CN108273542A - A kind of composite nanostructure copper catalyst, preparation method and its application - Google Patents
A kind of composite nanostructure copper catalyst, preparation method and its application Download PDFInfo
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- CN108273542A CN108273542A CN201810065581.5A CN201810065581A CN108273542A CN 108273542 A CN108273542 A CN 108273542A CN 201810065581 A CN201810065581 A CN 201810065581A CN 108273542 A CN108273542 A CN 108273542A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0333—Iron group metals or copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
- C07D307/44—Furfuryl alcohol
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
Abstract
The present invention provides a kind of composite nanostructure copper catalyst, and the catalyst is Cu/@TiO215 catalyst of/SBA, there are three features for such catalyst tool：TiO2It is coated on carrier S BA 15 with film layer (single-layer or multi-layer) and TiO is prepared215 complex carriers of/SBA；Nanometer Copper mainly exists in the form of copper simple substance；Nanometer Copper and TiO2Film layer can play the role of concerted catalysis.Invention additionally discloses a kind of preparation methods of above-mentioned composite nanostructure copper catalyst, including TiO2The preparation of 15 complex carriers of/SBA and Cu/@TiO2The preparation of 15 catalyst of/SBA, using the method, it is ensured that TiO2It is coated on carrier S BA 15 with film layer, and ensures that Nanometer Copper mainly exists in the form of copper simple substance.Invention additionally discloses a kind of applications of above-mentioned composite nanostructure copper catalyst, are mainly used for hydrogenation reaction, and during especially furfural selection Hydrogenation reacts for furfuryl alcohol, reaction condition is mild, and furfuryl alcohol conversion ratio and selectivity are high, highly practical.
Description
Technical field
The present invention relates to catalysis technical fields, particularly, are related to a kind of composite nanostructure copper catalyst, preparation method
And its application.
Background technology
Furfuryl alcohol is a kind of important Organic Chemicals, furan type resin, furfuryl alcohol-ureaformaldehyde tree for producing better performances
Fat and phenolic resin etc.；The fine chemical products such as medicine, pesticide, coating can also be produced；Furfuryl alcohol is the good of varnish, pigment etc. again
Good solvent and rocket fuel.Meanwhile furfuryl alcohol is widely used in the industries such as synthetic fibers, rubber again.Furfuryl alcohol is mainly derived from furfural
Deep processing, furfuryl alcohol is made by the selective hydrogenation of furfural, there is important economic value and practical significance.
Currently, furfuraldehyde hydrogenation catalyst mostly uses greatly single oxide carrier or porous mass class carrier, for example,
CN105148923A discloses a kind of molecular-layer deposition method and prepares metallic copper-oxide (Cu-MOx) hydrogenation catalyst preparation
Method.Including copper presoma uniform load is obtained copper in carrier surface by infusion process, the precipitation method and urea homogeneous precipitation method
Presoma, and copper-oxidate nano composite catalyst is obtained by MLD hybridized film coated copper presomas and post-processing.Due to this
A little methods are complicated for operation, and operating condition is harsh, so being not easy commercial introduction.CN103007941A discloses a kind of containing oxidation
Copper-silica (CuO-SiO2) composite oxides hydrogenation catalyst preparation method.Include being diluted with double weight
Silicon oxide colloid B is added in the colloid B formed through mantoquita and sodium hydroxide solution, after aging, being filtered, washed, drying
The composite oxides of copper oxide-silica are obtained, at a temperature of 160-450 DEG C, catalysis is made with hydrogen/nitrogen reduction activation
Agent.Copper content height, but also bad dispersibility are not only aoxidized in the made catalyst of this method.CN106749120A discloses one kind with carbon
Sour calcium and silica are mixed carrier, are 205-209 DEG C in reaction temperature, reaction pressure is using copper oxide as active component
6.3-6.6Mpa, the condition that the reaction time is 1-5h carries out furfural selective hydrogenation, although also having obtained higher conversion
Rate and selectivity, but still remain more harsh reaction condition.
Therefore, it develops a kind of mild reaction condition and conversion ratio and selective high catalyst is of great significance.
Invention content
The present invention provides the catalyst that a kind of reaction condition is mild and conversion ratio is high with selectivity, specific technical solution
It is：
A kind of composite nanostructure copper catalyst, the catalyst are Cu/@- TiO2/ SBA-15 catalyst.
