CN110270338B - Nickel and/or ruthenium ammonia decomposition catalyst and preparation method and application thereof - Google Patents
Nickel and/or ruthenium ammonia decomposition catalyst and preparation method and application thereof Download PDFInfo
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
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Abstract
The invention provides a nickel and/or ruthenium ammonia decomposition catalyst and a preparation method and application thereof, wherein the catalyst comprises an active component and a carrier; the active component is one or two of nickel and ruthenium, the carrier comprises graphitized activated carbon and an auxiliary agent, the auxiliary agent is one or more of alkali metal oxide and carbonate, alkaline earth metal oxide and carbonate and rare earth oxide, the carrier of the catalyst comprises graphitized activated carbon and the auxiliary agent, and the auxiliary agent can modify the carrier and improve the activity of the catalyst; in addition, the invention carries out high-temperature graphitization treatment on the activated carbon, on one hand, the stability of the catalyst is improved, on the other hand, strong interaction can be formed between the active component and the carrier carbon to generate electron transfer, which is beneficial to the reaction product N2And H2The low-temperature reaction activity of the ammonia is further improved, a good ammonia decomposition effect is achieved, and the treatment efficiency of the ammonia gas is improved.
Description
Technical Field
The invention relates to the technical field of ammonia decomposition, in particular to a nickel and/or ruthenium ammonia decomposition catalyst and a preparation method and application thereof.
Background
The ammonia decomposition catalyst is mainly applied to the field of environmental protection and the field of preparation of hydrogen and nitrogen. In the field of environmental protection, ammonia-containing waste gas of factories is decomposed under the action of an ammonia decomposition catalyst, so that ammonia gas in the waste gas is decomposed into nontoxic hydrogen and nitrogen and then is recycled to achieve the purpose of reducing pollution. In the field of hydrogen production, ammonia has the advantages of easy liquefaction, non-flammability, no toxicity at low concentration, high hydrogen storage density, mature production, storage and transportation technology, no carbon emission in the hydrogen production process and the like, so that the ammonia becomes a high-efficiency, clean and safe hydrogen storage carrier and can be used for preparing hydrogen under the action of an ammonia decomposition catalyst. The ammonia decomposition reaction mainly employs a noble metal catalyst represented by ruthenium and platinum and a non-noble metal catalyst represented by iron and nickel.
Chinese patent document CN1506299A discloses a nickel-based catalyst for producing hydrogen-nitrogen mixed gas by decomposing ammonia, which has a main active component of Ni; the carrier is SiO2Or Al2O3(ii) a The auxiliary agent is one or more of IA, IIA, IIIB, VIII or rare earth elements; wherein the weight percentage of nickel is 1-40%. The catalyst can be used for decomposing ammonia gas well, the use temperature of the catalyst is 650 ℃, the catalyst is reduced compared with the working temperature of 800 ℃ of the existing industrial catalyst, but the catalyst has low catalytic activity at the lower temperature, and the ammonia decomposition effect is poor.
Chinese patent document CN1506300A discloses a nitrogen mixed gas catalyst for hydrogen production by ammonia decomposition of ruthenium, the main active component of the catalyst is ruthenium; the carrier is CaO, MgO, TiO2、SiO2、Al2O3Or activated carbon; the auxiliary agent is one or more of IA, IIA, III A, IVA, IIIB or rare earth elements; wherein the weight percentage of the ruthenium is 0.1 to 10 percent. Compared with nickel-based catalyst, the catalyst has the advantages that the ammonia decomposition temperature is reduced, the reaction can be carried out at 550 ℃, the catalytic activity at the lower temperature is not high, the ammonia decomposition effect is poor, and the space velocity of the catalyst is only 3000h-1The ammonia gas treatment efficiency is low.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects of low-temperature catalytic activity, poor ammonia decomposition effect and low ammonia treatment efficiency of ammonia decomposition catalysts in the prior art, so that the nickel and/or ruthenium ammonia decomposition catalyst which is high in low-temperature catalytic activity, good in ammonia decomposition effect and high in ammonia treatment efficiency, and the preparation method and the application thereof are provided.
Therefore, the invention provides a nickel and/or ruthenium ammonia decomposition catalyst, which comprises an active component and a carrier; the active component is one or two of nickel and ruthenium, the carrier comprises graphitized activated carbon and an auxiliary agent, and the auxiliary agent is one or more of alkali metal oxide and carbonate, alkaline earth metal oxide and carbonate and rare earth oxide.
