprises precious metals Rh, Ru, Ag, Au and Pt and non-precious metals Cu, Zn, Mg, Al, Co and the like. In the literature, Chin J Catal, 2014 and 35 respectively adopt a uniform coprecipitation method, a deposition-precipitation method and a traditional coprecipitation method to prepare 3 types of Cu-ZnO-Al with similar compositions₂O₃The conversion rate of the catalyst to the glycerol is about 30 percent, the selectivity to the 1, 2-propylene glycol is over 90 percent, after the reaction,the crystal grain of Cu is obviously increased, the activity is reduced, and the reusability is poor. SpecPetrochem (Fine petrochemical, 2013, 30(3): 67-69). The method is characterized in that 1, 2-propylene glycol is prepared by carrying out hydrogenolysis on a glycerol aqueous solution by utilizing a Raney-Ni catalyst, the influence of each reaction condition on a reaction result is investigated through a single-factor experiment, and the result shows that when the dosage of the catalyst is 35% of the dosage of the glycerol, the reaction temperature is 170 ℃, the reaction time is 9h, the pressure in a kettle is 2.5MPa, and the mass fraction is 80% of the glycerol aqueous solution, the reaction is optimal, the conversion rate of the glycerol can reach 80% at most, the selectivity to the 1, 2-propylene glycol is about 50%, and the catalyst has a good repeated use effect. The document Chin J Catal (catalytic science report), 2012, 33(5):790 and 796 prepares Ni by an impregnation method and a temperature programmed reduction method₂P/SiO₂And Ni/SiO₂The catalyst is characterized and evaluated in hydrogenolysis performance, and research results show that Ni₂P/SiO₂They believe that glycerol hydrogenolysis first dehydrates to acetol on the acid center and then hydrogenates to 1, 2-propanediol on the metal active center.

German Degussa (CN93114516.3) takes glycerol as a raw material, uses 10-40 wt% of glycerol aqueous solution as the raw material at 250-340 ℃, and dehydrates the glycerol to generate acrolein and hydroxyacetone through a strong acid solid catalyst in the first step; secondly, hydrating acrolein in an acid catalyst to generate 3-hydroxypropionaldehyde; and thirdly, generating 1, 3-propylene glycol and 1, 2-propylene glycol through the hydrogenation reaction of 3-hydroxypropionaldehyde and hydroxyacetone. The yield of 1, 3-propanediol and 1, 2-propanediol relative to glycerol was 60% and 10%. The reaction period is long and the yield is low.

The german BASF company (CN95121742.9) uses a composite catalyst containing cobalt, copper, manganese and aluminum, and also uses a catalyst system containing inorganic acid or heteropoly acid to prepare 1, 2-propanediol by hydrogenation of glycerol. Under the conditions that the temperature is higher than 200 ℃ and the pressure is higher than 20MPa, the method can obtain the 1, 2-propylene glycol with high yield, but the reaction conditions are harsh, and the catalyst system is complex.

Chinese patent CN1061968C describes a method for preparing 1, 2-propylene glycol by the catalytic hydrogenolysis of glycerol at high temperature and high pressure, wherein the yield of 1, 2-propylene glycol can reach 95% by adopting a catalyst containing metal cobalt, copper, molybdenum and manganese, but the reaction pressure is 20-32 MPa, and the higher pressure causes the increase of the investment cost of the device and the increase of the operation difficulty.

A process for the gas phase hydrogenation of glycerol is reported in patent WO 2007/010299. The process adopts a Cu-based catalyst, adopts a methanol solution of glycerol as a raw material, has the reaction temperature of 160-260 ℃, the pressure of 1-3 MPa and the ratio of hydrogen to glycerol of 400: 1-600: 1, and can reach the selectivity of 1, 2-propylene glycol of 96 percent under the condition of 100 percent conversion of the glycerol. However, the gas phase glycerol feeding is adopted in the patent, and the boiling point of the glycerol is as high as 290 ℃, so that the energy consumption of the glycerol gasification process is high, and the operation cost of the device is inevitably increased. In addition, the process needs higher hydrogen-glycerol ratio, so that the single-pass utilization rate of hydrogen is lower, and the material consumption of hydrogen is increased.

