CN110270338A - A kind of nickel and/or ruthenium system ammonia decomposition catalyzer and its preparation method and application - Google Patents
A kind of nickel and/or ruthenium system ammonia decomposition catalyzer and its preparation method and application Download PDFInfo
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- CN110270338A CN110270338A CN201910537655.5A CN201910537655A CN110270338A CN 110270338 A CN110270338 A CN 110270338A CN 201910537655 A CN201910537655 A CN 201910537655A CN 110270338 A CN110270338 A CN 110270338A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8634—Ammonia
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- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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Abstract
The present invention provides a kind of nickel and/or ruthenium system ammonia decomposition catalyzer and its preparation method and application, which includes active component and carrier；The active component is one or both of nickel, ruthenium, the carrier includes graphitization active carbon and auxiliary agent, the auxiliary agent is one or more of oxide and carbonate, the oxide of alkaline-earth metal and carbonate, rare earth oxide of alkali metal, the carrier of the catalyst includes graphitization active carbon and auxiliary agent, auxiliary agent can be modified carrier, improve the activity of catalyst；In addition, the present invention handles active carbon through high temperature graphitization, the stability of catalyst is on the one hand improved, strong interaction can be formed between another aspect active component and carrier carbon, electronics transfer occurs, is conducive to reaction product N2And H2Desorption reach preferable ammonolysis craft effect to further increase its low-temperature reactivity, improve the treatment effeciency of ammonia.
Description
Technical field
The present invention relates to ammonolysis craft technical fields, and in particular to a kind of nickel and/or ruthenium system ammonia decomposition catalyzer and its preparation
Methods and applications.
Background technique
Ammonia decomposition catalyzer is mainly used in the preparation field of field of environment protection and hydrogen and nitrogen.In environmental protection
Field is decomposed into ammonia therein nontoxic by decomposing the ammonia-contaminated gas of factory under ammonia decomposition catalyzer effect
Hydrogen and nitrogen after recycled to achieve the purpose that pollution abatement.And in hydrogen preparation field, ammonia is easy to liquid due to having
Change, non-combustible, nonhazardous, hydrogen-storage density height, production storaging and transport technology are mature at low concentrations, and non-carbon-emitting etc. is excellent in hydrogen production process
Point becomes a kind of efficient, cleaning and safety hydrogen storage carrier, the system of hydrogen can be used under the action of ammonia decomposition catalyzer
It is standby.Ammonia decomposition reaction is mainly used using ruthenium, platinum as the noble metal catalyst of representative and using iron, nickel as the Non-precious Metal Catalysts of representative
Agent.
Chinese patent literature CN1506299A discloses a kind of Ni-based preparing hydrogen by ammonia decomposition nitrogen mixed gas catalyst, mainly lives
Property ingredient be Ni；Carrier is SiO2Or Al2O3；Auxiliary agent is I A, II A, III B, VIII or one or more of rare earth element；Wherein
Nickel weight percentage is 1-40%.Ammonia can preferably be decomposed using the catalyst, and the use temperature of the catalyst is
650 DEG C, 800 DEG C of more existing industrial catalyst operating temperature decreases, but its catalytic activity is low at the lower temperature, ammonia
Discomposing effect is not good enough.
Chinese patent literature CN1506300A discloses a kind of ruthenium base preparing hydrogen by ammonia decomposition nitrogen mixed gas catalyst, mainly lives
Property ingredient be ruthenium；Carrier is CaO, MgO, TiO2、SiO2、Al2O3Or active carbon；Auxiliary agent is I A, II A, III A, IVA, III B or dilute
One or more of earth elements；Wherein ruthenium weight percentage is 0.1-10%.Using the catalyst, with nickel-base catalyst phase
Than ammonolysis craft temperature decreases, and can be reacted at 550 DEG C, but its catalytic activity at the lower temperature is not high, ammonia
The discomposing effect of gas is not good enough, and the air speed that the catalyst uses is only 3000h-1, ammonia treatment effeciency is lower.
Summary of the invention
Therefore, the technical problem to be solved in the present invention is that overcoming the low-temperature catalyzed work of ammonia decomposition catalyzer in the prior art
Property low, ammonolysis craft less effective, the low defect of ammonia treatment effeciency, to provide, a kind of low-temperature catalytic activity is high, ammonolysis craft effect
Fruit is good, ammonia treatment effeciency is high nickel and/or ruthenium system ammonia decomposition catalyzer and its preparation method and application.
For this purpose, the present invention provides a kind of nickel and/or ruthenium system ammonia decomposition catalyzers, including, active component and carrier；It is described
Active component is one or both of nickel, ruthenium, and the carrier includes graphitization active carbon and auxiliary agent, and the auxiliary agent is alkali metal
Oxide and one or more of carbonate, the oxide of alkaline-earth metal and carbonate, rare earth oxide.
