CN105772024B - A kind of compound ammonia synthesis catalyst of iron ruthenium and preparation method thereof - Google Patents
A kind of compound ammonia synthesis catalyst of iron ruthenium and preparation method thereof Download PDFInfo
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
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Abstract
The invention discloses the compound ammonia synthesis catalysts of iron ruthenium and preparation method thereof of iron catalyst load ruthenium metal, it is active component, ferrum-based catalyst for carrier that the catalyst, which is using metal Ru, and/or by alkali metal, one or more of alkaline-earth metal and transition elements form co-catalyst.The adding method of activity component metal ruthenium includes ruthenium presoma mechanical mixture by a certain percentage, vapor deposition and liquid impregnation, and the pyrolysis processing in air, nitrogen and vacuum.Wherein co-catalyst can be molten on ferriferous oxide before ruthenium load or load simultaneously with ruthenium presoma.The present invention have equipment flowsheet it is simple, short preparation period, low energy consumption, have both ruthenium catalyst high activity and iron catalyst high stability the advantages that.
Description
Technical field
The invention belongs to catalyst technical fields, and in particular to a kind of compound ammonia synthesis catalyst of iron ruthenium and its preparation side
Method.
Background technique
Ammonia synthesis catalyst has century-old developing history, and the sustained improvement of catalyst is always that ammonia synthesizing industry reduces energy
One of critical path of consumption.
Traditional industrial ammonia synthesis catalyst is with Fe3O4(magnetic iron ore) is the fused iron catalyst of parent.It experienced nearly one
The development in century, it is highly developed, activity to improve again 0.5 percentage point it is also very difficult.1986, patent
CN1091997A discloses one kind with Fe1-xO(wustite) be parent new system catalyst.Fe1-xO ammonia synthesis catalyst has
Extra high activity is particularly easy to reduction, especially low active temperature, high mechanical strength and applicable H2/N2Range is wide and makes
The features such as with service life (being up to 10 years or more) is current highest active in the world, state-of-the-art fused iron catalyst of new generation.
1972, activity higher [the Journal when ruthenium catalyst of the discoveries such as Japanese scholars Ozaki is using active carbon as carrier
of Catalysis, 1972, 27(3): 424–431].1992, BP company, Britain cooperated with Kellogg company, the U.S., opened
Send out successfully using be graphitized the active carbon of high-specific surface area as carrier, with Ru3(CO)12For the ruthenium catalyst of parent.Catalyst tool
There is high activity, can be operated under low temperature, low-pressure.But it is being synthesized by the Carbon supports in the ruthenium catalyst of carrier of active carbon
Generation methane is easily reacted under the conditions of ammonia reaction (facing hydrogen), under the catalytic action of ruthenium with hydrogen, causes its carrier unstable, and with
The progress of methanation reaction lost without stopping, it is expensive to seriously affect its service life, and ruthenium natural resources shortage.
These all seriously affect the use of ruthenium catalyst, and its industrial application is caused to be very limited [Applied Catalysis
A: General. 208 (2001)271]。
For this purpose, patent CN102744060A uses BaTiO3, patent CN1390637A is using Al2O3And patent
CN101053835A uses oxide to substitute the methanation problem that active carbon carrys out resolved vector for carrier, but catalyst activity is remote
Far below using active carbon as the catalyst of carrier.The discovery of patent CN1382527A and US 4600571 is performed for more than active carbon
1900oThe inert gas high-temperature process of C can form graphitization active carbon and improve vector stabilisation to a certain extent.But
Activated carbon surface product sharply declines after high-temperature process, thus need to improve surface area by oxidation reaming.This breaks again to a certain extent
It is broken graphite-structure and causes carrier easily by methanation.
Therefore, because active component ruthenium inherently carbon is hydrogenated to the excellent catalyst of methane, so ruthenium catalyst
Methanation is difficult to avoid that.This is a fatal weakness of ruthenium catalyst, is the problem that must overcome.