At present, the production process for preparing 1, 2-propylene glycol by directly hydrogenolyzing glycerol is not applied to industrial production, mainly because the hydrogenolyzing reaction of glycerol has relatively high requirements on energy consumption and equipment, the separation difficulty of 1,2-PDO is high, and the like. Meanwhile, the catalyst has poor stability in the reaction process, short service life and relatively poor activity. Therefore, the development of a catalyst for preparing 1,2-PDO with high selectivity has very practical significance.

Disclosure of Invention

The purpose of the disclosure is to provide a supported catalyst, a preparation method thereof and a glycerol hydrogenation method, wherein the supported catalyst can obtain higher selectivity of 1, 2-propylene glycol when being used for glycerol hydrogenation reaction.

To achieve the above object, a first aspect of the present disclosure: providing a supported catalyst, which comprises a carrier, a first active component and a second active component, wherein the carrier contains manganese oxide molecular sieve OMS-2, the first active component is one or more metal components selected from VIII group metals, and the second active component is one or more metal components selected from VIB group metals;

the content of the carrier is 75-98 wt% based on the dry weight of the catalyst, and the content of the first metal component is 0.1-10 wt% and the content of the second metal component is 0.1-15 wt% calculated by metal elements.

Optionally, the carrier is 85 to 97 wt% based on the dry weight of the catalyst, and the first metal component is 0.2 to 5 wt% and the second metal component is 0.2 to 10 wt% based on the metal element.

Optionally, the weight ratio of the first active component to the second active component is 1: (0.5 to 10), preferably 1: (1-5).

Optionally, the first 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; the second active component is a Mo component, a W component or a Cr component, or a combination of two or three thereof.

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:

(1) reacting a first aqueous solution containing an oxidation state manganese compound, a reduction state manganese compound and a second active component precursor at 30-180 ℃ for 1-36 h, collecting a solid product, washing, drying and roasting to obtain a carrier doped with a second active component;

(2) adding alkali into a second aqueous solution containing a first active component precursor and the carrier doped with the second active component obtained in the step (1) to enable the pH value of the material after the alkali is added to be 3-8, stirring the material after the alkali is added for 1-12 h, standing for 1-24 h, and collecting a solid product.

Optionally, in step (1), the molar ratio of the second active component precursor to Mn in the first aqueous solution is 1: (0.1 to 500).

Optionally, in step (1), the oxidized manganese compound is potassium permanganate and potassium manganate, and the reduced manganese compound is manganese sulfate, manganese nitrate, manganese acetate or manganese chloride;

the molar ratio of the oxidized manganese compound to the reduced manganese compound is (0.5-3): 1.

optionally, in the step (2), after the alkali-added material is stirred for 1-12 hours, ultrasonic treatment is performed for 1-12 hours, and then the standing treatment is performed.

Optionally, in the step (2), the alkali is ammonia water, sodium hydroxide or potassium hydroxide, and the concentration of the alkali is 0.1-50% by weight.

Optionally, the first active ingredient precursor is a nitrate, acetate, sulfate, chloride, acid or complex of the first active ingredient, or a combination of two or three thereof; and/or the second active component precursor is a metal acid salt of the second active component.

Optionally, the method further comprises: in the step (2), collecting a solid product, and then drying and roasting the solid product;

the drying conditions include: the temperature is 30-350 ℃, and preferably 60-300 ℃; the time is 1-24 hours, preferably 2-12 hours;

the roasting conditions comprise: the temperature is 250-900 ℃, and preferably 350-800 ℃; the time is 0.5 to 12 hours, preferably 2 to 6 hours.

