CN110026196A - A kind of supported, heterogeneous catalyst and its preparation method and application - Google Patents
A kind of supported, heterogeneous catalyst and its preparation method and application Download PDFInfo
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- CN110026196A CN110026196A CN201910371246.2A CN201910371246A CN110026196A CN 110026196 A CN110026196 A CN 110026196A CN 201910371246 A CN201910371246 A CN 201910371246A CN 110026196 A CN110026196 A CN 110026196A
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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
- 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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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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
- 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
- B01J23/8913—Cobalt and noble metals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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Abstract
The invention belongs to catalysis material technical fields, and in particular to a kind of supported, heterogeneous catalyst and its preparation method and application.Supported, heterogeneous catalyst provided by the invention includes alumina nano tube and the cobalt/cobalt oxide for being deposited on the aluminium oxide nano tube outer surface, the present invention is using alumina nano tube as carrier, in cobalt/cobalt oxide of the outside deposition as active component of carrier, active component can be made evenly dispersed, and then obtain the higher catalyst of activity.Embodiment the result shows that, catalyst provided by the invention for epoxidation of styrene react when, selectively reach 74.3~94.8%, while conversion ratio reaches 77.2~91.4%.
Description
Technical field
The invention belongs to catalysis material technical fields, and in particular to a kind of supported, heterogeneous catalyst and preparation method thereof and
Using.
Background technique
Styryl oxide is a kind of important organic intermediate, is mainly used for synthetic perfume, medicine, prepares high grade paint
Deng, it is also possible to make epoxy resin diluent, UV- absorbent, fumet and stabilizer etc..Traditionally, Styryl oxide is benzene second
With stoichiometric ratio by homogeneous catalyst, such as transistion metal compound catalysis reaction is generated for alkene and peracid (peroxy acid)；It is this kind of to urge
Agent although catalytic activity with higher, but the peroxy acid that reaction is used is at high cost, and stability is poor, and homogeneously urges
The recycling of agent is at high cost.Therefore, a kind of novel catalyst is developed, is become with reducing the production cost of Styryl oxide
The main task currently faced.
Summary of the invention
The purpose of the present invention is to provide a kind of supported, heterogeneous catalyst, supported, heterogeneous catalyst provided by the invention
When for epoxidation of styrene reaction, selectivity with higher and conversion ratio.
To achieve the goals above, the invention provides the following technical scheme:
The present invention provides a kind of supported, heterogeneous catalyst, including alumina nano tube and it is deposited on the aluminium oxide and receives
The cobalt/cobalt oxide of mitron outer surface.
Preferably, the partial size of the cobalt/cobalt oxide be 1~2nm, deposition with a thickness of 4~5nm.
Preferably, the wall thickness of the alumina nano tube is 5~41nm.
Preferably, the supported, heterogeneous catalyst further includes Supplementary active compounds, the Supplementary active compounds deposition
In the inner surface of the alumina nano tube.
Preferably, the Supplementary active compounds include platinum.
Preferably, the mass content of the Supplementary active compounds is 3.5~5%；The partial size of the Supplementary active compounds is 2
~6nm.
The present invention provides a kind of preparation methods of supported, heterogeneous catalyst, comprising the following steps:
(1) on substrate by carbon nanofiber dispersion liquid coating, template is obtained after removing dispersing agent；
(2) deposition of aluminium oxide in the template that the step (1) obtains removes template through calcining, obtains aluminium oxide nano
Pipe；
(3) the outside deposition cobalt/cobalt oxide of the alumina nano tube obtained in the step (2), obtains supported, heterogeneous
Catalyst.
Preferably, further include depositing Supplementary active compounds in the template that the step (1) obtains, be then deposited with again
The operation of step (2) and step (3) is carried out in the template of Supplementary active compounds.
Preferably, described to be deposited as atomic layer deposition.
The present invention provides described in above-mentioned technical proposal supported, heterogeneous catalyst or above-mentioned technical proposal described in system
Application of the supported, heterogeneous catalyst that Preparation Method is prepared in styrene catalyzed epoxidation reaction.