The nickel and/or ruthenium system ammonia decomposition catalyzer, the active component are nickel, and by percentage to the quality, nickel, which accounts for, urges
The 8-24% of agent；The active component is ruthenium, and by percentage to the quality, ruthenium accounts for the 0.5-12% of catalyst；The active group
It is divided into nickel, ruthenium bimetallic, by percentage to the quality, nickel accounts for the 5-15% of catalyst, and ruthenium accounts for the 0.2-3% of catalyst.
The nickel and/or ruthenium system ammonia decomposition catalyzer, by percentage to the quality, graphitization active carbon account for the 85- of carrier
92%, auxiliary agent accounts for the 8-15% of carrier.
The nickel and/or ruthenium system ammonia decomposition catalyzer, the oxide and carbonate of the alkali metal include potassium oxide, oxygen
Change at least one of caesium, potassium carbonate；
The oxide and carbonate of the alkaline-earth metal include barium monoxide, magnesia, strontium oxide strontia, barium carbonate, in magnesium carbonate
At least one；
The rare earth oxide includes at least one of cerium oxide, lanthana, praseodymium oxide, neodymia.
The present invention provides the preparation methods of nickel and/or ruthenium system ammonia decomposition catalyzer described in one kind, including,
S1, it will be graphitized active carbon and promoter metal salt or oxide mixing and ball milling, formed, roasting obtains catalyst load
Body；
S2, activity component metal salt is dissolved in the water, obtains metal salt solution；
S3, using precipitating sedimentation or infusion process, the active component in the metal salt solution is carried on the catalysis
On agent carrier, the nickel and/or ruthenium system ammonia decomposition catalyzer are obtained.
The preparation method of the nickel and/or ruthenium system ammonia decomposition catalyzer, it is described graphitization active carbon preparation method be,
By active carbon in 1500 DEG C or more progress high-temperature process 12-24h, the graphitization active carbon is obtained.
The preparation method of the nickel and/or ruthenium system ammonia decomposition catalyzer, graphitization active carbon are mixed with promoter metal salt
After ball milling molding, granularity 0.1-0.8mm, the temperature of roasting is 1200-2000 DEG C.
The preparation method of the nickel and/or ruthenium system ammonia decomposition catalyzer, the activity component metal salt include nickel nitrate,
One or more of nickel chloride, nickel acetate, nitric acid ruthenium or ruthenic chloride；The promoter metal salt include nitrate, acetate or
One or more of chloride.
The preparation method of the nickel and/or ruthenium system ammonia decomposition catalyzer, the precipitating sedimentation specifically include,
S10, the catalyst carrier is dispersed in water, is heated to 50-80 DEG C, obtain liquid on earth；
S20, the metal salt solution and precipitating reagent are added simultaneously in the bottom liquid, control pH value is 8.0-10.5, is stirred
2-6h is mixed, is precipitated；
S30, by the washing of precipitate, drying, in 450-750 DEG C of roasting temperature 2-6h, through hydrogen reducing, obtain described
Catalyst；
Wherein, the precipitating reagent is one of sodium hydroxide, potassium hydroxide, potassium carbonate, ammonium carbonate, ammonium hydrogen carbonate or several
The aqueous solution of kind.
The preparation method of the nickel and/or ruthenium system ammonia decomposition catalyzer, in S10 step, the catalyst carrier point
It dissipates and uses ultrasonic disperse.
The preparation method of the nickel and/or ruthenium system ammonia decomposition catalyzer, the infusion process specifically include,
S100, it will be impregnated in the catalyst carrier addition metal salt solution, dry, obtain carried metal
Catalyst precursor；
S200, the catalyst precursor of the carried metal is obtained in 450-900 DEG C of roasting 2-6h through hydrogen reducing
The catalyst.
The preparation method of the nickel and/or ruthenium system ammonia decomposition catalyzer, in S100 step, the dipping and drying are carried out
2 times or more, until nickel or ruthenium content reach targeted loads amount.
It is prepared the present invention provides the nickel and/or ruthenium system ammonia decomposition catalyzer or the preparation method
The application of nickel and/or ruthenium system ammonia decomposition catalyzer in ammonolysis craft.
