CN116116428A - Ruthenium-nickel-supported metal oxide catalyst, preparation method and application thereof - Google Patents

Ruthenium-nickel-supported metal oxide catalyst, preparation method and application thereof Download PDF

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CN116116428A
CN116116428A CN202211606050.5A CN202211606050A CN116116428A CN 116116428 A CN116116428 A CN 116116428A CN 202211606050 A CN202211606050 A CN 202211606050A CN 116116428 A CN116116428 A CN 116116428A
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oxide catalyst
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CN116116428B (en
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高立东
甄崇礼
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Qingdao Chuangqixinneng Catalysis Technology Co ltd
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    • C01B2203/1082—Composition of support materials

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Abstract

The invention provides a ruthenium-nickel-supported metal oxide catalyst, a preparation method and application thereof. The active components of the metal oxide catalyst are Ru and Ni, the carrier is metal oxide, and the metal oxide comprises Al 2 O 3 BaO and CeO 2 Wherein the mass ratio of the three metal oxides Al 2 O 3 ：BaO：CeO 2 = (3-5): (1-3): (1-2). The active metal of the metal oxide catalyst adopts ruthenium and nickel, wherein the nickel is distributed on the surface of the carrier in smaller grains, and the adverse effect of uneven distribution of the nickel on active ingredient Ru is avoided. The metal oxide catalyst of the invention is utilized to catalyze ammonia synthesis reaction, and can realize ammonia conversion rate of up to 99% at a lower catalysis temperature of 600 ℃.

Description

Ruthenium-nickel-supported metal oxide catalyst, preparation method and application thereof
Technical Field
The invention relates to the field of preparation of catalyst materials for catalyzing ammonia decomposition reaction, in particular to a ruthenium-nickel-supported metal oxide catalyst, a preparation method and application thereof.
Background
In recent years, hydrogen energy is becoming one of the development directions of the future energy industry as a new energy source with environmental protection and high efficiency. Along with the gradual perfection of the whole hydrogen energy industry chain, hydrogen storage and transportation become one of the difficulties in current hydrogen energy popularization, and the hydrogen cannot be transported as conveniently as gasoline and diesel due to the inflammable and explosive properties of the hydrogen. By changing the form of hydrogen, the risk and cost of transportation can be reduced to some extent. Ammonia gas has been a widely used chemical product with a mature storage and transportation system, and the ammonia gas can be used as a storage medium to realize the linking of a hydrogen generating end and a hydrogen using end at lower cost and higher speed. Greatly quickens the development of the hydrogen energy industry.
The ammonia decomposition process applied at present generally uses a reaction temperature above 700 ℃, and the high reaction temperature on one hand provides higher requirements for device material selection and heat preservation process, thereby increasing the construction cost; on the other hand, the energy consumption of the whole process flow is increased, the energy efficiency of system operation is reduced, and the operation cost is further improved. The development of highly active catalysts is therefore one of the important problems in reducing ammonia cracking systems.
The invention relates to the technical field of ammonia decomposition, in particular to an ammonia decomposition catalyst, a preparation method and application thereof. The preparation method comprises the following steps: ball milling ruthenium acetate, magnesium acetate and potassium acetate to obtain metal salt mixture powder; roasting the metal salt mixture powder, and then reducing the metal salt mixture powder by hydrogen to obtain the ammonia decomposition catalyst. According to the preparation method of the ammonia decomposition catalyst, specific raw materials of ruthenium acetate, magnesium acetate and potassium acetate are added in a one-pot manner, metal salt mixture powder is obtained through ball milling treatment, and then the ammonia decomposition catalyst is prepared through roasting and hydrogen reduction. However, the catalyst prepared by the process has larger energy consumption due to the ball milling process, and the morphology of the catalyst can be changed in the forming process, so that the catalyst has certain difficulty in the practical application process.
Therefore, the development of a supported metal oxide catalyst suitable for catalyzing an ammonolysis reaction and having high catalytic activity and stability is a problem to be solved.
Disclosure of Invention
In order to solve the problems, the invention provides a ruthenium-nickel supported metal oxide catalyst, and the active metal of the metal oxide catalyst adopts ruthenium and nickel, wherein the nickel is distributed on the surface of a carrier in smaller grains, so that the adverse effect of uneven distribution of the nickel on active ingredient Ru is avoided. The metal oxide catalyst of the invention is utilized to catalyze ammonia synthesis reaction, and can realize ammonia conversion rate of up to 99% at a lower catalysis temperature of 600 ℃.
The invention provides a ruthenium-nickel-supported metal oxide catalyst, active components of the metal oxide catalyst are Ru and Ni, a carrier is metal oxide, and the metal oxide comprises Al 2 O 3 BaO and CeO 2 Wherein the mass ratio of the three metal oxides Al 2 O 3 ：BaO：CeO 2 ＝(3-5):(1-3):(1-2)。
Further, the Ru loading is 8% to 32%, preferably 10% to 20%, based on the mass of the support.
Further, the loading amount of Ni is 8% to 32%, preferably 10% to 20%, based on the mass of the support.
The invention also provides a preparation method of the metal oxide catalyst, which comprises the following steps:
step S1: preparing a metal salt solution: fully dissolving nitrate containing cerium, aluminum and barium in water at 60-70 ℃ to prepare a metal salt solution, and transferring the metal salt solution into a stirring kettle for continuous stirring;
step S2: coprecipitation reaction: slowly adding ammonia water with the mass concentration of 10-15% into the stirring kettle, and regulating the pH value of the suspension in the adding process until the pH value is 8.5-9.5, and stopping dropwise adding the ammonia water;
step S3: aging: precipitating and aging the suspension at 50-70 ℃ for 0.5-5h;
step S4: washing, drying and roasting the aged mixed precipitate;
step S5: according to the nickel loading amount, adding nickel nitrate and deionized water into the roasted solid, and carrying out reduced pressure distillation, drying, primary roasting, nitrogen replacement and secondary roasting on the mixed reaction liquid to obtain a nickel-loaded metal oxide catalyst;
step S6: and (3) according to the loading amount of ruthenium, impregnating the nickel-loaded metal oxide catalyst obtained in the step (S5) with an ethanol solution of ruthenium acetate, and carrying out reduced pressure distillation, drying and reduction on the mixed reaction solution to obtain the ruthenium-nickel-loaded metal oxide catalyst.
