CN109954493A - The rare-earth oxide supported ruthenium catalyst of preparing hydrogen by ammonia decomposition and preparation and application - Google Patents
The rare-earth oxide supported ruthenium catalyst of preparing hydrogen by ammonia decomposition and preparation and application Download PDFInfo
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
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Abstract
The rare-earth oxide supported ruthenium catalyst and preparation method thereof that the present invention relates to a kind of for preparing hydrogen by ammonia decomposition.Catalyst is using ruthenium as active constituent in the present invention, and using rare-earth oxide as carrier, the content of ruthenium counts quality as 1~10wt% of rare-earth oxide quality using ruthenium.Rare-earth oxide supported ruthenium catalyst is prepared using precipitating sedimentation, and obtained product is washed, dry, and rare-earth oxide supported ruthenium catalyst can be made in reduction.Preparation method of the present invention is simple, and the rare-earth oxide supported ruthenium catalyst of preparation has many advantages, such as that metal dispersion is good, catalytic activity is high, stability is good, can be used for being catalyzed preparing hydrogen by ammonia decomposition process, has good prospects for commercial application.
Description
Technical field
Present invention relates particularly to a kind of preparation of rare-earth oxide supported ruthenium catalyst for preparing hydrogen by ammonia decomposition and
It is applied.
Background technique
As environmental pollution and greenhouse effects are got worse, it is non-that the sustainable development that energy and environment face has become various countries
The great International Politics problem being often concerned about.A kind of secondary energy sources carrier of the hydrogen as high effect cleaning has density height, calorific value high
The advantage for waiting traditional energies incomparable extensively with raw material sources.In the latest 20 years, Hydrogen Energy and fuel cell the relevant technologies
It develops and utilizes and is classified as clean energy resource field primary study content by countries in the world.The scale of Hydrogen Energy, which utilizes, is related to the life of hydrogen
It produces, store and transports, using three related links, wherein the hydrogen storage technology of highly effective and safe is to influence hydrogen energy automobile to promote and apply
Key technology, and at present Hydrogen Energy large-scale application major technical barrier.
Other hydrogen producing technologies are compared, preparing hydrogen by ammonia decomposition (2NH3=N2+3H2) have following major advantage: (1) synthesis of ammonia,
The relevant technologies such as storage and transport and infrastructure are mature；(2) hydrazine yield is big, relative low price；(3) containing the high (hydrogen of hydrogen density
Content 17.7wt%), energy density is big；(4) easily stored transport；(5) process for making hydrogen is simple, and product is without COxNitrogen
And hydrogen；(6) environmental-friendly；(7) safety is good, explosion limit narrow range.In recent years, ammonia catalytic decomposition mentions for fuel cell
For no COxHydrogen technology, starts to receive widespread attention, it is considered to be solves one of the effective way in fuel cell Hydrogen Energy source.
Preparing hydrogen by ammonia decomposition technology of the ammonia as hydrogen source carrier is developed, realizes that with key associated with vehicle-mounted PEMFC system be exploitation as far as possible
With the ammonia decomposition catalyzer of high activity and high stability at a temperature of low.
The catalyst used of preparing hydrogen by ammonia decomposition reaction at present mainly includes noble metal catalyst (Ir, Pt using Ru as representative
Deng) and using Fe, Ni as the transition-metal catalyst (Co, Mo etc.) of representative.Fe and Ni base catalyst is cheap, but is catalyzed and lives
Property is lower, needs just to be able to achieve higher conversion at 700 DEG C or more.Supported ruthenium catalyst is considered as most effective ammonia point
Solve active catalyst.The carbon nanotube loaded ruthenium-based catalyst performance of Xu Baiqing et al. discovery is higher than common oxide carried
Ruthenium-based catalyst (Catalysis Today, 93-95 (2004), 27-38), the K-Ru/ as made from addition alkali metal promoter
CNTs is the current highest catalyst of activity.But Ru/CNTs catalyst stability is poor, the carbon nanometer under strongly reducing atmosphere
Methanation reaction can occur for pipe, and catalyst is caused gradually to inactivate.Xu Hengyong etc. is prepared using polyol process-homogeneous precipitation method
Ru/MgO catalyst (Catalysis Communications, 7 (2005), 148-152), the catalyst activity is obviously high
It compares in tradition ruthenium-based catalyst prepared by infusion process with Ru/CNTs still active relatively low.Up to the present, low cost preparation
With compared with high/low temperature catalytic activity ruthenium base ammonia decomposition catalyzer, being still the key technology for restricting the development of preparing hydrogen by ammonia decomposition technology
Bottleneck.
