CN111420657A

CN111420657A - Ru-based catalyst for synthesizing 3-pentanone through ethylene conversion and preparation method and application thereof

Info

Publication number: CN111420657A
Application number: CN202010298664.6A
Authority: CN
Inventors: 秦婷婷; 钟良枢; 唐志永; 李啸; 孙予罕
Original assignee: Shanghai Advanced Research Institute of CAS
Current assignee: Shanghai Advanced Research Institute of CAS
Priority date: 2020-04-16
Filing date: 2020-04-16
Publication date: 2020-07-17
Anticipated expiration: 2040-04-16
Also published as: CN111420657B

Abstract

The invention provides a Ru-based catalyst for synthesizing 3-pentanone by ethylene conversion and a preparation method and application thereof,the catalyst comprises a component A and a component B, wherein the component A is an oxide of an active component Ru, and the component B is at least one selected from a carbon-based material, an oxide of M1 and an oxide of M2; the oxide of M1 is selected from at least one of the oxides of the elements IIA, IIIA and IVA; m2 is selected from at least one of transition metal elements and rare earth metal elements. The catalyst can be operated at lower temperature and pressure, the selectivity of 3-pentanone is as high as 83%, and the selectivity of hydrogenation product ethane can be lower than 10%. Compared with the traditional method for synthesizing 3-pentanone, the method has the advantages of mild reaction conditions, easy product separation, low energy consumption, no acid and solvent introduction, and no CO₂Good discharge, atom economy, stability and the like.

Description

Ru-based catalyst for synthesizing 3-pentanone through ethylene conversion and preparation method and application thereof

Technical Field

The invention relates to the technical field of catalysts, and particularly relates to a Ru-based catalyst for synthesizing 3-pentanone by ethylene conversion, and a preparation method and application thereof.

Background

Hydroformylation of olefins with synthesis gas (H)₂+ CO) in the presence of a catalyst to form an aldehyde. The Co-based catalyst was first found to have hydroformylation activity, while the Rh-based catalyst gradually replaced the Co-based catalyst due to its high activity and high product selectivity. Although the Rh-based catalyst is excellent in performance, Rh is a noble metal, the storage capacity is limited, the cost is high, and the catalyst recovery is difficult. Generally, the main products of hydroformylation are aldehydes and corresponding alcohols, ketones often being considered by-products. The ketone can be used as an organic solvent, a raw material, a reaction intermediate and a terminal product of organic synthesis, and is an oxygen-containing chemical with high added value. The ketone obtained by the olefin hydroformylation route not only can effectively increase a carbon chain, but also can carry out subsequent conversion on a C ═ O double bond in the ketone to obtain a functionalized product. Of particular interest, among these, is the 3-pentanone obtained by conversion of ethylene, which is the simplest polyketone, generally considered to be two molecules of ethylene with one molecule of CO and one molecule of H₂Directly reacting to obtain the product. 3-pentanone has high boiling point and low volatility, and can be used as an excellent solvent. Meanwhile, 3-pentanone is also an important fine chemical raw material and has important application in the fields of medicines, pesticides and organic synthesis. In addition, 3-pentanone can also react with other molecules to generate renewable liquid fuels with different carbon numbers and high value-added products. 3-pentanone can also be used as fuelAnd (4) tracing the material. Another new use of 3-pentanone is the synthesis of high quality single layer graphene on Rh (111) by Chemical Vapor Deposition (CVD). In conclusion, 3-pentanone has wide application prospect and commercial value and is an important high value-added chemical.

The traditional method for preparing 3-pentanone comprises ketopropionate, 1-propanol catalytic conversion, 3-pentanol oxidation and the like. The propionic acid ketonization method or propionic acid decarboxylation method can carry out ketonization upgrading on propionic acid which is one of important components in the biological oil, namely, two molecules of propionic acid ketonization generate symmetrical 3-pentanone and generate CO byproduct₂And H₂O, thereby reducing the acidity and corrosiveness of the bio-oil and improving the calorific value and stability of the bio-oil. At present, the propionylation method is the mainstream method for producing 3-pentanone, and the catalyst of the method is mainly concentrated on CeO₂、MnO₂And ZrO₂Etc. and has high reaction temperature (usually over 300 deg.C), low catalytic activity, serious carbon deposition, and CO₂Large discharge amount, high energy consumption, strong corrosion to equipment (introduction of strong acid) and the like. The reports of 3-pentanone synthesis based on the ethylene conversion route are mostly carried out in a batch high-pressure reaction kettle with participation of a solvent, and are not beneficial to catalyst recovery and product separation.

The catalyst system is reasonably modified, so that the traditional homogeneous olefin hydroformylation reaction is heterogenized without participation of acid and solvent, and the catalyst recovery and product separation are facilitated. If product control is carried out in a targeted manner, it is of great importance to convert the main product from aldehydes or alcohols to ketones. In the reaction of heterogeneous ethylene conversion to synthesize 3-pentanone, besides the main reaction to produce 3-pentanone, there are also many side reactions, such as hydroformylation to produce propionaldehyde and subsequent hydrogenation of propionaldehyde to produce propanol, hydrogenation of ethylene to produce ethane, polymerization of ethylene under certain conditions, condensation of aldehyde or alcohol, and the like. Therefore, in order to synthesize 3-pentanone with high selectivity, it is necessary to not only improve the reactivity but also suppress the occurrence of side reactions.

Disclosure of Invention

The invention aims to provide a Ru-based catalyst for synthesizing 3-pentanone by ethylene conversion and a preparation method and application thereof, and mainly aims to provide the Ru-based catalyst for synthesizing the 3-pentanone by ethylene conversion and the preparation method and application thereofSolves the problems of harsh reaction conditions, high energy consumption, equipment corrosiveness and CO in the prior 3-pentanone production technology₂Discharge and the like.

To achieve the above and other related objects, a first aspect of the present invention provides a Ru-based catalyst for conversion of ethylene to synthesize 3-pentanone, comprising an a component which is an oxide of an active component Ru, and a B component selected from at least one of a carbon-based material, an oxide of M1, and an oxide of M2; the oxide of M1 is selected from at least one of the oxides of the elements IIA, IIIA and IVA; m2 is selected from at least one of transition metal elements and rare earth metal elements.

Preferably, the catalyst further comprises an oxide of M3, and M3 is selected from at least one of alkali metal elements.

Preferably, at least one of the following technical features is also included:

(1) the carbon-based material is selected from at least one of activated carbon, carbon nanotubes, carbon black, carbon nanofibers and graphene;

(2) the oxide of M1 is selected from Al₂O₃、SiO₂At least one of CaO, MgO, and BaO;

(3) the transition metal element is selected from at least one of Mn, Fe, Co, Cu, Zn, Mo, Zr, Ti, Pt and Nb;

(4) the rare earth metal element is selected from at least one of L a and Ce;

(5) the Ru element accounts for 0.08-5% of the total mass of the catalyst, such as 0.08-0.1%, 0.1-0.5%, 0.5-1%, 1-2%, 2-4% or 4-5%;

(6) the component B accounts for 60.7-99.8% of the total mass of the catalyst, such as 60.7-70.1%, 70.1-68.8%, 68.8-90.6%, 90.6-93.3%, 93.3-94.7%, 94.7-97.3%, 97.3-97.4%, 97.4-98.7%, 98.7-98.9%, 98.9-99.3% or 99.3-99.8%;

(7) when the component B is a carbon-based material and/or an oxide of M1 and an oxide of M2, the carbon-based material and/or the oxide of M1 account for 68.8-98.9%, such as 68.8-70.1% or 70.1-98.9%, and the oxide of M2 accounts for 1-27.2% of the total mass of the catalyst;

(8) m3 accounts for 0-5% of the total mass of the catalyst, such as 0-1%, 1-2% or 2-5%.

The second aspect of the present invention provides a method for producing the above Ru-based catalyst, the method being one selected from the following methods:

the preparation method I comprises the following steps:

1a) according to the composition ratio of the Ru-based catalyst, dissolving Ru salt in water to obtain an impregnation solution; or dissolving Ru salt and at least one of M2 salt and M3 salt in water to obtain an impregnation solution;

1b) dipping the dipping solution obtained in the step 1a) onto the component B in one step or step by an equal-volume dipping method, wherein after one-step dipping or after each step in step-by-step dipping, standing, drying and roasting are carried out to obtain the Ru-based catalyst;

the preparation method II comprises the following steps:

2a) dissolving Ru salt and at least one of metal salt of M1 and salt of M2 in water according to the composition ratio of the Ru-based catalyst to obtain mixed metal salt solution;

2b) dissolving a precipitant in water to obtain a precipitant solution;

2c) simultaneously dripping the mixed metal salt solution obtained in the step 2a) and the precipitant solution obtained in the step 2b) into mother liquor for coprecipitation to obtain a coprecipitation solution;

2d) aging, centrifuging, washing, drying and roasting the coprecipitation solution obtained in the step 2c) to obtain the Ru-based catalyst.

