CN1389295A - Ru-based ammonia synthesizing catalyst carried by nano carbon fiber and its prepn. - Google Patents
Ru-based ammonia synthesizing catalyst carried by nano carbon fiber and its prepn. Download PDFInfo
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- CN1389295A CN1389295A CN02122749A CN02122749A CN1389295A CN 1389295 A CN1389295 A CN 1389295A CN 02122749 A CN02122749 A CN 02122749A CN 02122749 A CN02122749 A CN 02122749A CN 1389295 A CN1389295 A CN 1389295A
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Abstract
The high-effective aommonia synthesis catalyst is formed from carrier and active component, its carrier is carbon nano fibre, and metal ruthenium is used as active component, its loading quantity is 0.1-8 wt%, alkaline earth metal is used as adjuvant, the mole ratio of adjuvant and ruthenium is 0.01-10. Its preparation method includes: oxidative pretreatment of carbon nano fibre carrier, soaking carrier in ruthenium compound solution, under the condition of hydrogen atmosphere making reduction for 0.5-10 hr. at 200-500 deg.C, then impregnating with alkaline earth metal or oxide adjuvant. Under the condition of that reaction gas volume space velocity is 3000 hr (-1) and reaction pressure is 3.0 MPa its ammonia synthesis rate can be up to 430 ml/h. gcat at 400 deg.C.
Description
Technical field
The present invention relates to the ammonia synthesis catalyst technology, relating in particular to a kind of is carrier with the carbon nano-fiber, and metal Ru is an active component, and alkaline-earth metal or oxide are new and effective ammonia synthesis catalyst of auxiliary agent and preparation method thereof.
Background technology
Ammonia synthesis catalyst is a most important catalyst in the ammonia synthesizing industry.It directly affects the output and the economic benefit of synthetic ammonia, also affects the operating condition of production of synthetic ammonia simultaneously.Traditional ammonia synthesis catalyst is with aluminium oxide, and potassium oxide etc. are the fused iron catalyst of auxiliary agent, but its operating pressure (10～30MPa) and operating temperature (450～550 ℃) all higher.In addition, though very ripe technically with fused iron catalyst synthetic ammonia under higher temperature and pressure, this system energy consumption height, harsh to the material requirement of equipment, operating flexibility is poor.Therefore it is very necessary reducing the ammonia synthesis temperature and pressure.The ruthenium-based ammonia synthetic catalyst that it is carrier that U.S.Patent 4 600 571 has narrated the active graphite charcoal of high temperature specially treated.Wherein active graphite charcoal is had the specially treated requirement, the ruthenium loading is greater than 6%.U.S.Patent 4 142 993 has described a kind of ammonia synthesis ruthenium-based catalyst, and its preparation route is as follows: the charcoal carrier is the dipping auxiliary agent earlier, and vacuum baking floods ruthenium trichloride again, makes catalyst through vacuum baking etc. again.But its preparation technology is loaded down with trivial details, and preparation facilities is rare, more difficult industrialization.In the method for preparing catalyst of U.S.Patent 3 830 753 narrations, the auxiliary agent of ruthenium-based catalyst adopts the alkali metal vacuum evaporation deposition to catalyst.This method industrial be infeasible.It is active component with the noble ruthenium that China publication CN1270081A relates to a kind of, alkaline earth/rare earth/alkali metal oxide is or/and hydroxide is auxiliary agent, and business-like absorbent charcoal material (AC) is high activity new ammonia synthesis catalyst of carrier and preparation method thereof.Document (Applied Surface Science 180 (2001) 328) report multi-walled carbon nano-tubes is arranged as the ruthenium-based ammonia synthetic catalyst carrier, adopt the method for dipping,, cause catalytic activity low because the active component decentralization is low.
Summary of the invention
The purpose of this invention is to provide a kind of new and effective ammonia synthesis catalyst and preparation method thereof.This catalyst has the ability that nitrogen and hydrogen is converted into ammonia under lower temperature and pressure.