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 manganese oxide molecular sieve OMS-2 as a carrier and loads active metal, is particularly suitable for catalyzing direct hydrogenation reaction of glycerol, can obviously improve the selectivity of a target product, and is more economic due to lower content of active metal with high cost.

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: providing a supported catalyst, which comprises a carrier, a first active component and a second active component, wherein the carrier contains manganese oxide molecular sieve OMS-2, the first active component is one or more metal components selected from VIII group metals, and the second active component is one or more metal components selected from VIB group metals; the content of the carrier is 75-98 wt% based on the dry weight of the catalyst, and the content of the first metal component is 0.1-10 wt% and the content of the second metal component is 0.1-15 wt% calculated by metal elements.

The inventor of the present disclosure finds in research that the manganese oxide molecular sieve OMS-2 has a mesh tunnel structure, has vacancies capable of loading metals inside, can be substituted by other metal elements for certain framework elements, and has a suitable pore size, strong hydrophobicity, moderate acidity and alkalinity, and strong hydrothermal stability, so that the catalyst prepared by using the manganese oxide molecular sieve OMS-2 as a carrier is particularly suitable for catalyzing glycerol hydrogenation reaction, and can effectively improve the selectivity of a target product. The first active component may be supported on the support, and the second active component may be dispersed on the support in a doped manner.

In order to further improve the catalytic activity of the catalyst, preferably, the carrier is contained in an amount of 85 to 97 wt% based on the dry weight of the catalyst, and the first metal component is contained in an amount of 0.2 to 5 wt% and the second metal component is contained in an amount of 0.2 to 10 wt% in terms of metal elements; more preferably, the carrier is contained in an amount of 90 to 96 wt%, and the first active component is contained in an amount of 0.2 to 4 wt% and the second active component is contained in an amount of 0.8 to 6 wt%, in terms of metal element, based on the dry weight of the catalyst.

According to the present disclosure, the ratio of the first active component to the second active component has a certain influence on the catalytic activity of the catalyst. In the present disclosure, the weight ratio of the first active component to the second active component may be 1: (0.5 to 10), preferably 1: (1-5).

Further, the first 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 thereof, and further, a Ru component and/or a Pt component, and most preferably, a Pt component. The second active component is a Mo component, a W component or a Cr component, or a combination of two or three of them, further is a Mo component and/or a W component, and most preferably is a W component.

Therefore, the second active component is doped in the process of preparing the carrier, and then the first active component is loaded on the carrier doped with the second active component by a deposition precipitation method, so that the use amount of the high-cost first active component is reduced, and the prepared catalyst is more economic and effective.

According to the present disclosure, in order to achieve the desired effect, in step (1), the molar ratio of the second active component precursor to Mn in the first aqueous solution may vary within a wide range, for example, may be 1: (0.1 to 500).

According to the present disclosure, in step (1), the oxidized manganese compound and the reduced manganese compound are relative; the oxidized manganese compound is generally referred to as containing a relatively high valence state of manganese (e.g., Mn)⁷⁺、Mn⁶⁺Etc.), for example, potassium permanganate or potassium manganate; the reduced manganese compound is generally referred to as containing relatively low levels of manganese (e.g., Mn)²⁺Etc.) and may be, for example, manganese sulfate, manganese nitrate, manganese acetate or manganese chloride. In order to achieve the ideal effect, the molar ratio of the oxidized manganese compound to the reduced manganese compound may be (0.5 to 3): 1. furthermore, in the preparation step, the washing is performed by washing the collected solid product with deionized water until the washing liquid is neutral (for example, pH 6 to 7). Drying is carried out after washing, and the drying conditions can comprise: the temperature is 80-350 ℃, preferably 100-300 ℃, and the time is 1-24 hours, preferably 2-12 hours. Then, roasting is carried out, and the roasting conditions can comprise: the temperature is 200-1000 ℃, preferably 300-800 ℃, and more preferably 350-700 ℃; the time is 1-10 h, preferably 2-8 h, and more preferably 3-6 h.

