CN106927514B - A method of preparing nitrosyl nitric acid ruthenium - Google Patents
A method of preparing nitrosyl nitric acid ruthenium Download PDFInfo
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- CN106927514B CN106927514B CN201710165689.7A CN201710165689A CN106927514B CN 106927514 B CN106927514 B CN 106927514B CN 201710165689 A CN201710165689 A CN 201710165689A CN 106927514 B CN106927514 B CN 106927514B
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- nitric acid
- ruthenium
- acid ruthenium
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- nitrosyl nitric
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G55/00—Compounds of ruthenium, rhodium, palladium, osmium, iridium, or platinum
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention discloses a kind of methods preparing nitrosyl nitric acid ruthenium.By metal Ru powder, vanadic anhydride (V2O5) be placed in porcelain crucible, it is then placed in micro-wave oven.First 1000W power microwaves is used to calcine certain time, then it uses 1400W ~ 1600W to calcine certain time again, is passed through air and metal Ru powder is aoxidized, generate ruthenium tetroxide gas, it collects gas and is passed into salpeter solution, then add sodium nitrite heating and condensing reflux；By the obtained solution containing nitrosyl nitric acid ruthenium, appropriate anhydrous ether is added and is extracted, then evaporates ether and obtain nitrosyl nitric acid ruthenium solid；This method raw material is easy to get, and product yield is high, easy to operate, and convenient for processing, and the solid nitrosyl nitric acid ruthenium obtained is halogen-free, and product purity is high, can be directly used for the preparation of catalyst.
Description
Technical field
It is specifically a kind of that Asia is directly prepared with metal Ru powder the present invention relates to a kind of synthetic method of noble ruthenium catalyst
The method of nitryl nitric acid ruthenium.
Background technology
Load ruthenium catalyst has good catalytic activity, in petrochemical industry, organic synthesis, environmental project, pharmacy work
The fields such as journey have a wide range of applications.Carrier, auxiliary agent and ruthenium activity presoma are to influence load ruthenium catalyst catalytic performance
Principal element.The electronic structure of ruthenium is 4d75s1, there is in all elements in the periodic table of elements most oxidation state, it is each
Kind electronic structure has a variety of geometries again, and the ruthenium complex to synthesize various provides good basis.Supported ruthenium is catalyzed
Active component ruthenium is introduced by ruthenium precursor compound in agent.Up to the present, before being used to prepare load ruthenium catalyst
Driving body mainly has hydrate ruthenium trichloride (RuCl3·nH2O), ten dicarbapentaborane, three ruthenium (Ru3(CO)12), nitrosyl nitric acid ruthenium (Ru (NO)
(NO3)3), potassium ruthenate (K2RuO4) etc..In the various compounds of ruthenium, RuCl3·nH2O is most common ruthenium compound, property
Matter is stablized, cheap, and water-soluble and part organic solvent is widely used in preparing load ruthenium catalyst.But due to this
Contain a large amount of chlorion in the active presoma of kind, remaining chlorion can not be complete on catalyst in catalyst preparation process
It removes, there is certain inhibiting effect to catalytic performance；Meanwhile research finds the ruthenium precursor compound such as Ru being halogen-free
(NO)(NO3)3And Ru3(CO)12It is to prepare the ideal presoma of load ruthenium catalyst, but the higher price of this kind of compound,
Hinder application in the industry.
And the salpeter solution that the nitrosyl nitric acid ruthenium overwhelming majority of commercial type is nitrosyl nitric acid ruthenium, it is nitrosyl
It is unstable to introduce the nitrosyl nitric acid ruthenium for not exclusively causing to prepare, only can just be stabilized in acid condition, is condensed into solid
The nitrosyl nitric acid ruthenium of part can resolve into metal Ru again after body.And this solution acidity is higher, is unfavorable for supported ruthenium and urges
The preparation of agent, while also influencing whether the catalytic activity of catalyst.So replacing nitrosyl with solid nitrosyl nitric acid ruthenium
Nitric acid ruthenium solution is used to prepare the active presoma of load ruthenium catalyst, increasingly attracts attention.The reason is that can be according to need
The concentration wanted prepares the dipping solution of the ruthenium of nitric acid containing nitrosyl, the pH values needed for catalyst can also be prepared with nitric acid adjusting, more
Be conducive to the preparation of load ruthenium catalyst.Therefore, in order to reduce cost, the mass production technique of solid nitrosyl nitric acid ruthenium
Research has important practical significance.