Further, in step S1, the mass ratio of the nitrates of Ce, al and Ba is (11-18): (1.7-5): (2.5-5).
Further, in step S1, the nitrate is preferably dissolved and mixed at a temperature of 65 ℃.
Further, in step S1, the prepared metal salt solution is transferred to a stirring kettle, and stirring is continuously performed at a speed of 300r/min or more.
Further, in the step S2, the adding time of the ammonia water is controlled to be 0.5-1 hour.
Further, in step S2, the temperature of the reaction vessel is controlled to 60 to 70 ℃, preferably 65 ℃ by a water bath.
Further, in step S2, the pH value of the suspension is continuously detected in the adding process, the dropping of ammonia water is stopped until the pH value is 8.5-9.5, and then the suspension is continuously stirred for 1h.
Further, in step S3, the aging is preferably performed at a temperature of 65 ℃ for 2 hours.
Further, in step S4, the mixed precipitate is washed with water and suction filtered several times until the pH after washing is between 6.5 and 7.8, preferably between 7 and 7.3.
Further, in step S4, the mixed precipitate is stirred for more than 40 minutes for the first washing, and more than 20 minutes for the remaining several times, and is washed three to five times.
Further, in step S4, the filtrate is dried overnight, preferably for 12 hours, in a constant temperature oven at a temperature of 90-105 ℃.
Further, in step S4, the filtrate is put into a muffle furnace to be baked at a temperature of 400-600 ℃ for 3-7 hours, preferably at a temperature of 450 ℃ for 6 hours, or at a temperature of 550 ℃ for 4 hours.
Further, in step S5, according to the nickel loading amount, adding a certain amount of nickel nitrate and deionized water into the roasted solid, stirring and mixing for 3-6 hours at 50-70 ℃, performing reduced pressure distillation on the mixed reaction liquid, and putting the obtained solid into a constant temperature drying oven at 50-70 ℃ for drying for 8-10 hours; then put into a tube furnace and introduced with H containing 5 to 15 percent 2 H of (2) 2 And Ar mixed gas, carrying out primary roasting for 4-6 hours at 550-650 ℃ to reduce oxides in the mixed gas into small-particle nickel elements which are distributed on the surface, replacing the surface by nitrogen after cooling, finally heating to above 200 ℃, and introducing air to carry out secondary roasting for 3-5 hours to oxidize and agglomerate the nickel obtained by the primary reduction on the surface, thereby freeing the position for subsequent ruthenium loading. From the eds energy spectrum of FIG. 6, it can be seen that nickel and ruthenium achieve very uniform dispersion.
Further, in step S6, according to the load of ruthenium, adding ruthenium acetate ethanol solution into the baked solid for soaking for 6 hours, then performing reduced pressure distillation, drying the obtained solid in a constant temperature drying oven at 80 ℃ for 8 hours, finally placing the sample in a tube furnace, and introducing H 2 Roasting at 400-450 ℃ for 3 hours to obtain the ruthenium-nickel-loaded metal oxide catalyst.
The invention also provides an application of the metal oxide catalyst for catalyzing ammonia decomposition reaction, which comprises the following steps:
filling the metal oxide catalyst into a fixed bed reactor, setting the air pressure to be 0-300kpa, controlling the reaction temperature to be 400-650 ℃, adopting a temperature programming controller to control, detecting data every 25 ℃, and setting the volume airspeed of ammonia to be 20000-25000 h -1 Is introduced into the reaction tube.
Further, the reaction temperature is preferably 600 to 650 ℃.
Further, the volume space velocity of the metal oxide catalyst is 20000 to 25000h -1 。
The beneficial effects of the invention are as follows:
(1) The invention provides a catalyst for decomposing ammonia under mild conditions, which ensures that active component Ru can exist uniformly on the surface of a carrier by changing the distribution of Ni elements on the surface of the carrier.
(2) The cost of the catalyst is effectively reduced on the basis of keeping the original catalytic activity by screening the proportion of the carrier and the active components, and meanwhile, the physical property is increased, so that the cost of the complete equipment can be effectively reduced;
(3) The catalyst has low activation temperature and high conversion rate, and can greatly improve the production efficiency and reduce the related cost when being applied to industrial production.
Drawings
FIG. 1 is a graph showing the evaluation of the catalytic activity of the catalyst A of example 1 and the catalyst J of comparative example 1 in the present invention.
FIG. 2 is a graph showing the evaluation of the catalytic activity of catalysts B and C obtained in examples 2 and 3 of the present invention under a change in the pH of washing.
FIG. 3 is a graph showing the evaluation of the catalytic activities of D and E of the catalysts obtained in examples 4 and 5 according to the present invention by changing the ratio of the carrier components.
Fig. 4 is a graph showing the evaluation of the catalytic activity of catalysts F and G obtained by changing the Ni content of the active ingredient in examples 6 and 7 of the present invention.
FIG. 5 is a graph showing the evaluation of the catalytic activity of catalysts H and I obtained by changing the content of Ru as an active ingredient in examples 8 and 9 of the present invention.
FIG. 6 is an eds energy spectrum of a catalyst in the process of the present invention showing the distribution of the individual elements.
Detailed Description
The invention is described in detail below with reference to examples:
example 1:
the active components of the metal oxide catalyst are Ru and Ni, the carrier is metal oxide, and the metal oxide comprises Al 2 O 3 BaO and CeO 2 Wherein the mass ratio of the three metal oxides Al 2 O 3 ：BaO：CeO 2 =5:3:2, ru loading of 3%, ni loading of 15%, based on the mass of the support.
