CN104001532B - Preparation method for supported metal cluster catalyst - Google Patents
Preparation method for supported metal cluster catalyst Download PDFInfo
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- CN104001532B CN104001532B CN201410197309.4A CN201410197309A CN104001532B CN 104001532 B CN104001532 B CN 104001532B CN 201410197309 A CN201410197309 A CN 201410197309A CN 104001532 B CN104001532 B CN 104001532B
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- China
- Prior art keywords
- carbonyl iron
- preparation
- metal cluster
- catalyst
- activated carbon
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- 239000003054 catalyst Substances 0.000 title claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 18
- 239000002184 metal Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 55
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 50
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- -1 carbonyl ferrous Chemical compound 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 238000007598 dipping method Methods 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- 230000003993 interaction Effects 0.000 abstract 1
- 230000004630 mental health Effects 0.000 abstract 1
- 239000003223 protective agent Substances 0.000 abstract 1
- 238000005086 pumping Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000007789 gas Substances 0.000 description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical compound [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000006324 decarbonylation Effects 0.000 description 1
- 238000006606 decarbonylation reaction Methods 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method for a supported metal cluster catalyst, belonging to the field of catalyst preparation. The preparation method comprises the following steps: dissolving carbonyl iron with an organic solvent, subjecting an n-pentane solution with dissolved carbonyl iron and active carbon to dipping in a vacuum instrument under the protection of nitrogen for 8 to 12 h and then removing the solvent under vacuum at a low temperature; in the vacuum instrument, allowing temperature to rise to 180 to 220 DEG C, regulating air pressure to 2 to 3 Pa and removing CO; and introducing hydrogen, carrying out reduction for 6 to 7 h, pumping out hydrogen until air pressure is 1 to 2 Pa and absorbing CO at the air pressure so as to obtain the target catalyst. According to the invention, strong interaction between carbonyl iron and a supporter is utilized, so the structure of carbonyl iron is more stable, and the problem that carbonyl iron is hard to preserve at normal temperature and normal pressure is overcome; since no protective agent is added, physical and mental health of research personnel is guaranteed and economic cost for storage of the catalyst is reduced.
Description
Technical field
The present invention relates to a kind of preparation method of supported metal cluster catalyst, belongs to field of catalyst preparation.
Background technology
With the continuous renewal of synthetic method, metal cluster core thing is organic in metal and catalytic field obtains important application.
The property for having many uniquenesses is constantly found, and the application for promoting carbonyl metal compound is paid attention to.And due to cluster network
Compound can as the new material of catalyst, for opening up new catalytic reaction, and show special catalysis activity in recent years its
Catalysis activity is widely noted.But due to transition-metal-carbonyl-complexes have at normal temperatures and pressures it is unstable, than
Such as Fe2(CO)9、Fe3(CO)12It is unstable in atmosphere Deng carbonyl iron, iron oxide can be gradually oxidized to, it is poisonous with volatility
Harmful, this just brings inconvenience to research.In order to overcome its unstability so that the convenience of research, to improving Fe2
(CO)9、Fe3(CO)12Corresponding research has been done Deng carbonyl iron stability at normal temperatures and pressures.
At present, with regard to improving Fe2(CO)9、Fe3(CO)12Deng carbonyl iron stability problem at normal temperatures and pressures, yet there are no
To the report for having correlation.
The content of the invention
It is an object of the invention to provide a kind of preparation method of supported metal cluster catalyst, i.e., with activated carbon as carrier and
Vacuscope, by low temperature desolvation, after decarbonylation base at 180 ~ 220 DEG C, Jing after hydrogen reducing, when extracting hydrogen out to 1 ~ 2Pa
CO absorption, prepares the supported metal cluster catalyst that metal cluster under normal temperature and pressure is capable of stable existence, improves the steady of metal cluster
It is qualitative.