Microwave is the technology to grow up early 1920s, is different from general conventional heating mode, is that material exists
" body heating " or " interior heating " as caused by dielectric loss in electromagnetic field.In terms of being initially applied to communication, since it has very
Good penetrability and selectivity, heating speed is fast, and substance mode of heating heats for body, can solve traditional heating mode generation
" cold " center " problem, while heated substance can absorb microwave energy, the heating rate of each section is identical in substance, and temperature is not present
Gradient, so substance is heated relatively uniform in decomposable process.Meanwhile microwave calcination has operation and equipment simple, defends safely
The features such as raw, easily controllable, technological process is short, and pollution is small, energy-efficient, improves working conditions, saving floor space, microwave adds
Thermal technology has been widely used for the industries such as food, light textile, medicine, agricultural.
Invention content
It is an object of the present invention to provide a kind of synthetic method directly preparing nitrosyl nitric acid ruthenium with metal Ru powder, the synthesis sides
Method has relatively big difference with existing method；Since existing method is usually that ruthenium is obtained RuCl by series of steps such as alkali fusions3·
xH2O or RuO4The effects that waiting intermediates, being then nitric acid obtains Ru (NO) (NO3)3Salpeter solution so that synthetic reaction compared with
Complexity, post-processing is cumbersome, not only needs very high temperature, it is also necessary to which longer time needs purity oxygen or ozone conduct
Oxidant, operating environment is than relatively hazardous.Meanwhile chloride can be also introduced, so as to cause impurity chlorine is contained in product, easily cause
Catalyst poisoning；And the present invention uses new method using metal Ru powder for starting material, and Asia is directly prepared using microwave calcination method
Nitryl nitric acid ruthenium not only avoids required prolonged high temperature, flammable gas when reaction, such as purity oxygen, brings
Danger, and synthesis step is simplified, reduce raw material dosage, hence it is evident that shorten the reaction time, improve reaction efficiency.
This method is raw material using metal Ru powder, prepares nitrosyl nitric acid ruthenium；Simplify synthesis step and post-processing, hence it is evident that
The reaction time is shortened, reaction efficiency is improved.
The technical solution adopted by the present invention is：Metal Ru, vanadic anhydride are placed in crucible, are put into micro-wave oven, first
Microwave calcination is carried out under 1000W power, is passed through air, and microwave calcination, air pair are then carried out under 1400W ~ 1600W power
Metal Ru is aoxidized, and ruthenium tetroxide gas is generated, and is collected gas and is passed into salpeter solution, then adds nitrous
Sour sodium or potassium nitrite heating and condensing reflux；By the obtained solution containing nitrosyl nitric acid ruthenium, anhydrous ether is added and is extracted
It takes, collects ether extraction liquid, then obtain nitrosyl nitric acid ruthenium solid after ether is evaporated；It chemically reacts route：
The metal Ru and the molar ratio of vanadic anhydride are 6~8:1, the flow velocity of air is 4000 ~ 5000 m3·h-1。
The metal Ru and the molar ratio of nitric acid are 1:4~5, the mass concentration of salpeter solution is 45% ~ 60%.
The metal Ru is 1 with the molar ratio of sodium nitrite or potassium nitrite:1.5 ~ 2, it is 6 ~ 8h to be heated to reflux the time.
The 1000W power microwaves calcine 15 ~ 20min, and 1400W ~ 1600W power microwaves calcine 60 ~ 100min.
Compared with prior art, the beneficial effects are mainly as follows：
Existing method is usually that ruthenium is obtained RuCl by series of steps such as alkali fusions3·xH2O or RuO4Equal intermediates, so
After the effects that being nitric acid obtain Ru (NO) (NO3)3Salpeter solution so that synthetic reaction is more complex, post-processing it is cumbersome, not only
Need very high temperature, it is also necessary to longer time.Meanwhile chloride can be also introduced, so as to cause impurity is contained in product
Chlorine easily causes catalyst poisoning；And the method that the present invention uses microwave calcination, it is directly prepared using metal Ru powder as starting material
Nitrosyl nitric acid ruthenium not only avoids required long-time high temperature, flammable gas when reaction, such as purity oxygen, brings
Danger, and synthesis step is simplified, reduce raw material dosage, hence it is evident that shorten the reaction time, improve reaction efficiency.
Specific implementation mode
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This.
Embodiment 1：
The vanadic anhydride of the ruthenium powder, 1.23g that weigh 5.0 g is placed in porcelain crucible, is then placed in micro-wave oven；It is passed through sky
Gas, holding air velocity are 4000m3·h-1, 15min is calcined under 1000W microwave powers, is then forged under 1400W microblogging powers
100min is burnt, metal Ru powder is aoxidized；By the RuO of generation4Gas imports 3 successively
In the absorption bottle of 45% salpeter solution, and the temperature for controlling salpeter solution is 70 DEG C, obtains Ru (NO3)3Acid solution.