Therefore, exploitation has high stability and height under the conditions of relative low temperature (400-500 DEG C) and higher reaction velocity
Active novel supported Ru base ammonia decomposition catalyzer, for promoting the development of preparing hydrogen by ammonia decomposition technology to have great importance.
Summary of the invention
The object of the present invention is to provide a kind of systems of rare-earth oxide supported ruthenium catalyst for preparing hydrogen by ammonia decomposition
Standby and application, ammonia decomposition catalyzer prepared by the present invention can resolve into ammonia conversion under lower temperature and higher space velocity
Nitrogen and hydrogen, and it is with good stability.
The present invention provides a kind of rare-earth oxide supported ruthenium catalyst for preparing hydrogen by ammonia decomposition, the catalyst with
Rare-earth oxide is carrier, and using ruthenium as active component, alkali and alkaline earth metal ions salt is auxiliary agent.
The content of the ruthenium counts quality as the 1~10% of carrier of rare-earth oxide quality using ruthenium；Rare earth gold used
Belonging to oxide carrier includes lanthana, cerium oxide, praseodymium oxide, neodymia, samarium oxide, europium oxide, gadolinium oxide, terbium oxide, oxidation
Dysprosium, holimium oxide, erbium oxide, thulium oxide, ytterbium oxide, any one in luteium oxide or two kinds or more.
High activity rare earth metal oxidation of the precipitating sedimentation preparation for preparing hydrogen by ammonia decomposition is utilized the present invention provides a kind of
The method of object supported ruthenium catalyst, method includes the following steps:
(1) carrier of rare-earth oxide is added in ruthenium precursor water solution in proportion and is stirred evenly, it will be a certain amount of
Urea is added in the ruthenium aqueous solution containing rare-earth oxide, is reacted 1~24 hour in 40~150 DEG C；
(2) after completion of the reaction, it filters, it is neutrality that product, which is washed with deionized to filtrate,.Product after drying restores
To rare-earth oxide supported ruthenium catalyst；
(3) rare-earth oxide after reduction carries in ruthenium catalyst, adds alkali metal and alkaline earth salt or hydroxide
As the promotor for improving catalytic activity.
The precipitation reaction temperature is 40~150 DEG C, and the precipitation reaction time is 1~24 hour.
The ruthenium presoma is any one in the rutheniums sources such as ruthenic chloride, nitric acid ruthenium, acetylacetone,2,4-pentanedione ruthenium and potassium perruthenate
Or two kinds or more.
The molar ratio of the urea and ruthenium is 10~300:1.
The reduction temperature is 200~700 DEG C.
Rare-earth oxide after reduction carries in ruthenium catalyst, can add alkali metallic sodium, potassium, rubidium, caesium and alkaline earth
Any one or two kinds of combination of the above objects in magnesium metal, calcium, the nitrate of barium, acetate or hydroxide are urged as improving
Change active promotor, the additive amount of alkali and alkaline earth metal ions auxiliary agent and the molar ratio of ruthenium are 0.1~5:1.
The rare-earth oxide load ruthenium provided by the invention that the preparation of precipitating sedimentation is utilized for preparing hydrogen by ammonia decomposition is urged
Agent can be used for the preparation of ammonolysis craft process without COxHydrogen.For pure ammonia, gas space velocity 36000mlg-1·h-1's
Under the conditions of ammonia can be fully converted to nitrogen and hydrogen at 500 DEG C.
Compared with prior art, provided by the present invention for the rare-earth oxide supported ruthenium catalyst of preparing hydrogen by ammonia decomposition
With following essential characteristics:
1. catalyst preparation process is simple and safe, it is easy to largely prepare.
2. rare-earth oxide supported ruthenium catalyst ammonolysis craft catalytic activity is higher than the best carbon nanotube of current performance
Supported ruthenium catalyst.
3. catalyst stability is good during ammonia decomposition reaction.