For achieving the above object, the invention provides a kind of ruthenium (Ru) base ammonia synthetic catalyst of carried by nano carbon fiber, carbon nano-fiber is a catalyst carrier, and containing ruthenium compound is the active component precursor, and alkaline earth metal compound is an auxiliary agent.
A kind of preparation method of ruthenium-based ammonia synthetic catalyst of carried by nano carbon fiber is earlier carrier to be carried out oxidation pre-treatment before the preparation catalyst, uses the ruthenium compound solution impregnating carrier then; Reduction is 0.5-10 hour under 200-500 ℃ of nitrogen atmosphere; Flood alkaline earth metal compound or oxides additive again, make after drying.
A kind of ruthenium-based ammonia synthetic catalyst of carried by nano carbon fiber, described catalyst are to be catalyst carrier by carbon nano-fiber, and containing ruthenium compound is the active component precursor, and alkaline earth metal compound is an auxiliary agent; Described metal Ru loading scope is 0.1-8wt%, is preferably in below the 1-5wt%.
The described ruthenium compound carbon nano-fiber that contains is charcoal nanofiber (CNFs), multi-walled carbon nano-tubes (MCNTs) or SWCN (SCNTs).
It is ruthenium trichloride, ruthenium, ruthenate or organic ruthenium that described active component contains ruthenium compound.
The mol ratio of metal Ru in the described catalyst and additive alkali earth metal compound is 0.01～10, is preferably 0.1-1.
A kind of preparation method of ruthenium-based ammonia synthetic catalyst of carried by nano carbon fiber is earlier carrier to be carried out oxidation pre-treatment before the preparation catalyst, uses the ruthenium compound solution impregnating carrier then; Reduction is 0.5-10 hour under 200-500 ℃ of nitrogen atmosphere; Flood the alkaline earth metal compound auxiliary agent again, make after drying.
Oxidation pre-treatment is to adopt red fuming nitric acid (RFNA) to carry out the oxidation pre-treatment carrier.
The maceration extract that described ruthenium compound is made can be the aqueous solution or organic solution; Organic solution is acetone, ethanol or cyclohexane.
It is carrier that catalyst of the present invention adopts new carbon-carbon nano-fiber, prepared efficient ammonia synthesis Ba/Ru catalyst, under temperate condition and very low Ba/Ru mol ratio, carried by nano carbon fiber activity of such catalysts specific activity charcoal supported catalyst active high nearly 3 times.
Catalyst of the present invention is used for ammonia synthesis, especially the ammonia synthesis in the chemical fertilizer industry or under the prerequisite that does not change existing ammonia synthesizer, the catalytic reactor of connecting also can improve the ammonia yield.
The specific embodiment
Embodiment 1
Ruthenium trichloride (or ruthenium and nitric acid ruthenium) is mixed with maceration extract in the water-soluble or organic solvent (methyl alcohol, ethanol, cyclohexane etc.), adds charcoal nanofiber (CNFs) carrier on rotary evaporator spin coating 4-5 hour.The charcoal nanofiber uses the red fuming nitric acid (RFNA) of 50-80% at 120-140 ℃ of oxidation processes 2-8h before dipping.The specific surface of charcoal nano fibre carrier is 50-150m
2/ g.Then in 100-120 ℃ of oven dry 5-10 hour, 200-500 ℃ under nitrogen atmosphere prereduction 1-5 hour.Flood auxiliary agent B a (NO again
3)
2The aqueous solution, then at 120 ℃ of dry 5-10 hours.Make the Ru-Ba/CNFs catalyst.
Change the addition of ruthenium precursor and auxiliary agent, can make serial ammonia synthesis catalyst with different Ru/Ba ratios.
Comparative example 2
Ruthenium trichloride is mixed with maceration extract in the water-soluble or organic solvent (methyl alcohol, ethanol, cyclohexane etc.), adds active carbon (AC) carrier on rotary evaporator spin coating 4-5 hour.The specific surface of absorbent charcoal carrier is 1290m
2/ g.Then in 100-120 ℃ of oven dry 5-10 hour, 200-500 ℃ under nitrogen atmosphere prereduction 1-5 hour.Flood auxiliary agent B a (NO again
3)
2The aqueous solution, then at 120 ℃ of dry 5-10 hours.Make the Ru-Ba/AC catalyst.
