CN103894227A - Preparation method of gold catalyst for preparing epoxypropane by virtue of propylene epoxidation - Google Patents
Preparation method of gold catalyst for preparing epoxypropane by virtue of propylene epoxidation Download PDFInfo
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- CN103894227A CN103894227A CN201410160967.6A CN201410160967A CN103894227A CN 103894227 A CN103894227 A CN 103894227A CN 201410160967 A CN201410160967 A CN 201410160967A CN 103894227 A CN103894227 A CN 103894227A
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- catalyst
- epoxidation
- propene
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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
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- 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
Abstract
The invention provides a preparation method of a gold catalyst for preparing epoxypropane by virtue of propylene epoxidation, relating to a gold catalyst. The method comprises the following steps: (1) drying and crushing plant Cacumen biotae to obtain plant Cacumen biotae dry powder, adding the dry powder into water, and vibrating and filtering, so as to obtain plant biomass lixivium; (2) adding titanium silicalite molecular sieves, a gold precursor chloroauric acid (HAuCl4) water solution and ionic liquid [Bpy][N(CN)2] into the water, so as to obtain a solution A; (3) adding the plant biomass lixivium obtained in the step (1) into the solution A obtained in the step (2), so as to obtain a solution B; and (4) carrying out suction filtration, washing, drying and activating on the solution B obtained in the step (3) so as to obtain the gold catalyst, wherein the gold catalyst is used for preparing the epoxypropane by virtue of the propylene epoxidation and is a powdery supported gold catalyst. The preparation method has the advantages of low cost, environmental friendliness and the like. The catalyst prepared by utilizing the preparation method is used for catalyzing the propylene epoxidation and has the advantages of good activity, high stability and the like.
Description
Technical field
The present invention relates to Au catalyst, especially relate to a kind of preparation method of Au catalyst of preparing epoxypropane by epoxidation of propene.
Background technology
Expoxy propane (being called for short PO) is the third-largest Organic chemical products that output is only second to polypropylene and acrylonitrile in acryloyl derivative, mainly for the production of PPG, and surfactant, propene carbonate and propane diols (PG) etc.Within 2012, PO yearly productive capacity in the world has exceeded 9,540,000 tons, wherein Asia is the fastest-rising area of production capacity, the demand growth of China and Middle East is the fastest, Chinese PO yearly productive capacity will have reached 1,880,000 tons in the end of the year 2012, expect China's expoxy propane demand in 2015 and estimate to reach 2,840,000 tons of left and right (CNPC and Economic of Chemical Engineering analysis 2013,6,51-53).The main production of current industrial production PO has chlorohydrination, conjugated oxidation and H
2o
2liquid phase oxidation, its flow process of chlorohydrination is short, and construction investment is few, but waste water, waste residue generation are large, and serious environment pollution, must process.And conjugated oxidation has overcome the problem such as environmental pollution and equipment corrosion of chlorohydrination, but technological process is long, and investment cost is high, and its economy is subject to a large amount of joint product restrictions (Ind En Chem Res, 2006,45,3447-3459).H
2o
2liquid phase oxidation faces H
2o
2preparation cost is high, uses the problems (J Mol Catal a-Chem1997,117,351-356) such as inconvenience.
Haruta etc. found to adopt the standby Au/TiO of deposition-precipitation (DP) legal system in 1998
2catalyst is at H
2with O
2the direct direct gas-phase epoxidation of catalyzing propone (J Catal, 1998,178,566-575) under atmosphere and relatively mild reaction temperature, the PO of generation selectively exceedes 90%.This preparation method is fairly simple, is a kind of new way of preparing expoxy propane.But in DP method, the utilization rate of gold is very low, conventionally deposits to (J Catal, 2004,226,156-170) in catalyst carrier less than 2% gold, although it is relatively high to adopt the activity and selectivity of the Au catalyst of preparing in this way, its stability has much room for improvement.Biological reducing method is also a kind of a kind of new method (Catal Commun2011 for preparing epoxidation of propylene Au catalyst, 12,830-833), the catalyst that the method is prepared has higher catalytic stability, but catalytic reaction temperature is higher, also there is similar problem (J Catal2011,283,192-201) in the biological reducing ionic liquid assistant load method proposing on this basis.