Specific embodiment
Below by specific embodiment, invention is further explained.Unless otherwise indicated, in description of the invention
It is not answered with numerical value such as all numbers, such as active component, temperature and time, gas conversions that occur in claims
This is understood to absolute exact value, and due to the standard deviation of measuring technique, the numerical value of measurement inevitably has certain experiment
Error.Above content is further described below by embodiment, it should be noted that these are specific real listed by the present invention
It applies example to be only limitted to illustrate the present invention, rather than makees the restriction in all senses to above content of the present invention.
Embodiment 1
It weighs 0.0314 gram of nitric acid ruthenium to be dissolved in 60ml water, it is water-soluble that 0.2 gram of praseodymium oxide is added to nitric acid ruthenium under stiring
In liquid, 1.18 grams of urea are added into above-mentioned suspension again after mixing evenly, it is then small respectively at 80 DEG C of reactions 8 under stiring
When.After completion of the reaction, it filters, product is washed repeatedly with deionized water, until filtrate is neutrality.Existed after product is dry with hydrogen
400 DEG C of reductase 12 hours obtain the praseodymium oxide supported ruthenium catalyst (5wt%Ru/Pr that ruthenium load capacity is 5wt%6O11)。
Embodiment 2
It weighs 0.0314 gram of nitric acid ruthenium to be dissolved in 60ml water, it is water-soluble that 0.2 gram of lanthana is added to nitric acid ruthenium under stiring
In liquid, 1.18 grams of urea are added into above-mentioned suspension again after mixing evenly, it is then small respectively at 80 DEG C of reactions 8 under stiring
When.After completion of the reaction, it filters, product is washed repeatedly with deionized water, until filtrate is neutrality.Existed after product is dry with hydrogen
400 DEG C of reductase 12 hours obtain the lanthana supported ruthenium catalyst (5wt%Ru/La that ruthenium load capacity is 5wt%2O3)。
Embodiment 3
It weighs 0.0314 gram of nitric acid ruthenium to be dissolved in 60ml water, it is water-soluble that 0.2 gram of cerium oxide is added to nitric acid ruthenium under stiring
In liquid, 1.18 grams of urea are added into above-mentioned suspension again after mixing evenly, it is then small respectively at 80 DEG C of reactions 8 under stiring
When.After completion of the reaction, it filters, product is washed repeatedly with deionized water, until filtrate is neutrality.Existed after product is dry with hydrogen
400 DEG C of reductase 12 hours obtain the cerium oxide supported ruthenium catalyst (5wt%Ru/CeO that ruthenium load capacity is 5wt%2)。
Embodiment 4
It weighs 0.00628 gram of nitric acid ruthenium to be dissolved in 80ml water, it is water-soluble that 0.2 gram of praseodymium oxide is added to nitric acid ruthenium under stiring
In liquid, 0.5 gram of urea is added into above-mentioned suspension again after mixing evenly, then under stiring respectively at 60 DEG C of reflow treatments
12 hours.After completion of the reaction, it filters, product is washed repeatedly with deionized water, until filtrate is neutrality.Hydrogen is used after product is dry
Gas restores 4 hours at 300 DEG C, obtains the praseodymium oxide supported ruthenium catalyst that ruthenium load capacity is 1wt%.
Embodiment 5
It weighs 0.01256 gram of nitric acid ruthenium to be dissolved in 90ml water, it is water-soluble that 0.2 gram of lanthana is added to nitric acid ruthenium under stiring
In liquid, 1.0 grams of urea are added into above-mentioned suspension again after mixing evenly, then under stiring respectively at 70 DEG C of reflow treatments
18 hours.After completion of the reaction, it filters, product is washed repeatedly with deionized water, until filtrate is neutrality.Hydrogen is used after product is dry
Gas restores 3 hours at 400 DEG C, obtains the lanthana supported ruthenium catalyst that ruthenium load capacity is 2wt%.
Embodiment 6
It weighs 0.01884 gram of nitric acid ruthenium to be dissolved in 100ml water, 0.2 gram of cerium oxide is added to nitric acid ruthenium water under stiring
In solution, 1.5 grams of urea are added into above-mentioned suspension again after mixing evenly, then under stiring at 90 DEG C of reflux
Reason 24 hours.After completion of the reaction, it filters, product is washed repeatedly with deionized water, until filtrate is neutrality.It is used after product is dry
Hydrogen obtains the cerium oxide supported ruthenium catalyst that ruthenium load capacity is 3wt% in 500 DEG C of reductase 12 hours.