The preparation method comprises the following steps:
weighing 35mL of deionized water, pouring the deionized water into a 100mL beaker, adding a magnetic stirring rod, stirring and heating in a constant-temperature magnetic stirrer, setting the temperature to 65 ℃, adding 2.52g of cerium nitrate hexahydrate, 9.38g of aluminum nitrate nonahydrate and 2.56g of barium nitrate into the beaker, and heating and stirring at 65 ℃ under the condition that the rotating speed of a stirring paddle is 300r/min;
dropwise adding 15% ammonia water into the metal nitrate solution, controlling the mixing time to be 30min, stopping dropwise adding after adjusting the pH value of the suspension to be about 9, and continuously stirring the mixed solution for 1h;
after stirring is stopped, aging the precipitate for 2 hours at a constant temperature of 65 ℃;
repeatedly washing the mixed precipitate with deionized water for four times, wherein the water consumption is 300ml each time, the stirring time of the first washing is one hour, then the washing time is half an hour each time, the washing is carried out until the pH value is between 7 and 7.3, and the filtrate is placed into a constant-temperature drying oven at 100 ℃ for drying overnight; placing the sample into a muffle furnace for roasting for 4 hours at 850 ℃ to obtain a metal oxide carrier;
then placing the carrier into a 100mL beaker, adding 2.5g of nickel nitrate and 40mL of deionized water, and stirring and mixing for 6h at 65 ℃ and 300r/min; then the liquid is distilled under reduced pressure, and the obtained solid is put into a constant temperature drying oven at 60 ℃ for drying for 8 hours; put into a tube furnace and 10% H is introduced 2 Roasting Ar mixture gas of (2) at 600 ℃ for 5 hours, replacing by nitrogen after cooling, heating to 200 ℃, switching to air for roasting for 3 hours, taking out, soaking for 6 hours by using 1.6mL ruthenium acetate ethanol solution with the molar concentration of 1mol/L, then decompressing and distilling, and putting the obtained solid into a constant-temperature drying oven at 80 ℃ for drying for 8 hours; put into a tube furnace and let in H 2 Roasting for 3 hours at 400 ℃ to obtain the ammonia decomposition catalyst A.
Testing activity: the prepared metal oxide powder is pressed into tablets and ground, particles with 40-60 meshes are sieved out, 0.1g of catalyst particles are weighed and put into a fixed bed stainless steel tube reactor for activity evaluation test of ammonia decomposition, the air pressure is normal pressure, and the volume space velocity is 20000h -1 Introducing the mixture into a reaction tube, wherein the reaction temperature is 450-650 ℃, and a temperature programming controller is adoptedAnd (3) performing control, namely detecting data once at 25 ℃, and performing online quantitative analysis on the gas by adopting a gas chromatograph using a TCD detector so as to obtain the conversion rate of ammonia. The results of the experiment are shown in FIG. 1.
It can be seen that catalyst a has a higher ammonia conversion at the same temperature and a lower catalytic temperature than the catalyst without Ni crystallites dispersed (comparative example 1).
Example 2:
the active components of the metal oxide catalyst are Ru and Ni, the carrier is metal oxide, and the metal oxide comprises Al 2 O 3 BaO and CeO 2 Wherein the mass ratio of the three metal oxides Al 2 O 3 ：BaO：CeO 2 =5:3:2, ru loading of 3%, ni loading of 15%, based on the mass of the support.
The preparation method comprises the following steps:
weighing 35mL of deionized water, pouring the deionized water into a 100mL beaker, adding a magnetic stirring rod, stirring and heating in a constant-temperature magnetic stirrer, setting the temperature to 65 ℃, adding 2.52g of cerium nitrate hexahydrate, 9.38g of aluminum nitrate nonahydrate and 2.56g of barium nitrate into the beaker, and heating and stirring at 65 ℃ under the condition that the rotating speed of a stirring paddle is 300r/min;
dropwise adding 15% ammonia water into the metal nitrate solution, controlling the mixing time to be 30min, stopping dropwise adding after adjusting the pH value of the suspension to be about 9, and continuously stirring the mixed solution for 1h;
after stirring is stopped, aging the precipitate for 2 hours at a constant temperature of 65 ℃;
repeatedly washing the mixed precipitate with deionized water for four times, wherein the water consumption is 300ml each time, the stirring time of the first washing is one hour, then the washing time is half an hour each time, the washing is carried out until the pH value is between 7.5 and 7.8, and the filtrate is placed into a constant temperature drying oven at 100 ℃ for drying overnight; placing the sample into a muffle furnace for roasting for 4 hours at 850 ℃ to obtain a metal oxide carrier;
then placing the carrier into a 100mL beaker, adding 2.5g of nickel nitrate and 40mL of deionized water, and stirring and mixing for 6h at 65 ℃ and 300r/min; the liquid is then introducedVacuum distilling, and drying the obtained solid in a constant temperature drying oven at 60 ℃ for 8 hours; put into a tube furnace and 10% H is introduced 2 Roasting Ar mixture gas of (2) at 600 ℃ for 5 hours, replacing by nitrogen after cooling, heating to 200 ℃, switching to air for roasting for 3 hours, taking out, soaking for 6 hours by using 1.6mL ruthenium acetate ethanol solution with the molar concentration of 1mol/L, then decompressing and distilling, and putting the obtained solid into a constant-temperature drying oven at 80 ℃ for drying for 8 hours; put into a tube furnace and let in H 2 Roasting for 3 hours at 400 ℃ to obtain the ammonia decomposition catalyst B.