Technical solution of the present invention has the advantages that
1. a kind of nickel provided by the invention and/or ruthenium system ammonia decomposition catalyzer, including, active component and carrier；The work
Property group be divided into one or both of nickel, ruthenium, the carrier includes graphitization active carbon and auxiliary agent, and the auxiliary agent is alkali metal
One or more of oxide and carbonate, the oxide of alkaline-earth metal and carbonate, rare earth oxide, the catalyst use
One or both of nickel, ruthenium are used as active component, can promote NH3Absorption dissociation, promote product N2Desorption, press down simultaneously
H processed2Absorption；In addition, the carrier of the catalyst includes that graphitization active carbon and auxiliary agent, auxiliary agent can be modified carrier,
The dispersion degree in the carrier of active component is improved, the interaction between carrier and active component is enhanced；Due to activated carbon surface
Functional group is abundant, and untreated active carbon is used as carrier, especially oxygen-containing because functional group participates in reaction in catalytic reaction process
The influence of functional group causes catalyst stability poor, and the present invention handles active carbon through high temperature graphitization, on the one hand reduces
The number of surface functional group, to effectively improve the stability of catalyst, on the other hand the carrier surface also remains a small amount of official
It can roll into a ball, can promote the dispersion of active component, the activity of catalyst be improved, and pass through functional group, between active component and carrier carbon
Strong interaction can be formed, the transfer of electronics occurs, weakens the interaction between active component and reaction intermediate, favorably
In reaction product N2And H2Desorption reach preferable ammonolysis craft effect to further increase its low-temperature catalytic activity, improve
The treatment effeciency of ammonia.
2. a kind of nickel provided by the invention and/or ruthenium system ammonia decomposition catalyzer, the active component is nickel, with quality percentage
Than meter, nickel accounts for the 8-24% of catalyst；The active component is ruthenium, and by percentage to the quality, ruthenium accounts for the 0.5-12% of catalyst；
The active component is nickel, ruthenium bimetallic, and by percentage to the quality, nickel accounts for the 5-15% of catalyst, and ruthenium accounts for the 0.2- of catalyst
3%, by limiting the content of active component, the interaction of active component and carrier can be enhanced, effectively decrease active component
With NH3Decomposition product NH2, interaction between N or H, be conducive to product N2And H2Desorption, to improve catalyst
Low-temperature catalytic activity, reach preferable ammonolysis craft effect, improve the treatment effeciency of ammonia.
3. a kind of nickel provided by the invention and/or ruthenium system ammonia decomposition catalyzer are graphitized active carbon by percentage to the quality
The 85-92% of carrier is accounted for, auxiliary agent accounts for the 8-15% of carrier, by limiting the content of graphitization active carbon and auxiliary agent, can be improved
Auxiliary agent guarantees that active component has a high degree of dispersion in the carrier to the modifying function of carrier, enhancing active component and carrier carbon it
Between interaction, promote the transfer that electronics occurs, weaken the interaction between active component and reaction intermediate, be conducive to
Reaction product N2And H2Desorption reach preferable ammonolysis craft effect to further increase its low-temperature catalytic activity, improve ammonia
The treatment effeciency of gas.
4. a kind of nickel provided by the invention and/or ruthenium system ammonia decomposition catalyzer, the oxide and carbonate of the alkali metal
Including at least one of potassium oxide, cesium oxide, potassium carbonate；The oxide and carbonate of the alkaline-earth metal include barium monoxide,
At least one of magnesia, strontium oxide strontia, barium carbonate, magnesium carbonate；The rare earth oxide includes cerium oxide, lanthana, oxidation
The dispersion degree of active component can be improved by using the above auxiliary agent at least one of praseodymium, neodymia, further enhances load
Interaction between body and active component promotes electronics transfer, improves the low-temperature reactivity of catalyst, improve the processing of ammonia
Efficiency.
5. it is provided by the invention one kind described in nickel and/or ruthenium system ammonia decomposition catalyzer preparation method, including, S1, general
It is graphitized active carbon and promoter metal salt or oxide mixing and ball milling, is formed, roasting obtains catalyst carrier；S2, by active group
Divide metal salt to be dissolved in the water, obtains metal salt solution；S3, using precipitating sedimentation or infusion process, by the metal salt solution
In active component be carried in the catalyst carrier, obtain the nickel and/or ruthenium system ammonia decomposition catalyzer, this method pass through
Graphitization active carbon and promoter metal salt are first mixed with carrier, then load active component again, can reinforce auxiliary agent to load
The modification of body, can be further directly by active component compared with auxiliary agent mutual load and only to be graphitized active carbon as carrier
The activity of catalyst is improved, is urged to obtain the ammonolysis craft that low-temperature catalytic activity is high, ammonolysis craft effect is good, ammonia treatment effeciency is high
Agent.