Preferably, at least one of the following technical features is also included:

(1) the Ru salt is at least one selected from ruthenium chloride, ruthenium iodide, ruthenium acetate, potassium chlororuthenate, ruthenium acetylacetonate, ruthenium nitrosyl nitrate, ruthenium carbonyl chloride and ammonium chlororuthenate;

(2) the salt of M2 is selected from at least one of nitrate, chloride and acetate of M2 element;

(3) the salt of M3 is selected from at least one of carbonate, nitrate, chloride, alkali ammonium salt, sulfate and acetate of M3 element;

(4) the impregnation solution and the component B do not simultaneously contain M2 element; that is, when the impregnation solution contains a salt of M2, the B component cannot be an oxide of M2 but only a carbon-based material, an oxide of M1; when the impregnation solution does not contain the salt of M2, the B component is selected from at least one of a carbon-based material, an oxide of M1, and an oxide of M2;

(5) in the step 1b), the dipping temperature is 5-25 ℃;

(6) in the step 1b), standing for 4-48 h;

(7) in the step 1b), the drying temperature is 80-120 ℃;

(8) in the step 1b), the drying time is 6-48 h;

(9) in the step 1b), the roasting temperature is 300-350 ℃;

(10) in the step 1b), the roasting time is 0.5-8 h;

(11) in the step 1b), the standing atmosphere is at least one selected from the group consisting of an air atmosphere, a nitrogen atmosphere and an argon atmosphere;

(12) in the step 1b), the drying atmosphere is at least one selected from the group consisting of an air atmosphere, a nitrogen atmosphere and an argon atmosphere;

(13) in the step 1b), the baking atmosphere is at least one selected from the group consisting of an air atmosphere, a nitrogen atmosphere and an argon atmosphere.

(14) In step 2b), the precipitant is selected from at least one of a precipitant containing an element M3 and a precipitant not containing an element M3;

(15) in step 2b), the precipitating agent is selected from Na₂CO₃、K₂CO₃、Rb₂CO₃、Cs₂CO₃、LiOH、NaOH、KOH、RbOH、CsOH、(NH₄)₂CO₃And NH₃·H₂At least one of O;

(16) in the step 2a), the total molar concentration of the mixed metal salt solution is 0.5-3 mol/L;

(17) in the step 2b), the molar concentration of the precipitant solution is 0.5-3 mol/L;

(18) in the step 2c), the mother liquor is deionized water;

(19) in the step 2c), the coprecipitation temperature is 10-80 ℃;

(20) in the step 2c), the pH value of the coprecipitation is 6-12;

(21) in the step 2d), the aging temperature is 20-80 ℃;

(22) in the step 2d), the aging time is 0.5-24 h;

(23) centrifuging and washing for 0-10 times in the step 2 d);

(24) in the step 2d), the drying temperature is 80-150 ℃;

(25) in the step 2d), the drying time is 6-48 h;

(26) in the step 2d), the roasting temperature is 300-350 ℃;

(27) in the step 2d), the roasting time is 0.5-8 h;

(28) in the step 2d), the drying atmosphere is at least one selected from air atmosphere, nitrogen atmosphere and argon atmosphere;

(29) in the step 2d), the roasting atmosphere is at least one selected from the group consisting of an air atmosphere, a nitrogen atmosphere and an argon atmosphere.

The third aspect of the invention provides the use of the Ru-based catalyst for the reaction of synthesizing 3-pentanone by converting ethylene.

Preferably, at least one of the following technical features is also included:

1) tabletting and forming the Ru-based catalyst, selecting 40-60-mesh catalyst and 40-60-mesh quartz sand, mixing the catalyst and the quartz sand according to a mass ratio of 1: 2-2: 1, and filling the mixture into a fixed bed;

2) the reaction conditions for synthesizing 3-pentanone by converting ethylene are as follows: the feed gas comprises C₂H₄、H₂And CO in a molar ratio of 8:2: 1-2: 3:3, and at an airspeed WHSV of 1000-4000 ml/(g)_catH), the reaction temperature is 100-200 ℃, and the reaction pressure is 1-3 MPa.

The Ru-based catalyst may or may not be subjected to reduction treatment before being used for conversion of ethylene to synthesize 3-pentanone.

When the reduction treatment is performed, the reducing atmosphere is at least one selected from the group consisting of hydrogen, carbon monoxide, synthesis gas, diluted hydrogen, diluted carbon monoxide and diluted synthesis gas, the diluted gas is an inert gas, and the volume fraction of the diluted gas is 90% or less.

When the reduction treatment is carried out, the reduction conditions are as follows: the reduction temperature is 200-400 ℃, the reduction time is 0.5-10 h, and the airspeed WHSV is 2000-8000 ml/(g)_catH); after the reduction is finished, the temperature is reduced to 80 ℃.

The Ru-based catalyst is used for the reaction of synthesizing 3-pentanone by converting ethylene, is a novel and alternative catalyst, and has the characteristics of simple and convenient preparation, easy repetition, good stability, low cost and the like. The Ru-based catalyst provided by the invention shows excellent catalytic performance in the reaction of synthesizing 3-pentanone by converting ethylene in a fixed bed, can be operated at a lower temperature and pressure, and has 3-pentanone selectivity as high as 83% and hydrogenation product ethane selectivity lower than 10%. Compared with the traditional method for synthesizing 3-pentanone, the method has the advantages of mild reaction conditions, easy product separation, low energy consumption, no acid and solvent introduction, and no CO₂Good discharge, atom economy, stability and the like. The characteristics enable the Ru-based catalyst provided by the invention to be easily repeated and industrially prepared, and have potential industrial application prospects.

Detailed Description

The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.

[ example 1 ]

Weighing ruthenium trichloride hydrate according to the proportion that Ru element accounts for 2% of the total mass of the catalyst, and dissolving the ruthenium trichloride hydrate into deionized water to obtain a Ru salt solution. 10g of activated carbon AC is weighed as a carrier, and the water absorption capacity is measured to be 2.5ml/g, and the activated carbon AC accounts for 97.4 percent of the total mass of the catalyst. And (3) dipping the Ru salt solution on active carbon AC, standing, drying and roasting. Wherein the standing condition is room temperature (about 25 ℃) standing for 12 hours under the air atmosphere; keeping the drying condition of the tube furnace in an argon atmosphere at 120 ℃ for 2 h; the roasting condition is that the roasting is carried out for 3 hours in a tubular furnace with an argon atmosphere at 330 ℃.

The above catalyst was evaluated for catalytic performance in a fixed bed. Weighing 1.5g of the catalyst and 3.0g of quartz sand particles, and mixing the catalyst and the quartz sand particles, wherein the catalyst and the quartz sand are 40-60 meshes. Introduction of C₂H₄/H₂Raw material gas of/CO 1:1:1, space velocity WHSV 2000 ml/(g)_catH), purging for 0.5h at normal temperature and normal pressure (25 ℃, 0.1MPa), back-pressing to 3MPa, and heating to 120 ℃ for reaction, wherein the performance results are shown in Table 1.

[ example 2 ]

Weighing ruthenium trichloride hydrate according to the proportion that Ru element accounts for 2% of the total mass of the catalyst, and dissolving the ruthenium trichloride hydrate into deionized water to obtain a Ru salt solution. 10g of activated carbon AC is weighed as a carrier, and the water absorption capacity is measured to be 2.5ml/g, and the activated carbon AC accounts for 97.4 percent of the total mass of the catalyst. And (3) dipping the Ru salt solution on active carbon AC, standing, drying and roasting. Wherein the standing condition is room temperature (about 25 ℃) standing for 12 hours under the air atmosphere; keeping the drying condition in a tubular furnace with argon atmosphere at 150 ℃ for 2 h; the roasting condition is that the roasting is carried out for 3 hours in a tubular furnace with an argon atmosphere at 330 ℃.

The above catalyst was evaluated for catalytic performance in a fixed bed. Weighing 1.5g of the catalyst and 3.0g of quartz sand particles, and mixing the catalyst and the quartz sand particles, wherein the catalyst and the quartz sand are 40-60 meshes. Introduction of C₂H₄/H₂Raw material gas of/CO 1:1:1, space velocity WHSV 2000 ml/(g)_catH), purging for 0.5h at normal temperature and normal pressure (25 ℃, 0.1MPa), back-pressing to 3MPa, and heating to 150 ℃ for reaction, wherein the performance results are shown in Table 1.