Change the addition of ruthenium precursor and auxiliary agent, can make serial ammonia synthesis catalyst with different Ru/Ba ratios.
Embodiment 3
Ammonia synthesis performance evaluation is carried out in the stainless steel reaction pipe.Catalyst amount 0.2 gram, reaction gas is nitrogen and hydrogen gaseous mixture, its nitrogen hydrogen ratio is 1: 3.Catalyst ammonia synthesis reaction performance to embodiment 1 preparation is estimated reaction pressure 3.0MPa, reaction velocity 3000hr
-1The catalyst of the nano-fibre supported different ruthenium loadings of charcoal is listed in table 1 at 350 ℃ and 400 ℃ of reaction results, and wherein the Ba/Ru mol ratio is 0.25.The ammonia synthesis reaction speed (ml/h.gcat.) of the different ruthenium loading of table 1 catalyst
Ruthenium loading (wt. reaction temperature catalyst
％) 350℃ 400℃Ru-Ba/CNFs-1 1.0 18 90Ru-Ba/CNFs-2 2.0 61 251Ru-Ba/CNFs-3 4.0 102 431Ru-Ba/CNFs-4 8.0 213 580
Embodiment 4
To the Ru loading is the Ru-Ba/CNFs catalyst of 4.0wt%, at reaction gas volume air speed 3000hr
-1, under the reaction pressure 3.0MPa condition, having investigated the influence of reaction temperature and Ba/Ru mol ratio to ammonia synthesis reaction speed, the result is as shown in table 2.Table 2 reaction temperature and Ba/Ru mol ratio are to the influence (ml/h.gcat.) of ammonia synthesis reaction speed
Reaction temperature Ba/Ru mol ratio (℃) 0 0.25 0.5 1.0 2.0350 0.9 102 117 108 102,375 2 259 191 189 177,400 4 430 360 334 329,425 5 555 493 467 452,450 7 555 525 484 476
As can be seen from Table 2, under reaction condition of the present invention, along with the increase of Ba/Ru mol ratio, ammonia synthesis reaction speed increases sharply earlier, reduces gradually then, and the Ba/Ru mol ratio is 0.25 to reach maximum.Along with the increase of reaction temperature, ammonia synthesis reaction speed increases earlier, is issued to maximum to uniform temperature, no longer increases.
Embodiment 5
To the Ru loading is 4.0wt%, and the Ba/Ru mol ratio is 0.25 Ru-Ba/CNFs catalyst, at reaction gas volume air speed 3000hr
-1, reaction temperature is under 400 ℃ of conditions, has investigated the influence of reaction pressure to ammonia synthesis reaction speed, the result is as shown in table 3.
Table 3 reaction pressure influences reaction pressure (MPa) 1.0 2.0 2.9 3.8 ammonia synthesis reaction speed 199 300 417 445 (ml/h.gcat.) to ammonia synthesis reaction speed
As seen from the above table, with the rising of reaction pressure, ammonia synthesis reaction speed is increase trend.But along with the increase of pressure, ammonia synthesis reaction speed increasing degree diminishes.Can predict that too high pressure has increased energy consumption, preferable reaction pressure is below 4.0MPa.Therefore, this catalyst can be used for not changing under the prerequisite of existing ammonia synthesizer, and the catalytic reactor of connecting also can improve the ammonia yield.
Embodiment 6
For the ruthenium loading is the 4wt% catalyst, has investigated the effect of different charcoal nanofibers.The charcoal nanofiber that adopts has: the charcoal nanofiber (CNFs) of vapor phase growth, multi-walled carbon nano-tubes (MCNTs) and SWCN (SCNTs).At reaction gas volume air speed 3000hr
-1, reaction pressure 3.0MPa and reaction temperature are under 400 ℃ of conditions, have investigated the influence of different charcoal nanofibers to the ammonia synthesis activity.Its result is as shown in table 4.