Summary of the invention
The object of the invention is intended to the preparation method of the Au catalyst that a kind of preparing epoxypropane by epoxidation of propene with advantages such as cost is low, environmental protections is provided.
The present invention includes following steps:
1) plant cacumen biotae is dried to rear pulverizing, obtain plant cacumen biotae dry powder, then be added to the water, vibration, filters, and obtains plant biomass leachate;
2) in water, add HTS, golden presoma gold chloride (HAuCl
4) aqueous solution and ionic liquid [Bpy] [N (CN)
2], obtain solution A;
3) the plant biomass leachate obtaining in step 1) is added to step 2) in the solution A that obtains, obtain solution B;
4) solution B step 3) being obtained is carried out suction filtration, and washing is dry, activates, and obtains the Au catalyst of preparing epoxypropane by epoxidation of propene, and the Au catalyst of the preparing epoxypropane by epoxidation of propene of gained is powdered loaded type Au catalyst.
In step 1), the proportioning of described plant cacumen biotae dry powder and water can be 10g: 1L, and wherein, plant cacumen biotae dry powder is calculated in mass, and water is calculated by volume; Described water can adopt deionized water, and described vibration can be placed in the shaking table 2h that vibrates.
In step 2) in, described water, HTS, ionic liquid [Bpy] [N (CN)
2] proportioning can be 50mL: 0.5g: (0～300) μ L, wherein water and ionic liquid [Bpy] [N (CN)
2] calculate by volume, HTS is calculated in mass.
In step 3), the water proportioning in addition and the step 1) of described plant biomass leachate can be 50mL: 1L.
In step 4), described washing can adopt deionized water washing, and described being dried can be dried 24h under 50 DEG C of vacuum, and described activation can activate 6h at 375 DEG C; The load capacity of the Au catalyst gold of the preparing epoxypropane by epoxidation of propene obtaining is 0.25%～4.0%.
Propylene catalytic epoxidation carries out in atmospheric fixed bed reaction unit.Reacting gas consists of C
3h
6/ H
2/ O
2/ N
2=1/1/1/7(volume ratio), air speed is 7000mLh
-1g
-1 cat, 220～300 DEG C of reaction temperatures, product is detected and is analyzed by gas-chromatography FID and TCD.
The present invention first mixes gold chloride water, HTS and ionic liquid; Au (III) ion and ionic liquid generation complexing back loading are at carrier surface; the protective effect of recycling plant biomass extract; prevent that catalyst from reuniting at roasting process gold nano grain; load type gold catalyst prepared by this method has higher activity, has good application prospect.
The present invention proposes a kind of new method of preparing epoxidation of propylene Au catalyst, the method is different from traditional DP method, biological reducing method and biological reducing ionic liquid assistant load method.First be at ionic liquid [Bpy] [N (CN) by Au (III) ion
2] load to carrier surface under the condition that exists, then add plant biomass extract, finally under certain atmosphere, process and be prepared into catalyst.The method and DP method difference are larger, in DP method, do not introduce ionic liquid and phyteral, and in biological reducing method and biological reducing ionic liquid assistant load method, Au nano particle reduces by phyteral and obtains, in the present invention, Au nano particle obtains by roasting, ionic liquid [Bpy] [N (CN)
2] play and the effect of Au (III) ion generation complexing, instead of the effect of assistant load.The method that the present invention proposes has the advantages such as cost is low, environmental protection.Adopt prepared catalyst epoxidation of propylene, it is active good to have, stability advantages of higher.
Brief description of the drawings
Fig. 1 is the transmission electron microscope TEM figure of the embodiment of the present invention 1 Au catalyst that makes preparing epoxypropane by epoxidation of propene.In figure, scale is 50nm.
Fig. 2 is the transmission electron microscope TEM figure of the embodiment of the present invention 2 Au catalyst that makes preparing epoxypropane by epoxidation of propene.In figure, scale is 50nm.
Detailed description of the invention
Below by embodiment, the invention will be further described.