Testing activity: the prepared metal oxide powder is pressed into tablets and ground, particles with 40-60 meshes are sieved out, 0.1g of catalyst particles are weighed and put into a fixed bed stainless steel tube reactor for activity evaluation test of ammonia decomposition, the air pressure is normal pressure, and the volume space velocity is 20000h -1 Introducing the reaction mixture into a reaction tube, controlling the reaction temperature to be 450-650 ℃, detecting data once at 25 ℃ by adopting a temperature programming controller, and performing online quantitative analysis on the gas by adopting a gas chromatograph using a TCD detector to obtain the conversion rate of ammonia. The results of the experiment are shown in FIG. 2.
Example 3:
the active components of the metal oxide catalyst are Ru and Ni, the carrier is metal oxide, and the metal oxide comprises Al 2 O 3 BaO and CeO 2 Wherein the mass ratio of the three metal oxides Al 2 O 3 ：BaO：CeO 2 =5:3:2, ru loading of 3%, ni loading of 15%, based on the mass of the support.
The preparation method comprises the following steps:
weighing 35mL of deionized water, pouring the deionized water into a 100mL beaker, adding a magnetic stirring rod, stirring and heating in a constant-temperature magnetic stirrer, setting the temperature to 65 ℃, adding 2.52g of cerium nitrate hexahydrate, 9.38g of aluminum nitrate nonahydrate and 2.56g of barium nitrate into the beaker, and heating and stirring at 65 ℃ under the condition that the rotating speed of a stirring paddle is 300r/min;
dropwise adding 15% ammonia water into the metal nitrate solution, controlling the mixing time to be 30min, stopping dropwise adding after adjusting the pH value of the suspension to be about 9, and continuously stirring the mixed solution for 1h;
after stirring is stopped, aging the precipitate for 2 hours at a constant temperature of 65 ℃;
repeatedly washing the mixed precipitate with deionized water for four times, wherein the water consumption is 300ml each time, the stirring time of the first washing is one hour, then the washing time is half an hour each time, the washing time is between pH=6.5 and 7, and the filtrate is placed into a constant temperature drying oven at 100 ℃ for drying overnight; placing the sample into a muffle furnace for roasting for 4 hours at 850 ℃ to obtain a metal oxide carrier;
then placing the carrier into a 100mL beaker, adding 2.5g of nickel nitrate and 40mL of deionized water, and stirring and mixing for 6h at 65 ℃ and 300r/min; then the liquid is distilled under reduced pressure, and the obtained solid is put into a constant temperature drying oven at 60 ℃ for drying for 8 hours; put into a tube furnace and 10% H is introduced 2 The Ar mixed gas of (2) is roasted for 5 hours at 600 ℃, is replaced by nitrogen after being cooled, is heated to 200 ℃ and is switched to air roasting for 3 hours,
taking out, soaking for 6 hours by using 1.6mL ruthenium acetate ethanol solution with the molar concentration of 1mol/L, then carrying out reduced pressure distillation, and putting the obtained solid into a constant temperature drying oven at 80 ℃ for drying for 8 hours; put into a tube furnace and let in H 2 Roasting at 400 ℃ for 3 hours to obtain the ammonia decomposition catalyst C.
Testing activity: the prepared metal oxide powder is pressed into tablets and ground, particles with 40-60 meshes are sieved out, 0.1g of catalyst particles are weighed and put into a fixed bed stainless steel tube reactor for activity evaluation test of ammonia decomposition, the air pressure is normal pressure, and the volume space velocity is 20000h -1 Introducing the reaction mixture into a reaction tube, controlling the reaction temperature to be 450-650 ℃, detecting data once at 25 ℃ by adopting a temperature programming controller, and performing online quantitative analysis on the gas by adopting a gas chromatograph using a TCD detector to obtain the conversion rate of ammonia. The results of the experiment are shown in FIG. 2.
As seen in FIG. 2, the optimum wash pH was found to be 7 to 7.3.
Example 4:
the active components of the metal oxide catalyst are Ru and Ni, the carrier is metal oxide, and the metal oxide comprises Al 2 O 3 BaO and CeO 2 Wherein the mass ratio of the three metal oxides Al 2 O 3 ：BaO：CeO 2 =5:4:1, ru loading of 3%, ni loading of 15%, based on the mass of the support.
The preparation method comprises the following steps:
weighing 35mL of deionized water, pouring the deionized water into a 100mL beaker, adding a magnetic stirring rod, stirring and heating in a constant-temperature magnetic stirrer, setting the temperature to 65 ℃, adding 1.26g of cerium nitrate hexahydrate, 9.38g of aluminum nitrate nonahydrate and 3.41g of barium nitrate into the beaker, and heating and stirring at 65 ℃ under the condition that the rotating speed of a stirring paddle is 300r/min;
dropwise adding 15% ammonia water into the metal nitrate solution, controlling the mixing time to be 30min, stopping dropwise adding after adjusting the pH value of the suspension to be about 9, and continuously stirring the mixed solution for 1h;
after stirring is stopped, aging the precipitate for 2 hours at a constant temperature of 65 ℃;
the mixed precipitate is repeatedly washed with deionized water and suction filtered four times, the water consumption is 300ml each time, the stirring time of the first washing is one hour, and then the washing time is half an hour each time. Washing to a pH of between 7 and 7.3, and drying the filtrate in a constant temperature drying oven at 100 ℃ overnight; placing the sample into a muffle furnace for roasting for 4 hours at 850 ℃ to obtain a metal oxide carrier;
then placing the carrier into a 100mL beaker, adding 2.5g of nickel nitrate and 40mL of deionized water, and stirring and mixing for 6h at 65 ℃ and 300r/min; then the liquid is distilled under reduced pressure, and the obtained solid is put into a constant temperature drying oven at 60 ℃ for drying for 8 hours; put into a tube furnace and 10% H is introduced 2 The Ar mixed gas of (2) is roasted for 5 hours at 600 ℃, is replaced by nitrogen after being cooled, is heated to 200 ℃ and is switched to air roasting for 3 hours,
taking out, soaking for 6 hours by using 1.5mL of ruthenium acetate ethanol solution with the molar concentration of 1mol/L and 30mL of deionized water, then carrying out reduced pressure distillation, and putting the obtained solid into a constant temperature drying oven at 80 ℃ for drying for 8 hours; put into a tube furnace and let in H 2 Roasting at 400 ℃ for 3 hours to obtain the ammonia decomposition catalyst D.
