CN104998643A - Au/BW11/Al2O3 catalyst and its preparation method and use - Google Patents

Au/BW11/Al2O3 catalyst and its preparation method and use Download PDF

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Publication number
CN104998643A
CN104998643A CN201510370303.7A CN201510370303A CN104998643A CN 104998643 A CN104998643 A CN 104998643A CN 201510370303 A CN201510370303 A CN 201510370303A CN 104998643 A CN104998643 A CN 104998643A
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catalyst
octene
cyclo
obtains
mixture
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朱明乔
乌莎贾米尔
陈新志
刘懿
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Zhejiang University ZJU
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Zhejiang University ZJU
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention discloses an Au/BW11/Al2O3 catalyst and its preparation method and use. Al2O3 is orderly loaded with BW11 and nano-gold so that the Au/BW11/Al2O3 catalyst is formed. The Al2O3 is used as a catalyst carrier and Au and BW11 are used as catalyst main active components. The Au/BW11/Al2O3 catalyst has high loading efficiency and a good dispersion degree. The Au/BW11/Al2O3 catalyst has the characteristics of high activity and good selectivity of cyclooctene epoxidation preparation of epoxycyclooctane and satisfies industrial production requirements.

Description

A kind of Au/BW 11/ Al 2o 3catalysts and its preparation method and purposes
Technical field
The present invention relates to a kind of Au/BW 11/ Al 2o 3catalyst and the application in cyclo-octene epoxidation thereof.
Background technology
From the angle of Synthetic Organic Chemistry basic research and commercial Application, the epoxidation reaction of alkene is certainly very important, because epoxide is epoxy resin, and the indispensable base stock of pigment and surfactant.They are the intermediates do not replaced in a lot of organic synthesis, as being the diversity of functional product in nucleophilic ring opening, from Small molecular to large-sized polymer and oligomer, contribute.Now, be the non-solvent epoxy system of oxidant for employing oxygen, molecular oxygen activation is in a mild condition still very difficult, and the process that oxygen and Electrophilic addition to alkene generate epoxides is still main challenge.
Polyoxometallate (POMs) obtains great concern in the past few decades, because they represent the important family of of inorganic material, obtain application because it has unique attribute and structure in various fields such as material science, catalysis, biology and medical science.
Specifically, POMs has a lot of miracle in catalysis, due to the acidity that it is intrinsic, the adjustable state of oxidation, activate many oxidants and improve oxidation stability, POMs is regarded as the metal oxide of similar solubility and is applied to acid catalysis and oxidation catalysis, is applied to homogeneous phase and heterogeneous catalysis too.
Except the catalytic property of POMs, its duct is also being inquired into as the carrier of nano particle (NPs) always, and its high anionic charge contributes to the stability improving catalyst, prevents the sintering of NPs.Prepare and the material of stabilized nanoscale yardstick as nm of gold time, POMs plays the role of a new development in this field.Nano catalyst due to load is successfully used to the epoxidation reaction of cycloolefin, producing hydrogen peroxide by direct synthesis, the esterification of oxidizing alcohol and oxidizing alcohol, the characteristic of POMs impels researcher to be applied to use in simple, efficient and room temperature technology synthetic metals NPs.POMs has become the traditional better stabilizing agent of organic stabilizer of the new ratio of a class.And the nano catalyst of POMs load is used for the challenge that alkene epoxidation remains new.