Embodiment 1
The preparation of plant biomass leachate: get 5g cacumen biotae dry powder in conical flask, add 500mL deionized water, put into water bath with thermostatic control shaking table (30 DEG C, 150r/min) vibration 2h, filter and by filtrate constant volume to 500mL, concentration is the plant biomass leachate that is decided to be 10g/L.
Get 50mL deionized water in conical flask, and add to it chlorauric acid solution and 150 μ L ionic liquid [Bpy] [N (CN) that 0.5g HTS, 1040 μ L concentration are 0.04856mol/L
2], and carry out suction filtration after stirring 1h, and wash by 500mL deionized water, dry 24h under 50 DEG C of vacuum, under 375 DEG C of air atmospheres, activate 6h, obtain powdered loaded type Au catalyst, embodiment 1 makes the transmission electron microscope TEM figure of Au catalyst of preparing epoxypropane by epoxidation of propene referring to Fig. 1.
On atmospheric fixed bed micro-reaction equipment, add 0.15g catalyst A, reacting gas consists of C
3h
6/ H
2/ O
2/ N
2=1/1/1/7(volume ratio), air speed is 4000mLh
-1g
-1 cat, reaction temperature is 300 DEG C, catalytic reaction the results are shown in Table 1.
Embodiment 2
Get 50mL deionized water in conical flask, and add to it chlorauric acid solution and 150 μ L ionic liquid [Bpy] [N (CN) that 0.5g HTS, 1040 μ L concentration are 0.04856mol/L
2], and add the leachate 50mL in example 1 after stirring 1h, and continue to carry out suction filtration after stirring 1h, and with the washing of 500mL deionized water, under 50 DEG C of vacuum, be dried 24h, under 375 DEG C of air atmospheres, activate 6h, obtain powdered loaded type Au catalyst.Evaluating catalyst condition is with embodiment 1, and catalytic reaction the results are shown in Table 1.Embodiment 2 makes the transmission electron microscope TEM figure of Au catalyst of preparing epoxypropane by epoxidation of propene referring to Fig. 2.
Embodiment 3
Get 50mL deionized water in conical flask, and add to it chlorauric acid solution and 50 μ L ionic liquid [Bpy] [N (CN) that 0.5g HTS, 1040 μ L concentration are 0.04856mol/L
2], and add the leachate 50mL in example 1 after stirring 1h, and continue to carry out suction filtration after stirring 1h, and with the washing of 500mL deionized water, under 50 DEG C of vacuum, be dried 24h, under 375 DEG C of air atmospheres, activate 6h, obtain powdered loaded type Au catalyst C.Air speed is 7000mLh
-1g
-1 cat, all the other evaluating catalyst conditions are with embodiment 1, and catalytic reaction the results are shown in Table 1.
Embodiment 4
Get 50mL deionized water in conical flask, and add to it chlorauric acid solution and 100 μ L ionic liquid [Bpy] [N (CN) that 0.5g HTS, 1040 μ L concentration are 0.04856mol/L
2], and add the leachate 50mL in example 1 after stirring 1h, and continue to carry out suction filtration after stirring 1h, and with the washing of 500mL deionized water, under 50 DEG C of vacuum, be dried 24h, under 375 DEG C of air atmospheres, activate 6h, obtain powdered loaded type Au catalyst D.Evaluating catalyst condition is with embodiment 3, and catalytic reaction the results are shown in Table 1.
Embodiment 5
Get 50mL deionized water in conical flask, and add to it chlorauric acid solution and 200 μ L ionic liquid [Bpy] [N (CN) that 0.5g HTS, 1040 μ L concentration are 0.04856mol/L
2], and add the leachate 50mL in example 1 after stirring 1h, and continue to carry out suction filtration after stirring 1h, and with the washing of 500mL deionized water, under 50 DEG C of vacuum, be dried 24h, under 375 DEG C of air atmospheres, activate 6h, obtain powdered loaded type Au catalyst E.Evaluating catalyst condition is with embodiment 3, and catalytic reaction the results are shown in Table 1.