Testing activity: the metal oxide to be preparedGrinding the powder into tablets, sieving out 40-60 mesh particles, weighing 0.1g of catalyst particles, placing into a fixed bed stainless steel tube reactor for activity evaluation test of ammonia decomposition, and taking the gas pressure as normal pressure and the volume space velocity of 20000h -1 Introducing the reaction mixture into a reaction tube, controlling the reaction temperature to be 450-650 ℃, detecting data once at 25 ℃ by adopting a temperature programming controller, and performing online quantitative analysis on the gas by adopting a gas chromatograph using a TCD detector to obtain the conversion rate of ammonia. The results of the obtained experiment are shown in FIG. 3.
Example 5:
the active components of the metal oxide catalyst are Ru and Ni, the carrier is metal oxide, and the metal oxide comprises Al 2 O 3 BaO and CeO 2 Wherein the mass ratio of the three metal oxides Al 2 O 3 ：BaO：CeO 2 =3:4:3, ru loading of 3%, ni loading of 15%, based on the mass of the support.
The preparation method comprises the following steps:
weighing 35mL of deionized water, pouring the deionized water into a 100mL beaker, adding a magnetic stirring rod, stirring and heating in a constant-temperature magnetic stirrer, setting the temperature to 65 ℃, adding 3.78g of cerium nitrate hexahydrate, 5.63g of aluminum nitrate nonahydrate and 3.41g of barium nitrate into the beaker, and heating and stirring at 65 ℃ under the condition that the rotating speed of a stirring paddle is 300r/min;
dropwise adding 15% ammonia water into the metal nitrate solution, controlling the mixing time to be 30min, stopping dropwise adding after adjusting the pH value of the suspension to be about 9, and continuously stirring the mixed solution for 1h;
after stirring is stopped, aging the precipitate for 2 hours at a constant temperature of 65 ℃;
the mixed precipitate is repeatedly washed with deionized water and suction filtered four times, the water consumption is 300ml each time, the stirring time of the first washing is one hour, and then the washing time is half an hour each time. Washing to a pH of between 7 and 7.3, and drying the filtrate in a constant temperature drying oven at 100 ℃ overnight; placing the sample into a muffle furnace for roasting for 4 hours at 850 ℃ to obtain a metal oxide carrier;
the carrier is then placedAdding 2.5g nickel nitrate and 40mL deionized water into a 100mL beaker, and stirring and mixing for 6h at 65 ℃ and 300r/min; then the liquid is distilled under reduced pressure, and the obtained solid is put into a constant temperature drying oven at 60 ℃ for drying for 8 hours; put into a tube furnace and 10% H is introduced 2 Roasting Ar mixed gas of (2) at 600 ℃ for 5 hours, cooling, replacing by nitrogen, heating to 200 ℃, and then switching to air roasting for 3 hours;
taking out, soaking for 6 hours by using 1.5mL ruthenium acetate ethanol solution with the molar concentration of 1mol/L, then carrying out reduced pressure distillation, and putting the obtained solid into a constant temperature drying oven at 80 ℃ for drying for 8 hours; put into a tube furnace and let in H 2 Roasting at 400 ℃ for 3 hours to obtain the ammonia decomposition catalyst E.
Testing activity: the prepared metal oxide powder is pressed into tablets and ground, particles with 40-60 meshes are sieved out, 0.1g of catalyst particles are weighed and put into a fixed bed stainless steel tube reactor for activity evaluation test of ammonia decomposition, the air pressure is normal pressure, and the volume space velocity is 20000h -1 Introducing the reaction mixture into a reaction tube, controlling the reaction temperature to be 450-650 ℃, detecting data once at 25 ℃ by adopting a temperature programming controller, and performing online quantitative analysis on the gas by adopting a gas chromatograph using a TCD detector to obtain the conversion rate of ammonia. The results of the obtained experiment are shown in FIG. 3.
It is seen from fig. 3 that changing the catalyst support has some effect on the catalyst performance, but still maintains a higher catalytic activity.
Example 6:
the active components of the metal oxide catalyst are Ru and Ni, the carrier is metal oxide, and the metal oxide comprises Al 2 O 3 BaO and CeO 2 Wherein the mass ratio of the three metal oxides Al 2 O 3 ：BaO：CeO 2 =5:3:2, ru loading of 3%, ni loading of 7.5%, based on the mass of the support.
The preparation method comprises the following steps:
weighing 35mL of deionized water, pouring the deionized water into a 100mL beaker, adding a magnetic stirring rod, stirring and heating in a constant-temperature magnetic stirrer, setting the temperature to 65 ℃, adding 2.52g of cerium nitrate hexahydrate, 9.38g of aluminum nitrate nonahydrate and 2.56g of barium nitrate into the beaker, and heating and stirring at 65 ℃ under the condition that the rotating speed of a stirring paddle is 300r/min;
dropwise adding 15% ammonia water into the metal nitrate solution, controlling the mixing time to be 30min, stopping dropwise adding after adjusting the pH value of the suspension to be about 9, and continuously stirring the mixed solution for 1h;
after stirring is stopped, aging the precipitate for 2 hours at a constant temperature of 65 ℃;
repeatedly washing the mixed precipitate with deionized water for four times, wherein the water consumption is 300ml each time, the stirring time of the first washing is one hour, then the washing time is half an hour each time, the washing is carried out until the pH value is between 7 and 7.3, and the filtrate is placed into a constant-temperature drying oven at 100 ℃ for drying overnight; placing the sample into a muffle furnace for roasting for 4 hours at 850 ℃ to obtain a metal oxide carrier;
then placing the carrier into a 100mL beaker, adding 1.25g of nickel nitrate and 40mL of deionized water, and stirring and mixing for 6h at 65 ℃ and 300r/min; then the liquid is distilled under reduced pressure, and the obtained solid is put into a constant temperature drying oven at 60 ℃ for drying for 8 hours; put into a tube furnace and 10% H is introduced 2 Roasting Ar mixed gas of (2) at 600 ℃ for 5 hours, cooling, replacing by nitrogen, heating to 200 ℃, and then switching to air roasting for 3 hours;
taking out, soaking for 6 hours by using 1.5mL ruthenium acetate ethanol solution with the molar concentration of 1mol/L, then carrying out reduced pressure distillation, and putting the obtained solid into a constant temperature drying oven at 80 ℃ for drying for 8 hours; put into a tube furnace and let in H 2 Roasting for 3 hours at 400 ℃ to obtain the ammonia decomposition catalyst F.