The different charcoal nanofibers of table 4 support Ba/Ru mol ratio ammonia synthesis reaction speed to the charcoal nanofiber Ru that influences of ammonia synthesis activity
Amount CNFs 4.0wt% 1.0 334ml/h.gcat.MCNTs 4.0wt% 1.0 154ml/h.gcat.SCNTs 4.0wt% 1.0 172ml/h.gcat.
As seen from Table 4, the ammonia synthesis activity has shown certain difference on different charcoal nanofibers.The ammonia synthesis activity is preferable on the charcoal nanofiber of vapor phase growth, and SWCN takes second place, and multi-walled carbon nano-tubes is lower.
Comparative example 7
Catalyst (the ruthenium loading is 4.0%) ammonia synthesis reaction performance to embodiment 2 and embodiment 1 preparation compares reaction pressure 3.0MPa, reaction velocity 3000hr
-1, 400 ℃ of reaction temperatures.The ammonia synthesis reaction performance that has compared the AC and the CNFs load Ru-Ba catalyst of different B a/Ru mol ratio.The results are shown in Table 5.
The ammonia synthesis reaction performance of table 5 AC and CNFs load Ru-Ba catalyst is catalyst B a/Ru mol ratio relatively
0 0.25 0.5 1.0 2.0Ru- 4 430 360 334 329Ba/CNFs-3Ru-Ba/AC 5 146 255 277 284
As seen from Table 5, absorbent charcoal carrier relatively, carbon nano-fiber has shown very high activity as Ru-Ba ammonia synthesis catalyst carrier, and the catalyst that carbon nano-fiber is made carrier has just shown best ammonia synthesis activity under very low Ba/Ru mol ratio.
Claims (13)
1. the ruthenium-based ammonia synthetic catalyst of a carried by nano carbon fiber is characterized in that, described catalyst is to be catalyst carrier by carbon nano-fiber, and containing ruthenium compound is the active component precursor, and alkaline earth metal compound is an auxiliary agent; Wherein metal Ru loading scope is 0.1-8wt%.
2. the Ruthenium base ammonia synthetic catalyst of carried by nano carbon fiber as claimed in claim 1 is characterized in that, the described ruthenium compound carbon nano-fiber that contains is the charcoal nanofiber.
3. the ruthenium-based ammonia synthetic catalyst of carried by nano carbon fiber as claimed in claim 1 is characterized in that, it is ruthenium trichloride, ruthenium, ruthenate or organic ruthenium that described active component contains ruthenium compound.
4. the ruthenium-based ammonia synthetic catalyst of carried by nano carbon fiber as claimed in claim 1 is characterized in that, metal Ru in the described catalyst and auxiliary agent mol ratio are 0.01-10.
5. the ruthenium-based ammonia synthetic catalyst of carried by nano carbon fiber as claimed in claim 1 is characterized in that, metal Ru in the described catalyst and auxiliary agent mol ratio are preferably 0.1-1.
6. the ruthenium-based ammonia synthetic catalyst of carried by nano carbon fiber as claimed in claim 1 is characterized in that, described metal Ru loading scope is preferably in below the 1-5wt%.
7. the preparation method of the ruthenium-based ammonia synthetic catalyst of a carried by nano carbon fiber is earlier the carbon nano-fiber carrier to be carried out oxidation pre-treatment before the preparation catalyst, uses the ruthenium compound solution impregnating carrier then; Reduction is 0.5-10 hour under 200-500 ℃ of nitrogen atmosphere; Flood alkaline earth metal compound again, make after drying.
8. the preparation method of the ruthenium-based ammonia synthetic catalyst of carried by nano carbon fiber as claimed in claim 7 is characterized in that, is to adopt concentrated nitric acid oxidation preliminary treatment carrier.
9. the preparation method of the ruthenium-based ammonia synthetic catalyst of carried by nano carbon fiber as claimed in claim 7 is characterized in that, the maceration extract that described ruthenium compound is made can be the aqueous solution or organic solution; Organic solution is acetone, ethanol or cyclohexane.