Supported, heterogeneous catalyst provided by the invention includes alumina nano tube and is deposited on the alumina nano tube
The cobalt/cobalt oxide of outer surface, the present invention using alumina nano tube as carrier, carrier outside deposition as active component
Cobalt/cobalt oxide can make active component evenly dispersed, and then obtain the higher catalyst of activity.Embodiment the result shows that, the present invention
It is raw when using styrene, acetonitrile and tert-butyl hydroperoxide as reactant when the catalyst of offer is reacted for epoxidation of styrene
Reach 74.3~94.8% at the selectivity of Styryl oxide, while conversion ratio reaches 77.2~91.4%；Reaction without using
Peroxy acid reduces reaction cost.
Detailed description of the invention
Fig. 1 is that the TEM of 1 gained supported, heterogeneous catalyst of the embodiment of the present invention schemes；
Fig. 2 is that the TEM of 3 gained supported, heterogeneous catalyst of the embodiment of the present invention schemes；
Fig. 3 is that the TEM of 6 gained supported, heterogeneous catalyst of the embodiment of the present invention schemes.
Specific embodiment
The present invention provides a kind of supported, heterogeneous catalyst, including alumina nano tube and it is deposited on the aluminium oxide and receives
The cobalt/cobalt oxide of mitron outer surface.
Supported, heterogeneous catalyst provided by the invention includes alumina nano tube, and the wall thickness of the alumina nano tube is excellent
It is selected as 5~41nm, more preferably 5~35nm, is further preferably 5~9nm.Internal diameter and length of the present invention to the alumina nano tube
No particular/special requirement is spent, is determined by template used dose of diameter and length；The diameter and length of the template are in preparation method
Introduction.The present invention can make active component be dispersed in the outer surface of nanotube using alumina nano tube as carrier, expand
The contact surface of active component and reaction substrate promotes the progress of catalysis reaction.
Supported, heterogeneous catalyst provided by the invention includes the cobalt oxidation for being deposited on the aluminium oxide nano tube outer surface
Object.In the present invention, cobalt/cobalt oxide is with CoOxIt indicates, wherein x is 4/3~2, and expression cobalt is mixed valence.In the present invention, institute
Stating cobalt/cobalt oxide is graininess, and the partial size of the cobalt/cobalt oxide is preferably 1~2nm；The thickness of the cobalt/cobalt oxide deposition is preferred
For 2~5nm, more preferably 3~4nm.In the present invention, the quality of the cobalt/cobalt oxide is preferably supported, heterogeneous catalyst matter
3~4.5%, more preferably the 3.5~4% of amount.
In the present invention, it is also preferable to include Supplementary active compounds, the auxiliary activity groups for the supported, heterogeneous catalyst
Divide deposition preferably in the inner surface of the alumina nano tube.In the present invention, the Supplementary active compounds preferably include platinum；Institute
The deposition for stating Supplementary active compounds preferably accounts for the 3.5~5% of supported, heterogeneous catalyst quality, more preferably 4%；It is described auxiliary
Helping active component is preferably graininess, and partial size is preferably 2~6nm, more preferably 2~3nm.
The present invention provides a kind of preparation methods of supported, heterogeneous catalyst, comprising the following steps:
(1) on substrate by carbon nanofiber dispersion liquid coating, template is obtained after removing dispersing agent；
(2) deposition of aluminium oxide in the template that the step (1) obtains removes template through calcining, obtains aluminium oxide nano
Pipe；
(3) cobalt/cobalt oxide is deposited on the alumina nano tube that the step (2) obtains, obtains supported, heterogeneous catalysis
Agent.
The present invention coats carbon nanofiber dispersion liquid on substrate, obtains template after removing dispersing agent.In the present invention,
The carbon nanofiber dispersion liquid preferably includes carbon nano-fiber and ethyl alcohol, and the diameter of the carbon nano-fiber is preferably 100~
120nm, more preferably 100nm；Length is preferably nanometer or micron level, specifically using well known to those skilled in the art commercially available
The stock size of product.In the present invention, the concentration of the carbon nanofiber dispersion liquid is preferably 0.01~0.1mg/mL, more excellent
It is selected as 0.02~0.08mg/mL, is further preferably 0.03~0.06mg/mL.System of the present invention to the carbon nanofiber dispersion liquid
Standby mode does not have particular/special requirement, using mode well known to those skilled in the art.