Testing activity: the prepared metal oxide powder is pressed into tablets and ground, particles with 40-60 meshes are sieved out, 0.1g of catalyst particles are weighed and put into a fixed bed stainless steel tube reactor for activity evaluation test of ammonia decomposition, the air pressure is normal pressure, and the volume space velocity is 20000h -1 Introducing the reaction mixture into a reaction tube, controlling the reaction temperature to be 450-650 ℃, detecting data once at 25 ℃ by adopting a temperature programming controller, and performing online quantitative analysis on the gas by adopting a gas chromatograph using a TCD detector to obtain the conversion rate of ammonia. The results of the obtained experiment are shown in FIG. 4.
Example 7
The active components of the metal oxide catalyst are Ru and Ni, the carrier is metal oxide, and the metal oxide comprises Al 2 O 3 BaO and CeO 2 Wherein the mass ratio of the three metal oxides Al 2 O 3 ：BaO：CeO 2 =5:3:2, ru loading of 3%, ni loading of 20%, based on the mass of the support.
The preparation method comprises the following steps:
weighing 35mL of deionized water, pouring the deionized water into a 100mL beaker, adding a magnetic stirring rod, stirring and heating in a constant-temperature magnetic stirrer, setting the temperature to 65 ℃, adding 2.52g of cerium nitrate hexahydrate, 9.38g of aluminum nitrate nonahydrate and 2.56g of barium nitrate into the beaker, and heating and stirring at 65 ℃ under the condition that the rotating speed of a stirring paddle is 300r/min;
dropwise adding 15% ammonia water into the metal nitrate solution, controlling the mixing time to be 30min, stopping dropwise adding after adjusting the pH value of the suspension to be about 9, and continuously stirring the mixed solution for 1h;
after stirring is stopped, aging the precipitate for 2 hours at a constant temperature of 65 ℃;
repeatedly washing the mixed precipitate with deionized water for four times, wherein the water consumption is 300ml each time, the stirring time of the first washing is one hour, then the washing time is half an hour each time, the washing is carried out until the pH value is between 7 and 7.3, and the filtrate is placed into a constant-temperature drying oven at 100 ℃ for drying overnight; placing the sample into a muffle furnace for roasting for 4 hours at 850 ℃ to obtain a metal oxide carrier;
then placing the carrier into a 100mL beaker, adding 3.75g of nickel nitrate and 40mL of deionized water, and stirring and mixing for 6h at 65 ℃ and 300r/min; then the liquid is distilled under reduced pressure, and the obtained solid is put into a constant temperature drying oven at 60 ℃ for drying for 8 hours; put into a tube furnace and 10% H is introduced 2 The Ar mixed gas of (2) is roasted for 5 hours at 600 ℃, is replaced by nitrogen after being cooled, is heated to 200 ℃ and is switched to air roasting for 3 hours,
after removal, the mixture was immersed in 1.5mL of ruthenium acetate ethanol solution having a molar concentration of 1mol/L for 6 hours, and then distilled under reduced pressure to obtainPutting the solid in a constant temperature drying oven at 80 ℃ for drying for 8 hours; put into a tube furnace and let in H 2 Roasting at 400 ℃ for 3 hours to obtain the ammonia decomposition catalyst G.
Testing activity: the prepared metal oxide powder is pressed into tablets and ground, particles with 40-60 meshes are sieved out, 0.1g of catalyst particles are weighed and put into a fixed bed stainless steel tube reactor for activity evaluation test of ammonia decomposition, the air pressure is normal pressure, and the volume space velocity is 20000h -1 Introducing the reaction mixture into a reaction tube, controlling the reaction temperature to be 450-650 ℃, detecting data once at 25 ℃ by adopting a temperature programming controller, and performing online quantitative analysis on the gas by adopting a gas chromatograph using a TCD detector to obtain the conversion rate of ammonia. The results of the obtained experiment are shown in FIG. 4.
It can be seen from fig. 4 that varying the nickel loading has some effect on the catalyst activity, but still maintains a higher catalytic activity.
Example 8:
the active components of the metal oxide catalyst are Ru and Ni, the carrier is metal oxide, and the metal oxide comprises Al 2 O 3 BaO and CeO 2 Wherein the mass ratio of the three metal oxides Al 2 O 3 ：BaO：CeO 2 =5:3:2, ru loading of 1.5%, ni loading of 15%, based on the mass of the support.