It is preferred in above technical scheme, TiO is prepared by sol-gel method2And SBA-15 is modified, obtain TiO2With
The complex carrier that SBA-15 is combined；Active ingredient copper is loaded on the complex carrier using impregnation-reduction method and is formed
Cu/@-TiO2/ SBA-15 catalyst；
Cu/@- the TiO2In/SBA-15 catalyst：The mass content of copper is 8-15%, TiO in complex carrier2Quality
Content is 8-20%.
It is preferred in above technical scheme, TiO in the complex carrier2Mass content be 10-15%.
Using the composite nanostructure copper catalyst of the present invention TiO is controlled using spontaneous Monolayer Dispersion principle2Carrying capacity,
TiO2With film layer (TiO2Single-layer or multi-layer) it is acted as coated on the SBA-15 carriers with high-specific surface area and regular pore structure one
For complex carrier, and nano particle copper is anchored on coated on the TiO on SBA-15 carriers again2Film layer (TiO2Single-layer or multi-layer)
On, Nanometer Copper and TiO2The concerted catalysis of film layer acts on, and can play best catalysis in the case where reaction condition is mild and make
With greatly improving conversion ratio and selectivity.
The present invention also provides a kind of preparation methods of above-mentioned composite nanostructure copper catalyst, specifically include following step
Suddenly：
Complex carrier is prepared, specifically：The solution A containing absolute ethyl alcohol and butyl titanate is prepared, is prepared containing water, ice vinegar
The B solution of acid and absolute ethyl alcohol；Under lasting stirring action, B solution is added dropwise in solution A, is used in combination concentrated nitric acid molten
Liquid adjusts pH value, and SBA-15 molecular sieves are added after 30-60min, are uniformly mixing to obtain colloidal sol；It will be settled into after colloidal sol sonic oscillation
Gel, gel is post-treated to obtain TiO2With atom film layer coated in the complex carrier on carrier S BA-15 molecular sieves；
Composite nanostructure copper catalyst is prepared, specifically：Under the action of lasting stirring, by complex carrier and copper nitrate
Solution and polyvinylpyrrolidone, which are uniformly mixed, obtains mixed solution, and mixed solution adjusts pH value with ammonium hydroxide, with the speed that 1 drop is per second
Degree addition hydrazine hydrate, is fully obtained by the reaction reaction product, obtains composite nanostructure copper catalyst by reaction product is post-treated.
It is preferred in above technical scheme, it prepares in complex carrier：The molar concentration of concentrated nitric acid is 0.02-0.08mol/L；
PH value is adjusted to 3-4；Butyl titanate, water, glacial acetic acid and absolute ethyl alcohol volume ratio be 1：2：1.5：(15-20), solution A and B
The volume ratio of absolute ethyl alcohol in solution is 1：1, TiO2Mass ratio with SBA-15 is (0.11-0.18)：1；Whipping temp is
40 DEG C -50 DEG C, stir speed (S.S.) 120-600r/min, mixing time 2-3h；The sonic oscillation time is 20-40min；When standing
Between be 6-12h；Post-processing includes drying and calcination, and drying temperature is 80 DEG C -90 DEG C, drying time 12-15h, calcination temperature
It is 500 DEG C -600 DEG C, calcination time 2.5-5h.
It is preferred in above technical scheme, it prepares in composite nanostructure copper catalyst：The molar concentration of the ammonium hydroxide is
3-5mol/L adjusts pH value to 8-9；The molar concentration of copper nitrate is 0.02-0.08mol/L, copper nitrate, polyvinylpyrrolidone
Molar ratio with hydrazine hydrate is 1：5：The mass ratio of (8-10), copper nitrate and complex carrier is (0.329-0.421)：1；Stirring temperature
Degree is 40 DEG C -50 DEG C, stir speed (S.S.) 120-600r/min；The post-processing includes filtering, washing and drying.
Using the preparation method of the present invention, its main feature is that：1, using spontaneous Monolayer Dispersion principle, TiO is controlled2Carrying capacity makes
TiO2With film layer (TiO2Single-layer or multi-layer) coated in TiO is prepared on carrier S BA-152/ SBA-15 complex carriers；2, ensure
Nanometer Copper mainly exists in the form of copper simple substance；3, Nanometer Copper and TiO2Film layer shows concerted catalysis effect.