The preparation method of supported metal cluster catalyst of the present invention specifically includes following steps：
（1）Take 40 ~ 60 mesh activated carbon be washed with deionized water suspend without muddy thing to supernatant for 4 ~ 6 times, pH value does not occur
Change, the drying at 100 ~ 120 DEG C obtains pretreated activated carbon in 6 ~ 8 hours；
（2）Carbonyl iron is dissolved in organic solvent, pretreated activated carbon will be obtained under nitrogen protection and is immersed in
In transition carbonyl ferrous solution；
（3）Removed after organic solvent at 40 ~ 60 DEG C by vacuscope, then temperature is increased to into 180 ~ 220 DEG C, air pressure is adjusted
Save to 2 ~ 3Pa and remove CO；
（4）After being passed through 6 ~ 7h of hydrogen reducing, when extracting hydrogen out to 1 ~ 2Pa, the CO absorption again under this air pressure obtains supported gold
Category cluster catalyst.
Transition-metal-carbonyl-complexes of the present invention are Fe2(CO)9、Fe3(CO)12。
Step of the present invention（2）Described in the consumption of activated carbon be：Activated carbon is 10 with the mass ratio of carbonyl iron:1~
10:2。
Step of the present invention（2）Described in impregnate dip time be 8 ~ 12h.
Step of the present invention（2）Described in organic solvent be in pentane solution (analysis pure), ether (analysis is pure)
It is a kind of.
Water used by the present invention is all deionized water.
From the beginning of the present invention impregnates under nitrogen protection from the pentane solution and activated carbon that have dissolved carbonyl iron, institute below
There is process all to carry out in vacuscope.
The invention aims on the basis of carbonyl iron construction is not changed, improve the steady of metal cluster core thing carbonyl iron
It is qualitative, so that the research of correlation is convenient.
The invention has the beneficial effects as follows：
（1）At normal temperatures and pressures carbonyl iron is unable to stable existence, volatile, toxic, and the catalyst after supporting can
Under being stable in the presence of normal temperature and pressure；
（2）Carbonyl iron after supporting reduces financial cost during storage under normal temperature and pressure；
（3）The catalyticing research of transition metal carbonyl compound is brought convenience.
Specific embodiment
The present invention is described in further detail with reference to specific embodiment, but the scope of the present invention is not limited to following institute
State content.
Embodiment 1
（1）Take 40 ~ 60 mesh activated carbon be washed with deionized water suspend without muddy thing to supernatant for 4 times, pH value does not change
Become, the drying at 100 DEG C obtains pretreated activated carbon in 8 hours；
（2）By Fe2(CO)9Pretreated activated carbon in organic solvent, is immersed in Fe by dissolving under nitrogen protection2
(CO)9In solution, wherein activated carbon and the mass ratio of carbonyl iron are 10:1, dip time is 8h；
（3）Removed after organic solvent at 60 DEG C by vacuscope, then temperature is increased to into 180 DEG C, air pressure adjustment to 2Pa
Removing CO；
（4）After being passed through hydrogen reducing 6h, when extracting hydrogen out to 1Pa, the CO absorption again under this air pressure obtains supporting Fe2
(CO)9Catalyst.
What the present embodiment was prepared supports Fe2(CO)9When catalyst is used to remove the cos in yellow phosphoric tail gas, will urge
Agent is loaded in the reactor of a diameter of 3cm；Reaction condition is:25 DEG C of water saturation temperature, the speed that yellow phosphoric tail gas passes through
5000h-1, cos concentration is 460ppm；The carbonyl Importation ＆ exportation of sulfur concentration in yellow phosphoric tail gas, cos are detected with sulphur phosphorus analyzer
Conversion ratio be more than 99%, at ambient pressure the conversion ratio of cos significantly improve, supported metal cluster catalyst catalyzing hydrolysis efficiency with
Time change it is as shown in table 1, when now removing the cos in tail gas at ambient pressure, conversion ratio reaches more than 99%, reduces
The condition of reaction is required.
Exposed Fe is not under equal conditions supported2(CO)9For the time dependent curve of catalytic hydrolysis of carbonyl sulfide efficiency
Figure, because pressure is not up to required, its cos conversion rate now is relatively low.