[ example 3 ]

Weighing ruthenium trichloride hydrate according to the proportion that Ru element accounts for 2% of the total mass of the catalyst, and dissolving the ruthenium trichloride hydrate into deionized water to obtain a Ru salt solution. 10g of activated carbon AC is weighed as a carrier, and the water absorption capacity is measured to be 2.5ml/g, and the activated carbon AC accounts for 97.4 percent of the total mass of the catalyst. And (3) dipping the Ru salt solution on active carbon AC, standing, drying and roasting. Wherein the standing condition is room temperature (about 25 ℃) standing for 12 hours under the air atmosphere; keeping the drying condition in a tubular furnace with argon atmosphere at 180 ℃ for 2 h; the roasting condition is that the roasting is carried out for 3 hours in a tubular furnace with an argon atmosphere at 330 ℃.

The above catalyst was evaluated for catalytic performance in a fixed bed. Weighing 1.5g of the catalyst and 3.0g of quartz sand particles, and mixing the catalyst and the quartz sand particles, wherein the catalyst and the quartz sand are 40-60 meshes. Introduction of C₂H₄/H₂Raw material gas of/CO 1:1:1, space velocity WHSV 2000 ml/(g)_catH), purging for 0.5h at normal temperature and normal pressure (25 ℃, 0.1MPa), back-pressing to 3MPa, and heating to 180 ℃ for reaction, wherein the performance results are shown in Table 1.

[ example 4 ]

The above catalyst was evaluated for catalytic performance in a fixed bed. Weighing 1.5g of the catalyst and 3.0g of quartz sand particles, and mixing the catalyst and the quartz sand particles, wherein the catalyst and the quartz sand are 40-60 meshes. Introduction of C₂H₄/H₂Raw material gas of/CO 1:1:1, space velocity WHSV 2000 ml/(g)_catH), purging for 0.5h at normal temperature and normal pressure (25 ℃, 0.1MPa), back-pressing to 3MPa, and heating to 200 ℃ for reaction, wherein the performance results are shown in Table 1.

[ example 5 ]

The above catalyst was evaluated for catalytic performance in a fixed bed. Weighing 1.5g of the catalyst and 3.0g of quartz sand particles, and mixing the catalyst and the quartz sand particles, wherein the catalyst and the quartz sand are 40-60 meshes. Introduction of C₂H₄/H₂Raw material gas of/CO 1:1:1, space velocity WHSV 2000 ml/(g)_catH), purging for 0.5h at normal temperature and normal pressure (25 ℃, 0.1MPa), back-pressing to 3MPa, and heating to 100 ℃ for reaction, wherein the performance results are shown in Table 1.

[ example 6 ]

The above catalyst was evaluated for catalytic performance in a fixed bed. Weighing 1.5g of the catalyst and 3.0g of quartz sand particles, and mixing the catalyst and the quartz sand particles, wherein the catalyst and the quartz sand are 40-60 meshes. Introducing 10% CO/N₂Reduction is carried out with the space velocity WHSV being 8000 ml/(g)_catH), the reduction temperature is 300 ℃ and is maintained for 5 h. After the reduction is finished, the temperature is reduced to 80 ℃, and C is introduced₂H₄/H₂Raw material gas of/CO 1:1:1, space velocity WHSV 2000 ml/(g)_catH), purging for 0.5h at normal temperature and normal pressure (25 ℃, 0.1MPa), back-pressing to 2MPa, and heating to 150 ℃ for reaction, wherein the performance results are shown in Table 1.

[ example 7 ]

The above catalyst was evaluated for catalytic performance in a fixed bed. Weighing 1.5g of the catalyst and 3.0g of quartz sand particles, and mixing the catalyst and the quartz sand particles, wherein the catalyst and the quartz sand are 40-60 meshes. Introduction of 10% H₂/N₂Reduction is carried out with the space velocity WHSV being 8000 ml/(g)_catH), the reduction temperature is 300 ℃ and is maintained for 5 h. After the reduction is finished, the temperature is reduced to 80 ℃, and C is introduced₂H₄/H₂Raw material gas of/CO 1:1:1, space velocity WHSV 2000 ml/(g)_catH), purging for 0.5h at normal temperature and normal pressure (25 ℃, 0.1MPa), back-pressing to 2MPa, and heating to 150 ℃ for reaction, wherein the performance results are shown in Table 1.

[ example 8 ]

The above catalyst was evaluated for catalytic performance in a fixed bed. Weighing 1.5g of the catalyst and 3.0g of quartz sand particles, and mixing the catalyst and the quartz sand particles, wherein the catalyst and the quartz sand are 40-60 meshes. Introduction of pure H₂Reduction is carried out with the space velocity WHSV being 8000 ml/(g)_catH), the reduction temperature is 300 ℃ and is maintained for 5 h. After the reduction is finished, the temperature is reduced to 80 ℃, and C is introduced₂H₄/H₂Raw material gas of/CO 1:1:1, space velocity WHSV 2000 ml/(g)_catH), purging for 0.5h at normal temperature and normal pressure (25 ℃, 0.1MPa), back-pressing to 2MPa, and heating to 150 ℃ for reaction, wherein the performance results are shown in Table 1.

[ example 9 ]

The above catalyst was evaluated for catalytic performance in a fixed bed. Weighing 1.5g of the catalyst and 3.0g of quartz sand particles, and mixing the catalyst and the quartz sand particles, wherein the catalyst and the quartz sand are 40-60 meshes. Introducing 10% syngas/N₂(H₂0.5 percent of CO, 8000 ml/(g) of airspeed WHSV_catH), the reduction temperature is 300 ℃ and is maintained for 5 h. After the reduction is finished, the temperature is reduced to 80 ℃, and C is introduced₂H₄/H₂Raw material gas of/CO 1:1:1, space velocity WHSV 2000 ml/(g)_catH), purging for 0.5h at normal temperature and normal pressure (25 ℃, 0.1MPa), back-pressing to 2MPa, and heating to 150 ℃ for reaction, wherein the performance results are shown in Table 1.

[ example 10 ]

The above catalyst was evaluated for catalytic performance in a fixed bed. Weighing 1.5g of the catalyst and 3.0g of quartz sand particles, and mixing the catalyst and the quartz sand particles, wherein the catalyst and the quartz sand are 40-60 meshes. Pure CO is introduced for reduction, and the space velocity WHSV is 8000 ml/(g)_catH), the reduction temperature is 300 ℃ and is maintained for 5 h. After the reduction is finished, the temperature is reduced to 80 ℃, and C is introduced₂H₄/H₂Raw material gas of/CO 1:1:1, space velocity WHSV 2000 ml/(g)_catH) ambient temperature and pressureAfter purging for 0.5h at 25 ℃ and 0.1MPa, the reaction was carried out under a back pressure of 2MPa and a temperature of 150 ℃ and the performance results are shown in Table 1.

[ example 11 ]

Weighing ruthenium trichloride hydrate according to the proportion that the Ru element accounts for 0.1 percent of the total mass of the catalyst, and dissolving the ruthenium trichloride hydrate into deionized water to obtain Ru salt solution. 10g of activated carbon AC is weighed as a carrier, and the water absorption capacity is measured to be 2.5ml/g, and the activated carbon AC accounts for 99.8 percent of the total mass of the catalyst. And (3) dipping the Ru salt solution on active carbon AC, standing, drying and roasting. Wherein the standing condition is room temperature (about 25 ℃) standing for 12 hours under the air atmosphere; keeping the drying condition of the tube furnace in an argon atmosphere at 120 ℃ for 2 h; the roasting condition is that the roasting is carried out for 3 hours in a tubular furnace with an argon atmosphere at 330 ℃.

[ example 12 ]

Weighing ruthenium trichloride hydrate according to the proportion that the Ru element accounts for 0.5 percent of the total mass of the catalyst, and dissolving the ruthenium trichloride hydrate into deionized water to obtain a Ru salt solution. 10g of activated carbon AC is weighed as a carrier, and the water absorption capacity is measured to be 2.5ml/g, and the activated carbon AC accounts for 99.3 percent of the total mass of the catalyst. And (3) dipping the Ru salt solution on active carbon AC, standing, drying and roasting. Wherein the standing condition is room temperature (about 25 ℃) standing for 12 hours under the air atmosphere; keeping the drying condition of the tube furnace in an argon atmosphere at 120 ℃ for 2 h; the roasting condition is that the roasting is carried out for 3 hours in a tubular furnace with an argon atmosphere at 330 ℃.