The present invention also provides a kind of application of above-mentioned composite nanostructure copper catalyst, the composite nanostructure copper is urged
Agent is used for hydrogenation reaction.
Preferred in above technical scheme, the composite nanostructure copper catalyst selects Hydrogenation for furfuryl alcohol for furfural
In reaction.
The composite nanostructure copper catalyst of the present invention is used for catalytic hydrogenation, selects Hydrogenation for chaff in particular for furfural
In alcohol reaction, has the following advantages：1, reaction condition is mild, and reaction temperature is low (110 DEG C -130 DEG C), H2Force down (0.9-
1.1MPa)；2, conversion ratio is up to 99.8%-100%, and selectivity is up to 98%.
Other than objects, features and advantages described above, the present invention also has other objects, features and advantages.
Below with reference to accompanying drawings, the present invention is described in further detail.
Description of the drawings
The attached drawing constituted part of this application is used to provide further understanding of the present invention, schematic reality of the invention
Example and its explanation are applied for explaining the present invention, is not constituted improper limitations of the present invention.In the accompanying drawings：
Fig. 1 is the 12%Cu/@- 15%TiO prepared in embodiment 12The XRD diagram of/SBA-15 catalyst；
Fig. 2 is the 12%Cu/@- 15%TiO prepared in embodiment 12/The HRTEM of SBA-15 catalyst schemes；
Fig. 3 is 15%TiO in embodiment 12The HRTEM of/SBA-15 complex carriers schemes；
Fig. 4 is the 10%Cu/@- 15%TiO prepared in embodiment 22The XRD diagram of/SBA-15 catalyst；
Fig. 5 is the 12%Cu/@- 20%TiO prepared in embodiment 32The XRD diagram of/SBA-15 catalyst.
Specific implementation mode
The embodiment of the present invention is described in detail below in conjunction with attached drawing, but the present invention can be limited according to claim
Fixed and covering multitude of different ways is implemented.
Embodiment 1：
A kind of composite nanostructure copper catalyst, specifically 12%Cu/@15%TiO2/ SBA-15 catalyst, wherein：Copper
Mass content be 12%, TiO in complex carrier2Mass content be 15%.
The specific preparation method of above-mentioned composite nanostructure copper catalyst is as follows：
1,15%TiO2Prepared by/SBA-15 complex carriers, specifically：It prepares anhydrous containing 0.75ml butyl titanates and 10ml
The solution A of ethyl alcohol；Prepare the B solution containing 1.5ml water, 1.125ml glacial acetic acid and 10ml absolute ethyl alcohols；Under continuous stirring will
B solution is added dropwise in solution A (stir speed (S.S.) 500r/min), and it is the dense of 0.02-0.08mol/L to add molar concentration
It is 3-4 that salpeter solution, which adjusts pH value,；The SBA-15 molecular sieves of 1g are added after 30min, continue to stir 2-3h at 45 DEG C, by gained
Colloidal sol vibrates in ultrasound to be settled into gel after 30min (the sonic oscillation time is 30min；Time of repose is 8h), products therefrom
The dry 12h at 80 DEG C, after 3h is calcined at 500 DEG C to get 15%TiO2/ SBA-15 complex carriers.
2,12%Cu/@15%TiO2/ SBA-15 catalyst preparations, specifically：Take 0.258g nitrate trihydrates copper dissolution in
In 14mL water, 0.592g PVP K-30s are dissolved in 34mL absolute ethyl alcohols, and two kinds of solution are uniformly mixed,
The 15%TiO of 0.5g is added2In/SBA-15 complex carriers, 4h is stirred under 70 DEG C (water-bath reflux)；It is with molar concentration then
It is 8-9 that the ammonium hydroxide of 3mol/L, which adjusts pH value, and the hydrazine hydrate (adding hydrazine hydrate with the speed that 1 drop is per second) of 0.7mL is added dropwise, continues to stir
2h is mixed, acquired solution is washed with absolute ethyl alcohol and deionized water, filtering, and 80 DEG C of vacuum drying 12h obtain 12%Cu/@15%TiO2/
SBA-15 catalyst.