The present invention does not have particular/special requirement to the substrate, using high temperature resistant, the material of surfacing, specifically can be
Quartz plate.The mode that the present invention coats the carbon nanofiber dispersion liquid does not have particular/special requirement, by the way of conventional.
After coating, the present invention carries out dispersing agent to the carbon nanofiber dispersion liquid coat and handles, and minimizing technology, which can be used, to be evaporated
Mode.After removing solvent, the present invention obtains template, and the template has uniform spiral structure.The present invention is preferably with carbon nanometer
Fiber is template, provides basis to prepare alumina nano tube.
After obtaining template, present invention deposition of aluminium oxide in the template removes template through calcining, obtains aluminium oxide nano
Pipe.In the present invention, the aluminium oxide is preferably using trimethyl aluminium and water as presoma, reacted generation.The present invention is preferably with three
Aluminium methyl and water are presoma, by atomic layer deposition method, the deposition of aluminium oxide in template.In the present invention, the atomic layer
Deposition (ALD) preferably carries out in atomic layer deposition vacuum reaction cavity；When deposition, the temperature of cavity is preferably 120~130
DEG C, more preferably 122~128 DEG C, be further preferably 125 DEG C；The pressure of cavity is preferably 40~60Pa, more preferably 45~
55Pa is further preferably 50Pa；The speed of the deposition is preferably 1~2nm/cycle, more preferably 1.4nm/cycle；It is described heavy
The long-pending time indicates that the number of deposition cycles is preferably 30~300 preferably with number of deposition cycles, be specifically as follows 30,35,
40,45,50,55,60,65,70,80,100,120,150,180,200 or 300.
After deposition of aluminium oxide, the present invention calcines resulting material after deposition, to remove carbon nano-fiber (template), obtains
To alumina nano tube.In the present invention, the temperature of the calcining is preferably 450~650 DEG C, and more preferably 475~625 DEG C,
It is further preferably 500~600 DEG C；The time of the calcining is preferably 1~3h, more preferably 1~2.5h, is further preferably 1.5~2h,
It is specifically as follows 1h, 1.5h, 2h, 2.5h or 3h；The calcining preferably carries out in air atmosphere.
After calcining, the present invention obtains supported, heterogeneous and urges in the outside deposition cobalt/cobalt oxide of the alumina nano tube
Agent.In the present invention, it is presoma that the cobalt/cobalt oxide, which is by cobaltocene and ozone, is obtained by deposition；The cobaltocene
Dosage with ozone is using well known to those skilled in the art.In the present invention, the deposition is preferably atomic layer deposition,
The atomic layer deposition preferably carries out in atomic layer deposition vacuum reaction chamber；When deposition, the temperature of cavity is preferably 230~
280 DEG C, more preferably 240~270 DEG C are further preferably 250 DEG C；The pressure of cavity is preferably 40~60Pa, more preferably 45~
55Pa is further preferably 50Pa；The time of the deposition indicates that the number of deposition cycles is preferably preferably with number of deposition cycles
20~50, more preferably 30~40.
The composition for the supported, heterogeneous catalyst that the present invention is prepared by above-mentioned preparation method includes aluminium oxide nano
The cobalt/cobalt oxide of the aluminium oxide nano tube outer surface is managed and is deposited on, with CoOx/Al2O3It indicates, can be considered that supported cobalt is catalyzed
Agent.
In the present invention, when the supported, heterogeneous catalyst further includes Supplementary active compounds, above-mentioned technical proposal institute
Stating further includes that Supplementary active compounds are deposited in obtained template in preparation method, is then being deposited with Supplementary active compounds again
The operation of above-mentioned steps (2) and step (3) is successively carried out in template.In the present invention, it is excellent when the Supplementary active compounds are platinum
Choosing uses (trimethyl) methyl cyclopentadiene to close platinum and ozone as presoma, is obtained by deposition.In the present invention, described (three
Methyl) methyl cyclopentadiene closes the amount ratio of platinum and ozone using well known to those skilled in the art；The deposition is preferred
For atomic layer deposition, more preferably carried out in atomic layer deposition vacuum reaction chamber.When deposition, the temperature of cavity is preferably 230~
280 DEG C, more preferably 240~270 DEG C；Chamber pressure is preferably 40~60Pa, more preferably 45~55Pa；Sedimentation time is with heavy
Product cycle-index indicates that number of deposition cycles is preferably 15~20.In the present invention, it deposits carrier gas used and preferably includes High Purity Nitrogen
Gas；The volume ratio of the carrier gas and vacuum reaction cavity is preferably 1/10~1/5min-1。
In the present invention, when including the deposition step of Supplementary active compounds, the composition of gained supported, heterogeneous catalyst
Alumina nano tube is preferably included, the cobalt/cobalt oxide of aluminium oxide nano tube outer surface is deposited on and is deposited in alumina nano tube
The Supplementary active compounds on surface；If Supplementary active compounds are indicated with R, supported, heterogeneous catalyst can use CoOx/Al2O3/R
Indicate, wherein x be 4/3~2, as Supplementary active compounds be platinum when, supported, heterogeneous catalyst can use CoOx/Al2O3/ Pt expression,
Wherein x is 4/3~2, can be considered the catalyst that Co and Pt are spatially separating.