The active component of the nickel and/or ruthenium ammonia decomposition catalyst is nickel, and the nickel accounts for 8-24% of the catalyst by mass percent; the active component is ruthenium, and the ruthenium accounts for 0.5-12% of the catalyst in percentage by mass; the active component is a nickel and ruthenium bimetal, wherein the nickel accounts for 5-15% of the catalyst, and the ruthenium accounts for 0.2-3% of the catalyst in percentage by mass.
The nickel and/or ruthenium ammonia decomposition catalyst comprises, by mass, graphitized activated carbon accounting for 85-92% of the carrier, and an auxiliary agent accounting for 8-15% of the carrier.
The nickel and/or ruthenium ammonia decomposition catalyst, the alkali metal oxide and carbonate comprises at least one of potassium oxide, cesium oxide and potassium carbonate;
the oxide and carbonate of the alkaline earth metal comprise at least one of barium oxide, magnesium oxide, strontium oxide, barium carbonate and magnesium carbonate;
the rare earth oxide comprises at least one of cerium oxide, lanthanum oxide, praseodymium oxide and neodymium oxide.
The invention provides a preparation method of the nickel and/or ruthenium ammonia decomposition catalyst, which comprises the following steps,
s1, mixing the graphitized activated carbon with an auxiliary agent metal salt or oxide, ball-milling, molding and roasting to obtain a catalyst carrier;
s2, dissolving the active component metal salt in water to obtain a metal salt solution;
s3, loading the active component in the metal salt solution on the catalyst carrier by adopting a precipitation deposition method or an impregnation method to obtain the nickel and/or ruthenium ammonia decomposition catalyst.
The preparation method of the nickel and/or ruthenium ammonia decomposition catalyst is characterized in that the preparation method of the graphitized activated carbon comprises the step of carrying out high-temperature treatment on the activated carbon at the temperature of more than 1500 ℃ for 12-24h to obtain the graphitized activated carbon.
The preparation method of the nickel and/or ruthenium ammonia decomposition catalyst comprises the steps of mixing the graphitized activated carbon with the auxiliary agent metal salt, performing ball milling molding, wherein the granularity is 0.1-0.8mm, and the roasting temperature is 1200-2000 ℃.
In the preparation method of the nickel and/or ruthenium ammonia decomposition catalyst, the active component metal salt comprises one or more of nickel nitrate, nickel chloride, nickel acetate, ruthenium nitrate or ruthenium chloride; the assistant metal salt comprises one or more of nitrate, acetate or chloride.
The preparation method of the nickel and/or ruthenium ammonia decomposition catalyst comprises the following steps of,
s10, dispersing the catalyst carrier in water, and heating to 50-80 ℃ to obtain a base solution;
s20, adding the metal salt solution and a precipitator into the base solution at the same time, controlling the pH value to be 8.0-10.5, and stirring for 2-6h to obtain a precipitate;
s30, washing and drying the precipitate, roasting for 2-6h at the temperature of 450-750 ℃, and reducing by hydrogen to obtain the catalyst;
wherein the precipitant is one or more aqueous solutions of sodium hydroxide, potassium carbonate, ammonium carbonate and ammonium bicarbonate.
In the preparation method of the nickel and/or ruthenium ammonia decomposition catalyst, in the step S10, the catalyst carrier is dispersed by ultrasonic dispersion.
The method for preparing the nickel and/or ruthenium ammonia decomposition catalyst comprises the following steps of,
s100, adding the catalyst carrier into the metal salt solution for dipping and drying to obtain a metal-loaded catalyst precursor;
s200, roasting the metal-loaded catalyst precursor at the temperature of 450-900 ℃ for 2-6h, and reducing by hydrogen to obtain the catalyst.
In the preparation method of the nickel and/or ruthenium ammonia decomposition catalyst, in the step S100, the dipping and drying are carried out for more than 2 times until the content of nickel or ruthenium reaches the target loading capacity.
The invention provides the application of the nickel and/or ruthenium ammonia decomposition catalyst or the nickel and/or ruthenium ammonia decomposition catalyst prepared by the preparation method in ammonia decomposition.