Obviously, iron catalyst is stable and activity is lower than ruthenium catalyst, and ruthenium catalyst activity is high and stability is urged not as good as iron
Agent.The purpose of the present invention is to provide the compound ammonia synthesis catalysts of iron ruthenium double activated component of a kind of high activity and high stability
And preparation method thereof.
Summary of the invention
The present invention utilizes the advantage of iron and ruthenium catalyst respectively, and the iron catalyst high using stability substitutes unstable as carrier
The active component ruthenium of high activity is carried on iron catalyst by fixed high-area carbon, and the double activated group of high activity and high stability is made
Divide compound ammonia synthesis catalyst.Catalyst of the present invention is using metal Ru as active component, using iron based ammonia synthesis catalyst as carrier, with
Alkali metal, one or more of alkaline-earth metal and transition elements are co-catalyst.Catalyst preparation process process letter of the present invention
It is single, the high stability of iron catalyst and the high activity of ruthenium catalyst are had both, in ammonia synthesizing industry and preparing hydrogen by ammonia decomposition industrial circle
There is extensive prospects for commercial application.
A kind of compound ammonia synthesis catalyst of iron ruthenium, it is characterised in that be supported on iron catalyst carrier by metal Ru
It obtains, the metal Ru load capacity is 0.1-5wt%, preferably 0.1-3wt%.
A kind of compound ammonia synthesis catalyst of iron ruthenium, it is characterised in that the iron catalyst carrier includes four oxidations
The molten mixture of three iron based ammonia synthesis catalysts, ferrous oxide catalyst for amino synthesis and ferriferous oxide, in which:
(1) Fe3O4Base ammonia synthetic catalyst is by major constituent Fe3O4With co-catalyst Al2O3、K2O, CaO, MgO etc. are formed, this
The dead catalyst or freshly prepd catalyst that invention is crossed using commercial product (such as A110 catalyst series) or industrial application；
(2) Fe1-xO base ammonia synthetic catalyst is by major constituent Fe1-xO and co-catalyst Al2O3、K2O、CaO、MgO、V2O5Etc. groups
The dead catalyst crossed at, the present invention using commercial product (such as A301, ZA-5, AmoMX-10 type catalyst) or industrial application or
Freshly prepd catalyst；
(3) molten mixture of ferriferous oxide is by Fe2O3And/or Fe3O4And/or FeO and its mixture form, using melting
Method preparation.
A kind of compound ammonia synthesis catalyst of iron ruthenium, it is characterised in that the lead compound of the metal Ru is
Ru3(CO)12、Ru(C5H7O2)3Or K2RuO4, preferably Ru3(CO)12Or Ru (C5H7O2)3。
A kind of compound ammonia synthesis catalyst of iron ruthenium, it is characterised in that it further include co-catalyst, the co-catalysis
The molar ratio of agent and metal Ru be 0~16:1, preferably 0.2~5:1, the co-catalyst be alkali metal, alkaline-earth metal and
One or more of transition metal, the lead compound of the co-catalyst are oxide, hydroxide, the nitre of each metal
Hydrochlorate or carbonate.
A kind of compound ammonia synthesis catalyst of iron ruthenium, it is characterised in that the alkali metal include sodium, potassium, rubidium and
Caesium；Alkaline-earth metal includes calcium, magnesium and barium；Transition metal includes vanadium, titanium and zirconium.
A kind of preparation method of the compound ammonia synthesis catalyst of iron ruthenium, it is characterised in that specifically includes the following steps:
1) active component ruthenium precursor compound is supported on iron catalyst carrier, the obtained compound ammonia synthesis of product iron ruthenium
Catalyst precursor；
2) the active component ruthenium precursor compound in the compound ammonia synthesis catalyst presoma of iron ruthenium is decomposed into metal Ru,
And be supported on iron catalyst carrier, the compound ammonia synthesis catalyst of iron ruthenium that ruthenium dispersion degree is high, stability is good is made.