The above catalyst was evaluated for catalytic performance in a fixed bed. Weighing 1.5g of the catalyst and 3.0g of quartz sand particles, and mixing the catalyst and the quartz sand particles, wherein the catalyst and the quartz sand are 40-60 meshes. Introduction of C₂H₄/H₂Raw material gas of/CO 1:1:1, space velocity WHSV 2000 ml/(g)_catH), purging at normal temperature and pressure (25 ℃, 0.1MPa) for 0.5After h, the reaction was carried out under a back pressure of 3MPa and at a temperature of 150 ℃ with the performance results shown in Table 1.

[ example 13 ]

Weighing ruthenium trichloride hydrate according to the proportion that the Ru element accounts for 1 percent of the total mass of the catalyst, and dissolving the ruthenium trichloride hydrate into deionized water to obtain Ru salt solution. 10g of activated carbon AC is weighed as a carrier, and the water absorption capacity is measured to be 2.5ml/g, and the activated carbon AC accounts for 98.7 percent of the total mass of the catalyst. And (3) dipping the Ru salt solution on active carbon AC, standing, drying and roasting. Wherein the standing condition is room temperature (about 25 ℃) standing for 12 hours under the air atmosphere; keeping the drying condition of the tube furnace in an argon atmosphere at 120 ℃ for 2 h; the roasting condition is that the roasting is carried out for 3 hours in a tubular furnace with an argon atmosphere at 330 ℃.

[ example 14 ]

And weighing ruthenium trichloride hydrate according to the proportion that the Ru element accounts for 5 percent of the total mass of the catalyst, and dissolving the ruthenium trichloride hydrate into deionized water to obtain a Ru salt solution. 10g of activated carbon AC is weighed as a carrier, and the water absorption capacity is measured to be 2.5ml/g, and the activated carbon AC accounts for 93.4 percent of the total mass of the catalyst. And (3) dipping the Ru salt solution on active carbon AC, standing, drying and roasting. Wherein the standing condition is room temperature (about 25 ℃) standing for 12 hours under the air atmosphere; keeping the drying condition of the tube furnace in an argon atmosphere at 120 ℃ for 2 h; the roasting condition is that the roasting is carried out for 3 hours in a tubular furnace with an argon atmosphere at 330 ℃.

The above catalyst was evaluated for catalytic performance in a fixed bed. Weighing 1.5g of the catalyst and 3.0g of quartz sand particles, and mixing the catalyst and the quartz sand particles, wherein the catalyst and the quartz sand are 40-60 meshes. Introduction of C₂H₄/H₂Raw material gas of/CO 1:1:1, space velocity WHSV 2000 ml/(g)_catH), purging at normal temperature and normal pressure (25 ℃, 0.1MPa) for 0.5h, then back-pressing to 3MPa, and heating to the temperatureThe performance results of the reaction at 150 ℃ are shown in Table 1.

[ example 15 ]

The above catalyst was evaluated for catalytic performance in a fixed bed. Weighing 1.5g of the catalyst and 3.0g of quartz sand particles, and mixing the catalyst and the quartz sand particles, wherein the catalyst and the quartz sand are 40-60 meshes. Introduction of C₂H₄/H₂Raw material gas of/CO 1:1:1, space velocity WHSV 2000 ml/(g)_catH), purging for 0.5h at normal temperature and normal pressure (25 ℃, 0.1MPa), back-pressing to 1MPa, and heating to 150 ℃ for reaction, wherein the performance results are shown in Table 1.

[ example 16 ]

The above catalyst was evaluated for catalytic performance in a fixed bed. Weighing 1.5g of the catalyst and 3.0g of quartz sand particles, and mixing the catalyst and the quartz sand particles, wherein the catalyst and the quartz sand are 40-60 meshes. Introduction of C₂H₄/H₂Raw material gas of/CO 1:1:1, space velocity WHSV 2000 ml/(g)_catH), purging at normal temperature and normal pressure (25 ℃, 0.1MPa) for 0.5h, back-pressing to 2MPa, heating to 150 ℃ for reaction, and obtaining the performanceThe results are shown in Table 1.

[ example 17 ]

Weighing ruthenium trichloride hydrate according to the proportion that Ru element accounts for 2% of the total mass of the catalyst, and dissolving the ruthenium trichloride hydrate into deionized water to obtain a Ru salt solution. Weighing 10g of Al₂O₃As a carrier, it had a water absorption of 1.7ml/g, Al₂O₃Accounting for 97.4 percent of the total mass of the catalyst. Immersing Ru salt solution in Al₂O₃And standing, drying and roasting. Wherein the standing condition is room temperature (about 25 ℃) standing for 12 hours under the air atmosphere; keeping the drying condition of the tube furnace in an argon atmosphere at 120 ℃ for 2 h; the roasting condition is that the roasting is carried out for 3 hours in a tubular furnace with an argon atmosphere at 330 ℃.

[ example 18 ]

Weighing ruthenium trichloride hydrate according to the proportion that Ru element accounts for 2% of the total mass of the catalyst, and dissolving the ruthenium trichloride hydrate into deionized water to obtain a Ru salt solution. Weighing 10g of SiO₂As a carrier, the water absorption was found to be 1.4ml/g, SiO₂Accounting for 97.4 percent of the total mass of the catalyst. Dipping Ru salt solution into SiO₂And standing, drying and roasting. Wherein the standing condition is room temperature (about 25 ℃) standing for 12 hours under the air atmosphere; keeping the drying condition of the tube furnace in an argon atmosphere at 120 ℃ for 2 h; the roasting condition is that the roasting is carried out for 3 hours in a tubular furnace with an argon atmosphere at 330 ℃.

The above catalyst was evaluated for catalytic performance in a fixed bed. Weighing 1.5g of the catalyst and 3.0g of quartz sand particles, and mixing the catalyst and the quartz sand particles, wherein the catalyst and the quartz sand are 40-60 meshes. Introduction of C₂H₄/H₂Raw material gas of/CO 1:1:1, space velocity WHSV 2000 ml/(g)_catH), purging at normal temperature and normal pressure (25 ℃, 0.1MPa) for 0.5h, back pressure to 3MPa, and temperature rise to 150The reaction was carried out at a temperature of ℃ and the results of the properties are shown in Table 1.

[ example 19 ]

Weighing ruthenium trichloride hydrate according to the proportion that Ru element accounts for 2% of the total mass of the catalyst and dissolving the ruthenium trichloride hydrate into deionized water to obtain a Ru salt solution, and weighing sodium carbonate according to the proportion that Na element accounts for 2% of the total mass of the catalyst and dissolving the sodium carbonate into deionized water to obtain a Na salt solution. Weighing 10g of Al₂O₃As a carrier, it had a water absorption of 1.7ml/g, Al₂O₃Accounting for 94.7 percent of the total mass of the catalyst. Immersing Ru salt solution in Al₂O₃And then, after standing, drying and roasting, soaking in Na salt solution, and then standing, drying and roasting. Wherein the standing condition is room temperature (about 25 ℃) standing for 12 hours under the air atmosphere; keeping the drying condition of the tube furnace in an argon atmosphere at 120 ℃ for 2 h; the roasting condition is that the roasting is carried out for 3 hours in a tubular furnace with an argon atmosphere at 330 ℃.

[ example 20 ]

Weighing ruthenium trichloride hydrate according to the proportion that Ru element accounts for 2% of the total mass of the catalyst and dissolving the ruthenium trichloride hydrate into deionized water to obtain a Ru salt solution, and weighing sodium carbonate according to the proportion that Na element accounts for 2% of the total mass of the catalyst and dissolving the sodium carbonate into deionized water to obtain a Na salt solution. Weighing 10g of SiO₂As a carrier, the water absorption was found to be 1.4ml/g, SiO₂Accounting for 94.7 percent of the total mass of the catalyst. Dipping Ru salt solution in SiO₂And then, after standing, drying and roasting, soaking in Na salt solution, and then standing, drying and roasting. Wherein the standing condition is room temperature (about 25 ℃) standing for 12 hours under the air atmosphere; keeping the drying condition of the tube furnace in an argon atmosphere at 120 ℃ for 2 h; the roasting condition is that the roasting is carried out for 3 hours in a tubular furnace with an argon atmosphere at 330 ℃.