By Ru (NO obtained above3)3Acid solution be all placed in neck round bottom flask, be slowly added to 5.12g's
NaNO2Powder, is stirred and heating and condensing reflux 6h under the conditions of 80 DEG C, solution colour gradually become dark red black, and cooling is molten
Liquid, and place it in separatory funnel, the anhydrous ether that 83mL is added extracts 3 times, collects ether extraction liquid, is spin-dried for diethyl ether solution
Obtain yellow-brown solid 15.0g, calculated yield 95.6%.Using KBr tablettings, the infrared of solid nitrosyl nitric acid ruthenium is determined
Spectrogram.In 1917.18 cm-1There is the characteristic absorption peak of ruthenium and nitrosyl radical (Ru-NO) coordination in place, with Ru (NO) (NO3)3
Feature structure parameter matches.
Embodiment 2：
The vanadic anhydride of the ruthenium powder, 2.4g that weigh 10.0 g is placed in porcelain crucible, is then placed in micro-wave oven, is passed through sky
Gas, holding air velocity are 4500m3·h-1, 17min is calcined under 1000W microwave powers, is then forged under 1500W microwave powers
80min is burnt, metal Ru powder is aoxidized.By the RuO of generation4It is 50% that gas imports 3 equipped with 56.0g mass concentrations successively
Salpeter solution absorption bottle in, and control salpeter solution temperature be 70 DEG C, obtain Ru (NO3)3Acid solution.
By Ru (NO obtained above3)3Acid solution be all placed in neck round bottom flask, be slowly added to the KNO of 14.7g2
Powder stirs and is heated to reflux under the conditions of 80 DEG C 7h, and solution colour gradually becomes dark red black, cooling solution, and is set
In separatory funnel, the anhydrous ether that 168mL is added extracts 4 times, collects ether extraction liquid, is spin-dried for diethyl ether solution and obtains brown color
Solid 30.20g, calculated yield 96.3%.Using KBr tablettings, the infrared spectrogram of solid nitrosyl nitric acid ruthenium is determined.
1920.75 cm-1There is the characteristic absorption peak of ruthenium and nitrosyl radical (Ru-NO) coordination in place, with Ru (NO) (NO3)3Feature structure
Parameter matches.
Embodiment 3：
The vanadic anhydride of the ruthenium powder, 3.86g that weigh 15.0 g is placed in porcelain crucible, is then placed in micro-wave oven, is passed through
Air, holding air velocity are 5000m3·h-1, 19min is calcined under 1000W microwave powers, then under 1600W microblogging powers
60min is calcined, metal Ru powder is aoxidized.By the RuO of generation4Gas imports 3 successively
In the absorption bottle of 55% salpeter solution, and the temperature for controlling salpeter solution is 70 DEG C, obtains Ru (NO3)3Acid solution.
By Ru (NO obtained above3)3Acid solution be all placed in neck round bottom flask, be slowly added to 20.5g's
NaNO2Powder stirs and is simultaneously heated to reflux 8h under the conditions of 80 DEG C, and solution colour gradually becomes dark red black, cools down solution, and will
It is placed in separatory funnel, and the anhydrous ether that 255mL is added extracts 3 times, collects ether extraction liquid, is spin-dried for diethyl ether solution and obtains palm fibre
Yellow solid 46.47g, calculated yield 98.7%.Using KBr tablettings, the infrared spectrum of solid nitrosyl nitric acid ruthenium is determined
Figure.In 1915.33 cm-1There is the characteristic absorption peak of ruthenium and nitrosyl radical (Ru-NO) coordination in place, with Ru (NO) (NO3)3Feature
Structural parameters match.
Embodiment 4：
The vanadic anhydride of the ruthenium powder, 6.0g that weigh 20.0 g is placed in porcelain crucible, is then placed in micro-wave oven, is passed through sky
Gas, holding air velocity are 5000m3·h-1, 20min is calcined under 1000W microwave powers, is then forged under 1600W microblogging powers
60min is burnt, metal Ru powder is aoxidized.By the RuO of generation4Gas imports 3 successively
In the absorption bottle of 55% salpeter solution, and the temperature for controlling salpeter solution is 70 DEG C, obtains Ru (NO3)3Acid solution.