6. the preparation method of nickel described in one kind provided by the invention and/or ruthenium system ammonia decomposition catalyzer, graphitization activity
After charcoal and the molding of promoter metal salt mixing and ball milling, granularity 0.1-0.8mm, the temperature of roasting is 1200-2000 DEG C, passes through control
Granularity and maturing temperature, can modification with accelerating auxiliaries to carrier, guarantee that active component in the carrier can be with high degree of dispersion, into one
Step improves the activity of catalyst, to obtain the ammonolysis craft that low-temperature catalytic activity is high, ammonolysis craft effect is good, ammonia treatment effeciency is high
Catalyst.
7. the nickel and/or ruthenium system ammonia decomposition catalyzer provided by the invention or the preparation method are prepared
The application in ammonolysis craft of nickel and/or ruthenium system ammonia decomposition catalyzer ammonia can efficiently be divided using above-mentioned catalyst
The stability of solution, catalyst is high, and low-temperature catalytic activity is high, ammonolysis craft effect is good, ammonia treatment effeciency is high.
Specific embodiment
Technical solution of the present invention is clearly and completely described below, it is clear that described embodiment is the present invention
A part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not having
Every other embodiment obtained under the premise of creative work is made, shall fall within the protection scope of the present invention.
Embodiment 1
A kind of nickel system ammonia decomposition catalyzer is present embodiments provided, including, active component nickel 0.8g and carrier 9.2g；Its
In, carrier includes auxiliary agent potassium oxide 1.38g and graphitization active carbon 7.82g.
The preparation method of above-mentioned nickel system ammonia decomposition catalyzer is present embodiments provided, including,
S1, in inert gas environment, active carbon is subjected to high-temperature process 18h under 1500 DEG C of temperatures above, obtains stone
Inkization active carbon forms graphitization active carbon 7.82g and 2.97g potassium nitrate mixing and ball milling, granularity 0.1-0.15mm,
1200 DEG C of roasting temperatures, obtain catalyst carrier.
S2,2.48g nickel nitrate is dissolved in the water, obtains metal salt solution, wherein the concentration of metal ion is 1mol/L.
S3, the catalyst carrier ultrasonic disperse Yu Shuizhong for obtaining S1, are heated to 50 DEG C, obtain liquid on earth.
S4, the sodium hydroxide that metal salt solution and concentration that S2 is obtained are 5mol/L is added simultaneously in the liquid of bottom, controls pH
Value is 8.0, stirs 2h, is precipitated.
S5, the washing of precipitate that S4 is obtained, drying are 20% with hydrogen volume score in 450 DEG C of roasting temperature 6h
The mixed gas of hydrogen and nitrogen restores 3h at a temperature of 800 DEG C, obtains ammonia decomposition catalyzer.
At different temperatures, activity rating is carried out to the catalyst using pure ammonia gas, catalyst is 60-80 mesh, filling
0.2g, air speed is 15000mL/ (gh), according to formula ammonia dissociation rate=(ammonia content after initial ammonia content-processing)/initial ammonia
Content * 100% calculates the resolution ratio of ammonia, the results are shown in Table 1.
Embodiment 2
A kind of nickel system ammonia decomposition catalyzer is present embodiments provided, including, active component nickel 1.6g and carrier 8.4g；Its
In, carrier includes auxiliary agent barium monoxide 1.01g and graphitization active carbon 7.39g.
The preparation method of above-mentioned nickel system ammonia decomposition catalyzer is present embodiments provided, including,
S1, in inert gas environment, active carbon is subjected to high-temperature process 18h under 1500 DEG C of temperatures above, obtains stone
1.72g barium nitrate and 7.39g are graphitized active carbon mixing and ball milling, formed, granularity 0.3-0.5mm by inkization active carbon,
1600 DEG C of roasting temperatures, obtain catalyst carrier.
S2,3.5g nickel chloride is dissolved in the water, obtains metal salt solution, wherein the concentration of metal ion is 3mol/L.
S3, it catalyst carrier that S1 is obtained is added in the metal salt solution that S2 is obtained impregnates, dry, then soaked
Stain and drying obtain the catalyst precursor of carried metal until nickel is all carried on carrier.
S4, by the catalyst precursor of the obtained carried metal of S3 in 450 DEG C of roasting 6h, be 35% with hydrogen volume score
Hydrogen and the mixed gas of nitrogen restore 5h at a temperature of 650 DEG C, obtain ammonia decomposition catalyzer.
At different temperatures, activity rating is carried out to the catalyst using pure ammonia gas, catalyst is 60-80 mesh, filling
0.2g, air speed is 15000mL/ (gh), according to formula ammonia dissociation rate=(ammonia content after initial ammonia content-processing)/initial ammonia
Content * 100% calculates the resolution ratio of ammonia, the results are shown in Table 1.