Embodiment 7
It weighs 0.0205 gram of ruthenic chloride to be dissolved in 60ml water, 0.2 gram of neodymia is added to chlorination ruthenium solution under stiring
In, 2.0 grams of urea are added into above-mentioned suspension again after mixing evenly, it is then small respectively at 70 DEG C of reflow treatments 8 under stiring
When.After completion of the reaction, it filters, product is washed repeatedly with deionized water, until filtrate is neutrality.Existed after product is dry with hydrogen
600 DEG C of reductase 12 hours obtain the neodymia supported ruthenium catalyst that ruthenium load capacity is 5wt%.Neodymia load after reduction
In ruthenium catalyst, neodymia supported ruthenium catalyst is modified using potassium hydroxide as auxiliary agent, method is molten with potassium hydroxide
Liquid oxide impregnation neodymium supported ruthenium catalyst, wherein the molar ratio of potassium and ruthenium is 0.5:1.
Embodiment 8
It weighs 0.0202 gram of potassium perruthenate to be dissolved in 30ml water, 0.2 gram of samarium oxide is added to potassium perruthenate under stiring
In solution, 1.5 grams of urea are added into above-mentioned suspension again after mixing evenly, then under stiring at 120 DEG C of reflux
Reason 8 hours.After completion of the reaction, it filters, product is washed repeatedly with deionized water, until filtrate is neutrality.Hydrogen is used after product is dry
Gas obtains the samarium oxide supported ruthenium catalyst that ruthenium load capacity is 5wt% in 250 DEG C of reductase 12 hours.Samarium oxide after reduction
It carries in ruthenium catalyst, samarium oxide supported ruthenium catalyst is modified using potassium carbonate as auxiliary agent, method is to use solution of potassium carbonate
Oxide impregnation samarium supported ruthenium catalyst, wherein the molar ratio of potassium and ruthenium is 2:1.
Embodiment 9
It weighs 0.01884 gram of nitric acid ruthenium to be dissolved in 90ml water, it is water-soluble that 0.2 gram of europium oxide is added to nitric acid ruthenium under stiring
In liquid, 0.5 gram of urea is added into above-mentioned suspension again after mixing evenly, then under stiring respectively at 50 DEG C of reflow treatments 8
Hour.After completion of the reaction, it filters, product is washed repeatedly with deionized water, until filtrate is neutrality.Hydrogen is used after product is dry
In 350 DEG C of reductase 12 hours, the europium oxide supported ruthenium catalyst that ruthenium load capacity is 3wt% is obtained.Europium oxide after reduction is negative
It carries in ruthenium catalyst, europium oxide supported ruthenium catalyst is modified using cesium nitrate as auxiliary agent, method is with cesium nitrate solution
Oxide impregnation europium supported ruthenium catalyst, wherein the molar ratio of caesium and ruthenium is 3:1.
Embodiment 10
It weighs 0.0123 gram of ruthenic chloride to be dissolved in 120ml water, 0.2 gram of gadolinium oxide is added to chlorination ruthenium solution under stiring
In, 1.5 grams of urea are added into above-mentioned suspension again after mixing evenly, it is then small respectively at 90 DEG C of reflow treatments 8 under stiring
When.After completion of the reaction, it filters, product is washed repeatedly with deionized water, until filtrate is neutrality.Existed after product is dry with hydrogen
450 DEG C of reductase 12 hours obtain the gadolinium oxide supported ruthenium catalyst that ruthenium load capacity is 3wt%.Gadolinium oxide load after reduction
In ruthenium catalyst, gadolinium oxide supported ruthenium catalyst is modified using cesium carbonate as auxiliary agent, method is to be soaked with cesium carbonate solution
Stain gadolinium oxide supported ruthenium catalyst, wherein the molar ratio of caesium and ruthenium is 4:1.