As can be seen from Table 1：Catalyst after improvement not only can be present at normal temperatures and pressures, also improve carbonyl iron and exist
To the conversion ratio of cos under normal pressure.
The conversion ratio of cos under the normal pressure of table 1
Embodiment 2
（1）Take 40 ~ 60 mesh activated carbon be washed with deionized water suspend without muddy thing to supernatant for 5 times, pH value does not change
Become, the drying at 105 DEG C obtains pretreated activated carbon in 7.5 hours；
（2）By Fe2(CO)9Pretreated activated carbon in organic solvent, is immersed in Fe by dissolving under nitrogen protection2
(CO)9In solution, wherein activated carbon and the mass ratio of carbonyl iron are 10:2, dip time is 10h；
（3）Removed after organic solvent at 55 DEG C by vacuscope, then temperature is increased to into 200 DEG C, air pressure adjustment is arrived
2.5Pa removes CO；
（4）After being passed through hydrogen reducing 6.2h, when extracting hydrogen out to 1.2Pa, the CO absorption again under this air pressure is supported
Fe2(CO)9Catalyst.
What the present embodiment was prepared supports Fe2(CO)9When catalyst is used to remove the cos in yellow phosphoric tail gas, will urge
Agent is loaded in the reactor of a diameter of 3cm；Reaction condition is:25 DEG C of water saturation temperature, speed 5000h that tail gas passes through-1,
Cos concentration is 460ppm；The carbonyl Importation ＆ exportation of sulfur concentration in tail gas is detected with sulphur phosphorus analyzer, the conversion ratio of cos is big
In 99%, at ambient pressure the conversion ratio of cos is significantly improved.
The conversion ratio of cos under the normal pressure of table 2
Embodiment 3
（1）Take 40 ~ 60 mesh activated carbon be washed with deionized water suspend without muddy thing to supernatant for 6 times, pH value does not change
Become, the drying at 110 DEG C obtains pretreated activated carbon in 7 hours；
（2）By Fe2(CO)9Pretreated activated carbon in organic solvent, is immersed in Fe by dissolving under nitrogen protection2
(CO)9In solution, wherein activated carbon and the mass ratio of carbonyl iron are 10:1.5, dip time is 9h；
（3）Removed after organic solvent at 40 DEG C by vacuscope, then temperature is increased to into 210 DEG C, air pressure adjustment to 3Pa
Removing CO；
（4）After being passed through hydrogen reducing 6.5h, when extracting hydrogen out to 1.8Pa, the CO absorption again under this air pressure is supported
Fe2(CO)9Catalyst.
What the present embodiment was prepared supports Fe2(CO)9When catalyst is used to remove the cos in vehicle exhaust, will urge
Agent is loaded in the reactor of a diameter of 3cm；Reaction condition is:25 DEG C of water saturation temperature, speed 5000h that tail gas passes through-1,
Cos concentration is 460ppm；The carbonyl Importation ＆ exportation of sulfur concentration in tail gas is detected with sulphur phosphorus analyzer, the conversion ratio of cos is big
In 99%, at ambient pressure the conversion ratio of cos is significantly improved.
The conversion ratio of cos under the normal pressure of table 3
Embodiment 4
（1）Take 40 ~ 60 mesh activated carbon be washed with deionized water suspend without muddy thing to supernatant for 4 times, pH value does not change
Become, the drying at 120 DEG C obtains pretreated activated carbon in 6 hours；
（2）By Fe3(CO)12Pretreated activated carbon in organic solvent, is immersed in Fe by dissolving under nitrogen protection3
(CO)12In solution, wherein activated carbon and the mass ratio of carbonyl iron are 10:1.2, dip time is 12h；
（3）Removed after organic solvent at 48 DEG C by vacuscope, then temperature is increased to into 220 DEG C, air pressure adjustment is arrived
208Pa removes CO；
（4）After being passed through hydrogen reducing 7h, when extracting hydrogen out to 2Pa, the CO absorption again under this air pressure obtains supporting Fe3
(CO)12Catalyst.