By Ru (NO obtained above3)3Acid solution be all placed in neck round bottom flask, be slowly added to 29.56g's
KNO2Powder stirs and is simultaneously heated to reflux 8h under the conditions of 80 DEG C, and solution colour gradually becomes dark red black, cools down solution, and will
It is placed in separatory funnel, and the anhydrous ether that 306mL is added extracts 3 ~ 4 times, collects ether extraction liquid, is spin-dried for diethyl ether solution and obtains
Yellow-brown solid 60.3g, calculated yield 96.1%.Using KBr tablettings, the infrared spectrum of solid nitrosyl nitric acid ruthenium is determined
Figure.In 1914.86 cm-1There is the characteristic absorption peak of ruthenium and nitrosyl radical (Ru-NO) coordination in place, with Ru (NO) (NO3)3Feature
Structural parameters match.
Embodiment 5：
The vanadic anhydride of the ruthenium powder, 7.51g that weigh 25.0 g is placed in porcelain crucible, is then placed in micro-wave oven.It is passed through
Air, holding air velocity are 5000m3·h-1, 20min is calcined under 1000W microwave powers, then under 1600W microblogging powers
60min is calcined, metal Ru powder is aoxidized.By the RuO of generation4Gas imports 3 successively
In the absorption bottle of 60% salpeter solution, and the temperature for controlling salpeter solution is 70 DEG C, obtains Ru (NO3)3Acid solution.
By Ru (NO obtained above3)3Acid solution be all placed in neck round bottom flask, be slowly added to 34.16g's
NaNO2Powder stirs and is simultaneously heated to reflux 8h under the conditions of 80 DEG C, and solution colour gradually becomes dark red black, cools down solution, and will
It is placed in separatory funnel, and the anhydrous ether that 390mL is added extracts 3 ~ 4 times, collects ether extraction liquid, is spin-dried for diethyl ether solution and obtains
Yellow-brown solid 76.03g, calculated yield 96.9%.Using KBr tablettings, the infrared light of solid nitrosyl nitric acid ruthenium is determined
Spectrogram.In 1918.81 cm-1There is the characteristic absorption peak of ruthenium and nitrosyl radical (Ru-NO) coordination in place, with Ru (NO) (NO3)3It is special
Sign structural parameters match.
Claims (5)
1. a kind of method preparing nitrosyl nitric acid ruthenium, it is characterised in that：Metal Ru, vanadic anhydride are placed in crucible, first
Microwave calcination is carried out under 1000W power, is passed through air, and microwave calcination, air pair are then carried out under 1400W ~ 1600W power
Metal Ru is aoxidized, and ruthenium tetroxide gas is generated, and is collected gas and is passed into salpeter solution, then adds nitrous
Sour sodium or potassium nitrite heating and condensing reflux；By the obtained solution containing nitrosyl nitric acid ruthenium, anhydrous ether is added and is extracted
It takes, collects ether extraction liquid, then obtain nitrosyl nitric acid ruthenium solid after ether is evaporated.
2. the method according to claim 1 for preparing nitrosyl nitric acid ruthenium, it is characterised in that：Metal Ru and vanadic anhydride
Molar ratio be 6~8:1, the flow velocity of air is 4000 ~ 5000m3·h-1。
3. the method according to claim 1 for preparing nitrosyl nitric acid ruthenium, it is characterised in that：Mole of metal Ru and nitric acid
Than being 1:4~5, the mass concentration of salpeter solution is 45% ~ 60%.
4. the method according to claim 1 for preparing nitrosyl nitric acid ruthenium, it is characterised in that：Metal Ru and sodium nitrite or
The molar ratio of potassium nitrite is 1:1.5 ~ 2, it is 6 ~ 8h to be heated to reflux the time.
5. the method according to claim 1 for preparing nitrosyl nitric acid ruthenium, it is characterised in that：1000W power microwaves are calcined
15 ~ 20min, 1400W ~ 1600W power microwave calcine 60 ~ 100min.
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| CN102616868A (en) * | 2012-03-05 | 2012-08-01 | 阳光凯迪新能源集团有限公司 | Method for preparing solid nitrosyl ruthenium nitrate by using dead catalyst containing ruthenium |
| CN104556250A (en) * | 2014-12-19 | 2015-04-29 | 昆明珀玺金属材料有限公司 | New method for preparing ruthenium nitrosyl nitrate solution or pure crystal |
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| US7704483B2 (en) * | 2005-04-29 | 2010-04-27 | Cabot Corporation | High surface area tetragonal zirconia and processes for synthesizing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102616868A (en) * | 2012-03-05 | 2012-08-01 | 阳光凯迪新能源集团有限公司 | Method for preparing solid nitrosyl ruthenium nitrate by using dead catalyst containing ruthenium |
| CN104556250A (en) * | 2014-12-19 | 2015-04-29 | 昆明珀玺金属材料有限公司 | New method for preparing ruthenium nitrosyl nitrate solution or pure crystal |
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