Embodiment 11
It weighs 0.02364 gram of acetylacetone,2,4-pentanedione ruthenium to be dissolved in 80ml water, 0.2 gram of terbium oxide is added to levulinic under stiring
In ketone ruthenium solution, 1.5 grams of urea are added into above-mentioned suspension again after mixing evenly, are then returned under stiring respectively at 130 DEG C
Stream process 4 hours.After completion of the reaction, it filters, product is washed repeatedly with deionized water, until filtrate is neutrality.After product is dry
With hydrogen in 550 DEG C of reductase 12 hours, the terbium oxide supported ruthenium catalyst that ruthenium load capacity is 3wt% is obtained.Oxygen after reduction
Change in terbium supported ruthenium catalyst, terbium oxide supported ruthenium catalyst is modified using potassium hydroxide as auxiliary agent, method is to use hydrogen
Potassium oxide solution oxide impregnation terbium supported ruthenium catalyst, wherein the molar ratio of potassium and ruthenium is 5:1.
Embodiment 12
It weighs 0.01212 gram of potassium perruthenate to be dissolved in 50ml water, 0.2 gram of dysprosia is added to potassium perruthenate under stiring
In solution, 1.0 grams of urea are added into above-mentioned suspension again after mixing evenly, then under stiring at 110 DEG C of reflux
Reason 24 hours.After completion of the reaction, it filters, product is washed repeatedly with deionized water, until filtrate is neutrality.It is used after product is dry
Hydrogen obtains the dysprosia supported ruthenium catalyst that ruthenium load capacity is 3wt% in 650 DEG C of reductase 12 hours.Oxidation after reduction
In dysprosium supported ruthenium catalyst, dysprosia supported ruthenium catalyst is modified using potassium nitrate as auxiliary agent, method is to use potassium nitrate
Solution oxide impregnation dysprosium supported ruthenium catalyst, wherein the molar ratio of potassium and ruthenium is 0.5:1.
Embodiment 13
It weighs 0.0628 gram of nitric acid ruthenium to be dissolved in 70ml water, it is water-soluble that 0.2 gram of holimium oxide is added to nitric acid ruthenium under stiring
In liquid, 0.5 gram of urea is added into above-mentioned suspension again after mixing evenly, then under stiring respectively at 60 DEG C of reflow treatments
24 hours.After completion of the reaction, it filters, product is washed repeatedly with deionized water, until filtrate is neutrality.Hydrogen is used after product is dry
Gas obtains the holimium oxide supported ruthenium catalyst that ruthenium load capacity is 10wt% in 320 DEG C of reductase 12 hours.Holimium oxide after reduction
In supported ruthenium catalyst, holimium oxide supported ruthenium catalyst is modified using potassium carbonate as auxiliary agent, method is molten with potassium carbonate
Liquid oxide impregnation holmium supported ruthenium catalyst, wherein the molar ratio of potassium and ruthenium is 1:1.
Embodiment 14
It weighs 0.0410 gram of ruthenic chloride to be dissolved in 90ml water, 0.2 gram of erbium oxide is added to chlorination ruthenium solution under stiring
In, 1.8 grams of urea are added into above-mentioned suspension again after mixing evenly, it is then small respectively at 90 DEG C of reflow treatments 2 under stiring
When.After completion of the reaction, it filters, product is washed repeatedly with deionized water, until filtrate is neutrality.Existed after product is dry with hydrogen
420 DEG C of reductase 12 hours obtain the erbium oxide supported ruthenium catalyst that ruthenium load capacity is 10wt%.Erbium oxide load after reduction
In ruthenium catalyst, erbium oxide supported ruthenium catalyst is modified using cesium nitrate as auxiliary agent, method is to be soaked with cesium nitrate solution
Stain erbium oxide supported ruthenium catalyst, wherein the molar ratio of caesium and ruthenium is 2:1.
Embodiment 15
It weighs 0.0788 gram of acetylacetone,2,4-pentanedione ruthenium to be dissolved in 120ml water, 0.2 gram of thulium oxide is added to levulinic under stiring
In ketone ruthenium solution, 2.6 grams of urea are added into above-mentioned suspension again after mixing evenly, are then returned under stiring respectively at 110 DEG C
Stream process 12 hours.After completion of the reaction, it filters, product is washed repeatedly with deionized water, until filtrate is neutrality.Product is dry
The thulium oxide supported ruthenium catalyst that ruthenium load capacity is 10wt% is obtained in 520 DEG C of reductase 12 hours with hydrogen afterwards.After reduction
In thulium oxide supported ruthenium catalyst, thulium oxide supported ruthenium catalyst is modified using cesium carbonate as auxiliary agent, method is to use carbon
Sour caesium solution oxide impregnation thulium supported ruthenium catalyst, wherein the molar ratio of caesium and ruthenium is 3:1.