What the present embodiment was prepared supports Fe3(CO)12When catalyst is used to remove the cos in vehicle exhaust, will urge
Agent is loaded in the reactor of a diameter of 3cm；Reaction condition is:25 DEG C of water saturation temperature, speed 5000h that tail gas passes through-1,
Cos concentration is 460ppm；The carbonyl Importation ＆ exportation of sulfur concentration in tail gas is detected with sulphur phosphorus analyzer, the conversion ratio of cos is big
In 99%, at ambient pressure the conversion ratio of cos is significantly improved.
The conversion ratio of cos under the normal pressure of table 4
Claims (4)
1. a kind of preparation method of supported metal cluster catalyst, it is characterised in that specifically include following steps：
（1）Take 40 ~ 60 mesh activated carbon be washed with deionized water suspend without muddy thing to supernatant for 4 ~ 6 times, pH value does not change,
The drying at 100 ~ 120 DEG C obtains pretreated activated carbon in 6 ~ 8 hours；
（2）Carbonyl iron is dissolved in organic solvent, activated carbon is immersed in carbonyl ferrous solution under nitrogen protection；
（3）Removed after organic solvent at 40 ~ 60 DEG C by vacuscope, then temperature is increased to into 180 ~ 220 DEG C, air pressure adjustment is arrived
2 ~ 3Pa removes CO；
（4）After being passed through 6 ~ 7h of hydrogen reducing, when extracting hydrogen out to 1 ~ 2Pa, the CO absorption again under this air pressure obtains supported metal cluster
Catalyst；
The carbonyl iron is Fe2(CO)9Or Fe3(CO)12。
2. the preparation method of supported metal cluster catalyst according to claim 1, it is characterised in that：Step（2）Middle activated carbon
It is 10 with the mass ratio of carbonyl iron:1~10:2.
3. the preparation method of supported metal cluster catalyst according to claim 1, it is characterised in that：Step（2）Described in soak
The dip time of stain is 8 ~ 12h.
4. the preparation method of supported metal cluster catalyst according to claim 1, it is characterised in that：Step（2）Described in have
Machine solvent is the one kind in pentane solution, ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201410197309.4A CN104001532B (en) | 2014-05-12 | 2014-05-12 | Preparation method for supported metal cluster catalyst |
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| CN201410197309.4A CN104001532B (en) | 2014-05-12 | 2014-05-12 | Preparation method for supported metal cluster catalyst |
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| CN104001532B true CN104001532B (en) | 2017-04-12 |
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| CN105797776B (en) * | 2016-03-29 | 2019-06-11 | 昆明理工大学 | A kind of preparation method of carrier-borne transition metal carbonyls catalyst |
| CN111234259A (en) * | 2020-04-24 | 2020-06-05 | 昭通学院 | Method for efficiently preparing ferrous metal organic framework material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1537674A (en) * | 2003-04-15 | 2004-10-20 | 北京化工大学 | Iron/active carbon catalyst used for preparing ethylene, propylene, butylene from synthetic gas |
| CN101099932A (en) * | 2007-05-23 | 2008-01-09 | 江苏天一超细金属粉末有限公司 | High-efficient iron-series catalyst and its preparation method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101209862A (en) * | 2007-12-25 | 2008-07-02 | 金川集团有限公司 | Method for preparing carbonyl iron |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1537674A (en) * | 2003-04-15 | 2004-10-20 | 北京化工大学 | Iron/active carbon catalyst used for preparing ethylene, propylene, butylene from synthetic gas |
| CN101099932A (en) * | 2007-05-23 | 2008-01-09 | 江苏天一超细金属粉末有限公司 | High-efficient iron-series catalyst and its preparation method |
Non-Patent Citations (1)
| Title |
|---|
| Hydrogenation of CO on carbon-supported iron catalysts prepared from iron penta-carbonyl;F. RODRíGUEZ-REINOSO et al.;《Applied Catalysis》;19861231;第21卷;第252页实验部分 * |
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