The technical scheme of the invention has the following advantages:
1. the invention provides a nickel and/or ruthenium ammonia decomposition catalyst, which comprises an active component and a carrier; the catalyst adopts one or two of nickel and ruthenium as active components and can promote NH by adopting one or two of nickel and ruthenium as the active components3Promoting the product N by adsorption and dissociation2While suppressing H2Adsorption of (3); in addition, the carrier of the catalyst comprises graphitized activated carbon and an auxiliary agent, wherein the auxiliary agent can modify the carrier, improve the dispersion degree of the active components in the carrier and enhance the interaction between the carrier and the active components; because the surface functional groups of the activated carbon are rich, the untreated activated carbon is used as a carrier, and the stability of the catalyst is poor due to the participation of the functional groups in the reaction, particularly the influence of oxygen-containing functional groups, in the catalytic reaction process, the activated carbon is graphitized at high temperature, so that the number of the surface functional groups is reduced, the stability of the catalyst is effectively improved, and a small amount of functional groups are remained on the surface of the carrier, the dispersion of active components can be promoted, the activity of the catalyst is improved, and strong interaction can be formed between the active components and the carrier carbon through the functional groups, so that the electron transfer is generated, the interaction between the active components and reaction intermediate products is weakened, and the reaction product N is favorable for reacting2And H2So as to further improve the low-temperature catalytic activity of the ammonia, achieve better ammonia decomposition effect and improve the treatment efficiency of ammonia.
2. The invention provides a nickel and/or ruthenium ammonia decomposition catalyst, wherein the active component is nickel, and the nickel accounts for 8-24% of the catalyst by mass percent; the active component is ruthenium, and the ruthenium accounts for 0.5-12% of the catalyst in percentage by mass; the active component is a nickel-ruthenium bimetal, the nickel accounts for 5-15% of the catalyst and the ruthenium accounts for 0.2-3% of the catalyst in percentage by mass, and the interaction of the active component and the carrier can be enhanced and the active component and NH can be effectively weakened by limiting the content of the active component3NH as a decomposition product of2N or H, in favor of the product N2And H2The desorption is carried out, so that the low-temperature catalytic activity of the catalyst is improved, a better ammonia decomposition effect is achieved, and the treatment efficiency of ammonia gas is improved.
3. The invention provides a nickel and/or ruthenium ammonia decomposition catalyst, which comprises, by mass, graphitized activated carbon accounting for 85-92% of a carrier, and an auxiliary agent accounting for 8-15% of the carrier, wherein the modification effect of the auxiliary agent on the carrier can be improved by limiting the contents of the graphitized activated carbon and the auxiliary agent, so that the active component has high dispersity in the carrier, the interaction between the active component and the carrier carbon is enhanced, the transfer of electrons is promoted, the interaction between the active component and a reaction intermediate product is weakened, and a reaction product N is facilitated2And H2So as to further improve the low-temperature catalytic activity of the ammonia, achieve better ammonia decomposition effect and improve the treatment efficiency of ammonia.
4. The invention provides a nickel and/or ruthenium ammonia decomposition catalyst, wherein the oxide and carbonate of alkali metal comprise at least one of potassium oxide, cesium oxide and potassium carbonate; the oxide and carbonate of the alkaline earth metal comprise at least one of barium oxide, magnesium oxide, strontium oxide, barium carbonate and magnesium carbonate; the rare earth oxide comprises at least one of cerium oxide, lanthanum oxide, praseodymium oxide and neodymium oxide, and the auxiliary agent can improve the dispersity of the active components, further enhance the interaction between the carrier and the active components, promote electron transfer, improve the low-temperature reaction activity of the catalyst and improve the treatment efficiency of ammonia gas.
5. The preparation method of the nickel and/or ruthenium ammonia decomposition catalyst comprises the steps of S1, mixing graphitized activated carbon with auxiliary agent metal salt or oxide, ball milling, molding and roasting to obtain a catalyst carrier; s2, dissolving the active component metal salt in water to obtain a metal salt solution; s3, loading the active component in the metal salt solution on the catalyst carrier by adopting a precipitation deposition method or an impregnation method to obtain the nickel and/or ruthenium ammonia decomposition catalyst, wherein the method comprises the steps of firstly mixing graphitized activated carbon and auxiliary agent metal salt to prepare the carrier, and then loading the active component, so that the modification of the auxiliary agent on the carrier can be enhanced, and compared with the method that only the graphitized activated carbon is used as the carrier and the active component and the auxiliary agent are directly loaded together, the activity of the catalyst can be further improved, so that the ammonia decomposition catalyst with high low-temperature catalytic activity, good ammonia decomposition effect and high ammonia treatment efficiency is obtained.
6. According to the preparation method of the nickel and/or ruthenium ammonia decomposition catalyst, graphitized activated carbon and auxiliary agent metal salt are mixed and ball-milled for molding, the granularity is 0.1-0.8mm, the roasting temperature is 1200-2000 ℃, and the modification of the auxiliary agent on a carrier can be promoted by controlling the granularity and the roasting temperature, so that the active components can be highly dispersed in the carrier, the activity of the catalyst is further improved, and the ammonia decomposition catalyst with high low-temperature catalytic activity, good ammonia decomposition effect and high ammonia treatment efficiency is obtained.