According to the present disclosure, in order to further improve the catalytic activity of the catalyst, the method may further include: in the step (2), after the alkali-added material is stirred for 1-12 hours, ultrasonic treatment is carried out for 1-12 hours, and then the standing treatment is carried out. The sonication can be carried out in a conventional sonication apparatus.

According to the present disclosure, in the step (2), the alkali may be various common alkali liquids or alkali solutions, for example, ammonia water, sodium hydroxide or potassium hydroxide, and further, the concentration of the alkali may be 0.1 to 50 wt%.

According to the present disclosure, the first active ingredient precursor refers to a compound containing the first active ingredient, such as a nitrate, acetate, sulfate, chloride, acid, or complex of the first active ingredient, or a combination of two or three thereof; for example, when the first component is a Pt component, the first active component precursor may be chloroplatinic acid, tetraammineplatinum dichloride, or the like. The second active component precursor is a compound containing the second active component, such as a metalate which can be the second active component; for example, when the second component is the W component, the second active component precursor may be sodium tungstate, ammonium metatungstate, or the like.

According to the present disclosure, the carrier, the first active component precursor, and the second active component precursor are used in amounts such that, in the prepared catalyst, the carrier has a content of 75 to 98 wt%, preferably 85 to 97 wt%, based on the dry weight of the catalyst, and the first active component has a content of 0.1 to 10 wt%, preferably 0.1 to 15 wt%, and the second active component has a content of 0.2 to 5 wt%, preferably 0.2 to 10 wt%, calculated on the basis of metal elements.

According to the present disclosure, the method may further comprise: and (2) collecting the solid product, and then drying and roasting. 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 30-350 ℃, and preferably 60-300 ℃; the time is 1 to 24 hours, preferably 2 to 12 hours. The conditions for the firing may include: the temperature is 250-900 ℃, preferably 300-850 ℃, and more preferably 350-800 ℃; the time is 0.5 to 12 hours, preferably 1 to 8 hours, and more preferably 2 to 6 hours.

The catalyst disclosed by the invention has higher catalytic activity and 1, 2-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

Dissolving 3.17g of potassium permanganate in 40.55g of deionized water, heating and stirring to dissolve the potassium permanganate to form a potassium permanganate solution, adding 0.27g of sodium tungstate into 3.64g of a 50 wt% manganese nitrate solution, and uniformly stirring to obtain a sodium tungstate-containing manganese nitrate solution, wherein W: the Mn molar ratio is 1: and 37, mixing the two solutions, transferring the mixed solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction at 180 ℃ for 24 hours. The resulting brown precipitate was washed several times with deionized water until the pH of the washing solution was 7, and then the solid product was dried at 120 ℃ overnight and calcined at 400 ℃ for 4h to give OMS-2 support Z1 doped with 0.8 wt% W.

Adding 25ml of water into 1g of the carrier Z1, dropwise adding 0.37g of a tetrammine platinum dichloride solution with the platinum content of 1.35 wt% into the carrier Z1, uniformly stirring, dropwise adding a dilute ammonia water solution with the concentration of 0.28 wt% into the mixture until the pH value is 7, stirring for 2h, then transferring the mixture into an ultrasonic instrument for ultrasonic treatment for 2h, standing for 12h, evaporating the solution at 70 ℃, roasting the solid product at 400 ℃ for 2h to obtain the catalyst A1 prepared in the embodiment, wherein the composition of the catalyst A1 is 0.4 wt% of Pt/0.8 wt% of W-OMS-2 calculated by metal elements and based on the dry weight of the catalyst.