[ example 21 ]

Weighing ruthenium trichloride hydrate according to the proportion that Ru element accounts for 2% of the total mass of the catalyst and dissolving the ruthenium trichloride hydrate into deionized water to obtain a Ru salt solution, and weighing sodium carbonate according to the proportion that Na element accounts for 5% of the total mass of the catalyst and dissolving the sodium carbonate into deionized water to obtain a Na salt solution. Weighing 10g of SiO₂As a carrier, the water absorption was found to be 1.4ml/g, SiO₂Accounting for 90.6 percent of the total mass of the catalyst. Dipping Ru salt solution in SiO₂And then, after standing, drying and roasting, soaking in Na salt solution, and then standing, drying and roasting. Wherein the standing condition is room temperature (about 25 ℃) standing for 12 hours under the air atmosphere; keeping the drying condition of the tube furnace in an argon atmosphere at 120 ℃ for 2 h; the roasting condition is that the roasting is carried out for 3 hours in a tubular furnace with an argon atmosphere at 330 ℃.

[ example 22 ]

Weighing ruthenium trichloride hydrate according to the proportion that Ru element accounts for 2% of the total mass of the catalyst and dissolving the ruthenium trichloride hydrate into deionized water to obtain a Ru salt solution, and weighing sodium carbonate according to the proportion that Na element accounts for 2% of the total mass of the catalyst and dissolving the sodium carbonate into deionized water to obtain a Na salt solution. Weighing 10g of SiO₂As a carrier, the water absorption was found to be 1.4ml/g, SiO₂Accounting for 94.7 percent of the total mass of the catalyst.Immersing Ru salt solution and Na salt solution in SiO solution simultaneously₂And standing, drying and roasting. Wherein the standing condition is room temperature (about 25 ℃) standing for 12 hours under the air atmosphere; keeping the drying condition of the tube furnace in an argon atmosphere at 120 ℃ for 2 h; the roasting condition is that the roasting is carried out for 3 hours in a tubular furnace with an argon atmosphere at 330 ℃.

[ example 23 ]

Weighing ruthenium trichloride hydrate according to the proportion that Ru element accounts for 2% of the total mass of the catalyst and dissolving the ruthenium trichloride hydrate into deionized water to obtain a Ru salt solution, and weighing sodium carbonate according to the proportion that Na element accounts for 2% of the total mass of the catalyst and dissolving the sodium carbonate into deionized water to obtain a Na salt solution. Weighing 10g of SiO₂As a carrier, the water absorption was found to be 1.4ml/g, SiO₂Accounting for 94.7 percent of the total mass of the catalyst. Firstly, Na salt solution is soaked in SiO₂And then, after standing, drying and roasting, dipping the Ru salt solution, and standing, drying and roasting. Wherein the standing condition is room temperature (about 25 ℃) standing for 12 hours under the air atmosphere; keeping the drying condition of the tube furnace in an argon atmosphere at 120 ℃ for 2 h; the roasting condition is that the roasting is carried out for 3 hours in a tubular furnace with an argon atmosphere at 330 ℃.

[ example 24 ]

Weighing ruthenium trichloride hydrate according to the proportion that Ru element accounts for 2% of the total mass of the catalyst, and dissolving the ruthenium trichloride hydrate into deionized water to obtain a Ru salt solution. 10g of CaO was weighed as a carrier, and the water absorption was measured to be 0.4ml/g, and CaO accounted for 97.4% of the total mass of the catalyst. And dipping the Ru salt solution on CaO, standing, drying and roasting. Wherein the standing condition is room temperature (about 25 ℃) standing for 12 hours under the air atmosphere; keeping the drying condition of the tube furnace in an argon atmosphere at 120 ℃ for 2 h; the roasting condition is that the roasting is carried out for 3 hours in a tubular furnace with an argon atmosphere at 330 ℃.

The above catalyst was evaluated for catalytic performance in a fixed bed. Weighing 1.5g of the catalyst and 3.0g of quartz sand particles, and mixing the catalyst and the quartz sand particles, wherein the catalyst and the quartz sand are 40-60 meshes. Introduction of C₂H₄/H₂Raw material gas of/CO 1:1:1, space velocity WHSV 2000 ml/(g)_catH), purging for 0.5h at normal temperature and normal pressure (25 ℃, 0.1MPa), back-pressing to 2MPa, and heating to 150 ℃ for reaction, wherein the performance results are shown in Table 1.

[ example 25 ]

Weighing ruthenium trichloride hydrate according to the proportion that Ru element accounts for 2% of the total mass of the catalyst, and dissolving the ruthenium trichloride hydrate into deionized water to obtain a Ru salt solution. 10g of MgO is weighed as a carrier, and the water absorption capacity is measured to be 0.5ml/g, and the MgO accounts for 97.4 percent of the total mass of the catalyst. Dipping the Ru salt solution on MgO, standing, drying and roasting. Wherein the standing condition is room temperature (about 25 ℃) standing for 12 hours under the air atmosphere; keeping the drying condition of the tube furnace in an argon atmosphere at 120 ℃ for 2 h; the roasting condition is that the roasting is carried out for 3 hours in a tubular furnace with an argon atmosphere at 330 ℃.

[ example 26 ]

Weighing ruthenium trichloride hydrate according to the proportion that Ru element accounts for 2% of the total mass of the catalyst, and dissolving the ruthenium trichloride hydrate into deionized water to obtain a Ru salt solution. 10g of BaO was weighed as a carrier, and the water absorption was measured to be 0.3ml/g, and the BaO accounted for 97.4% of the total mass of the catalyst. And dipping the Ru salt solution on BaO, standing, drying and roasting. Wherein the standing condition is room temperature (about 25 ℃) standing for 12 hours under the air atmosphere; keeping the drying condition of the tube furnace in an argon atmosphere at 120 ℃ for 2 h; the roasting condition is that the roasting is carried out for 3 hours in a tubular furnace with an argon atmosphere at 330 ℃.

[ example 27 ]

Weighing ruthenium trichloride hydrate according to the proportion that Ru element accounts for 2% of the total mass of the catalyst, and dissolving the ruthenium trichloride hydrate into deionized water to obtain a Ru salt solution. 10g of CeO were weighed₂As a carrier, the water absorption was found to be 0.3ml/g, CeO₂Accounting for 97.4 percent of the total mass of the catalyst. Immersing Ru salt solution in CeO₂And standing, drying and roasting. Wherein the standing condition is room temperature (about 25 ℃) standing for 12 hours under the air atmosphere; keeping the drying condition of the tube furnace in an argon atmosphere at 120 ℃ for 2 h; the roasting condition is that the roasting is carried out for 3 hours in a tubular furnace with an argon atmosphere at 330 ℃.

[ example 28 ]

Weighing ruthenium trichloride hydrate according to the proportion that Ru element accounts for 2% of the total mass of the catalyst, and dissolving the ruthenium trichloride hydrate into deionized water to obtain a Ru salt solution. Weighing 10g MnO₂As a carrier, measuring its uptakeWater amount of 0.2ml/g, MnO₂Accounting for 97.4 percent of the total mass of the catalyst. Immersing Ru salt solution in MnO₂And standing, drying and roasting. Wherein the standing condition is room temperature (about 25 ℃) standing for 12 hours under the air atmosphere; keeping the drying condition of the tube furnace in an argon atmosphere at 120 ℃ for 2 h; the roasting condition is that the roasting is carried out for 3 hours in a tubular furnace with an argon atmosphere at 330 ℃.

[ example 29 ]

Weighing ruthenium trichloride hydrate according to the proportion that Ru element accounts for 2% of the total mass of the catalyst, and dissolving the ruthenium trichloride hydrate into deionized water to obtain a Ru salt solution. 10g of ZrO were weighed₂As a support, the water absorption was found to be 0.3ml/g, ZrO₂Accounting for 97.4 percent of the total mass of the catalyst. Impregnating solution of Ru salt in ZrO₂And standing, drying and roasting. Wherein the standing condition is room temperature (about 25 ℃) standing for 12 hours under the air atmosphere; keeping the drying condition of the tube furnace in an argon atmosphere at 120 ℃ for 2 h; the roasting condition is that the roasting is carried out for 3 hours in a tubular furnace with an argon atmosphere at 330 ℃.

[ example 30 ]

Weighing ruthenium trichloride hydrate according to the proportion that Ru element accounts for 2% of the total mass of the catalyst, and dissolving the ruthenium trichloride hydrate into deionized water to obtain a Ru salt solution. Weighing 10g of Co₃O₄As a carrier, measuredThe water absorption capacity of the material is 0.7ml/g, Co₃O₄Accounting for 97.4 percent of the total mass of the catalyst. Immersing Ru salt solution in Co₃O₄And standing, drying and roasting. Wherein the standing condition is room temperature (about 25 ℃) standing for 12 hours under the air atmosphere; keeping the drying condition of the tube furnace in an argon atmosphere at 120 ℃ for 2 h; the roasting condition is that the roasting is carried out for 3 hours in a tubular furnace with an argon atmosphere at 330 ℃.