Embodiment 3
A kind of nickel system ammonia decomposition catalyzer is present embodiments provided, including, active component nickel 2.4g and carrier 7.6g；Its
In, carrier includes auxiliary agent cerium oxide 0.61g and graphitization active carbon 6.99g.
The preparation method of above-mentioned nickel system ammonia decomposition catalyzer is present embodiments provided, including,
S1, in inert gas environment, active carbon is subjected to high-temperature process 18h under 1500 DEG C of temperatures above, obtains stone
1.16g cerous nitrate and 6.99g are graphitized active carbon mixing and ball milling, formed, granularity 0.6-0.8mm by inkization active carbon,
2000 DEG C of roasting temperatures, obtain catalyst carrier.
S2,7.2g nickel acetate is dissolved in the water, obtains metal salt solution, wherein the concentration of metal ion is 3mol/L.
S3, it catalyst carrier that S1 is obtained is added in the metal salt solution that S2 is obtained impregnates, dry, then soaked
Stain and drying obtain the catalyst precursor of carried metal until nickel is all carried on carrier.
S4, by the catalyst precursor of the obtained carried metal of S3 in 675 DEG C of roasting 4h, be 50% with hydrogen volume score
Hydrogen and the mixed gas of nitrogen restore 8h at a temperature of 500 DEG C, obtain ammonia decomposition catalyzer.
At different temperatures, activity rating is carried out to the catalyst using pure ammonia gas, catalyst is 60-80 mesh, filling
0.2g, air speed is 15000mL/ (gh), according to formula ammonia dissociation rate=(ammonia content after initial ammonia content-processing)/initial ammonia
Content * 100% calculates the resolution ratio of ammonia, the results are shown in Table 1.
Embodiment 4
A kind of ruthenium system ammonia decomposition catalyzer is present embodiments provided, including, active component ruthenium 0.05g and carrier 9.95g；Its
In, carrier includes auxiliary agent cesium oxide 1.49g and graphitization active carbon 8.46g.
The preparation method of above-mentioned ruthenium system ammonia decomposition catalyzer is present embodiments provided, including,
S1, in inert gas environment, active carbon is subjected to high-temperature process 18h under 1500 DEG C of temperatures above, obtains stone
Inkization active carbon forms graphitization active carbon 8.46g and 1.78g cesium chloride mixing and ball milling, granularity 0.1-0.15mm,
1200 DEG C of roasting temperatures, obtain catalyst carrier.
S2,0.14g nitric acid ruthenium is dissolved in the water, obtains metal salt solution, wherein the concentration of metal ion is 1mol/L.
S3, the catalyst carrier ultrasonic disperse Yu Shuizhong for obtaining S1, are heated to 65 DEG C, obtain liquid on earth.
S4, the potassium hydroxide that metal salt solution and concentration that S2 is obtained are 5mol/L is added simultaneously in the liquid of bottom, controls pH
Value is 9.0, stirs 6h, is precipitated.
S5, the washing of precipitate that S4 is obtained, drying are 20% with hydrogen volume score in 600 DEG C of roasting temperature 4h
The mixed gas of hydrogen and nitrogen restores 3h at a temperature of 800 DEG C, obtains catalyst.
At different temperatures, activity rating is carried out to the catalyst using pure ammonia gas, catalyst is 60-80 mesh, filling
0.2g, air speed is 15000mL/ (gh), according to formula ammonia dissociation rate=(ammonia content after initial ammonia content-processing)/initial ammonia
Content * 100% calculates the resolution ratio of ammonia, the results are shown in Table 1.
Embodiment 5
A kind of ruthenium system ammonia decomposition catalyzer is present embodiments provided, including, active component ruthenium 0.6g and carrier 9.4g；Its
In, carrier includes auxiliary agent magnesia 1.13g and graphitization active carbon 8.27g.
The preparation method of above-mentioned ruthenium system ammonia decomposition catalyzer is present embodiments provided, including,
S1, in inert gas environment, active carbon is subjected to high-temperature process 18h under 1500 DEG C of temperatures above, obtains stone
2.66g magnesium chloride and 8.27g are graphitized active carbon mixing and ball milling, formed, granularity 0.3-0.5mm by inkization active carbon,
1600 DEG C of roasting temperatures, obtain catalyst carrier.
S2,1.22g ruthenic chloride is dissolved in the water, obtains metal salt solution, wherein the concentration of metal ion is 3mol/L.
S3, it catalyst carrier that S1 is obtained is added in the metal salt solution that S2 is obtained impregnates, dry, then soaked
Stain and drying obtain the catalyst precursor of carried metal until ruthenium is all carried on carrier.
S4, by the catalyst precursor of the obtained carried metal of S3 in 900 DEG C of roasting 2h, be 35% with hydrogen volume score
Hydrogen and the mixed gas of nitrogen restore 5h at a temperature of 650 DEG C, obtain ammonia decomposition catalyzer.