Embodiment 16
It weighs 0.0404 gram of potassium perruthenate to be dissolved in 60ml water, 0.2 gram of ytterbium oxide is added to potassium perruthenate under stiring
In solution, 2.2 grams of urea are added into above-mentioned suspension again after mixing evenly, then under stiring at 130 DEG C of reflux
Reason 8 hours.After completion of the reaction, it filters, product is washed repeatedly with deionized water, until filtrate is neutrality.Hydrogen is used after product is dry
Gas obtains the ytterbium oxide supported ruthenium catalyst that ruthenium load capacity is 10wt% in 620 DEG C of reductase 12 hours.Ytterbium oxide after reduction
In supported ruthenium catalyst, ytterbium oxide supported ruthenium catalyst is modified using potassium hydroxide as auxiliary agent, method is to use hydroxide
Potassium solution oxide impregnation ytterbium supported ruthenium catalyst, wherein the molar ratio of potassium and ruthenium is 4:1.
Embodiment 17
It weighs 0.05024 gram of nitric acid ruthenium to be dissolved in 90ml water, it is water-soluble that 0.2 gram of luteium oxide is added to nitric acid ruthenium under stiring
In liquid, 0.6 gram of urea is added into above-mentioned suspension again after mixing evenly, then under stiring respectively at 100 DEG C of reflow treatments
8 hours.After completion of the reaction, it filters, product is washed repeatedly with deionized water, until filtrate is neutrality.Hydrogen is used after product is dry
In 400 DEG C of reductase 12 hours, the luteium oxide supported ruthenium catalyst that ruthenium load capacity is 8wt% is obtained.Luteium oxide after reduction is negative
It carries in ruthenium catalyst, luteium oxide supported ruthenium catalyst is modified using potassium nitrate as auxiliary agent, method is to use potassium nitrate solution
Oxide impregnation lutetium supported ruthenium catalyst, wherein the molar ratio of potassium and ruthenium is 5:1.
Embodiment 18
Ammonia point is carried out to rare-earth oxide supported ruthenium catalyst prepared by Examples 1 to 3 in ammonia decomposition device
Solve reactivity evaluation.Reactor is the quartz ampoule fixed bed reactors that internal diameter is 6mm, the catalyst 50mg after taking reduction, ammonia
Gas velocity is 30ml/min, reaction velocity 36000mlh-1·gcat -1, reaction temperature be 400 DEG C, 450 DEG C, 500 DEG C,
550 DEG C, ammonolysis craft catalytic reaction activity test result is shown in Table 1.As can be seen from the table, prepared by the embodiment of the present invention 1~3
Catalyst activity is higher than Ru/CNT catalyst, and catalyst has good stability.
1 catalyst catalytic performance of table is summarized
Preparation method of the present invention is simple, is prepared by that cost is relatively low, and the rare-earth oxide of preparation carries ruthenium catalyst tool
Have the advantages that metal dispersion is good, catalytic activity is high, stability is good, can be used for being catalyzed preparing hydrogen by ammonia decomposition process.
Claims (10)
1. the rare-earth oxide of preparing hydrogen by ammonia decomposition carries ruthenium catalyst, it is characterised in that: the catalyst activity component is ruthenium,
Carrier is rare-earth oxide, wherein adding or not adding alkali metal salt and/or alkali salt as auxiliary agent.
2. the rare-earth oxide of preparing hydrogen by ammonia decomposition according to claim 1 carries ruthenium catalyst, it is characterised in that: described
The content of ruthenium counts quality as the 1~10% of carrier of rare-earth oxide quality using ruthenium, and preferably 3~6%；Rare earth metal used
Oxide carrier includes lanthana, cerium oxide, praseodymium oxide, neodymia, samarium oxide, europium oxide, gadolinium oxide, terbium oxide, dysprosia,
Holimium oxide, erbium oxide, thulium oxide, ytterbium oxide, any one in luteium oxide or two kinds or more.