The present invention separately provides preparation described in supported, heterogeneous catalyst or above-mentioned technical proposal described in above-mentioned technical proposal
Application of the supported, heterogeneous catalyst that method is prepared in styrene catalyzed epoxidation reaction.In the present invention, described
The system of epoxidation of styrene reaction preferably includes styrene, tert-butyl hydroperoxide, acetonitrile and catalyst；The styrene with
The ratio of the amount of the substance of tert-butyl hydroperoxide is preferably 1:(1~4), more preferably 1:(1~3), it is further preferably 1:2；It is described
The amount ratio of acetonitrile and styrene is preferably (15~30) mL:3.5mmol, more preferably (18~25) mL:3.5mmol, then excellent
It is selected as 20mL:3.5mmol.
In the present invention, in the epoxidation of styrene reaction, on the basis of the styrene of 3.5mmol, the use of catalyst
Amount is preferably 1.2~7.5mg/mmol, more preferably 1.4~7.2mg/mmol, is further preferably 1.5~7.0mg/mmol.
In the present invention, the epoxidation of styrene reaction preferably carries out in hydrogen or air atmosphere, the reaction
Temperature is preferably 78~85 DEG C, and more preferably 80 DEG C；The time of the reaction is preferably 7~10h, more preferably 8h；It is described anti-
It should preferably carry out under agitation；The speed of the stirring is preferably 650~800r/min, more preferably 700r/min.
In the present invention, with conversion ratio and selectivity for evaluation index, the selectivity refers to anti-the catalytic activity of catalyst
Quality (or mole) ratio of styrene consumed by Styryl oxide and total styrene material consumed should be generated；The choosing
Selecting property is 74.3~94.8%；
The conversion ratio refers under certain condition, a certain component reaction generate the consumption (amount of quality or substance) of product with
The ratio (amount of quality or substance) of total amount before the component reaction；The conversion ratio of the supported, heterogeneous catalyst is preferably 77.2~
91.4%.
In order to further illustrate the present invention, supported, heterogeneous provided by the invention is catalyzed with reference to the accompanying drawings and examples
Agent and its preparation method and application is described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
Load type Co OxThe preparation of catalyst
Carbon nano-fiber is scattered in ethyl alcohol, forms the carbon nano-fiber alcohol dispersion liquid that concentration is 0.03g/mL；Front three
Base aluminium and water are as presoma depositing Al2O3；CoO is deposited using cobaltocene and ozone as presomaxNanoparticle.
(1) carbon nano-fiber alcohol dispersion liquid is uniformly coated on glass sheet surface, is placed into atomic layer deposition after being evaporated
In vacuum reaction cavity；
(2) using the carbon nano-fiber prepared in step (1) as template, the temperature of cavity is 125 when controlling deposition of aluminium oxide
DEG C, chamber pressure 50Pa.The Al of 50 recurring numbers is first deposited using ALD2O3Form oxide nano.
(3) sample that step (2) obtains is calcined in air and removes the template of carbon nano-fiber for 500 DEG C, then sink again
Product CoOxNanoparticle obtains alumina nano tube load C oOxCatalyst (x is 4/3~2), is labeled as CoOx/50Al2O3.It is heavy
Product CoOxWhen nanoparticle, the temperature control of cavity is 250 DEG C, and chamber pressure control is 50Pa.