7. The nickel and/or ruthenium ammonia decomposition catalyst or the application of the nickel and/or ruthenium ammonia decomposition catalyst prepared by the preparation method in ammonia decomposition provided by the invention can be used for efficiently decomposing ammonia, and the catalyst has the advantages of high stability, high low-temperature catalytic activity, good ammonia decomposition effect and high ammonia treatment efficiency.
Detailed Description
The technical solutions of the present invention are described clearly and completely below, and it is obvious that the described embodiments are some, not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
This example provides a nickel-based ammonia decomposition catalyst, including, active component nickel 0.8g and carrier 9.2 g; wherein, the carrier comprises 1.38g of auxiliary agent potassium oxide and 7.82g of graphitized activated carbon.
This example provides a method for preparing the above nickel-based ammonia decomposition catalyst, comprising,
s1, performing high-temperature treatment on the activated carbon at the temperature of more than 1500 ℃ for 18h in an inert gas environment to obtain graphitized activated carbon, mixing 7.82g of graphitized activated carbon with 2.97g of potassium nitrate, performing ball milling, molding to obtain a catalyst carrier with the particle size of 0.1-0.15mm, and roasting at the temperature of 1200 ℃ to obtain the catalyst carrier.
S2, dissolving 2.48g of nickel nitrate in water to obtain a metal salt solution, wherein the concentration of metal ions is 1 mol/L.
S3, ultrasonically dispersing the catalyst carrier obtained in the S1 in water, and heating to 50 ℃ to obtain a base solution.
S4, adding the metal salt solution obtained in the step S2 and sodium hydroxide with the concentration of 5mol/L into the base solution at the same time, controlling the pH value to be 8.0, and stirring for 2 hours to obtain a precipitate.
S5, washing and drying the precipitate obtained in the S4, roasting the precipitate at the temperature of 450 ℃ for 6 hours, and reducing the precipitate for 3 hours at the temperature of 800 ℃ by using a mixed gas of hydrogen and nitrogen with the volume fraction of 20% of hydrogen to obtain the ammonia decomposition catalyst.
The activity of the catalyst was evaluated at various temperatures using pure ammonia gas, the catalyst was 60 to 80 mesh, 0.2g was packed, the space velocity was 15000mL/(g · h), and the ammonia decomposition rate was calculated according to the formula (initial ammonia content-treated ammonia content)/initial ammonia content 100%, and the results are shown in table 1.
Example 2
This example provides a nickel-based ammonia decomposition catalyst, including, 1.6g of active component nickel and 8.4g of carrier; wherein, the carrier comprises 1.01g of auxiliary agent barium oxide and 7.39g of graphitized activated carbon.
This example provides a method for preparing the above nickel-based ammonia decomposition catalyst, comprising,
s1, performing high-temperature treatment on the activated carbon at the temperature of more than 1500 ℃ for 18h in an inert gas environment to obtain graphitized activated carbon, mixing and ball-milling 1.72g of barium nitrate and 7.39g of graphitized activated carbon, molding to obtain a catalyst carrier with the particle size of 0.3-0.5mm, and roasting at the temperature of 1600 ℃ to obtain the catalyst carrier.
S2, dissolving 3.5g of nickel chloride in water to obtain a metal salt solution, wherein the concentration of metal ions is 3 mol/L.
And S3, adding the catalyst carrier obtained in the step S1 into the metal salt solution obtained in the step S2 for dipping, drying, dipping and drying until all nickel is loaded on the carrier, so as to obtain the metal-loaded catalyst precursor.
S4, roasting the metal-loaded catalyst precursor obtained in the step S3 at 450 ℃ for 6 hours, and reducing the metal-loaded catalyst precursor for 5 hours at 650 ℃ by using a mixed gas of hydrogen and nitrogen with the hydrogen volume fraction of 35% to obtain the ammonia decomposition catalyst.
The activity of the catalyst was evaluated at various temperatures using pure ammonia gas, the catalyst was 60 to 80 mesh, 0.2g was packed, the space velocity was 15000mL/(g · h), and the ammonia decomposition rate was calculated according to the formula (initial ammonia content-treated ammonia content)/initial ammonia content 100%, and the results are shown in table 1.
Example 3
This example provides a nickel-based ammonia decomposition catalyst, including, active component nickel 2.4g and carrier 7.6 g; wherein, the carrier comprises 0.61g of auxiliary agent cerium oxide and 6.99g of graphitized activated carbon.