Summary of the invention
The object of the invention is to provide a kind of Au/BW11/Al2O3 Catalysts and its preparation method and purposes.
A kind of Au/BW 11/ Al 2o 3catalyst, by Au, BW 11and Al 2o 3composition, wherein Au and BW 11as the main active of catalyst, the mass percentage of Au is 1.0%, BW 11mass percentage be 20.0%; γ-Al 2o 3as the carrier of catalyst, its mass percentage > 75%.
Described Au is the metal of Au, the metal oxide of Au or the two mixture.
Described BW 11for Keggin-type polyoxometallate.
The carrier of described catalyst is γ-Al 2o 3.
A kind of described for the epoxidised Au/BW of cyclo-octene 11/ Al 2o 3the preparation method of catalyst, comprises the steps:
1) 100g sodium tungstate and 6.66g boric acid are dissolved in 170 mL boiling water, obtain mixture solution;
2) in said mixture solution, dropwise add hydrochloric acid 64 mL of 6 M and keep pH value to be 6, vigorous stirring obtains wolframic acid to dissolve original sodium tungstate;
3) above-mentioned steps 2) solution that obtains boils 1 h and is then incubated 24 h at 4 ° of C, and isolated by filtration precipitates, and drips 33g KCl and obtain sylvite precipitation in filtrate;
4) sylvite is deposited in 335 mL warm water, removes insoluble part, then again obtaining sylvite precipitation by adding 33g KCl, being BW 11;
5) 5 mL chlorauric acid solution dilute with waters, Keep agitation also joins 5g carrier γ-Al 2o 3with in the mixture of 50mL water;
6) above-mentioned steps 5) mixture that obtains is incubated 1 h at 30 ° of C, adds NaOH to keep pH=10;
7) above-mentioned steps 6) mixture that obtains is heated to 70 ° of C and adds formaldehyde as reducing agent, obtains solid Au/Al 2o 3;
8) isolated by filtration step 7) gained Au/Al 2o 3solids washed with water is to remove chlorion;
9) step 8) Au/Al that obtains 2o 3at dry 16 h of 110 ° of C;
10) by 1g Au/Al 2o 3with 0.2g BW 11add in 30 mL conductivity waters and stir 36 h at 30 ° of C, then 100 ° of C dryings, preserve the Au/BW obtained 11/ Al 2o 3.
Described preparation method is used for the epoxidised Au/BW of cyclo-octene 11/ Al 2o 3want first roasting 3h before catalyst reaction, sintering temperature is from 100 ° of C to 600 ° of C.
Described Au/BW 11/ Al 2o 3catalyst is used for cyclo-octene selective epoxidation and generates epoxide ring octane.
The beneficial effect that the present invention compared with prior art has:
1) the epoxidised conversion ratio of cyclo-octene and selective good;
2) mild condition;
3) without the need to solvent;
4) with the molecular oxygen of green for oxidant instead of traditional toxic oxygen agent.
Accompanying drawing explanation
Fig. 1 is Au/BW 11/ Al 2o 3fT-IR spectrogram;
Fig. 2 a is keggin type BW 11xRD spectra;
Fig. 2 b is Au/Al 2o 3xRD spectra;
Fig. 2 c is Au/BW 11/ Al 2o 3xRD spectra.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is described further.
Au/BW 11/ Al 2o 3the preparation of catalyst:
100g sodium tungstate and 6.66g boric acid are dissolved in 170 mL boiling water, obtain mixture solution; In said mixture solution, dropwise add hydrochloric acid 64 mL of 6 M and keep pH value to be 6, vigorous stirring obtains wolframic acid to dissolve original sodium tungstate, the solution obtained boils 1 h and is then incubated 24 h at 4 ° of C, and isolated by filtration precipitates, and drips 33g KCl and obtain sylvite precipitation in filtrate; Sylvite is deposited in 335 mL warm water, removes insoluble part, then again obtaining sylvite precipitation by adding 33g KCl, being BW 11, its XRD as shown in Figure 2 a.5 mL chlorauric acid solution dilute with waters, Keep agitation also joins 5g carrier γ-Al 2o 3with in the mixture of 50mL water; The mixture obtained is incubated 1 h at 30 ° of C, adds NaOH to keep pH=10, is then heated to 70 ° of C and adds formaldehyde as reducing agent, isolated by filtration gained Au/Al 2o 3solid, washes with water to remove chlorion, then obtains solid Au/Al at dry 16 h of 110 ° of C 2o 3, its XRD as shown in Figure 2 b; By 1g Au/Al 2o 3with 0.2g BW 11add in 30 mL conductivity waters and stir 36 h at 30 ° of C, then 100 ° of C dryings, preserve the Au/BW obtained 11/ Al 2o 3, as shown in Figure 2 c, FT-IR figure as shown in Figure 1 for its XRD.
In catalyst activity evaluation, product adopts gas chromatographic analysis, and capillary column is SE-54 (30 m × 0.32mm × 0.5 μm), and detector is flame ionization detector (FID).N-hexane is as internal standard compound.
embodiment 1
Catalyst activity is evaluated.0.25 g catalyst is be placed in a PTFE-lined autoclave (volume=20mL), the cyclo-octene of 5 g after 500 ° of C calcining, reacts 24 hours as the molecular oxygen of oxidant and TBHP initator under the pressure of 0.4 MPa at 80 ° of C.The conversion ratio obtaining cyclo-octene oxidation is 42.92%, and the selective of epoxide ring octane is 90.02%.
embodiment 2
Catalyst activity is evaluated.For reaction after the 0.15 g catalyst circulation 3 times of 500 ° of C calcining.5 g cyclo-octene, react 24 hour at 80 ° of C as the molecular oxygen of oxidant and TBHP initator under the pressure of 0.4 MPa.The conversion ratio obtaining cyclo-octene oxidation is 36.59%, and the selective of epoxide ring octane is 85.29%.
embodiment 3
Catalyst activity is evaluated.Reaction is used at 0.15 g catalyst of 500 ° of C calcinings.5 g cyclo-octene are dissolved in the solution of 2-dichloroethanes and acetonitrile 1:1, react 24 hours as the molecular oxygen of oxidant and TBHP initator under the pressure of 0.4 MPa at 80 ° of C.The conversion ratio obtaining cyclo-octene oxidation is 46.64%, and the selective of epoxide ring octane is 97.31%.
embodiment 4
Catalyst activity is evaluated.Reaction is used at 0.15 g catalyst of 600 ° of C calcinings.5 g cyclo-octene, react 24 hour at 80 ° of C as the molecular oxygen of oxidant and TBHP initator under the pressure of 0.4 MPa.The conversion ratio obtaining cyclo-octene oxidation is 40.93%, and the selective of epoxide ring octane is 88.91%.
embodiment 5
Catalyst activity is evaluated.For reaction after 0.15 g catalyst of 500 ° of C calcinings.5 g cyclo-octene, react 24 hour at 100 ° of C as the molecular oxygen of oxidant and TBHP initator under the pressure of 0.4 MPa.The conversion ratio obtaining cyclo-octene oxidation is 42.67%, and the selective of epoxide ring octane is 86.04%.
embodiment 6
Catalyst activity is evaluated.For reaction after 0.15 g catalyst of 500 ° of C calcinings.5 g cyclo-octene, react 48 hour at 100 ° of C as the molecular oxygen of oxidant and TBHP initator under the pressure of 0.4 MPa.The conversion ratio obtaining cyclo-octene oxidation is 43.11%, and the selective of epoxide ring octane is 84.41%.
embodiment 7
Catalyst activity is evaluated.For reaction after 0.15 g catalyst of 500 ° of C calcinings.5 g cyclo-octene and react 24 hours at 80 ° of C as the TBHP of oxidant.The conversion ratio obtaining cyclo-octene oxidation is 50.80%, and the selective of epoxide ring octane is 97.04%.