It is characterized using pattern of the transmission scanning electron microscope to products obtained therefrom, as a result as shown in Figure 1.It can be with by the TEM of Fig. 1
Find out, CoOxNanoparticle uniform load in aluminium oxide nano pipe outer wall, aluminium oxide tube wall with a thickness of 7nm.
Catalyst activity evaluation is carried out in the three-necked flask of 50mL: 20mL acetonitrile, 3.5mmol being added into three-necked flask
Styrene, 7mmol tert-butyl hydroperoxide, this catalyst sample of 8mg.Then it is 80 DEG C in reaction temperature, is stirred under air atmosphere
Mix reaction.After reacting 8h, the conversion ratio of styrene is 91.0%, and the selectivity of epoxy product is 74.3%.
It is 80 DEG C in reaction temperature according to above-mentioned dosage addition acetonitrile, styrene, tert-butyl hydroperoxide and catalyst,
After being stirred to react 8h under atmosphere of hydrogen, the conversion ratio of styrene is 87.8%, and the selectivity of epoxy product is 75.9%.
Embodiment 2
Pt and CoOxIt is spatially separating the preparation of catalyst
Carbon nano-fiber is dissolved in ethyl alcohol, forms the carbon nano-fiber alcohol dispersion liquid that concentration is 0.03g/mL；Front three
Base aluminium and water are as presoma depositing Al2O3；Platinum and ozone, which are closed, using (trimethyl) methyl cyclopentadiene deposits Pt nanometers as presoma
Particle；CoO is deposited using cobaltocene and ozone as presomaxNanoparticle.
(1) on the glass sheet by carbon nano-fiber coating, it is placed into after being evaporated in atomic layer deposition vacuum reaction cavity, first
Deposit the Pt nanoparticle of 20 recurring numbers, sedimentary condition: the temperature of cavity is 250 DEG C, chamber pressure 50Pa, deposition process
In with the volume ratio of carrier gas and vacuum reaction cavity be 1/8min-1Carrier gas is passed through to cavity；
(2) Al of 30 recurring numbers is then deposited on the Pt nanoparticle layers of step (1)2O3Oxide nano is formed,
Sedimentary condition: the temperature of cavity is 125 DEG C, chamber pressure 50Pa；
(3) sample of step (2) is calcined in air and removes the template of carbon nano-fiber for 500 DEG C, last redeposition 35
The CoO of a circulationxNanoparticle, sedimentary condition are identical as the sedimentary condition of Pt nanoparticle；Obtain Pt and CoOxIt is spatially separating
Catalyst is labeled as CoOx/30Al2O3/ Pt (x is 4/3~2).
Gained catalyst is characterized using transmission electron microscope, wherein aluminium oxide with a thickness of 5nm, Pt nanoparticle quilt
Confinement is in oxide nano, CoOxNanoparticle is dispersed in the outer surface of oxide nano.
Catalyst activity evaluation is carried out in the three-necked flask of 50mL: 20mL acetonitrile, 3.5mmol being added into three-necked flask
Styrene, 7mmol tert-butyl hydroperoxide, 5mg catalyst sample.Then it is 80 DEG C in reaction temperature, is stirred under atmosphere of hydrogen
Reaction.After reacting 8h, the conversion ratio of styrene is 78.2%, and the selectivity of epoxy product is 93.9%.
Embodiment 3
Pt and CoOxIt is spatially separating the preparation of catalyst
Catalyst is prepared according to the method for embodiment 2, the difference is that, deposit the Al of 50 recurring numbers2O3Form oxidation
Object nanotube.It is characterized using structure of the transmission electron microscope to gained catalyst, as a result as shown in Fig. 2, Pt nanoparticle is limited
Domain in oxide nano, Pt nanoparticle average diameter size be 2.5nm, aluminium oxide tube wall with a thickness of 7nm, CoOx(x
It is 4/3~2) nanoparticle is dispersed in the outer surface of oxide nano, catalyst samples are obtained, group becomes CoOx/
50Al2O3/Pt。
It tests the catalytic activity of catalyst: 20mL acetonitrile, 3.5mmol styrene, the tertiary fourth of 7mmol being added into three-necked flask
Base hydrogen peroxide, this catalyst sample of 8mg.It then is 80 DEG C in reaction temperature, after being stirred to react 8h under atmosphere of hydrogen, styrene
Conversion ratio be 77.2%, the selectivity of epoxy product is 94.8%.