At different temperatures, activity rating is carried out to the catalyst using pure ammonia gas, catalyst is 60-80 mesh, filling
0.2g, air speed is 15000mL/ (gh), according to formula ammonia dissociation rate=(ammonia content after initial ammonia content-processing)/initial ammonia
Content * 100% calculates the resolution ratio of ammonia, the results are shown in Table 1.
Embodiment 6
A kind of ruthenium system ammonia decomposition catalyzer is present embodiments provided, including, active component ruthenium 1.2g and carrier 8.8g；Its
In, carrier includes auxiliary agent lanthana 0.7g and graphitization active carbon 8.1g.
The preparation method of above-mentioned ruthenium system ammonia decomposition catalyzer is present embodiments provided, including,
S1, in inert gas environment, active carbon is subjected to high-temperature process 18h under 1500 DEG C of temperatures above, obtains stone
1.05g lanthanum chloride and 8.1g are graphitized active carbon mixing and ball milling, formed, granularity 0.6-0.8mm by inkization active carbon,
2000 DEG C of roasting temperatures, obtain catalyst carrier.
S2,2.45g ruthenic chloride is dissolved in the water, obtains metal salt solution, wherein the concentration of metal ion is 3mol/L.
S3, it catalyst carrier that S1 is obtained is added in the metal salt solution that S2 is obtained impregnates, dry, then soaked
Stain and drying obtain the catalyst precursor of carried metal until ruthenium is all carried on carrier.
S4, by the catalyst precursor of the obtained carried metal of S3 in 450 DEG C of roasting 6h, be 50% with hydrogen volume score
Hydrogen and the mixed gas of nitrogen restore 8h at a temperature of 500 DEG C, obtain ammonia decomposition catalyzer.
At different temperatures, activity rating is carried out to the catalyst using pure ammonia gas, catalyst is 60-80 mesh, filling
0.2g, air speed is 15000mL/ (gh), according to formula ammonia dissociation rate=(ammonia content after initial ammonia content-processing)/initial ammonia
Content * 100% calculates the resolution ratio of ammonia, the results are shown in Table 1.
Embodiment 7
A kind of nickel/ruthenium system ammonia decomposition catalyzer is present embodiments provided, including, active component ruthenium 0.02g, active component nickel
0.5g and carrier 9.48g；Wherein, carrier includes auxiliary agent potassium carbonate 1.42g and graphitization active carbon 8.06g.
Above-mentioned nickel/ruthenium system ammonia decomposition catalyzer preparation method is present embodiments provided, including,
S1, in inert gas environment, active carbon is subjected to high-temperature process 18h under 1500 DEG C of temperatures above, obtains stone
Inkization active carbon forms graphitization active carbon 8.06g and 2.02g potassium acetate mixing and ball milling, granularity 0.1-0.15mm,
1200 DEG C of roasting temperatures, obtain catalyst carrier.
S2,1.55g nickel nitrate, 0.06g nitric acid ruthenium are dissolved in the water, obtain metal salt solution, wherein metal ion
Concentration is 1mol/L.
S3, the catalyst carrier ultrasonic disperse Yu Shuizhong for obtaining S1, are heated to 80 DEG C, obtain liquid on earth.
S4, the potassium carbonate that metal salt solution and concentration that S2 is obtained are 5mol/L is added simultaneously in the liquid of bottom, controls pH value
It is 10.5, stirs 6h, precipitated.
S5, the washing of precipitate that S4 is obtained, drying are 20% with hydrogen volume score in 750 DEG C of roasting temperature 2h
The mixed gas of hydrogen and nitrogen restores 3h at a temperature of 800 DEG C, obtains catalyst.
At different temperatures, activity rating is carried out to the catalyst using pure ammonia gas, catalyst is 60-80 mesh, filling
0.2g, air speed is 15000mL/ (gh), according to formula ammonia dissociation rate=(ammonia content after initial ammonia content-processing)/initial ammonia
Content * 100% calculates the resolution ratio of ammonia, the results are shown in Table 1.
Embodiment 8
A kind of nickel/ruthenium system ammonia decomposition catalyzer is present embodiments provided, including, active component ruthenium 0.15g, active component nickel
1g and carrier 8.85g；Wherein, carrier includes auxiliary agent strontium oxide strontia 1.06g and graphitization active carbon 7.79g.