The preparation method comprises the following steps:
weighing 35mL of deionized water, pouring the deionized water into a 100mL beaker, adding a magnetic stirring rod, stirring and heating in a constant-temperature magnetic stirrer, setting the temperature to 65 ℃, adding 2.52g of cerium nitrate hexahydrate, 9.38g of aluminum nitrate nonahydrate and 2.56g of barium nitrate into the beaker, and heating and stirring at 65 ℃ under the condition that the rotating speed of a stirring paddle is 300r/min;
dropwise adding 15% ammonia water into the metal nitrate solution, controlling the mixing time to be 30min, stopping dropwise adding after adjusting the pH value of the suspension to be about 9, and continuously stirring the mixed solution for 1h;
after stirring is stopped, aging the precipitate for 2 hours at a constant temperature of 65 ℃;
the mixed precipitate is repeatedly washed with deionized water and suction filtered four times, the water consumption is 300ml each time, the stirring time of the first washing is one hour, and then the washing time is half an hour each time. Washing to a pH of between 7 and 7.3, and drying the filtrate in a constant temperature drying oven at 100 ℃ overnight; placing the sample into a muffle furnace for roasting for 4 hours at 850 ℃ to obtain a metal oxide carrier;
then placing the carrier into a 100mL beaker, adding 2.5g of nickel nitrate and 40mL of deionized water, and stirring and mixing for 6h at 65 ℃ and 300r/min; then the liquid is distilled under reduced pressure, and the obtained solid is put into a constant temperature drying oven at 60 ℃ for drying for 8 hours; put into a tube furnace and 10% H is introduced 2 Roasting Ar mixed gas of (2) at 600 ℃ for 5 hours, cooling, replacing by nitrogen, heating to 200 ℃, and then switching to air roasting for 3 hours;
taking out, soaking for 6 hours by using 0.8mL ruthenium acetate ethanol solution with the molar concentration of 1mol/L, then carrying out reduced pressure distillation, and putting the obtained solid into a constant temperature drying oven at 80 ℃ for drying for 8 hours; put into a tube furnace and let in H 2 Roasting for 3 hours at 400 ℃ to obtain the ammonia decomposition catalyst H.
Testing activity: the prepared metal oxide powder is pressed into tablets and ground, particles with 40-60 meshes are sieved out, 0.1g of catalyst particles are weighed and put into a fixed bed stainless steel tube reactor for activity evaluation test of ammonia decomposition, the air pressure is normal pressure, and the volume space velocity is 20000h -1 Introducing the reaction mixture into a reaction tube, controlling the reaction temperature to be 450-650 ℃, detecting data once at 25 ℃ by adopting a temperature programming controller, and performing online quantitative analysis on the gas by adopting a gas chromatograph using a TCD detector to obtain the conversion rate of ammonia. The results of the obtained experiment are shown in FIG. 5.
Example 9:
the active components of the metal oxide catalyst are Ru and Ni, the carrier is metal oxide, and the metal oxide comprises Al 2 O 3 BaO and CeO 2 Wherein the mass ratio of the three metal oxides Al 2 O 3 ：BaO：CeO 2 =5:3:2, ru loading of 6%, ni loading of 15%, based on the mass of the support.
The preparation method comprises the following steps:
weighing 35mL of deionized water, pouring into a 100mL beaker, adding a magnetic stirring rod, stirring and heating in a constant-temperature magnetic stirrer, setting the temperature to 65 ℃, adding 2.52g of cerium nitrate hexahydrate, 9.38g of aluminum nitrate nonahydrate and 2.56g of barium nitrate into the beaker, heating and stirring at 65 ℃, keeping the rotating speed of a stirring paddle at 300r/min,
dropwise adding 15% ammonia water into the metal nitrate solution, controlling the mixing time to be 30min, stopping dropwise adding after adjusting the pH value of the suspension to be about 9, and continuously stirring the mixed solution for 1h;
after stirring is stopped, aging the precipitate for 2 hours at a constant temperature of 65 ℃;
the mixed precipitate is repeatedly washed with deionized water and suction filtered four times, the water consumption is 300ml each time, the stirring time of the first washing is one hour, and then the washing time is half an hour each time. Washing to a pH of between 7 and 7.3, and drying the filtrate in a constant temperature drying oven at 100 ℃ overnight; placing the sample into a muffle furnace for roasting for 4 hours at 850 ℃ to obtain a metal oxide carrier;
then placing the carrier into a 100mL beaker, adding 2.5g of nickel nitrate and 40mL of deionized water, and stirring and mixing for 6h at 65 ℃ and 300r/min; then the liquid is distilled under reduced pressure, and the obtained solid is put into a constant temperature drying oven at 60 ℃ for drying for 8 hours; put into a tube furnace and 10% H is introduced 2 Roasting Ar mixed gas of (2) at 600 ℃ for 5 hours, cooling, replacing by nitrogen, heating to 200 ℃, and then switching to air roasting for 3 hours;
taking out, soaking for 6 hours by using 3.2mL ruthenium acetate ethanol solution with the molar concentration of 1mol/L, then carrying out reduced pressure distillation, and putting the obtained solid into a constant temperature drying oven at 80 ℃ for drying for 8 hours; placing the mixture into a tube furnace, introducing H2, and roasting the mixture at 400 ℃ for 3 hours to obtain the ammonia decomposition catalyst I.
Testing activity: the prepared metal oxide powder is pressed into tablets and ground, particles with 40-60 meshes are sieved out, 0.1g of catalyst particles are weighed and put into a fixed bed stainless steel tube reactor for activity evaluation test of ammonia decomposition, the air pressure is normal pressure, and the volume space velocity is 20000h -1 Introducing the mixture into a reaction tube, wherein the reaction temperature is 450-650 ℃ and the process is adoptedThe sequential heating controller is used for controlling, detecting data once at 25 ℃, and carrying out online quantitative analysis on the gas by adopting a gas chromatograph using a TCD detector so as to obtain the conversion rate of ammonia. The results of the obtained experiment are shown in FIG. 5.
It can be seen in fig. 5 that changing the loading of ruthenium increases the activity of the catalyst significantly, but the increase in loading also increases the cost of the catalyst further.