This example provides a method for preparing the above nickel-based ammonia decomposition catalyst, comprising,
s1, performing high-temperature treatment on the activated carbon at the temperature of more than 1500 ℃ for 18h in an inert gas environment to obtain graphitized activated carbon, mixing 1.16g of cerium nitrate and 6.99g of graphitized activated carbon, performing ball milling, molding to obtain a catalyst carrier with the particle size of 0.6-0.8mm, and roasting at the temperature of 2000 ℃ to obtain the catalyst carrier.
S2, dissolving 7.2g of nickel acetate in water to obtain a metal salt solution, wherein the concentration of metal ions is 3 mol/L.
And S3, adding the catalyst carrier obtained in the step S1 into the metal salt solution obtained in the step S2 for dipping, drying, dipping and drying until all nickel is loaded on the carrier, so as to obtain the metal-loaded catalyst precursor.
S4, roasting the metal-loaded catalyst precursor obtained in the step S3 at 675 ℃ for 4h, and reducing the metal-loaded catalyst precursor by using a mixed gas of hydrogen and nitrogen with the volume fraction of 50% of hydrogen at 500 ℃ for 8h to obtain the ammonia decomposition catalyst.
The activity of the catalyst was evaluated at various temperatures using pure ammonia gas, the catalyst was 60 to 80 mesh, 0.2g was packed, the space velocity was 15000mL/(g · h), and the ammonia decomposition rate was calculated according to the formula (initial ammonia content-treated ammonia content)/initial ammonia content 100%, and the results are shown in table 1.
Example 4
This example provides a ruthenium-based ammonia decomposition catalyst comprising 0.05g of ruthenium as an active component and 9.95g of a carrier; wherein, the carrier comprises 1.49g of auxiliary agent cesium oxide and 8.46g of graphitized activated carbon.
This example provides a method for preparing the ruthenium-based ammonia decomposition catalyst, comprising,
s1, performing high-temperature treatment on the activated carbon at the temperature of more than 1500 ℃ for 18h in an inert gas environment to obtain graphitized activated carbon, mixing 8.46g of graphitized activated carbon with 1.78g of cesium chloride, performing ball milling, molding to obtain a product with the particle size of 0.1-0.15mm, and roasting at the temperature of 1200 ℃ to obtain the catalyst carrier.
S2, dissolving 0.14g of ruthenium nitrate in water to obtain a metal salt solution, wherein the concentration of metal ions is 1 mol/L.
S3, ultrasonically dispersing the catalyst carrier obtained in the S1 in water, and heating to 65 ℃ to obtain a base solution.
S4, adding the metal salt solution obtained in the step S2 and potassium hydroxide with the concentration of 5mol/L into the base solution at the same time, controlling the pH value to be 9.0, and stirring for 6 hours to obtain a precipitate.
S5, washing and drying the precipitate obtained in the S4, roasting for 4 hours at the temperature of 600 ℃, and reducing for 3 hours at the temperature of 800 ℃ by using a mixed gas of hydrogen and nitrogen with the volume fraction of 20% of hydrogen to obtain the catalyst.
The activity of the catalyst was evaluated at various temperatures using pure ammonia gas, the catalyst was 60 to 80 mesh, 0.2g was packed, the space velocity was 15000mL/(g · h), and the ammonia decomposition rate was calculated according to the formula (initial ammonia content-treated ammonia content)/initial ammonia content 100%, and the results are shown in table 1.
Example 5
This example provides a ruthenium-based ammonia decomposition catalyst comprising 0.6g of ruthenium as an active component and 9.4g of a carrier; wherein, the carrier comprises 1.13g of auxiliary agent magnesium oxide and 8.27g of graphitized activated carbon.
This example provides a method for preparing the ruthenium-based ammonia decomposition catalyst, comprising,
s1, performing high-temperature treatment on the activated carbon at the temperature of more than 1500 ℃ for 18h in an inert gas environment to obtain graphitized activated carbon, mixing 2.66g of magnesium chloride and 8.27g of graphitized activated carbon, performing ball milling, molding to obtain a catalyst carrier with the particle size of 0.3-0.5mm, and roasting at the temperature of 1600 ℃ to obtain the catalyst carrier.
S2, 1.22g of ruthenium chloride is dissolved in water to obtain a metal salt solution, wherein the concentration of metal ions is 3 mol/L.
And S3, adding the catalyst carrier obtained in the step S1 into the metal salt solution obtained in the step S2 for dipping, drying, dipping and drying until all ruthenium is loaded on the carrier, so as to obtain the metal-loaded catalyst precursor.