3. the rare-earth oxide of preparing hydrogen by ammonia decomposition according to claim 1 or 2 carries ruthenium catalyst, it is characterised in that:
Rare-earth oxide supported ruthenium catalyst can add one of alkali metallic sodium, potassium, rubidium, caesium and alkaline-earth metal magnesium, calcium, barium
Or two kinds or more nitrate, any one or two kinds of combination of the above objects in acetate or hydroxide live as catalysis is improved
Property auxiliary agent, the molar ratio of auxiliary agent and ruthenium is 0.1~5:1.
4. the preparation side that the high activity rare-earth oxide of preparing hydrogen by ammonia decomposition according to claim 1 carries ruthenium catalyst
Method, it is characterised in that: method includes the following steps:
Carrier of rare-earth oxide is added in ruthenium precursor water solution in proportion and is stirred evenly, by urea be added to containing
In the ruthenium aqueous solution of rare-earth oxide, reacted 1~24 hour in 40~150 DEG C (preferably 50~120 DEG C)；
After completion of the reaction, it filters, it is neutrality that product, which is washed with deionized to filtrate,；Rare earth can be made in product reduction after drying
Metal oxide supported ruthenium catalyst；
Rare-earth oxide after reduction carries in ruthenium catalyst, does not add or add alkali metal and/or alkaline earth salt or hydrogen-oxygen
Compound is as the promotor for improving catalytic activity.
5. the rare-earth oxide of preparing hydrogen by ammonia decomposition according to claim 4 carries the preparation method of ruthenium catalyst, special
Sign is: ruthenium presoma be any one or two kinds in the rutheniums source such as ruthenic chloride, nitric acid ruthenium, acetylacetone,2,4-pentanedione ruthenium and potassium perruthenate with
On.
6. the rare-earth oxide according to claim 4 for preparing hydrogen by ammonia decomposition carries the preparation method of ruthenium catalyst,
It is characterized by: the molar ratio of urea and ruthenium is 10~300:1, preferably 50~200:1.
7. the rare-earth oxide of preparing hydrogen by ammonia decomposition according to claim 4 carries the preparation method of ruthenium catalyst, special
Sign is: reduction temperature is 200~700 DEG C, preferably 300~600 DEG C.
8. the rare-earth oxide of preparing hydrogen by ammonia decomposition according to claim 3 carries the preparation method of ruthenium catalyst, special
Sign is: rare-earth oxide supported ruthenium catalyst can add alkali metallic sodium, potassium, rubidium, caesium and alkaline-earth metal magnesium, calcium, barium
In the nitrate of any one or two kinds or more, any one or two kinds of combination of the above objects in acetate or hydroxide make
For the auxiliary agent for improving catalytic activity, the molar ratio of auxiliary agent and ruthenium is 0.1~5:1, preferably 0.5~3:1.
9. the rare-earth oxide of preparing hydrogen by ammonia decomposition carries the application of ruthenium catalyst according to claim 1, it is characterised in that:
The catalyst prepares hydrogen for ammonolysis craft process.
10. application according to claim 9, it is characterised in that: the catalyst is free of CO for the preparation of ammonolysis craft processx's
Hydrogen, x are 1 or 2.
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| CN112007641A (en) * | 2020-07-20 | 2020-12-01 | 浙江工业大学 | High-dispersion Ru/ABOxSupported catalyst and preparation method and application thereof |
| CN112387274A (en) * | 2019-08-14 | 2021-02-23 | 中国科学院大连化学物理研究所 | Preparation method of supported ruthenium-based catalyst |
| CN112387276A (en) * | 2019-08-15 | 2021-02-23 | 中国科学院大连化学物理研究所 | Supported ruthenium cluster catalyst for ammonia synthesis and preparation method and application thereof |
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| CN115485066A (en) * | 2020-02-07 | 2022-12-16 | 牛津大学科技创新有限公司 | Catalytic material and use thereof |
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| CN112774676A (en) * | 2019-11-11 | 2021-05-11 | 中国科学院大连化学物理研究所 | Rare earth oxide supported ruthenium catalyst and preparation method and application thereof |
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| CN111939907A (en) * | 2020-09-21 | 2020-11-17 | 浙江工业大学 | Catalyst for low-temperature ammonia decomposition hydrogen production and preparation method and application thereof |
| CN113289620A (en) * | 2021-06-23 | 2021-08-24 | 北京单原子催化科技有限公司 | Monoatomic ruthenium catalyst, preparation method and application |
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