Comparative example 1
35mL of deionized water was measured and poured into a 100mL beaker, and a magnetic stirring rod was added to stir and heat in a constant temperature magnetic stirrer, setting the temperature at 65 ℃. Adding 2.52g of cerium nitrate hexahydrate, 9.38g of aluminum nitrate nonahydrate and 2.56g of barium nitrate into a beaker, under the condition of heating and stirring at 65 ℃, dropwise adding 15% ammonia water into a metal nitrate solution at the speed of 300r/min, controlling the mixing time to be 30min, stopping dropwise adding after adjusting the pH value of the suspension to be about 9, and continuously stirring the mixed solution for 1h; after stirring is stopped, aging the precipitate for 2 hours at a constant temperature of 65 ℃; the mixed precipitate is repeatedly washed with deionized water and suction filtered four times, the water consumption is 300ml each time, the stirring time of the first washing is one hour, and then the washing time is half an hour each time. Washing to a pH of between 7 and 7.3, and drying the filtrate in a constant temperature drying oven at 100 ℃ overnight; and (3) placing the sample into a muffle furnace, and roasting for 4 hours at 850 ℃ to obtain the metal oxide carrier. Then placing the carrier into a 100mL beaker, adding 1.6mL ruthenium acetate ethanol solution with the molar concentration of 1mol/L for soaking for 6h, then carrying out reduced pressure distillation, and placing the obtained solid into a constant temperature drying oven at 80 ℃ for drying for 8h; put into a tube furnace and let in H 2 Roasting for 3 hours at 400 ℃ to obtain the ammonia decomposition catalyst J. The rest steps are the same as in example 1, and the experimental results are shown in fig. 1.
The above description is only of the preferred embodiment of the present invention, and is not intended to limit the present invention in any other way, but is intended to cover any modifications or equivalent variations according to the technical spirit of the present invention, which fall within the scope of the present invention as defined by the appended claims.

Claims (10)

1. A ruthenium-nickel-supported metal oxide catalystCharacterized in that the active components of the metal oxide catalyst are Ru and Ni, the carrier is metal oxide, and the metal oxide comprises Al 2 O 3 BaO and CeO 2 Wherein the mass ratio of the three metal oxides Al 2 O 3 ：BaO：CeO 2 ＝(3-5):(1-3):(1-2)。
2. Metal oxide catalyst according to claim 1, characterized in that the loading of Ru is 8% -32%, preferably 10% -20% based on the mass of the support.
3. Metal oxide catalyst according to claim 1, characterized in that the loading of Ni is 8-32%, preferably 10-20% based on the mass of the support.
4. A method for preparing a metal oxide catalyst according to any one of claims 1 to 3, characterized in that the method comprises the steps of:
step S1: preparing a metal salt solution: fully dissolving nitrate containing cerium, aluminum and barium in water at 60-70 ℃ to prepare a metal salt solution, and transferring the metal salt solution into a stirring kettle for continuous stirring;
step S2: coprecipitation reaction: slowly adding ammonia water with the mass concentration of 10-15% into the stirring kettle, and regulating the pH value of the suspension in the adding process until the pH value is 8.5-9.5, and stopping dropwise adding the ammonia water;
step S3: aging: precipitating and aging the suspension at 50-70 ℃ for 0.5-5h;
step S4: washing, drying and roasting the aged mixed precipitate;
step S5: according to the nickel loading amount, adding nickel nitrate and deionized water into the roasted solid, and carrying out reduced pressure distillation, drying, primary roasting, nitrogen replacement and secondary roasting on the mixed reaction liquid to obtain a nickel-loaded metal oxide catalyst;
step S6: and (3) according to the loading amount of ruthenium, impregnating the nickel-loaded metal oxide catalyst obtained in the step (S5) with an ethanol solution of ruthenium acetate, and carrying out reduced pressure distillation, drying and reduction on the mixed reaction solution to obtain the ruthenium-nickel-loaded metal oxide catalyst.
5. The method for producing a metal oxide catalyst according to claim 4, wherein in step S1, the mass ratio of nitrates of Ce, al and Ba is (11-18): (1.7-5): (2.5-5).
6. The method for preparing a metal oxide catalyst according to claim 5, wherein in step S2, the pH value of the suspension is continuously detected during the addition process until the pH value is 8.5 to 9.5, and then the dropwise addition of ammonia water is stopped, and the suspension is stirred for 1 hour.
7. The method for preparing a metal oxide catalyst according to claim 4, wherein in step S4, the mixed precipitate is washed with water and suction filtered several times until the pH after washing is between 6.5 and 7.8, preferably between 7 and 7.3.
8. The method for preparing a metal oxide catalyst according to claim 7, wherein in step S4, the filtrate is put into a muffle furnace and calcined at a temperature of 400-600 ℃ for 3-7 hours, preferably at a temperature of 450 ℃ for 6 hours, or at a temperature of 550 ℃ for 4 hours.
9. The method for preparing a metal oxide catalyst according to claim 4, wherein in step S5, a certain amount of nickel nitrate and deionized water are added into the baked solid according to the nickel loading, the mixture is stirred and mixed for 3-6 hours at 50-70 ℃, the mixed reaction liquid is subjected to reduced pressure distillation, and the obtained solid is put into a constant temperature drying oven at 50-70 ℃ for drying for 8-10 hours; then put into a tube furnace and introduced with H containing 5 to 15 percent 2 H of (2) 2 And Ar mixed gas, and performing first roasting at 550-650 ℃ for 4-6 hours to reduce oxides therein into small-particle nickel element distributionAnd (3) replacing the surface with nitrogen after cooling, heating to above 200 ℃, and introducing air to perform secondary roasting for 3-5 to oxidize and agglomerate the nickel obtained by the primary reduction on the surface, thereby freeing a position for subsequent ruthenium loading.
10. Use of a metal oxide catalyst according to any of claims 1-3 for catalyzing an ammonolysis reaction, comprising the steps of:
filling the metal oxide catalyst into a fixed bed reactor, setting the air pressure to be 0-300kpa, controlling the reaction temperature to be 400-650 ℃, adopting a temperature programming controller to control, detecting data every 25 ℃, and setting the volume airspeed of ammonia to be 20000-25000 h -1 Is introduced into the reaction tube.
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