[ example 31 ]

Weighing ruthenium trichloride hydrate according to the proportion that Ru element accounts for 2% of the total mass of the catalyst, and dissolving the ruthenium trichloride hydrate into deionized water to obtain a Ru salt solution. 10g of Fe are weighed₂O₃As a carrier, it had a water absorption of 0.7ml/g, Fe₂O₃Accounting for 97.4 percent of the total mass of the catalyst. Immersing Ru salt solution in Fe₂O₃And standing, drying and roasting. Wherein the standing condition is room temperature (about 25 ℃) standing for 12 hours under the air atmosphere; keeping the drying condition of the tube furnace in an argon atmosphere at 120 ℃ for 2 h; the roasting condition is that the roasting is carried out for 3 hours in a tubular furnace with an argon atmosphere at 330 ℃.

[ example 32 ]

Weighing ruthenium trichloride hydrate according to the proportion that Ru element accounts for 2% of the total mass of the catalyst, and dissolving the ruthenium trichloride hydrate into deionized water to obtain a Ru salt solution. 10g of CuO is weighed as a carrier, and the water absorption capacity is measured to be 0.7ml/g, and the CuO accounts for 97.4 percent of the total mass of the catalyst. Dipping the Ru salt solution on CuO, standing, drying and roasting. Wherein the standing condition is room temperature (about 25 ℃) standing for 12 hours under the air atmosphere; keeping the drying condition of the tube furnace in an argon atmosphere at 120 ℃ for 2 h; the roasting condition is that the roasting is carried out for 3 hours in a tubular furnace with an argon atmosphere at 330 ℃.

[ example 33 ]

Weighing a certain amount of ruthenium trichloride hydrate and 50% of manganese nitrate solution, dissolving the ruthenium trichloride hydrate and the 50% of manganese nitrate solution together in deionized water to prepare 1 mol/L mixed metal salt solution, wherein Ru accounts for 4% of the total mass of the catalyst, Mn oxide accounts for 93.3% of the total mass of the catalyst, and anhydrous sodium carbonate is weighed according to the condition that alkali metal Na accounts for 1% of the total mass of the catalyst and is dissolved in deionized water to prepare 2 mol/L precipitator solution.

100ml of deionized water is added into a beaker, the mixed metal salt and the precipitant solution are dripped into the beaker at the same time, and the mixture is stirred and mixed evenly. The temperature of coprecipitation was 20 ℃ and the pH of coprecipitation was 8. After titration, aging is carried out for 2 hours at 20 ℃, after aging, centrifugal washing is carried out for 6 times, then the mixture is placed in a 100 ℃ oven for drying for 12 hours, and finally the mixture is roasted in a muffle furnace for 3 hours at 330 ℃, wherein the drying and roasting are carried out in the air atmosphere.

[ example 34 ]

Weighing a certain amount of ruthenium trichloride hydrate and 50% of manganese nitrate solution, dissolving the ruthenium trichloride hydrate and the 50% of manganese nitrate solution together in deionized water to prepare 1 mol/L mixed metal salt solution, wherein the Ru accounts for 1% of the total mass of the catalyst, the oxide of Mn accounts for 97.3% of the total mass of the catalyst, and weighing anhydrous sodium carbonate according to the condition that the alkali metal Na accounts for 1% of the total mass of the catalyst, and dissolving the anhydrous sodium carbonate in the deionized water to prepare 2 mol/L precipitator solution.

[ example 35 ]

Weighing a certain amount of ruthenium trichloride hydrate and 50% of manganese nitrate solution, dissolving the ruthenium trichloride hydrate and the 50% of manganese nitrate solution together in deionized water to prepare 1 mol/L mixed metal salt solution, wherein Ru accounts for 4% of the total mass of the catalyst, Mn oxide accounts for 94.7% of the total mass of the catalyst, and a certain amount of (NH)₄)₂CO₃Dissolving in deionized water to prepare 2 mol/L precipitant solution.

[ example 36 ]

Weighing ruthenium trichloride hydrate according to the proportion that Ru element accounts for 2 percent of the total mass of the catalyst and dissolving the ruthenium trichloride hydrate into deionized water to obtain Ru salt solution, weighing lithium hydroxide according to the proportion that L i element accounts for 2 percent of the total mass of the catalyst and dissolving the lithium hydroxide into deionized water to obtain L i salt solution, weighing 10g of SiO₂As a carrier, the water absorption was found to be 1.4ml/g, SiO₂Accounting for 94.7 percent of the total mass of the catalyst. Dipping Ru salt solution in SiO₂Then the mixture is placed still, dried and roasted, and then L i salt solution is soaked, and then the mixture is placed still, dried and roasted, wherein the standing condition is that the mixture is placed still for 12 hours at room temperature (about 25 ℃) in air atmosphere, the drying condition is that the mixture is kept for 2 hours at 120 ℃ in a tube furnace in argon atmosphere, and the roasting condition is that the mixture is roasted for 3 hours at 330 ℃ in the tube furnace in argon atmosphere.

[ example 37 ]

And weighing ruthenium trichloride hydrate according to the proportion that the Ru element accounts for 2% of the total mass of the catalyst and dissolving the ruthenium trichloride hydrate into deionized water to obtain a Ru salt solution, and weighing potassium carbonate according to the proportion that the K element accounts for 2% of the total mass of the catalyst and dissolving the potassium carbonate into deionized water to obtain a K salt solution. Weighing 10g of SiO₂As a carrier, the water absorption was found to be 1.4ml/g, SiO₂Is a catalyst94.7 percent of the total mass. Dipping Ru salt solution in SiO₂And then, after standing, drying and roasting, soaking the mixture in K salt solution, and then standing, drying and roasting. Wherein the standing condition is room temperature (about 25 ℃) standing for 12 hours under the air atmosphere; keeping the drying condition of the tube furnace in an argon atmosphere at 120 ℃ for 2 h; the roasting condition is that the roasting is carried out for 3 hours in a tubular furnace with an argon atmosphere at 330 ℃.

[ example 38 ]

Weighing ruthenium trichloride hydrate according to the proportion that the Ru element accounts for 2% of the total mass of the catalyst and dissolving the ruthenium trichloride hydrate into deionized water to obtain a Ru salt solution, and weighing rubidium carbonate according to the proportion that the Rb element accounts for 2% of the total mass of the catalyst and dissolving the rubidium carbonate into the deionized water to obtain an Rb salt solution. Weighing 10g of SiO₂As a carrier, the water absorption was found to be 1.4ml/g, SiO₂Accounting for 94.7 percent of the total mass of the catalyst. Dipping Ru salt solution in SiO₂And then the Rb salt solution is soaked after standing, drying and roasting, and then the obtained product is obtained after standing, drying and roasting. Wherein the standing condition is room temperature (about 25 ℃) standing for 12 hours under the air atmosphere; keeping the drying condition of the tube furnace in an argon atmosphere at 120 ℃ for 2 h; the roasting condition is that the roasting is carried out for 3 hours in a tubular furnace with an argon atmosphere at 330 ℃.

[ example 39 ]

Weighing ruthenium trichloride hydrate according to the proportion that Ru element accounts for 2% of the total mass of the catalyst and dissolving the ruthenium trichloride hydrate into deionized water to obtain a Ru salt solution, and weighing rubidium carbonate according to the proportion that Cs element accounts for 2% of the total mass of the catalyst and dissolving the rubidium carbonate into deionized water to obtain a Cs salt solution. Weighing 10g of SiO₂As a carrier, the water absorption was found to be 1.4ml/g, SiO₂Accounting for 94.7 percent of the total mass of the catalyst. Dipping Ru salt solution in SiO₂And then, after standing, drying and roasting, soaking the Cs salt solution, and then standing, drying and roasting. Wherein the standing condition is room temperature (about 25 ℃) standing for 12 hours under the air atmosphere; keeping the drying condition of the tube furnace in an argon atmosphere at 120 ℃ for 2 h; the roasting condition is that the roasting is carried out for 3 hours in a tubular furnace with an argon atmosphere at 330 ℃.

[ example 40 ]

The above catalyst was evaluated for catalytic performance in a fixed bed. Weighing 1.5g of the catalyst and 3.0g of quartz sand particles, and mixing the catalyst and the quartz sand particles, wherein the catalyst and the quartz sand are 40-60 meshes. Introducing 10% CO/N₂Reduction is carried out with the space velocity WHSV being 8000 ml/(g)_catH), the reduction temperature was 200 ℃ and held for 5 h. After the reduction is finished, the temperature is reduced to 80 ℃, and C is introduced₂H₄/H₂Raw material gas of/CO 1:1:1, space velocity WHSV 2000 ml/(g)_catH), purging for 0.5h at normal temperature and normal pressure (25 ℃, 0.1MPa), back-pressing to 2MPa, and heating to 150 ℃ for reaction, wherein the performance results are shown in Table 1.