The preparation method of a kind of compound ammonia synthesis catalyst of iron ruthenium, it is characterised in that co-catalysis is added in step 1)
The molar ratio of agent, the co-catalyst and metal Ru is 0~16:1, and preferably 0.2~5:1, the co-catalyst is alkali
One or more of metal, alkaline-earth metal and transition metal, the lead compound of the co-catalyst are the oxygen of each metal
Compound, hydroxide, nitrate or carbonate, preferably the alkali metal includes sodium, potassium, rubidium and caesium；Alkaline-earth metal includes
Calcium, magnesium and barium；Transition metal includes vanadium, titanium and zirconium.
The preparation method of a kind of compound ammonia synthesis catalyst of iron ruthenium, it is characterised in that active in the step 1)
Component ruthenium precursor compound is supported on iron catalyst carrier using mechanical mixing, vapour deposition process or liquid-phase impregnation process,
It is preferred that using mechanical mixing and vapour deposition process.
A kind of preparation method of compound ammonia synthesis catalyst of iron ruthenium, it is characterised in that the mechanical mixing packet
Include ball milling, grinding, stirring, pneumatic stirring or industrial advanced mechanical mixer mixing；The vapour deposition process includes changing
Learn vapor deposition, physical vapour deposition (PVD) or plasma gas phase deposition；The liquid-phase impregnation process includes equi-volume impregnating, mistake
Infusion process, multiple maceration, dipper precipitation method are measured, or in liquid-phase system, prepares nanometer using reducing agent reduction ruthenium ion
Ruthenium particle, then be impregnated on iron catalyst carrier by above-mentioned dipping method.
The preparation method of a kind of compound ammonia synthesis catalyst of iron ruthenium, it is characterised in that used in the step 2)
Active component ruthenium precursor compound in the compound ammonia synthesis catalyst presoma of iron ruthenium is decomposed into metal Ru by heat treating process, and
It is supported on iron catalyst carrier, the pyrolysis processing is specially active component ruthenium precursor compound in vacuum, air, nitrogen
Pyrolysis is carried out under gas or hydrogen atmosphere, so that it is decomposed into zero-valent metal ruthenium, and be supported on carrier, and reaction condition is temperature
Spend 100~500 DEG C, 0.01~5MPa of pressure, the reaction time 0.5~24 hour, preferably 100~200 DEG C of temperature, pressure 0.01
~1MPa.
Catalyst of the invention can be applied in the fields such as ammonia synthesizing industry and preparing hydrogen by ammonia decomposition industry, and the present invention
Preparation process it is simple, equipment requirement is low, and the time is shorter, without waste liquid generate, more meet environmental requirement, there is preferable industry to answer
Use prospect.
Detailed description of the invention
Fig. 1 be ruthenium load before (left side) afterwards (in) and react after (right side) catalyst SEM image.
Specific embodiment
The present invention is described further for son combined with specific embodiments below, but protection scope of the present invention is not limited by it
System.
Embodiment 1
KNO is weighed respectively with assay balance313.1g BaCO32.6g, Al2O318.1g CaCO332.0g, MgO7.5g, iron
These materials are put into mortar and are fully ground, are uniformly mixed, are subsequently placed in electric smelter by powder 232g, selected magnetite powder 704g
Middle melting, fusant obtain Fe after cooled and solidified1-xO base catalyst obtains the Fe of 14-18 mesh granularity through broken, screening1- xO based catalyst carrier.The ferrum-based catalyst carrier 8.0g, Ru are weighed respectively3(CO)12 The load capacity of 0.0337g(ruthenium is 0.2
Wt ﹪), be then fitted into mixer, after mixing, be loaded into sublimation apparatus together, vacuumize pressure is maintained at-
Then 0.1MPa heats up, the 5h that distils at 140 DEG C is to get with Fe1-xO base catalyst is the composite catalyst of carrier.Then it urges
For agent in 150 DEG C of air atmospheres, 0.05MPa handles 4h to get iron ruthenium composite catalyst.
Scanning electron microscope (SEM) photograph behind catalyst load front and back and reaction, as shown in Figure 1.