S4, roasting the metal-loaded catalyst precursor obtained in the step S3 at 900 ℃ for 2h, and reducing the metal-loaded catalyst precursor for 5h at 650 ℃ by using a mixed gas of hydrogen and nitrogen with the volume fraction of the hydrogen being 35% to obtain the ammonia decomposition catalyst.
The activity of the catalyst was evaluated at various temperatures using pure ammonia gas, the catalyst was 60 to 80 mesh, 0.2g was packed, the space velocity was 15000mL/(g · h), and the ammonia decomposition rate was calculated according to the formula (initial ammonia content-treated ammonia content)/initial ammonia content 100%, and the results are shown in table 1.
Example 6
This example provides a ruthenium-based ammonia decomposition catalyst comprising, as an active component, 1.2g of ruthenium and 8.8g of a carrier; wherein, the carrier comprises 0.7g of auxiliary agent lanthanum oxide and 8.1g of graphitized activated carbon.
This example provides a method for preparing the ruthenium-based ammonia decomposition catalyst, comprising,
s1, performing high-temperature treatment on the activated carbon at the temperature of more than 1500 ℃ for 18h in an inert gas environment to obtain graphitized activated carbon, mixing 1.05g of lanthanum chloride and 8.1g of graphitized activated carbon, performing ball milling, molding to obtain a catalyst carrier with the particle size of 0.6-0.8mm, and roasting at the temperature of 2000 ℃ to obtain the catalyst carrier.
S2, 2.45g of ruthenium chloride is dissolved in water to obtain a metal salt solution, wherein the concentration of metal ions is 3 mol/L.
And S3, adding the catalyst carrier obtained in the step S1 into the metal salt solution obtained in the step S2 for dipping, drying, dipping and drying until all ruthenium is loaded on the carrier, so as to obtain the metal-loaded catalyst precursor.
S4, roasting the metal-loaded catalyst precursor obtained in the step S3 at 450 ℃ for 6 hours, and reducing the metal-loaded catalyst precursor for 8 hours at 500 ℃ by using a mixed gas of hydrogen and nitrogen with the volume fraction of 50% of hydrogen to obtain the ammonia decomposition catalyst.
The activity of the catalyst was evaluated at various temperatures using pure ammonia gas, the catalyst was 60 to 80 mesh, 0.2g was packed, the space velocity was 15000mL/(g · h), and the ammonia decomposition rate was calculated according to the formula (initial ammonia content-treated ammonia content)/initial ammonia content 100%, and the results are shown in table 1.
Example 7
This example provides a nickel/ruthenium-based ammonia decomposition catalyst comprising 0.02g of ruthenium as an active component, 0.5g of nickel as an active component, and 9.48g of a carrier; wherein, the carrier comprises 1.42g of auxiliary agent potassium carbonate and 8.06g of graphitized activated carbon.
This example provides a method for preparing the above nickel/ruthenium-based ammonia decomposition catalyst, comprising,
s1, performing high-temperature treatment on the activated carbon at the temperature of more than 1500 ℃ for 18h in an inert gas environment to obtain graphitized activated carbon, mixing 8.06g of the graphitized activated carbon with 2.02g of potassium acetate, performing ball milling, molding to obtain a product with the particle size of 0.1-0.15mm, and roasting at the temperature of 1200 ℃ to obtain the catalyst carrier.
S2, dissolving 1.55g of nickel nitrate and 0.06g of ruthenium nitrate in water to obtain a metal salt solution, wherein the concentration of metal ions is 1 mol/L.
S3, ultrasonically dispersing the catalyst carrier obtained in the S1 in water, and heating to 80 ℃ to obtain a base solution.
S4, adding the metal salt solution obtained in the step S2 and potassium carbonate with the concentration of 5mol/L into the base solution at the same time, controlling the pH value to be 10.5, and stirring for 6 hours to obtain a precipitate.
And S5, washing and drying the precipitate obtained in the S4, roasting for 2 hours at the temperature of 750 ℃, and reducing for 3 hours at the temperature of 800 ℃ by using a mixed gas of hydrogen and nitrogen with the volume fraction of 20% of hydrogen to obtain the catalyst.
The activity of the catalyst was evaluated at various temperatures using pure ammonia gas, the catalyst was 60 to 80 mesh, 0.2g was packed, the space velocity was 15000mL/(g · h), and the ammonia decomposition rate was calculated according to the formula (initial ammonia content-treated ammonia content)/initial ammonia content 100%, and the results are shown in table 1.
Example 8
This example provides a nickel/ruthenium-based ammonia decomposition catalyst comprising 0.15g of ruthenium as an active component, 1g of nickel as an active component, and 8.85g of a carrier; wherein, the carrier comprises 1.06g of auxiliary agent strontium oxide and 7.79g of graphitized activated carbon.