Example 2

Dissolving 3.17g of potassium permanganate in 40.55g of deionized water, heating and stirring to dissolve the potassium permanganate to form a potassium permanganate solution, adding 0.27g of sodium tungstate into 3.64g of a 50 wt% manganese nitrate solution, and uniformly stirring to obtain a sodium tungstate-containing manganese nitrate solution, wherein W: the Mn molar ratio is 1: and 37, mixing the two solutions, transferring the mixed solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction at 180 ℃ for 24 hours. The resulting brown precipitate was washed several times with deionized water until the pH of the washing solution was 7, and then the solid product was dried at 120 ℃ overnight and calcined at 400 ℃ for 4h to give OMS-2 support Z2 doped with 0.8 wt% W.

Adding 25ml of water into 1g of the carrier Z2, dropwise adding 0.74g of a tetrammine platinum dichloride solution with the platinum content of 1.35 wt% into the carrier Z2, uniformly stirring, dropwise adding a dilute ammonia water solution with the concentration of 0.28 wt% into the mixture until the pH value is 7, stirring for 2h, then transferring the mixture into an ultrasonic instrument for ultrasonic treatment for 2h, standing for 12h, evaporating the solution at 70 ℃, roasting the solid product at 400 ℃ for 2h to obtain the catalyst A2 prepared in the embodiment, wherein the composition of the catalyst A2 is 0.8 wt% of Pt/0.8 wt% of W-OMS-2 calculated by metal elements and based on the dry weight of the catalyst.

Example 3

Dissolving 3.17g of potassium permanganate in 40.55g of deionized water, heating and stirring to dissolve the potassium permanganate to form a potassium permanganate solution, adding 0.2g of sodium molybdate to 3.64g of a 50 wt% manganese nitrate solution, and uniformly stirring to obtain a manganese nitrate solution containing sodium molybdate, wherein Mo: the Mn molar ratio is 1: and 37, mixing the two solutions, transferring the mixed solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction at 180 ℃ for 24 hours. The resulting brown precipitate was washed several times with deionized water until the pH of the washing solution became 7, and then the solid product was dried overnight at 120 ℃ and calcined at 400 ℃ for 4h to obtain OMS-2 support Z3 doped with 0.8 wt% Mo.

Adding 25ml of water into 1g of the carrier Z3, dropwise adding 1.32g of a cobalt nitrate solution with the cobalt content of 16 wt% into the carrier Z3, uniformly stirring, dropwise adding a dilute ammonia water solution with the concentration of 0.28 wt% into the mixture until the pH value is 7, stirring for 2h, then moving the mixture into an ultrasonic instrument for ultrasonic treatment for 2h, standing for 12h, then evaporating the solution at 70 ℃, and roasting the solid product at 400 ℃ for 2h to obtain the catalyst A3 prepared in the embodiment, wherein the composition of the catalyst A3 is 0.4 wt% of Co/0.8 wt% of Mo-OMS-2 based on the metal elements and the weight of the catalyst on a dry basis.

Example 4

Dissolving 3.17g of potassium permanganate in 40.55g of deionized water, heating and stirring to dissolve the potassium permanganate to form a potassium permanganate solution, adding 0.84g of chromium nitrate into 3.64g of 50 wt% manganese nitrate solution, and uniformly stirring to obtain a manganese nitrate solution containing chromium nitrate, wherein the weight ratio of Cr: the Mn molar ratio is 1: 21, mixing the two solutions, transferring the mixed solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction at 180 ℃ for 24 hours. The resulting brown precipitate was washed several times with deionized water until the pH of the washing solution became 7, and then the solid product was dried at 120 ℃ overnight and calcined at 400 ℃ for 4h to obtain OMS-2 carrier Z4 doped with 1.4 wt% Cr.

Adding 25ml of water into 1g of the carrier Z4, dropwise adding 1.42g of a palladium chloride solution with the palladium content of 2.356 wt% into the carrier Z4, uniformly stirring, dropwise adding a dilute ammonia water solution with the concentration of 0.28 wt% into the mixture until the pH value is 7, stirring for 2h, then transferring the mixture into an ultrasonic instrument for ultrasonic treatment for 2h, standing for 12h, then evaporating the solution at 70 ℃, and roasting the solid product at 400 ℃ for 2h to obtain the catalyst A4 prepared in the example, wherein the catalyst A4 comprises 1.5 wt% of Pd/2.5 wt% of Cr-OMS-2 in terms of metal elements and based on the weight of the dry catalyst.