Embodiment 2
1 process of embodiment is repeated, the load capacity of original ruthenium is become 1.0%.This is weighed with Fe1-xO base catalyst is carrier
Composite catalyst presoma 8.0g, be then loaded into sublimation apparatus, vacuumize sublimation apparatus pressure is maintained at-
Then 0.1MPa heats up, the 5h that distils at 140 DEG C is to get with Fe1-xO base catalyst is the composite catalyst of carrier.Then it urges
For agent in 200 DEG C of nitrogen atmospheres, 0.1MPa handles 4h to get iron ruthenium composite catalyst.
Embodiment 3
KNO is weighed respectively with assay balance313.1g BaCO3 2.6g, Al2O318.1g CaCO332.0g MgO
7.5g, iron powder 23g, selected magnetite powder 940g.Then these materials are put into mortar and are fully ground, are uniformly mixed, then put
Enter in electric smelter and melt together, fusant obtains Fe after cooled and solidified3O4Base catalyst obtains 14-18 through broken, screening
The carrier of mesh granularity weighs the carrier 8.0g, Ru3(CO)12 The load capacity of 0.1281g(ruthenium is 0.76 wt ﹪), then together
It is fitted into mixer, is obtained after mixing with Fe3O4Base catalyst is the composite catalyst presoma of carrier.Then catalyst
In 400 DEG C of air atmospheres, 0.06MPa handles 8h to get iron ruthenium composite catalyst.
Embodiment 4
Weigh iron powder 78.3g, selected magnetite powder 921.7g respectively with assay balance.Then these materials are put into and are ground
It is fully ground, is uniformly mixed in alms bowl, place into electric smelter and melt together, fusant is obtained by 47.3% after cooled and solidified
Fe2O3, 46.4%FeO composition molten mixture, obtain the carrier of 14-18 mesh granularity through broken, screening, weigh the carrier
8.0g、Ru3(CO)12 The load capacity of 0.2696g(ruthenium is 1.6 wt ﹪), then it is fitted into mixer together, after mixing
To using the molten mixture of ferriferous oxide as the composite catalyst of carrier.Then catalyst handles 6h in 250 DEG C of vacuum atmospheres, i.e.,
Obtain iron ruthenium composite catalyst.
Embodiment 5
Business Fe is weighed with assay balance1-xO base ammonia synthetic catalyst (A301 or ZA-5 or AmoMX-10 type) 8.0g, Ru3
(CO)12 The load capacity of 0.4381g(ruthenium is 2.6wt ﹪), it is fitted into sublimation apparatus vacuumizes after mixing, protect its pressure
It holds in -0.1MPa, then heats to constant temperature at 140 DEG C and distil 5h to get with business Fe1-xO base ammonia synthetic catalyst is carrier
Composite catalyst.
Embodiment 6
Embodiment 1 is repeated, Fe is prepared1-xO base catalyst.Fe is weighed respectively1-xO based catalyst carrier 8.0g, Ru3
(CO)12 The load capacity of 0.2022g(ruthenium is 1.2 wt ﹪), KNO30.056 g or CsNO3Then 0.066 g is packed into mixed together
In clutch, obtained after mixing with Fe1-xO base catalyst is carrier, the composite catalyst forerunner for adding co-catalyst K or Cs
Body.Then again under 120 DEG C of nitrogen atmospheres, 1MPa handles 4h, obtains iron ruthenium composite catalyst.
Embodiment 7
Embodiment 1 is repeated, Fe is prepared1-xO base catalyst.Fe is weighed respectively1-xO based catalyst carrier 8.0g, Ru
(C5H7O2)3 The load capacity of 0.0630g(ruthenium is 0.2 wt ﹪), Ba (NO3)2Then 0.024g is fitted into mixer together, mix
It obtains after closing uniformly with Fe1-xO base catalyst is carrier, the composite catalyst presoma for adding cocatalyst B a.Then again 120
DEG C nitrogen atmosphere handles 1h under 0.1MPa, obtains iron ruthenium composite catalyst.