This example provides a method for preparing the above nickel/ruthenium-based ammonia decomposition catalyst, comprising,
s1, performing high-temperature treatment on the activated carbon at the temperature of more than 1500 ℃ for 18h in an inert gas environment to obtain graphitized activated carbon, mixing and ball-milling 1.61g of strontium chloride and 7.79g of graphitized activated carbon, molding to obtain a catalyst carrier with the particle size of 0.3-0.5mm, and roasting at the temperature of 1600 ℃ to obtain the catalyst carrier.
S2, dissolving 2.19g of nickel chloride and 0.31g of ruthenium chloride in water to obtain a metal salt solution, wherein the concentration of metal ions is 3 mol/L.
And S3, adding the catalyst carrier obtained in the step S1 into the metal salt solution obtained in the step S2 for dipping, drying, dipping and drying until nickel and ruthenium are completely loaded on the carrier, so as to obtain the metal-loaded catalyst precursor.
S4, roasting the metal-loaded catalyst precursor obtained in the step S3 at 675 ℃ for 4 hours, and reducing the metal-loaded catalyst precursor for 5 hours at 650 ℃ by using a mixed gas of hydrogen and nitrogen with the hydrogen volume fraction of 35% to obtain the ammonia decomposition catalyst.
The activity of the catalyst was evaluated at various temperatures using pure ammonia gas, the catalyst was 60 to 80 mesh, 0.2g was packed, the space velocity was 15000mL/(g · h), and the ammonia decomposition rate was calculated according to the formula (initial ammonia content-treated ammonia content)/initial ammonia content 100%, and the results are shown in table 1.
Example 9
This example provides a nickel/ruthenium-based ammonia decomposition catalyst comprising 0.3g of ruthenium as an active component, 1.5g of nickel as an active component, and 8.2g of a carrier; wherein, the carrier comprises 0.66g of auxiliary agent praseodymium oxide and 7.54g of graphitized activated carbon.
This example provides a method for preparing the above nickel/ruthenium-based ammonia decomposition catalyst, comprising,
s1, performing high-temperature treatment on the activated carbon at the temperature of more than 1500 ℃ for 18 hours in an inert gas environment to obtain graphitized activated carbon, mixing and ball-milling 0.98g of praseodymium chloride and 7.54g of graphitized activated carbon, molding to obtain a catalyst carrier with the particle size of 0.6-0.8mm, and roasting at the temperature of 2000 ℃ to obtain the catalyst carrier.
S2, dissolving 4.5g of nickel acetate and 0.61g of ruthenium chloride in water to obtain a metal salt solution, wherein the concentration of metal ions is 3 mol/L.
And S3, adding the catalyst carrier obtained in the step S1 into the metal salt solution obtained in the step S2 for dipping, drying, dipping and drying until nickel and ruthenium are completely loaded on the carrier, so as to obtain the metal-loaded catalyst precursor.
S4, roasting the metal-loaded catalyst precursor obtained in the step S3 at 900 ℃ for 2h, and reducing the metal-loaded catalyst precursor by using a mixed gas of hydrogen and nitrogen with the volume fraction of 50% at 500 ℃ for 8h to obtain the ammonia decomposition catalyst.
The activity of the catalyst was evaluated at various temperatures using pure ammonia gas, the catalyst was 60 to 80 mesh, 0.2g was packed, the space velocity was 15000mL/(g · h), and the ammonia decomposition rate was calculated according to the formula (initial ammonia content-treated ammonia content)/initial ammonia content 100%, and the results are shown in table 1.
Comparative example 1
The catalyst used in this comparative example was the catalyst in chinese patent document CN1506299A example 4, and the activity of the catalyst was evaluated at different temperatures by using pure ammonia gas, the catalyst was 60 to 80 mesh, the loading was 0.2g, the space velocity was 15000mL/(g · h), and the ammonia decomposition rate was calculated according to the formula (initial ammonia content-treated ammonia content)/initial ammonia content x 100%, and the results are shown in table 1.
Comparative example 2
The catalyst used in this comparative example was the catalyst in example 6 of chinese patent document CN1506300A, and the activity of the catalyst was evaluated at different temperatures by using pure ammonia gas, the catalyst was 60 to 80 mesh, the loading was 0.2g, the space velocity was 15000mL/(g · h), and the decomposition rate of ammonia was calculated according to the formula (initial ammonia content-treated ammonia content)/initial ammonia content 100%, and the results are shown in table 1.