12%Cu/@15%TiO obtained by the present embodiment2The XRD diagram of/SBA-15 catalyst refers to Fig. 1, and HRTEM figures refer to
Fig. 2,15%TiO2The HRTEM figures of/SBA-15 complex carriers refer to Fig. 3, can be seen that from Fig. 1-Fig. 3：TiO2With atomic layer film layer
(TiO2Single-layer or multi-layer) it is coated on carrier S BA-15 and (refers to Fig. 2,3)；XRD diagram shows Nanometer Copper mainly with copper simple substance shape
Formula exists.
Embodiment 2：
With embodiment 1, the difference is that catalyst is 10%Cu/@15%TiO2/ SBA-15 catalyst.10%Cu/@15%
TiO2The XRD diagram of/SBA-15 catalyst refers to Fig. 4, as can be seen from Figure 4：TiO2With atomic layer film layer (TiO2Single layer is more
Layer) coated on carrier S BA-15；XRD diagram shows that Nanometer Copper is mainly that copper simple substance form exists.
Embodiment 3：
With embodiment 1, the difference is that catalyst is 12%Cu/@20%TiO2/ SBA-15 catalyst.12%Cu/@20%
TiO2The XRD diagram of/SBA-15 catalyst refers to Fig. 5, as can be seen from Figure 5：TiO2With atomic layer film layer (TiO2Single layer is more
Layer) coated on carrier S BA-15；XRD diagram shows that Nanometer Copper is mainly that copper simple substance form exists.
Embodiment 4：
12%Cu/@- the 15%TiO that will be prepared in above-described embodiment 12/ SBA-15 catalyst adds for being catalyzed furfural selection
Hydrogen reacts.Take 1.6mmol furfurals, 0.15g catalyst 12%Cu/@- 15%TiO2/ SBA-15 and 15mL isopropanols are incorporated in height
It presses in reaction kettle, is passed through H2After displacing the air in reaction kettle, H is closed2Valve, when temperature in the kettle reaches 125 DEG C of reaction temperatures
Afterwards, it is passed through H2, H2Pressure 1.0MPa opens stirring (950-1050rpm) and starts to react, reacts 4h, after reaction, cooling, from
The heart, reaction solution carry out gas chromatographic analysis.Furfural conversion ratio is 99.8%, and furfuryl alcohol is selectively 97.77%.
In conjunction with the embodiments known to 4 and comparative example 1-2：Nanometer Copper and TiO in composite nanostructure copper catalyst of the present invention2Film
Layer can play the role of concerted catalysis, and under the premise of reaction condition is mild, furfural can ensure high conversion ratio and high simultaneously
Selectivity, it is highly practical.
Embodiment 5：
With embodiment 4,12%Cu/@- 15%TiO prepared by embodiment 1 are added2/ SBA-15 catalyst 0.15g；
1.6mmol furfurals, 15mL isopropanols, in 130 DEG C of reaction 4h of reaction temperature.Furfural conversion ratio is 99.9%, and furfuryl alcohol is selectively
96.03%.
Embodiment 6：
With embodiment 4,12%Cu/@- 15%TiO prepared by embodiment 1 are added2/ SBA-15 catalyst 0.15g,
1.6mmol furfurals, 15mL isopropanols, in 120 DEG C of reaction 4h of reaction temperature.Furfural conversion ratio is 93.74%, and furfuryl alcohol is selectively
98.59%.
Embodiment 7：
With embodiment 4,10%Cu/@- 15%TiO prepared by embodiment 2 are added2/ SBA-15 catalyst 0.15g,
1.6mmol furfurals, 15mL isopropanols, in 125 DEG C of reaction 4h of reaction temperature.Furfural conversion ratio is 94.9%, and furfuryl alcohol is selectively
97.32%.
Embodiment 8：
With embodiment 4,12%Cu/@- 20%TiO prepared by embodiment 3 are added2/ SBA-15 catalyst 0.15g,
1.6mmol furfurals, 15mL isopropanols, in 125 DEG C of reaction 4h of reaction temperature.Furfural conversion ratio is 85.22%, and furfuryl alcohol is selectively
95.95%.
Embodiment 9：
With embodiment 4,12%Cu/@- 20%TiO prepared by embodiment 3 are added2/ SBA-15 catalyst 0.15g,
1.6mmol furfurals, 15mL isopropanols, in 120 DEG C of reaction 4h of reaction temperature.Furfural conversion ratio is 76.4%, and furfuryl alcohol is selectively
98.09%.