Embodiment 8
Embodiment 1 is repeated, Fe is prepared1-xO base catalyst.Fe is weighed respectively1-xO based catalyst carrier 8.0g, Ru
(C5H7O2)3 The load capacity of 0.0630g(ruthenium is 0.2 wt ﹪), Ba (NO3)2 0.024g、KNO30.056 g, then fills together
Enter in mixer, is obtained after mixing with Fe1-xO base catalyst is carrier, the composite catalyst for adding co-catalyst K and Ba
Presoma.Then 120 DEG C of nitrogen atmospheres again handle 0.5h under 0.1MPa, obtain iron ruthenium composite catalyst
Embodiment 9
Embodiment 1 is repeated, Fe is prepared1-xO base catalyst.Fe is weighed respectively1-xO based catalyst carrier 8.0g, Ba
(NO3)20.024g and KNO30.056 g.Then the material weighed up is fitted into agitating device.Added after mixing
Iron catalyst after adding co-catalyst.Then Ru is weighed again3(CO)12 The load capacity of 0.1687g(ruthenium is 1 ﹪).Then will claim
Iron catalyst after the ruthenium and addition auxiliary agent that have taken is fitted into sublimation apparatus.It vacuumizes, sublimation apparatus pressure is maintained at-
0.1MPa.Then it heats up, the 5h that distils at 140 DEG C, under -0.1MPa is to get catalyst.
Embodiment 10
Embodiment 1 is repeated, Fe is prepared1-xO base catalyst.100mL ethylene glycol solution is measured to be added in three-necked flask,
Then sodium acetate 0.3g is weighed respectively, ruthenium trichloride 0.1581g is added in three-necked flask together after having claimed, then starts to warm up,
150 DEG C isothermal reaction 30 minutes in whipping process.Solution is centrifuged 15min under the conditions of 8000r/min and obtains Ru- after reaction
Then 0.05g Ba (NO is added after centrifugation by its ultrasonic dissolution in dehydrated alcohol in NPs3)2, 2mL ammonium hydroxide is added after stirring.
Then ultrasonic disperse adds 8g Fe1-xO based catalyst carrier.Dehydrated alcohol quick wash is used after dipping 3h, is then being dried
Dry 3h at 100 DEG C, obtains composite catalyst after dry in case.
Embodiment 11
Catalyst activity evaluation carries out in high pressure activating test device.Reactor is the fixed bed of 14 mm of internal diameter.Catalysis
Agent particle is 1.0-1.4 mm, and stacking volume is 2 ml, and Catalyst packing is in the isothermal region of reactor.Reaction gas is ammonia high temperature
Decompose the hydrogen nitrogen mixed gas that obtained H-N ratio is 3:1.Before reaction, catalyst is in 5MPa, 30000h-1, H2/N2=3 it is mixed
It closes in gas, temperature is to restore 4h, 8h, 8 h and 4 h respectively at 400 DEG C, 425 DEG C, 450 DEG C and 475 DEG C.After reduction, 10
MPa, 10000 h-1And reactor outlet ammonia density is measured respectively under the conditions of 375 DEG C, 400 DEG C and 425 DEG C.The various embodiments described above
Measurement result it is as shown in table 1.
The ammonia synthesis reaction activity of 1 embodiment of table
As shown in Table 1, catalyst of the invention has high ammonia synthesis reaction activity.It is carrier with other ferriferous oxides
Patent Reference's discovery, catalyst compares under the same conditions in patent CN102921413A and CN102744060A, they
The active highest of catalyst is respectively 15.8% and 7.42% at 425 DEG C of catalyst.The activity of catalyst significantly mentions through the invention
It is high.