TABLE 1 evaluation results of catalyst Activity in examples 1 to 9 and comparative examples 1 to 2
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (8)
1. A nickel and/or ruthenium ammonia decomposition catalyst is characterized by comprising an active component and a carrier; the active component is one or two of nickel and ruthenium, the carrier comprises graphitized activated carbon and an auxiliary agent, and the auxiliary agent is one or more of alkali metal oxide, alkaline earth metal oxide and rare earth oxide;
the preparation method of the nickel and/or ruthenium ammonia decomposition catalyst comprises the following steps,
s1, mixing the graphitized activated carbon with an auxiliary agent metal salt or oxide, ball-milling, molding and roasting to obtain a catalyst carrier;
s2, dissolving the active component metal salt in water to obtain a metal salt solution;
s3, loading active components in the metal salt solution on the catalyst carrier by adopting a precipitation deposition method or an immersion method to obtain the nickel and/or ruthenium ammonia decomposition catalyst;
the oxide of the alkali metal comprises at least one of potassium oxide and cesium oxide;
the oxide of the alkaline earth metal comprises at least one of barium oxide, magnesium oxide and strontium oxide;
the rare earth oxide comprises at least one of cerium oxide, lanthanum oxide, praseodymium oxide and neodymium oxide;
the graphitized activated carbon accounts for 85-92% of the carrier and the auxiliary agent accounts for 8-15% of the carrier in percentage by mass;
after the graphitized activated carbon and the assistant metal salt are mixed and ball-milled and molded, the granularity is 0.1-0.8mm, and the roasting temperature is 1200-2000 ℃.
2. The nickel and/or ruthenium-based ammonia decomposition catalyst according to claim 1, wherein the active component is nickel, and the nickel accounts for 8 to 24% of the catalyst by mass percent; the active component is ruthenium, and the ruthenium accounts for 0.5-12% of the catalyst in percentage by mass; the active component is a nickel and ruthenium bimetal, wherein the nickel accounts for 5-15% of the catalyst, and the ruthenium accounts for 0.2-3% of the catalyst in percentage by mass.
3. A method for preparing the nickel and/or ruthenium-based ammonia decomposition catalyst according to claim 1 or 2, comprising,
s1, mixing the graphitized activated carbon with an auxiliary agent metal salt or oxide, ball-milling, molding and roasting to obtain a catalyst carrier;
s2, dissolving the active component metal salt in water to obtain a metal salt solution;
s3, loading the active component in the metal salt solution on the catalyst carrier by adopting a precipitation deposition method or an impregnation method to obtain the nickel and/or ruthenium ammonia decomposition catalyst.
4. The method for preparing a nickel and/or ruthenium-based ammonia decomposition catalyst as claimed in claim 3, wherein the graphitized activated carbon is mixed with an auxiliary metal salt and ball-milled to form a product having a particle size of 0.1-0.8mm and a calcination temperature of 1200-2000 ℃.
5. The method for preparing a nickel and/or ruthenium-based ammonia decomposition catalyst according to claim 3, wherein the active component metal salt comprises one or more of nickel nitrate, nickel chloride, nickel acetate, ruthenium nitrate, or ruthenium chloride; the assistant metal salt comprises one or more of nitrate, acetate or chloride.
6. The method for preparing a nickel and/or ruthenium-based ammonia decomposition catalyst according to claim 3, wherein the precipitation deposition method specifically comprises,
s10, dispersing the catalyst carrier in water, and heating to 50-80 ℃ to obtain a base solution;
s20, adding the metal salt solution and a precipitator into the base solution at the same time, controlling the pH value to be 8.0-10.5, and stirring for 2-6h to obtain a precipitate;
s30, washing and drying the precipitate, roasting for 2-6h at the temperature of 450-750 ℃, and reducing by hydrogen to obtain the catalyst;
wherein the precipitant is one or more aqueous solutions of sodium hydroxide, potassium carbonate, ammonium carbonate and ammonium bicarbonate.
7. The method for preparing a nickel and/or ruthenium-based ammonia decomposition catalyst according to claim 3, wherein the impregnation method specifically comprises,
s100, adding the catalyst carrier into the metal salt solution for dipping and drying to obtain a metal-loaded catalyst precursor;
s200, roasting the metal-loaded catalyst precursor at the temperature of 450-900 ℃ for 2-6h, and reducing by hydrogen to obtain the catalyst.
8. Use of the nickel and/or ruthenium-based ammonia decomposition catalyst according to claim 1 or 2, or the nickel and/or ruthenium-based ammonia decomposition catalyst produced by the production method according to any one of claims 3 to 7 for ammonia decomposition.
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