Claims (7)

1. an Au/BW 11/ Al 2o 3catalyst, is characterized in that, it is by Au, BW 11and Al 2o 3composition, wherein Au and BW 11as the main active of catalyst, the mass percentage of Au is 1.0%, BW 11mass percentage be 20.0%; γ-Al 2o 3as the carrier of catalyst, its mass percentage > 75%.
2. one according to claim 1 is used for the epoxidised Au/BW of cyclo-octene 11/ Al 2o 3catalyst, is characterized in that, described Au is the metal of Au, the metal oxide of Au or the two mixture.
3. one according to claim 1 is used for the epoxidised Au/BW of cyclo-octene 11/ Al 2o 3catalyst, is characterized in that described BW 11for Keggin-type polyoxometallate.
4. one according to claim 1 is used for the epoxidised Au/BW of cyclo-octene 11/ Al 2o 3catalyst, is characterized in that, the carrier of described catalyst is γ-Al 2o 3.
5. one kind as claimed in claim 1 for the epoxidised Au/BW of cyclo-octene 11/ Al 2o 3the preparation method of catalyst, is characterized in that, comprises the steps:
1) 100g sodium tungstate and 6.66g boric acid are dissolved in 170 mL boiling water, obtain mixture solution;
2) in said mixture solution, dropwise add hydrochloric acid 64 mL of 6 M and keep pH value to be 6, vigorous stirring obtains wolframic acid to dissolve original sodium tungstate;
3) above-mentioned steps 2) solution that obtains boils 1 h and is then incubated 24 h at 4 ° of C, and isolated by filtration precipitates, and drips 33g KCl and obtain sylvite precipitation in filtrate;
4) sylvite is deposited in 335 mL warm water, removes insoluble part, then again obtaining sylvite precipitation by adding 33g KCl, being BW 11;
5) 5 mL chlorauric acid solution dilute with waters, Keep agitation also joins 5g carrier γ-Al 2o 3with in the mixture of 50mL water;
6) above-mentioned steps 5) mixture that obtains is incubated 1 h at 30 ° of C, adds NaOH to keep pH=10;
7) above-mentioned steps 6) mixture that obtains is heated to 70 ° of C and adds formaldehyde as reducing agent, obtains solid Au/Al 2o 3;
8) isolated by filtration step 7) gained Au/Al 2o 3solids washed with water is to remove chlorion;
9) step 8) Au/Al that obtains 2o 3at dry 16 h of 110 ° of C;
10) by 1g Au/Al 2o 3with 0.2g BW 11add in 30 mL conductivity waters and stir 36 h at 30 ° of C, then 100 ° of C dryings, preserve the Au/BW obtained 11/ Al 2o 3.
6. preparation method according to claim 5, is characterized in that, for the epoxidised Au/BW of cyclo-octene 11/ Al 2o 3want first roasting 3h before catalyst reaction, sintering temperature is from 100 ° of C to 600 ° of C.
7. an Au/BW according to claim 1 11/ Al 2o 3the purposes of catalyst, is characterized in that, generates epoxide ring octane for cyclo-octene selective epoxidation.
CN201510370303.7A 2015-06-30 2015-06-30 Au/BW11/Al2O3 catalyst and its preparation method and use Pending CN104998643A (en)

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
CN108993581A (en) * 2018-07-13 2018-12-14 浙江大学 Load type metal polyoxy hydrochlorate hybrid catalyst and its preparation method and application
CN110165045A (en) * 2019-04-08 2019-08-23 中国科学院物理研究所 W-B alloy material and spin electric device based on spin-orbit torque
CN110420637A (en) * 2019-08-06 2019-11-08 北京化工大学 A kind of W modified support carried metal Pd prepares the method and its application of composite catalyst
CN114225931A (en) * 2021-11-24 2022-03-25 中山大学 Molybdenum-loaded silicon-doped titanium dioxide catalyst and preparation method and application thereof

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CN101822990A (en) * 2010-04-02 2010-09-08 浙江大学 Supported nano gold catalyst for cyclohexane oxidation and preparation method thereof
CN101966464A (en) * 2010-09-07 2011-02-09 浙江大学 Supported nano gold catalyst for cyclohexene oxidation and preparation method thereof

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CN101804347A (en) * 2010-04-02 2010-08-18 浙江大学 Preparation method and purpose of supported nano-gold catalyst for cyclohexene oxide
CN101822990A (en) * 2010-04-02 2010-09-08 浙江大学 Supported nano gold catalyst for cyclohexane oxidation and preparation method thereof
CN101966464A (en) * 2010-09-07 2011-02-09 浙江大学 Supported nano gold catalyst for cyclohexene oxidation and preparation method thereof

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108993581A (en) * 2018-07-13 2018-12-14 浙江大学 Load type metal polyoxy hydrochlorate hybrid catalyst and its preparation method and application
CN110165045A (en) * 2019-04-08 2019-08-23 中国科学院物理研究所 W-B alloy material and spin electric device based on spin-orbit torque
CN110420637A (en) * 2019-08-06 2019-11-08 北京化工大学 A kind of W modified support carried metal Pd prepares the method and its application of composite catalyst
CN114225931A (en) * 2021-11-24 2022-03-25 中山大学 Molybdenum-loaded silicon-doped titanium dioxide catalyst and preparation method and application thereof
CN114225931B (en) * 2021-11-24 2023-11-03 中山大学 Molybdenum-loaded silicon-doped titanium dioxide catalyst and preparation method and application thereof

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