10. the preparation method of the ruthenium-based ammonia synthetic catalyst of carried by nano carbon fiber as claimed in claim 7 is characterized in that, described ruthenium loading scope is 0.1-8wt%.
11. the preparation method of the ruthenium-based ammonia synthetic catalyst of carried by nano carbon fiber as claimed in claim 7 is characterized in that, described ruthenium loading scope is preferably in below the 1-5wt%.
12. the preparation method of the ruthenium-based ammonia synthetic catalyst of carried by nano carbon fiber as claimed in claim 7 is characterized in that, the mol ratio of metal Ru in the described catalyst and additive alkali earth metal compound is 0.01～10.
13. the preparation method of the ruthenium-based ammonia synthetic catalyst of carried by nano carbon fiber as claimed in claim 7 is characterized in that, the mol ratio mol ratio of metal Ru in the described catalyst and additive alkali earth metal compound is preferably 0.1-1.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100421788C (en) * | 2006-03-03 | 2008-10-01 | 厦门大学 | Mixed ruthenium base amino synthetic catalyst and its preparing method |
| CN100464841C (en) * | 2006-12-29 | 2009-03-04 | 华东理工大学 | Noble metal electrocatalyst based on nano carbon fiber and its preparing method |
| CN101912792A (en) * | 2010-08-06 | 2010-12-15 | 华东理工大学 | Catalyst used in preparation of COx-free hydrogen through ammonia decomposition reaction and preparation method thereof |
| CN106881085A (en) * | 2017-03-16 | 2017-06-23 | 兰州理工大学 | The catalyst and preparation method and process for selective hydrogenation of hydroquinones hydrogenation |
| CN107413341A (en) * | 2017-06-09 | 2017-12-01 | 武汉大学 | A kind of ruthenium-based catalyst for being carried on SrNb2 O6 surface and its preparation method and application |
| CN110270375A (en) * | 2019-07-01 | 2019-09-24 | 北京化工大学 | A kind of unsaturation carbon-carbon triple bond selective hydrocatalyst and preparation method thereof |
-
2002
- 2002-06-10 CN CN02122749A patent/CN1131101C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100421788C (en) * | 2006-03-03 | 2008-10-01 | 厦门大学 | Mixed ruthenium base amino synthetic catalyst and its preparing method |
| CN100464841C (en) * | 2006-12-29 | 2009-03-04 | 华东理工大学 | Noble metal electrocatalyst based on nano carbon fiber and its preparing method |
| CN101912792A (en) * | 2010-08-06 | 2010-12-15 | 华东理工大学 | Catalyst used in preparation of COx-free hydrogen through ammonia decomposition reaction and preparation method thereof |
| CN101912792B (en) * | 2010-08-06 | 2013-03-06 | 华东理工大学 | Catalyst used in preparation of COx-free hydrogen through ammonia decomposition reaction and preparation method thereof |
| CN106881085A (en) * | 2017-03-16 | 2017-06-23 | 兰州理工大学 | The catalyst and preparation method and process for selective hydrogenation of hydroquinones hydrogenation |
| CN107413341A (en) * | 2017-06-09 | 2017-12-01 | 武汉大学 | A kind of ruthenium-based catalyst for being carried on SrNb2 O6 surface and its preparation method and application |
| CN107413341B (en) * | 2017-06-09 | 2019-08-20 | 武汉大学 | A kind of ruthenium-based catalyst and its preparation method and application being carried on SrNb2 O6 surface |
| CN110270375A (en) * | 2019-07-01 | 2019-09-24 | 北京化工大学 | A kind of unsaturation carbon-carbon triple bond selective hydrocatalyst and preparation method thereof |
| CN110270375B (en) * | 2019-07-01 | 2020-09-11 | 北京化工大学 | Unsaturated carbon-carbon triple bond selective hydrogenation catalyst and preparation method thereof |
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| CN1131101C (en) | 2003-12-17 |
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