Above-mentioned nickel/ruthenium system ammonia decomposition catalyzer preparation method is present embodiments provided, including,
S1, in inert gas environment, active carbon is subjected to high-temperature process 18h under 1500 DEG C of temperatures above, obtains stone
1.61g strontium chloride and 7.79g are graphitized active carbon mixing and ball milling, formed, granularity 0.3-0.5mm by inkization active carbon,
1600 DEG C of roasting temperatures, obtain catalyst carrier.
S2,2.19g nickel chloride, 0.31g ruthenic chloride are dissolved in the water, obtain metal salt solution, wherein metal ion
Concentration is 3mol/L.
S3, it catalyst carrier that S1 is obtained is added in the metal salt solution that S2 is obtained impregnates, dry, then soaked
Stain and drying obtain the catalyst precursor of carried metal until nickel and ruthenium are all carried on carrier.
S4, by the catalyst precursor of the obtained carried metal of S3 in 675 DEG C of roasting 4h, be 35% with hydrogen volume score
Hydrogen and the mixed gas of nitrogen restore 5h at a temperature of 650 DEG C, obtain ammonia decomposition catalyzer.
At different temperatures, activity rating is carried out to the catalyst using pure ammonia gas, catalyst is 60-80 mesh, filling
0.2g, air speed is 15000mL/ (gh), according to formula ammonia dissociation rate=(ammonia content after initial ammonia content-processing)/initial ammonia
Content * 100% calculates the resolution ratio of ammonia, the results are shown in Table 1.
Embodiment 9
A kind of nickel/ruthenium system ammonia decomposition catalyzer is present embodiments provided, including, active component ruthenium 0.3g, active component nickel
1.5g and carrier 8.2g；Wherein, carrier includes auxiliary agent praseodymium oxide 0.66g and graphitization active carbon 7.54g.
Above-mentioned nickel/ruthenium system ammonia decomposition catalyzer preparation method is present embodiments provided, including,
S1, in inert gas environment, active carbon is subjected to high-temperature process 18h under 1500 DEG C of temperatures above, obtains stone
0.98g praseodymium chloride and 7.54g are graphitized active carbon mixing and ball milling, formed, granularity 0.6-0.8mm by inkization active carbon,
2000 DEG C of roasting temperatures, obtain catalyst carrier.
S2,4.5g nickel acetate, 0.61g ruthenic chloride are dissolved in the water, obtain metal salt solution, wherein metal ion is dense
Degree is 3mol/L.
S3, it catalyst carrier that S1 is obtained is added in the metal salt solution that S2 is obtained impregnates, dry, then soaked
Stain and drying obtain the catalyst precursor of carried metal until nickel and ruthenium are all carried on carrier.
S4, by the catalyst precursor of the obtained carried metal of S3 in 900 DEG C of roasting 2h, be 50% with hydrogen volume score
Hydrogen and the mixed gas of nitrogen restore 8h at a temperature of 500 DEG C, obtain ammonia decomposition catalyzer.
At different temperatures, activity rating is carried out to the catalyst using pure ammonia gas, catalyst is 60-80 mesh, filling
0.2g, air speed is 15000mL/ (gh), according to formula ammonia dissociation rate=(ammonia content after initial ammonia content-processing)/initial ammonia
Content * 100% calculates the resolution ratio of ammonia, the results are shown in Table 1.
Comparative example 1
The catalyst that this comparative example uses is the catalyst in Chinese patent literature CN1506299A embodiment 4, in difference
At a temperature of, activity rating is carried out to the catalyst using pure ammonia gas, catalyst is 60-80 mesh, loads 0.2g, air speed is
15000mL/ (gh), according to formula ammonia dissociation rate=(ammonia content after initial ammonia content-processing)/initial ammonia content * 100%,
The resolution ratio for calculating ammonia, the results are shown in Table 1.
Comparative example 2
The catalyst that this comparative example uses is the catalyst in Chinese patent literature CN1506300A embodiment 6, in difference
At a temperature of, activity rating is carried out to the catalyst using pure ammonia gas, catalyst is 60-80 mesh, loads 0.2g, air speed is
15000mL/ (gh), according to formula ammonia dissociation rate=(ammonia content after initial ammonia content-processing)/initial ammonia content * 100%,
The resolution ratio for calculating ammonia, the results are shown in Table 1.
Catalyst activity evaluation result in table 1 embodiment 1-9 and comparative example 1-2
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
1. a kind of nickel and/or ruthenium system ammonia decomposition catalyzer, which is characterized in that including active component and carrier；The active component
For one or both of nickel, ruthenium, the carrier includes graphitization active carbon and auxiliary agent, and the auxiliary agent is the oxide of alkali metal
With one or more of carbonate, the oxide of alkaline-earth metal and carbonate, rare earth oxide.