Embodiment 6
Get 50mL deionized water in conical flask, and add to it chlorauric acid solution and 100 μ L ionic liquid [Bpy] [N (CN) that 0.5g HTS, 1040 μ L concentration are 0.04856mol/L
2], and add the leachate 50mL in example 1 after stirring 1h, and continue to carry out suction filtration after stirring 1h, and with the washing of 500mL deionized water, under 50 DEG C of vacuum, be dried 24h, under 375 DEG C of air atmospheres, activate 6h, obtain powdered loaded type Au catalyst F.Catalytic reaction temperature is 280 DEG C, and all the other evaluating catalyst conditions are with embodiment 3, and catalytic reaction the results are shown in Table 1.
Embodiment 7
Get 50mL deionized water in conical flask, and add to it chlorauric acid solution and 100 μ L ionic liquid [Bpy] [N (CN) that 0.5g HTS, 1040 μ L concentration are 0.04856mol/L
2], and add the leachate 50mL in example 1 after stirring 1h, and continue to carry out suction filtration after stirring 1h, and with the washing of 500mL deionized water, under 50 DEG C of vacuum, be dried 24h, under 375 DEG C of air atmospheres, activate 6h, obtain powdered loaded type Au catalyst G.Catalytic reaction temperature is 260 DEG C, and all the other evaluating catalyst conditions are with embodiment 3, and catalytic reaction the results are shown in Table 1.
Embodiment 8
Get 50mL deionized water in conical flask, and add to it chlorauric acid solution and 100 μ L ionic liquid [Bpy] [N (CN) that 0.5g HTS, 1040 μ L concentration are 0.04856mol/L
2], and add the leachate 50mL in example 1 after stirring 1h, and continue to carry out suction filtration after stirring 1h, and with the washing of 500mL deionized water, under 50 DEG C of vacuum, be dried 24h, under 375 DEG C of air atmospheres, activate 6h, obtain powdered loaded type Au catalyst H.Catalytic reaction temperature is 240 DEG C, and all the other evaluating catalyst conditions are with embodiment 3, and catalytic reaction the results are shown in Table 1.
Embodiment 9
Get 50mL deionized water in conical flask, and add to it chlorauric acid solution and 100 μ L ionic liquid [Bpy] [N (CN) that 0.5g HTS, 1040 μ L concentration are 0.04856mol/L
2], and add the leachate 50mL in example 1 after stirring 1h, and continue to carry out suction filtration after stirring 1h, and with the washing of 500mL deionized water, under 50 DEG C of vacuum, be dried 24h, under 375 DEG C of air atmospheres, activate 6h, obtain powdered loaded type Au catalyst I.Catalytic reaction temperature is 220 DEG C, and all the other evaluating catalyst conditions are with embodiment 3, and catalytic reaction the results are shown in Table 1.
Table 1
Table 1 provides the catalytic reaction result of embodiment 1～9.
Claims (10)
1. the preparation method of the Au catalyst of preparing epoxypropane by epoxidation of propene, is characterized in that comprising the following steps:
1) plant cacumen biotae is dried to rear pulverizing, obtain plant cacumen biotae dry powder, then be added to the water, vibration, filters, and obtains plant biomass leachate;
2) in water, add HTS, golden presoma gold chloride (HAuCl
4) aqueous solution and ionic liquid [Bpy] [N (CN)
2], obtain solution A;
3) the plant biomass leachate obtaining in step 1) is added to step 2) in the solution A that obtains, obtain solution B;
4) solution B step 3) being obtained is carried out suction filtration, and washing is dry, activates, and obtains the Au catalyst of preparing epoxypropane by epoxidation of propene, and the Au catalyst of the preparing epoxypropane by epoxidation of propene of gained is powdered loaded type Au catalyst.
2. the preparation method of the Au catalyst of preparing epoxypropane by epoxidation of propene as claimed in claim 1, it is characterized in that in step 1), the proportioning of described plant cacumen biotae dry powder and water is 10g: 1L, wherein, plant cacumen biotae dry powder is calculated in mass, and water is calculated by volume.