Example 5

Dissolving 3.17g of potassium permanganate in 40.55g of deionized water, heating and stirring to dissolve the potassium permanganate to form a potassium permanganate solution, adding 0.54g of sodium tungstate into 3.64g of a 50 wt% manganese nitrate solution, and uniformly stirring to obtain a sodium tungstate-containing manganese nitrate solution, wherein W: the Mn molar ratio is 1: and 37, mixing the two solutions, transferring the mixed solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction at 180 ℃ for 24 hours. The resulting brown precipitate was washed several times with deionized water until the pH of the washing solution was 7, and then the solid product was dried at 120 ℃ overnight and calcined at 400 ℃ for 4h to give OMS-2 support Z5 doped with 1.6 wt% W.

Adding 25ml of water into 1g of the carrier Z5, dropwise adding 0.18g of a tetrammine platinum dichloride solution with the platinum content of 1.35 wt% into the carrier Z5, uniformly stirring, dropwise adding a dilute ammonia water solution with the concentration of 0.28 wt% into the mixture until the pH value is 7, stirring for 2h, then transferring the mixture into an ultrasonic instrument for ultrasonic treatment for 2h, standing for 12h, evaporating the solution at 70 ℃, roasting the solid product at 400 ℃ for 2h to obtain the catalyst A5 prepared in the embodiment, wherein the composition of the catalyst A5 is 0.2 wt% of Pt/1.6 wt% of W-OMS-2 calculated by metal elements and based on the dry weight of the catalyst.

Example 6

Dissolving 3.17g of potassium permanganate in 40.55g of deionized water, heating and stirring to dissolve the potassium permanganate to form a potassium permanganate solution, adding 0.27g of sodium tungstate into 3.64g of a 50 wt% manganese nitrate solution, and uniformly stirring to obtain a sodium tungstate-containing manganese nitrate solution, wherein W: the Mn molar ratio is 1: and 37, mixing the two solutions, transferring the mixed solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction at 180 ℃ for 24 hours. The resulting brown precipitate was washed several times with deionized water until the pH of the washing solution was 7, and then the solid product was dried at 120 ℃ overnight and calcined at 400 ℃ for 4h to give OMS-2 support Z6 doped with 0.8 wt% W.

Adding 25ml of water into 1g of the carrier Z6, dropwise adding 1.51g of a tetrammine platinum dichloride solution with the platinum content of 1.35 wt% into the carrier Z6, uniformly stirring, dropwise adding a 0.28 wt% dilute ammonia water solution into the mixture until the pH value is 7, stirring for 2h, then moving the mixture into an ultrasonic instrument for ultrasonic treatment for 2h, standing for 12h, evaporating the solution at 70 ℃, and roasting a solid product at 400 ℃ for 2h to obtain the catalyst A6 prepared in the example, wherein the composition of the catalyst A6 is 1.6 wt% of Pt/0.8 wt% of W-OMS-2 calculated by metal elements and based on the dry weight of the catalyst.

Example 7

Dissolving 3.17g of potassium permanganate in 40.55g of deionized water, heating and stirring to dissolve the potassium permanganate to form a potassium permanganate solution, adding 0.08g of sodium tungstate into 3.64g of a 50 wt% manganese nitrate solution, and uniformly stirring to obtain a sodium tungstate-containing manganese nitrate solution, wherein W: the Mn molar ratio is 1: 148, mixing the two solutions, transferring the mixed solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction at 180 ℃ for 24 hours. The resulting brown precipitate was washed several times with deionized water until the pH of the washing solution was 7, and then the solid product was dried at 120 ℃ overnight and calcined at 400 ℃ for 4h to give OMS-2 support Z7 doped with 0.2 wt% W.