Embodiment 10：
With embodiment 4, the mixing speed in embodiment 4 is adjusted to 700rpm, the conversion ratio of furfural is 79.17%, chaff
The selectivity of alcohol is 98.53%.
Comparative example 1：
With 0.15g catalyst 12%Cu/TiO2, reaction condition is the same as embodiment 4.Furfural conversion ratio is 16.78%, furfuryl alcohol choosing
Selecting property is 90.14%.
Comparative example 2：
With 0.15g catalyst 12%Cu/SBA-15, reaction condition is the same as embodiment 4.Furfural conversion ratio is 24.42%, furfuryl alcohol
Selectivity is 97.79%.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, any made by repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of composite nanostructure copper catalyst, it is characterised in that：The catalyst is Cu/@- TiO2/ SBA-15 catalyst.
2. composite nanostructure copper catalyst according to claim 1, it is characterised in that：It is prepared by sol-gel method
TiO2And SBA-15 is modified, obtain TiO2The complex carrier combined with SBA-15；Active ingredient copper is born using impregnation-reduction method
It is downloaded on the complex carrier and forms Cu/@- TiO2/ SBA-15 catalyst；
Cu/@- the TiO2In/SBA-15 catalyst：The mass content of copper is 8-15%, TiO in complex carrier2Mass content
For 8-20%.
3. composite nanostructure copper catalyst according to claim 2, it is characterised in that：TiO in the complex carrier2's
Mass content is 10-15%.
4. a kind of preparation method of composite nanostructure copper catalyst as described in claim 1-3 any one, feature exist
In：Specifically include following steps：
Complex carrier is prepared, specifically：Prepare the solution A containing absolute ethyl alcohol and butyl titanate, prepare containing water, glacial acetic acid with
And the B solution of absolute ethyl alcohol；Under lasting stirring action, B solution is added dropwise in solution A, concentrated nitric acid solution tune is used in combination
PH value is saved, SBA-15 molecular sieves are added after 30-60min, are uniformly mixing to obtain colloidal sol；It is solidifying by being settled into after colloidal sol sonic oscillation
Glue, gel is post-treated to obtain TiO2With film layer coated in the complex carrier on carrier S BA-15 molecular sieves；
Composite nanostructure copper catalyst is prepared, specifically：Under the action of lasting stirring, by complex carrier and copper nitrate solution
It is uniformly mixed with polyvinylpyrrolidone and obtains mixed solution, mixed solution adjusts pH value with ammonium hydroxide, adds hydrazine hydrate, fully anti-
Reaction product should be obtained, obtains composite nanostructure copper catalyst by reaction product is post-treated.
5. the preparation method of composite nanostructure copper catalyst according to claim 4, it is characterised in that：Prepare compound load
In body：The molar concentration of concentrated nitric acid is 0.02-0.08mol/L；PH value is adjusted to 3-4；Butyl titanate, water, glacial acetic acid and anhydrous
The volume ratio of ethyl alcohol is 1：2：1.5：The volume ratio of 15-20, the absolute ethyl alcohol in solution A and B solution are 1：1；TiO2With SBA-
15 mass ratio is 0.11-0.18：1；Whipping temp is 40 DEG C -50 DEG C, stir speed (S.S.) 120-600r/min, and mixing time is
2-3h；The sonic oscillation time is 20-40min；Time of repose is 6-12h；Post-processing includes drying and calcination, drying temperature 80
DEG C -90 DEG C, drying time 12-15h, calcination temperature is 500 DEG C -600 DEG C, calcination time 2.5-5h.
6. the preparation method of composite nanostructure copper catalyst according to claim 4, it is characterised in that：Prepare compound receive
In rice structure copper catalyst：The molar concentration of the ammonium hydroxide is 3-5mol/L, adjusts pH value to 8-9；The molar concentration of copper nitrate
Molar ratio for 0.02-0.08mol/L, copper nitrate, polyvinylpyrrolidone and hydrazine hydrate is 1：5：8-10, copper nitrate with it is compound
The mass ratio of carrier is 0.329-0.421：1；Whipping temp is 40 DEG C -50 DEG C, stir speed (S.S.) 120-600r/min；After described
Processing includes filtering, washing and drying.