[ example 41 ] to provide a pharmaceutical composition

The above catalyst was evaluated for catalytic performance in a fixed bed. Weighing 1.5g of the catalyst and 3.0g of quartz sand particles, and mixing the catalyst and the quartz sand particles, wherein the catalyst and the quartz sand are 40-60 meshes. Introducing 10% CO/N₂Reduction is carried out with the space velocity WHSV being 8000 ml/(g)_catH), the reduction temperature was 400 ℃ and held for 5 h. After the reduction is finished, the temperature is reduced to 80 ℃, and C is introduced₂H₄/H₂Raw material gas of/CO 1:1:1, space velocity WHSV 2000 ml/(g)_catH), purging for 0.5h at normal temperature and normal pressure (25 ℃, 0.1MPa), back-pressing to 2MPa, and heating to 150 ℃ for reaction, wherein the performance results are shown in Table 1.

[ example 42 ]

The catalyst is catalyzed in a fixed bedCan be evaluated. Weighing 1.5g of the catalyst and 3.0g of quartz sand particles, and mixing the catalyst and the quartz sand particles, wherein the catalyst and the quartz sand are 40-60 meshes. Introduction of C₂H₄/H₂Raw material gas of 6:1: 1/CO, space velocity WHSV 4000 ml/(g)_catH), purging for 0.5h at normal temperature and normal pressure (25 ℃, 0.1MPa), back-pressing to 2MPa, and heating to 150 ℃ for reaction, wherein the performance results are shown in Table 1.

[ example 43 ]

The above catalyst was evaluated for catalytic performance in a fixed bed. Weighing 1.5g of the catalyst and 3.0g of quartz sand particles, and mixing the catalyst and the quartz sand particles, wherein the catalyst and the quartz sand are 40-60 meshes. Introduction of C₂H₄/H₂Raw material gas of/CO 2:3:3, space velocity WHSV 4000 ml/(g)_catH), purging for 0.5h at normal temperature and normal pressure (25 ℃, 0.1MPa), back-pressing to 2MPa, and heating to 150 ℃ for reaction, wherein the performance results are shown in Table 1.

[ example 44 ]

The above catalyst was evaluated for catalytic performance in a fixed bed. 1.5g of the above catalyst was weighedThe catalyst is mixed with 3.0g of quartz sand particles, and the catalyst and the quartz sand are 40-60 meshes. Introduction of C₂H₄/H₂Raw material gas of/CO 2:2:1, space velocity WHSV 4000 ml/(g)_catH), purging for 0.5h at normal temperature and normal pressure (25 ℃, 0.1MPa), back-pressing to 2MPa, and heating to 150 ℃ for reaction, wherein the performance results are shown in Table 1.

[ example 45 ]

The above catalyst was evaluated for catalytic performance in a fixed bed. Weighing 1.5g of the catalyst and 3.0g of quartz sand particles, and mixing the catalyst and the quartz sand particles, wherein the catalyst and the quartz sand are 40-60 meshes. Introduction of C₂H₄/H₂Raw material gas of 8:2: 1/CO, space velocity WHSV 4000 ml/(g)_catH), purging for 0.5h at normal temperature and normal pressure (25 ℃, 0.1MPa), back-pressing to 2MPa, and heating to 150 ℃ for reaction, wherein the performance results are shown in Table 1.

[ example 46 ]

Weighing ruthenium trichloride hydrate according to the proportion that Ru element accounts for 2% of the total mass of the catalyst, and dissolving the ruthenium trichloride hydrate into deionized water to obtain a Ru salt solution. 5g of MoO are weighed₃As a carrier, the water absorption was measured to be 0.4ml/g, MoO₃Accounting for 97.4 percent of the total mass of the catalyst. Dipping Ru salt solution in MoO₃And standing, drying and roasting. Wherein the standing condition is room temperature (about 25 ℃) standing for 12 hours under the air atmosphere; keeping the drying condition of the tube furnace in an argon atmosphere at 120 ℃ for 2 h; the roasting condition is that the roasting is carried out for 3 hours in a tubular furnace with an argon atmosphere at 330 ℃.

The above catalyst was evaluated for catalytic performance in a fixed bed. 1.5g of the above catalyst and 3.0g of quartz sand were weighedMixing the particles, wherein the catalyst and the quartz sand are both 40-60 meshes. Introduction of C₂H₄/H₂Raw material gas of/CO 1:1:1, space velocity WHSV 2000 ml/(g)_catH), purging for 0.5h at normal temperature and normal pressure (25 ℃, 0.1MPa), back-pressing to 2MPa, and heating to 150 ℃ for reaction, wherein the performance results are shown in Table 1.

[ example 47 ]

Weighing ruthenium trichloride hydrate according to the proportion that Ru element accounts for 2% of the total mass of the catalyst, and dissolving the ruthenium trichloride hydrate into deionized water to obtain a Ru salt solution. 5g of TiO are weighed₂As a carrier, the water absorption was found to be 0.7ml/g, TiO₂Accounting for 97.4 percent of the total mass of the catalyst. Impregnating solution of Ru salt in TiO₂And standing, drying and roasting. Wherein the standing condition is room temperature (about 25 ℃) standing for 12 hours under the air atmosphere; keeping the drying condition of the tube furnace in an argon atmosphere at 120 ℃ for 2 h; the roasting condition is that the roasting is carried out for 3 hours in a tubular furnace with an argon atmosphere at 330 ℃.

[ example 48 ]

Weighing ruthenium trichloride hydrate according to the proportion that Ru element accounts for 2% of the total mass of the catalyst, and dissolving the ruthenium trichloride hydrate into deionized water to obtain a Ru salt solution. Weighing 5g of PtO₂As a carrier, the water absorption was found to be 0.5ml/g, PtO₂Accounting for 97.4 percent of the total mass of the catalyst. Immersing Ru salt solution in PtO₂And standing, drying and roasting. Wherein the standing condition is room temperature (about 25 ℃) standing for 12 hours under the air atmosphere; keeping the drying condition of the tube furnace in an argon atmosphere at 120 ℃ for 2 h; the roasting condition is that the roasting is carried out for 3 hours in a tubular furnace with an argon atmosphere at 330 ℃.

The above catalyst was evaluated for catalytic performance in a fixed bed. Weighing 1.5g of the catalyst and mixing with 3.0g of quartz sand particlesThe catalyst and the quartz sand are both 40-60 meshes. Introduction of C₂H₄/H₂Raw material gas of/CO 1:1:1, space velocity WHSV 2000 ml/(g)_catH), purging for 0.5h at normal temperature and normal pressure (25 ℃, 0.1MPa), back-pressing to 2MPa, and heating to 150 ℃ for reaction, wherein the performance results are shown in Table 1.

[ example 49 ]

Weighing ruthenium trichloride hydrate according to the proportion that Ru element accounts for 2% of the total mass of the catalyst, and dissolving the ruthenium trichloride hydrate into deionized water to obtain a Ru salt solution. Weighing 5g of Nb₂O₅As a carrier, it had a water absorption of 0.5ml/g, Nb₂O₅Accounting for 97.4 percent of the total mass of the catalyst. Immersing Ru salt solution in Nb₂O₅And standing, drying and roasting. Wherein the standing condition is room temperature (about 25 ℃) standing for 12 hours under the air atmosphere; keeping the drying condition of the tube furnace in an argon atmosphere at 120 ℃ for 2 h; the roasting condition is that the roasting is carried out for 3 hours in a tubular furnace with an argon atmosphere at 330 ℃.

[ example 50 ]

Weighing ruthenium trichloride hydrate according to the proportion that Ru element accounts for 2 percent of the total mass of the catalyst, dissolving the ruthenium trichloride hydrate into deionized water to obtain Ru salt solution, weighing 5g L a₂O₃As a carrier, the water absorption capacity was found to be 0.5ml/g, L a₂O₃97.4% of the total mass of the catalyst, and L a was impregnated with a Ru salt solution₂O₃And standing, drying and roasting. Wherein the standing condition is room temperature (about 25 ℃) standing for 12 hours under the air atmosphere; keeping the drying condition of the tube furnace in an argon atmosphere at 120 ℃ for 2 h; the roasting condition is that the roasting is carried out for 3 hours in a tubular furnace with an argon atmosphere at 330 ℃.