Adding 25ml of water into 1g of the carrier Z7, dropwise adding 3.5g of a tetrammine platinum dichloride solution with the platinum content of 1.35 wt% into the carrier Z7, uniformly stirring, dropwise adding a 0.28 wt% dilute ammonia water solution into the mixture until the pH value is 7, stirring for 2 hours, then moving the mixture into an ultrasonic instrument for ultrasonic treatment for 2 hours, standing for 12 hours, evaporating the solution to dryness at 70 ℃, and roasting the solid product at 400 ℃ for 2 hours to obtain the catalyst A7 prepared in the embodiment, wherein the composition of the catalyst A7 is 2.5 wt% of Pt/0.2 wt% of W-OMS-2 calculated by metal elements and based on the dry weight of the catalyst.

Example 8

Dissolving 3.17g of potassium permanganate in 40.55g of deionized water, heating and stirring to dissolve the potassium permanganate to form a potassium permanganate solution, adding 0.04g of sodium tungstate into 3.64g of a 50 wt% manganese nitrate solution, and uniformly stirring to obtain a sodium tungstate-containing manganese nitrate solution, wherein W: the Mn molar ratio is 1: 296, mixing the two solutions, transferring the mixture into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 24 hours at 180 ℃. The resulting brown precipitate was washed several times with deionized water until the pH of the washing solution was 7, and then the solid product was dried at 120 ℃ overnight and calcined at 400 ℃ for 4h to give OMS-2 support Z8 doped with 0.1 wt% W.

Adding 25ml of water into 1g of the carrier Z8, dropwise adding 0.11g of a tetrammine platinum dichloride solution with the platinum content of 1.35 wt% into the carrier Z8, uniformly stirring, dropwise adding a dilute ammonia water solution with the concentration of 0.28 wt% into the mixture until the pH value is 7, stirring for 2h, then transferring the mixture into an ultrasonic instrument for ultrasonic treatment for 2h, standing for 12h, evaporating the solution at 70 ℃, roasting the solid product at 400 ℃ for 2h to obtain the catalyst A8 prepared in the embodiment, wherein the catalyst A8 comprises 0.12 wt% of Pt/0.1 wt% of W-OMS-2 in terms of metal elements and based on the dry weight of the catalyst.

Example 9

Dissolving 3.17g of potassium permanganate in 40.55g of deionized water, heating and stirring to dissolve the potassium permanganate to form a potassium permanganate solution, adding 5.4g of sodium tungstate into 3.64g of 50 wt% manganese sulfate solution, and uniformly stirring to obtain a sodium tungstate-containing manganese sulfate solution, wherein W: the Mn molar ratio is 1: 0.38, mixing the two solutions, transferring the mixture into a hydrothermal reaction kettle, and carrying out hydrothermal reaction at 180 ℃ for 24 hours. The resulting brown precipitate was washed several times with deionized water until the pH of the washing solution was 7, and then the solid product was dried at 120 ℃ overnight and calcined at 400 ℃ for 4h to give 15 wt% W-doped OMS-2 support Z9.

Adding 25ml of water into 1g of the carrier Z9, dropwise adding 8.1g of a tetrammine platinum dichloride solution with the platinum content of 1.35 wt% into the carrier Z9, uniformly stirring, dropwise adding a dilute ammonia water solution with the concentration of 0.28 wt% into the mixture until the pH value is 7, stirring for 2h, then transferring the mixture into an ultrasonic instrument for ultrasonic treatment for 2h, standing for 12h, evaporating the solution at 70 ℃, roasting the solid product at 400 ℃ for 2h to obtain the catalyst A9 prepared in the embodiment, wherein the composition of the catalyst A9 is 6 wt% Pt/15 wt% W-OMS-2 based on the metal element and the dry weight of the catalyst.