7. a kind of application of composite nanostructure copper catalyst as described in claim 1-3 any one, it is characterised in that：Institute
Composite nanostructure copper catalyst is stated for hydrogenation reaction.
8. the application of composite nanostructure copper catalyst according to claim 7, it is characterised in that：The composite Nano knot
During structure copper catalyst is reacted for furfural selection Hydrogenation for furfuryl alcohol.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109529912A (en) * | 2018-12-28 | 2019-03-29 | 湘潭大学 | Furfural hydrogenation prepares furfuryl alcohol composite nanostructure copper catalyst and preparation method thereof |
| CN111111744A (en) * | 2020-01-03 | 2020-05-08 | 云南大学 | Catalyst for catalyzing furfuryl alcohol preparation reaction by furfural hydrogenation, preparation method and application thereof |
| CN111710873A (en) * | 2020-06-23 | 2020-09-25 | 深圳市德立新材料科技有限公司 | Method for preparing ultrathin lithium battery copper foil through photocatalytic deposition |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070282138A1 (en) * | 2006-05-31 | 2007-12-06 | Richards Ryan M | Supported polyoxometalates and process for their preparation |
| CN101954290A (en) * | 2010-08-23 | 2011-01-26 | 北京科技大学 | Novel composite carrier SCR flue gas denitration catalyst |
| CN103007978A (en) * | 2012-12-28 | 2013-04-03 | 湘潭大学 | Nanometer metal catalyst as well as preparation method and application thereof |
| CN105126897A (en) * | 2015-07-29 | 2015-12-09 | 中国科学院山西煤炭化学研究所 | SBA-15 molecular sieve-carried copper-based catalyst and its preparation method and use |
| CN105148923A (en) * | 2015-10-10 | 2015-12-16 | 中国科学院山西煤炭化学研究所 | Preparation method for Cu-based hydrogenation catalyst |
-
2018
- 2018-01-23 CN CN201810065581.5A patent/CN108273542B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070282138A1 (en) * | 2006-05-31 | 2007-12-06 | Richards Ryan M | Supported polyoxometalates and process for their preparation |
| CN101954290A (en) * | 2010-08-23 | 2011-01-26 | 北京科技大学 | Novel composite carrier SCR flue gas denitration catalyst |
| CN103007978A (en) * | 2012-12-28 | 2013-04-03 | 湘潭大学 | Nanometer metal catalyst as well as preparation method and application thereof |
| CN105126897A (en) * | 2015-07-29 | 2015-12-09 | 中国科学院山西煤炭化学研究所 | SBA-15 molecular sieve-carried copper-based catalyst and its preparation method and use |
| CN105148923A (en) * | 2015-10-10 | 2015-12-16 | 中国科学院山西煤炭化学研究所 | Preparation method for Cu-based hydrogenation catalyst |
Non-Patent Citations (2)
| Title |
|---|
| 宋华等，: ""Cu/TiO2-SiO2催化剂的制备及糠醛选择加氢活性研究"", 《化学工业与工程技术》 * |
| 郭美玲等，: ""Cu-TiO2/SBA-15光催化剂的制备及光催化性能"", 《科技论坛》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109529912A (en) * | 2018-12-28 | 2019-03-29 | 湘潭大学 | Furfural hydrogenation prepares furfuryl alcohol composite nanostructure copper catalyst and preparation method thereof |
| CN109529912B (en) * | 2018-12-28 | 2021-09-24 | 湘潭大学 | Composite nano-structure copper catalyst for preparing furfuryl alcohol by furfural hydrogenation and preparation method thereof |
| CN111111744A (en) * | 2020-01-03 | 2020-05-08 | 云南大学 | Catalyst for catalyzing furfuryl alcohol preparation reaction by furfural hydrogenation, preparation method and application thereof |
| CN111710873A (en) * | 2020-06-23 | 2020-09-25 | 深圳市德立新材料科技有限公司 | Method for preparing ultrathin lithium battery copper foil through photocatalytic deposition |
| CN111710873B (en) * | 2020-06-23 | 2021-09-17 | 深圳市德立新材料科技有限公司 | Method for preparing ultrathin lithium battery copper foil through photocatalytic deposition |
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