3. the preparation method of the Au catalyst of preparing epoxypropane by epoxidation of propene as claimed in claim 1, is characterized in that in step 1) described hydromining deionized water.
4. the preparation method of the Au catalyst of preparing epoxypropane by epoxidation of propene as claimed in claim 1, is characterized in that in step 1), and described vibration is to be placed in the shaking table 2h that vibrates.
5. the preparation method of the Au catalyst of preparing epoxypropane by epoxidation of propene as claimed in claim 1, is characterized in that in step 2) in, described water, HTS, ionic liquid [Bpy] [N (CN)
2] proportioning be 50mL: 0.5g: (0～300) μ L, wherein water and ionic liquid [Bpy] [N (CN)
2] calculate by volume, HTS is calculated in mass.
6. the preparation method of the Au catalyst of preparing epoxypropane by epoxidation of propene as claimed in claim 1, is characterized in that in step 3), in the addition of described plant biomass leachate and step 1), the volume ratio of water is 50mL: 1L.
7. the preparation method of the Au catalyst of preparing epoxypropane by epoxidation of propene as claimed in claim 1, is characterized in that in step 4), and described washing adopts deionized water washing.
8. the preparation method of the Au catalyst of preparing epoxypropane by epoxidation of propene as claimed in claim 1, is characterized in that in step 4), described dry be dry 24h under 50 DEG C of vacuum.
9. the preparation method of the Au catalyst of preparing epoxypropane by epoxidation of propene as claimed in claim 1, is characterized in that in step 4), described activation is to activate 6h at 375 DEG C.
10. the preparation method of the Au catalyst of preparing epoxypropane by epoxidation of propene as claimed in claim 1, is characterized in that in step 4), the load capacity of the Au catalyst gold of described preparing epoxypropane by epoxidation of propene is 0.25%～4.0%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110721741A (en) * | 2019-09-27 | 2020-01-24 | 厦门大学 | Preparation method of gold catalyst for synthesizing propylene oxide |
| CN115125574A (en) * | 2022-06-30 | 2022-09-30 | 大连理工大学 | Method for connecting carbon-based electrocatalyst and TS-1 thermal catalyst in series and application of carbon-based electrocatalyst and TS-1 thermal catalyst in-situ preparation of propylene oxide by electrocatalytic oxygen reduction |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6337412B1 (en) * | 2000-04-25 | 2002-01-08 | Chemical Research & Licensing Company | Three stage propylene oxide process |
| CN101940946A (en) * | 2010-08-24 | 2011-01-12 | 厦门大学 | Preparation method for propylene epoxidation catalyst |
| CN101961663A (en) * | 2010-09-10 | 2011-02-02 | 厦门大学 | Biological in-situ reduction preparation method of catalyst for synthesizing epoxy-propane |
-
2014
- 2014-04-21 CN CN201410160967.6A patent/CN103894227B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6337412B1 (en) * | 2000-04-25 | 2002-01-08 | Chemical Research & Licensing Company | Three stage propylene oxide process |
| CN101940946A (en) * | 2010-08-24 | 2011-01-12 | 厦门大学 | Preparation method for propylene epoxidation catalyst |
| CN101961663A (en) * | 2010-09-10 | 2011-02-02 | 厦门大学 | Biological in-situ reduction preparation method of catalyst for synthesizing epoxy-propane |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110721741A (en) * | 2019-09-27 | 2020-01-24 | 厦门大学 | Preparation method of gold catalyst for synthesizing propylene oxide |
| CN115125574A (en) * | 2022-06-30 | 2022-09-30 | 大连理工大学 | Method for connecting carbon-based electrocatalyst and TS-1 thermal catalyst in series and application of carbon-based electrocatalyst and TS-1 thermal catalyst in-situ preparation of propylene oxide by electrocatalytic oxygen reduction |
| CN115125574B (en) * | 2022-06-30 | 2024-02-27 | 大连理工大学 | Method for connecting carbon-based electrocatalyst and TS-1 thermal catalyst in series and application of carbon-based electrocatalyst and TS-1 thermal catalyst in preparing propylene oxide in situ through electrocatalytic oxygen reduction |
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