Claims (4)
1. a kind of compound ammonia synthesis catalyst of iron ruthenium, it is characterised in that it is supported on iron catalyst carrier and is obtained by metal Ru, institute
The metal Ru load capacity stated is 0.1-5wt%, and the iron catalyst carrier includes ferroso-ferric oxide base ammonia synthetic catalyst, oxygen
Change the molten mixture of ferrous base ammonia synthetic catalyst and ferriferous oxide, the precursor compound of metal Ru is Ru3(CO)12、Ru
(C5H7O2)3Or K2RuO4；
The compound ammonia synthesis catalyst of iron ruthenium is obtained by following steps:
1) active component ruthenium precursor compound iron is supported on using mechanical mixing, vapour deposition process or liquid-phase impregnation process to urge
On agent carrier, the compound ammonia synthesis catalyst presoma of iron ruthenium is obtained；
2) the active component ruthenium precursor compound in the compound ammonia synthesis catalyst presoma of iron ruthenium is decomposed using heat treating process
It for metal Ru, and is supported on iron catalyst carrier, the compound ammonia synthesis catalysis of iron ruthenium that ruthenium dispersion degree is high, stability is good is made
Agent.
2. a kind of compound ammonia synthesis catalyst of iron ruthenium as described in claim 1, it is characterised in that addition in the step 1)
The molar ratio of co-catalyst, the co-catalyst and metal Ru is 0.2~5:1, and the co-catalyst is alkali metal, alkaline earth
One or more of metal and transition metal, the precursor compound of the co-catalyst are oxide, the hydrogen of each metal
Oxide, nitrate or carbonate, the alkali metal are sodium, potassium, rubidium and caesium；Alkaline-earth metal is calcium, magnesium and barium；Transition metal
For vanadium, titanium and zirconium.
3. a kind of compound ammonia synthesis catalyst of iron ruthenium as described in claim 1, it is characterised in that the mechanical mixing packet
Include ball milling, grinding or stirring；The vapour deposition process includes chemical vapor deposition, physical vapour deposition (PVD) or plasma chemical vapor
Deposition；The liquid-phase impregnation process includes equi-volume impregnating, excessive infusion process, multiple maceration, dipper precipitation method.
4. a kind of compound ammonia synthesis catalyst of iron ruthenium as described in claim 1, it is characterised in that described in the step 2)
Heat treatment be specially active component ruthenium precursor compound carry out thermally decomposing under vacuum, air, nitrogen or hydrogen atmosphere it is anti-
Answer, so that it is decomposed into zero-valent metal ruthenium, and be supported on carrier, reaction condition be 100~500 DEG C of temperature, pressure 0.01~
5MPa, reaction time 0.5~24 hour.
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| CN106799232B (en) * | 2016-12-15 | 2019-08-06 | 浙江工业大学 | A kind of iron based ammonia synthesis catalyst and its preparation method and application of the Nanoscale Iron modification of solid state chemical reaction preparation |
| CN108435179B (en) * | 2018-05-04 | 2020-11-20 | 山东师范大学 | Preparation method of double-activity monatomic ammonia synthesis catalyst |
| CN110280268B (en) * | 2019-07-03 | 2023-04-07 | 北京氦舶科技有限责任公司 | Synthetic ammonia catalyst and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU988327A1 (en) * | 1981-03-31 | 1983-01-15 | Институт Общей И Неорганический Химии Ан Бсср | Catalyst for ammonia synthesis |
| CN102744060A (en) * | 2012-07-23 | 2012-10-24 | 福州大学 | BaTiO3-supported ruthenium ammonia synthesis catalyst, and preparation method thereof |
| CN103626635A (en) * | 2013-11-28 | 2014-03-12 | 中国科学院新疆理化技术研究所 | Adamantine dimethyl carbinol synthesizing method |
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2016
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU988327A1 (en) * | 1981-03-31 | 1983-01-15 | Институт Общей И Неорганический Химии Ан Бсср | Catalyst for ammonia synthesis |
| CN102744060A (en) * | 2012-07-23 | 2012-10-24 | 福州大学 | BaTiO3-supported ruthenium ammonia synthesis catalyst, and preparation method thereof |
| CN103626635A (en) * | 2013-11-28 | 2014-03-12 | 中国科学院新疆理化技术研究所 | Adamantine dimethyl carbinol synthesizing method |
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