Dosage, reaction temperature and time are same as above, and react under air atmosphere, and the conversion ratio of styrene is 91.4%, and epoxy produces
The selectivity of object is 76.2%.
Embodiment 4
Catalyst is prepared according to method same as Example 3, the difference is that the aluminium oxide of 65 recurring numbers of deposition,
Preparation gained sample marking is CoOx/65Al2O3/ Pt reacts gained catalyst samples in hydrogen atmosphere, and test is urged
The catalytic performance of agent, the conversion ratio of styrene are 80.3%, and the selectivity of epoxy product is 86.5%.
Embodiment 5
Pt and CoOxIt is spatially separating the preparation of catalyst
Catalyst is prepared according to the method for embodiment 2, the difference is that, deposit the Al of 80 recurring numbers2O3Form oxidation
Object nanotube.It is characterized using structure of the transmission electron microscope to gained catalyst, as a result similar to Example 3, Pt nanoparticle
By confinement in oxide nano, Pt nanoparticle average diameter size is 2.5nm, aluminium oxide tube wall with a thickness of 10nm,
CoOxNanoparticle is dispersed in the outer surface of oxide nano, and composition is labeled as CoOx/80Al2O3/ Pt (x be 4/3~
2)。
20mL acetonitrile, 3.5mmol styrene, 7mmol tert-butyl hydroperoxide, this catalysis of 12mg are added into three-necked flask
Agent sample.Then it is 80 DEG C in reaction temperature, is stirred to react under atmosphere of hydrogen.After reacting 8h, the conversion ratio of styrene is
83.7%, the selectivity of epoxy product is 77.1%.
Embodiment 6
Pt and CoOxIt is spatially separating the preparation of catalyst
Catalyst is prepared according to the method for embodiment 2, the difference is that, deposit the Al of 100 recurring numbers2O3Form oxygen
Compound nanotube.It is characterized using structure of the transmission electron microscope to gained catalyst, as shown in Figure 3, the results showed that: Pt nanoparticle
Son by confinement in oxide nano, Pt nanoparticle average diameter size be 2.5nm, aluminium oxide tube wall with a thickness of
14nm, CoOx(x is 4/3~2) nanoparticle is dispersed in the outer surface of oxide nano, and composition is labeled as CoOx/
100Al2O3/Pt。
20mL acetonitrile, 3.5mmol styrene, 7mmol tert-butyl hydroperoxide, this catalysis of 15mg are added into three-necked flask
Agent sample.Then it is 80 DEG C in reaction temperature, is stirred to react under atmosphere of hydrogen.After reacting 8h, the conversion ratio of styrene is
84.9%, the selectivity of epoxy product is 76.8%.
Embodiment 7
Pt and CoOxIt is spatially separating the preparation of catalyst
Catalyst is prepared according to the method for embodiment 2, the difference is that, step (2) deposits the Al of 300 recurring numbers2O3
Oxide nano is formed, step (3) calcination temperature is 600 DEG C.Table is carried out using structure of the transmission electron microscope to gained catalyst
Sign, it is as a result close with embodiment 2: Pt nanoparticle by confinement in oxide nano, CoOxNanoparticle is dispersed in
The outer surface of oxide nano, chemical composition are labeled as CoOx/300Al2O3/Pt。
20mL acetonitrile, 3.5mmol styrene, 7mmol tert-butyl hydroperoxide, this catalysis of 35mg are added into three-necked flask
Agent sample.Then it is 80 DEG C in reaction temperature, is stirred to react under atmosphere of hydrogen.After reacting 8h, the conversion ratio of styrene is
86.6%, the selectivity of epoxy product is 75.1%.
Comparative example 1
The preparation of supporting Pt base catalyst
Catalyst is prepared according to the method for embodiment 2, the difference is that, step (2) deposits the Al of 50 recurring numbers2O3
Oxide nano is formed, step does not deposit CoO in (3)xNanoparticle.Labeled as Al2O3/ Pt, the Pt base catalysis of as confinement
Agent.