2. nickel according to claim 1 and/or ruthenium system ammonia decomposition catalyzer, which is characterized in that the active component is nickel,
By percentage to the quality, nickel accounts for the 8-24% of catalyst；The active component is ruthenium, and by percentage to the quality, ruthenium accounts for catalyst
0.5-12%；The active component is nickel, ruthenium bimetallic, and by percentage to the quality, nickel accounts for the 5-15% of catalyst, and ruthenium, which accounts for, urges
The 0.2-3% of agent.
3. nickel according to claim 1 or 2 and/or ruthenium system ammonia decomposition catalyzer, which is characterized in that with mass percent
Meter, graphitization active carbon account for the 85-92% of carrier, and auxiliary agent accounts for the 8-15% of carrier.
4. nickel according to claim 1-3 and/or ruthenium system ammonia decomposition catalyzer, which is characterized in that the alkali gold
The oxide and carbonate of category include at least one of potassium oxide, cesium oxide, potassium carbonate；
The oxide and carbonate of the alkaline-earth metal include barium monoxide, magnesia, strontium oxide strontia, barium carbonate, in magnesium carbonate extremely
Few one kind；
The rare earth oxide includes at least one of cerium oxide, lanthana, praseodymium oxide, neodymia.
5. the preparation method of a kind of described in any item nickel of claim 1-4 and/or ruthenium system ammonia decomposition catalyzer, feature exist
In, including,
S1, it will be graphitized active carbon and promoter metal salt or oxide mixing and ball milling, formed, roasting obtains catalyst carrier；
S2, activity component metal salt is dissolved in the water, obtains metal salt solution；
S3, using precipitating sedimentation or infusion process, the active component in the metal salt solution is carried on the catalyst and is carried
On body, the nickel and/or ruthenium system ammonia decomposition catalyzer are obtained.
6. the preparation method of nickel according to claim 5 and/or ruthenium system ammonia decomposition catalyzer, which is characterized in that graphitization
After active carbon and the molding of promoter metal salt mixing and ball milling, granularity 0.1-0.8mm, the temperature of roasting is 1200-2000 DEG C.
7. the preparation method of nickel according to claim 5 or 6 and/or ruthenium system ammonia decomposition catalyzer, which is characterized in that described
Activity component metal salt includes one or more of nickel nitrate, nickel chloride, nickel acetate, nitric acid ruthenium or ruthenic chloride；The auxiliary agent
Metal salt includes one or more of nitrate, acetate or chloride.
8. according to the preparation method of the described in any item nickel of claim 5-7 and/or ruthenium system ammonia decomposition catalyzer, feature exists
In, the precipitating sedimentation specifically includes,
S10, the catalyst carrier is dispersed in water, is heated to 50-80 DEG C, obtain liquid on earth；
S20, the metal salt solution and precipitating reagent are added simultaneously in the bottom liquid, control pH value is 8.0-10.5, stirs 2-
6h is precipitated；
S30, by the washing of precipitate, drying, obtain the catalysis through hydrogen reducing in 450-750 DEG C of roasting temperature 2-6h
Agent；
Wherein, the precipitating reagent is one or more of sodium hydroxide, potassium hydroxide, potassium carbonate, ammonium carbonate, ammonium hydrogen carbonate
Aqueous solution.
9. according to the preparation method of the described in any item nickel of claim 5-7 and/or ruthenium system ammonia decomposition catalyzer, feature exists
In, the infusion process specifically includes,
S100, it will be impregnated in the catalyst carrier addition metal salt solution, dry, obtain the catalysis of carried metal
Agent presoma；
S200, by the catalyst precursor of the carried metal in 450-900 DEG C of roasting 2-6h, through hydrogen reducing, obtain described
Catalyst.
10. described in the described in any item nickel of claim 1-4 and/or ruthenium system ammonia decomposition catalyzer or claim any one of 5-9
The application in ammonolysis craft of the preparation method nickel and/or ruthenium system ammonia decomposition catalyzer that are prepared.
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| CN113694922A (en) * | 2021-09-29 | 2021-11-26 | 石河子大学 | Supported catalyst for ammonia decomposition and preparation method thereof |
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| CN113694922B (en) * | 2021-09-29 | 2023-08-18 | 石河子大学 | Supported catalyst for ammonia decomposition and preparation method thereof |
| CN113694922A (en) * | 2021-09-29 | 2021-11-26 | 石河子大学 | Supported catalyst for ammonia decomposition and preparation method thereof |
| CN114887643A (en) * | 2022-05-13 | 2022-08-12 | 佛山仙湖实验室 | Catalyst for preparing hydrogen by ammonolysis and preparation method thereof |
| CN114887643B (en) * | 2022-05-13 | 2023-12-05 | 佛山仙湖实验室 | Catalyst for producing hydrogen by ammonia pyrolysis and preparation method thereof |
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