Example 10

A catalyst was prepared as in example 1, except that, without sonication, the mixture after addition of aqueous ammonia was stirred for 2h and allowed to stand for 12h, the solution was evaporated to dryness at 70 ℃ and the solid product was calcined at 400 ℃ for 2h to give catalyst A10 prepared in this example having a composition of catalyst A10 of 0.4 wt.% Pt/0.8 wt.% W-OMS-2, calculated as metal elements and based on the dry weight of the catalyst.

Test examples

The catalytic activity of the catalyst prepared in example 1-10 in catalyzing the hydrogenation reaction of glycerol was tested.

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 Agilent 7890 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, 2-propanediol selectivity (%): the molar amount of 1, 2-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, 2-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 supported catalyst, characterized in that the catalyst comprises a carrier, a first active component, and a second active component, the carrier contains manganese oxide molecular sieve OMS-2, and the first active component is one or more metal components selected from Group VIII metals, and the second active component is one or more metal components selected from Group VIB metals;

Based on the dry weight of the catalyst, the content of the carrier is 75 to 98 wt %, in terms of metal elements, the content of the first metal component is 0.1 to 10 wt %, and the content of the second metal component is 0.1 to 10 wt %. The content is 0.1 to 15% by weight.

2 . The catalyst according to claim 1 , wherein, based on the dry weight of the catalyst, the content of the carrier is 85-97 wt %, and in terms of metal elements, the content of the first metal component is 0.2 ∼5 wt%, and the content of the second metal component is 0.2∼10 wt%.

3 . The catalyst according to claim 1 , wherein, in terms of metal elements, the weight ratio of the first active component to the second active component is 1:(0.5～10), preferably 1:(1～10. 4 . 5).

4. The catalyst according to claim 1, wherein the first 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 A combination of one or three; the second active component is a Mo component, a W component or a Cr component, or a combination of two or three of them.

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

(1) The first aqueous solution containing the oxidized manganese compound, the reduced manganese compound, and the precursor of the second active component is reacted at 30 to 180° C. for 1 to 36 hours, and the solid product is collected, washed, dried and calcined to obtain a compound doped with a carrier for the second active ingredient;

(2) Add alkali to the second aqueous solution containing the first active component precursor and the carrier doped with the second active component obtained in step (1) so that the pH value of the material after alkali addition is 3 ~8, after stirring the alkali-added material for 1-12 hours, stand for 1-24 hours, and collect the solid product.

6. The method according to claim 5, wherein, in step (1), in the first aqueous solution, in the first aqueous solution, the molar ratio of the second active component precursor to Mn is 1:(0.1 ~500).

7. The method according to claim 5, wherein, in step (1), the oxidized manganese compounds are potassium permanganate and potassium manganate, and the reduced manganese compounds are manganese sulfate, manganese nitrate, manganese acetate or manganese chloride; and/or,

The molar ratio of the oxidized manganese compound and the reduced manganese compound is (0.5-3):1.

8 . The method according to claim 5 , wherein, in step (2), after the alkali-added material is stirred for 1-12 hours, ultrasonic treatment is performed for 1-12 hours, and then the standing treatment is performed.

9. The method according to claim 5, wherein, in step (2), the alkali is ammonia water, sodium hydroxide or potassium hydroxide, and the concentration of the alkali is 0.1-50% by weight.

10. The method of claim 5, wherein the first active component precursor is a nitrate, acetate, sulfate, chloride, acid or complex of the first active component, or A combination of two or three of them; and/or, the second active component precursor is a metal salt of the second active component.

11. The method according to claim 5, wherein, the method further comprises: in step (2), the step of drying and roasting after collecting the solid product; and/or,

The drying conditions include: the temperature is 30-350°C, preferably 60-300°C; the time is 1-24 hours, preferably 2-12 hours; and/or,

The roasting conditions include: the temperature is 250-900° C., preferably 350-800° C.; and the time is 0.5-12 h, preferably 2-6 h.

12. A method for hydrogenating 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.

13. The method according to claim 12, 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.