Catalyst activity evaluation is carried out in the three-necked flask of 50mL.20mL acetonitrile, 3.5mmol are added into three-necked flask
Styrene, 7mmol tert-butyl hydroperoxide, this catalyst sample of 8mg.Then it is 80 DEG C in reaction temperature, is stirred under air atmosphere
Mix reaction.After reacting 8h, the conversion ratio of styrene is 17.7%, and the selectivity of epoxy product is 72.4%.
The catalytic performance of 1 gained catalyst of Examples 1 to 7 and comparative example is listed in Table 1 below.
1 Examples 1 to 7 of table and 1 supported, heterogeneous catalyst structure of comparative example and catalytic performance test result
By 3 test result of table it is found that supported, heterogeneous catalyst provided by the invention is urged for styrene catalyzed epoxidation
When changing reaction, CoOxIt is main active site, when without CoOxWhen, the conversion ratio of styrene is significantly affected, selective phase
To lower；And contain CoOxWhen, it is catalyzed the conversion ratio of styrene and selectivity in reaction and is in higher level；The presence pair of Pt
The conversion ratio and selectivity of styrene have certain facilitation.
In addition, under hydrogen atmosphere, Pt and CoOxThe wall thickness of alumina nano tube in catalyst is spatially separating to catalyst
Catalytic performance also has certain influence, works as Al2O3When the wall thickness of nanotube is about 7nm (50 circulations), styrene in catalysis reaction
Selectivity can reach 94.8%.
As seen from the above embodiment, supported, heterogeneous catalyst provided by the invention is born using alumina nano tube as carrier
After carrying active component cobalt/cobalt oxide, the conversion ratio and selectivity of styrene catalysis reaction can be improved, this is for large scale preparation ring
Oxygen vinylbenzene is advantageous.
The present invention also provides the preparation method of supported, heterogeneous catalyst, this method preparation is simple, easily-controllable, repeatability
Height, and the control to aluminium oxide nano tube thickness can be realized by the adjustment of deposition parameter.
Although above-described embodiment is made that detailed description to the present invention, it is only a part of the embodiment of the present invention,
Rather than whole embodiments, people can also obtain other embodiments under the premise of without creativeness according to the present embodiment, these
Embodiment belongs to the scope of the present invention.
Claims (10)
1. a kind of supported, heterogeneous catalyst, including alumina nano tube and the cobalt for being deposited on the aluminium oxide nano tube outer surface
Oxide.
2. supported, heterogeneous catalyst as described in claim 1, which is characterized in that the partial size of the cobalt/cobalt oxide be 1~
2nm, deposition with a thickness of 4~5nm.
3. supported, heterogeneous catalyst as described in claim 1, which is characterized in that the wall thickness of the alumina nano tube is
5~41nm.
4. supported, heterogeneous catalyst as claimed in any one of claims 1 to 3, which is characterized in that further include auxiliary activity group
Point, the Supplementary active compounds are deposited on the inner surface of the alumina nano tube.
5. supported, heterogeneous catalyst as claimed in claim 4, which is characterized in that the Supplementary active compounds include platinum.
6. supported, heterogeneous catalyst as claimed in claim 5, which is characterized in that the mass content of the Supplementary active compounds
It is 3.5~5%；The partial size of the Supplementary active compounds is 2~6nm.
7. a kind of preparation method of supported, heterogeneous catalyst, comprising the following steps:
(1) on substrate by carbon nanofiber dispersion liquid coating, template is obtained after removing dispersing agent；
(2) deposition of aluminium oxide in the template that the step (1) obtains removes template through calcining, obtains alumina nano tube；
(3) the outside deposition cobalt/cobalt oxide of the alumina nano tube obtained in the step (2) obtains supported, heterogeneous catalysis
Agent.
8. preparation method as claimed in claim 7, which is characterized in that further include sinking in the template that the step (1) obtains
Product Supplementary active compounds, then carry out the operation of step (2) and step (3) in the template for be deposited with Supplementary active compounds again.
9. preparation method as claimed in claim 7 or 8, which is characterized in that described to be deposited as atomic layer deposition.
10. any one of the described in any item supported, heterogeneous catalyst of claim 1~6 or claim 7~9 the preparation side
Application of the supported, heterogeneous catalyst that method is prepared in styrene catalyzed epoxidation reaction.
Priority Applications (1)
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