Catalytic performance of the above catalyst in a fixed bedAnd (6) evaluating. Weighing 1.5g of the catalyst and 3.0g of quartz sand particles, and mixing the catalyst and the quartz sand particles, wherein the catalyst and the quartz sand are 40-60 meshes. Introduction of C₂H₄/H₂Raw material gas of/CO 1:1:1, space velocity WHSV 2000 ml/(g)_catH), purging for 0.5h at normal temperature and normal pressure (25 ℃, 0.1MPa), back-pressing to 2MPa, and heating to 150 ℃ for reaction, wherein the performance results are shown in Table 1.

[ example 51 ]

A certain amount of ruthenium trichloride hydrate and cobalt nitrate are weighed and dissolved in deionized water to obtain a mixed metal salt solution, wherein the Ru element accounts for 2% of the total mass of the catalyst, and the Co oxide accounts for 27.2% of the total mass of the catalyst. 10g of AC is weighed as a carrier, and the water absorption capacity is measured to be 2.5ml/g, wherein the AC accounts for 70.1 percent of the total mass of the catalyst. And (3) soaking the mixed metal salt solution on AC, standing, drying and roasting. Wherein the standing condition is room temperature (about 25 ℃) standing for 12 hours under the air atmosphere; keeping the drying condition of the tube furnace in an argon atmosphere at 120 ℃ for 2 h; the roasting condition is that the roasting is carried out for 3 hours in a tubular furnace with an argon atmosphere at 330 ℃.

[ example 52 ]

A certain amount of ruthenium trichloride hydrate, cobalt nitrate and aluminum nitrate are weighed and dissolved in deionized water to obtain a mixed metal salt solution, wherein the Ru element accounts for 2% of the total mass of the catalyst, the Co oxide accounts for 27.2% of the total mass of the catalyst, and the Al oxide accounts for 9.4% of the total mass of the catalyst. 10g of AC was weighed out as a carrier, and the water absorption was found to be 1.4ml/g, with the AC accounting for 60.7% of the total mass of the catalyst. And (3) soaking the mixed metal salt solution on AC, standing, drying and roasting. Wherein the standing condition is room temperature (about 25 ℃) standing for 12 hours under the air atmosphere; keeping the drying condition of the tube furnace in an argon atmosphere at 120 ℃ for 2 h; the roasting condition is that the roasting is carried out for 3 hours in a tubular furnace with an argon atmosphere at 330 ℃.

[ example 53 ]

Weighing a certain amount of ruthenium trichloride hydrate, cobalt nitrate and aluminum nitrate, and dissolving the ruthenium trichloride hydrate, the cobalt nitrate and the aluminum nitrate in deionized water to obtain a mixed metal salt solution of 1 mol/L, wherein the Ru element accounts for 2% of the total mass of the catalyst, the Co oxide accounts for 27.2% of the total mass of the catalyst, and the Al oxide accounts for 68.8% of the total mass of the catalyst, and weighing anhydrous sodium carbonate by taking alkali metal Na as 1% of the total mass of the catalyst, and dissolving the anhydrous sodium carbonate in the deionized water to prepare a precipitator solution of 2 mol/L.

Adding 100ml of deionized water into a beaker, and mixing the above mixed metal salt solution and Na₂CO₃And dripping the precipitant solution into the beaker, and uniformly stirring. The temperature of coprecipitation was 20 ℃ and the pH of coprecipitation was 8. After titration, aging is carried out for 2 hours at 20 ℃, after aging, centrifugal washing is carried out for 6 times, then the mixture is placed in a 100 ℃ oven for drying for 12 hours, and finally the mixture is roasted in a muffle furnace for 3 hours at 330 ℃, wherein the drying and roasting are carried out in the air atmosphere.

[ example 54 ]

Weighing a certain amount of ruthenium trichloride hydrate and cobalt nitrate, and dissolving in deionized water to obtain a mixed metal salt solutionIn the catalyst, the Ru element accounts for 0.08 percent of the total mass of the catalyst, and the Co oxide accounts for 1 percent of the total mass of the catalyst. Weighing 10g of SiO₂As a carrier, the water absorption was found to be 1.4ml/g, SiO₂Accounting for 98.9 percent of the total mass of the catalyst. Soaking mixed metal salt solution in SiO₂And standing, drying and roasting. Wherein the standing condition is room temperature (about 25 ℃) standing for 12 hours under the air atmosphere; keeping the drying condition of the tube furnace in an argon atmosphere at 120 ℃ for 2 h; the roasting condition is that the roasting is carried out for 3 hours in a tubular furnace with an argon atmosphere at 330 ℃.

Table 1 example catalyst performance results

As can be seen from Table 1, the Ru catalyst prepared by the method shows excellent catalytic performance in the reaction of efficiently synthesizing 3-pentanone by fixed bed ethylene conversion. Can be operated at lower temperatures and pressures, with 3-pentanone selectivity as high as 83%, and the hydrogenation product ethane selectivity can be less than 10%. The Ru-based catalyst provided by the project is simple to prepare, easy to repeat, good in stability and has a potential industrial application prospect.

The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.

Claims

1. The Ru-based catalyst for synthesizing 3-pentanone by converting ethylene comprises an A component and a B component, wherein the A component is an oxide of an active component Ru, and the B component is selected from at least one of a carbon-based material, an oxide of M1 and an oxide of M2; the oxide of M1 is selected from at least one of the oxides of the elements IIA, IIIA and IVA; m2 is selected from at least one of transition metal elements and rare earth metal elements.

2. The Ru-based catalyst of claim 1, wherein the catalyst further comprises an oxide of M3, and M3 is selected from at least one of the alkali metal elements.

3. The Ru-based catalyst according to claim 1 or 2, further comprising at least one of the following technical features:

(4) the rare earth metal element is selected from at least one of L a and Ce;

(5) the Ru element accounts for 0.08-5% of the total mass of the catalyst;

(6) the component B accounts for 60.7-99.8% of the total mass of the catalyst;

(7) when the component B is a carbon-based material and/or an oxide of M1 and an oxide of M2, the carbon-based material and/or the oxide of M1 account for 68.8-98.9% of the total mass of the catalyst, and the oxide of M2 accounts for 1-27.2% of the total mass of the catalyst;

(8) m3 accounts for 0-5% of the total mass of the catalyst.

4. A method for preparing a Ru-based catalyst according to any one of claims 1 to 3, wherein the method for preparing is selected from one of the following methods:

the preparation method I comprises the following steps:

the preparation method II comprises the following steps:

2b) dissolving a precipitant in water to obtain a precipitant solution;

5. The method of preparing a Ru-based catalyst according to claim 4, further comprising at least one of the following technical features:

(4) the impregnation solution and the component B do not simultaneously contain M2 element;

(5) in the step 1b), the dipping temperature is 5-25 ℃;

(6) in the step 1b), standing for 4-48 h;

(7) in the step 1b), the drying temperature is 80-180 ℃;

(8) in the step 1b), the drying time is 2-48 h;

(9) in the step 1b), the roasting temperature is 300-350 ℃;

(10) in the step 1b), the roasting time is 0.5-8 h;

(18) in the step 2c), the mother liquor is deionized water;

(19) in the step 2c), the coprecipitation temperature is 10-80 ℃;

(20) in the step 2c), the pH value of the coprecipitation is 6-12;

(21) in the step 2d), the aging temperature is 20-80 ℃;

(22) in the step 2d), the aging time is 0.5-24 h;

(23) centrifuging and washing for 0-10 times in the step 2 d);

(24) in the step 2d), the drying temperature is 80-150 ℃;

(25) in the step 2d), the drying time is 6-48 h;

(26) in the step 2d), the roasting temperature is 300-350 ℃;

(27) in the step 2d), the roasting time is 0.5-8 h;

6. Use of a Ru-based catalyst according to any one of claims 1 to 3 in a reaction for the conversion of ethylene to 3-pentanone.

7. Use of a Ru-based catalyst according to claim 6, further comprising at least one of the following technical features:

8. Use of a Ru-based catalyst according to claim 6, wherein the Ru-based catalyst is subjected to reduction treatment or not before use in the synthesis of 3-pentanone by conversion of ethylene.

9. Use of a Ru-based catalyst according to claim 8, wherein the reducing atmosphere when the reduction treatment is performed is at least one selected from the group consisting of hydrogen, carbon monoxide, synthesis gas, diluted hydrogen, diluted carbon monoxide and diluted synthesis gas, the diluted gas is an inert gas, and the volume fraction of the diluted gas is 90% or less.

10. Use of a Ru-based catalyst according to claim 8, wherein when the reduction treatment is carried out, the reduction conditions are: the reduction temperature is 200-400 ℃, the reduction time is 0.5-10 h, and the airspeed WHSV is 2000-8000 ml/(g)_catH); after the reduction is finished, the temperature is reduced to 80 ℃.