CN101822990A - Supported nano gold catalyst for cyclohexane oxidation and preparation method thereof - Google Patents
Supported nano gold catalyst for cyclohexane oxidation and preparation method thereof Download PDFInfo
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- CN101822990A CN101822990A CN 201010140045 CN201010140045A CN101822990A CN 101822990 A CN101822990 A CN 101822990A CN 201010140045 CN201010140045 CN 201010140045 CN 201010140045 A CN201010140045 A CN 201010140045A CN 101822990 A CN101822990 A CN 101822990A
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- nano gold
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Abstract
The invention discloses a supported nano gold catalyst for cyclohexane oxidation and a preparation method thereof. The supported nano gold catalyst is composed of Au, Al, Co, Zr and Ce, wherein Au is used as a main active ingredient of the catalyst with the weight percentage content being 1.0 percent; Al is used as a carrier of the catalyst with the weight percentage content being more than or equal to 90 percent; and Co, Zr and Ce are used as supporting active ingredients of the catalyst with the weight percentage content being 1-7 percent. The preparation method comprises the following steps: modifying the carrier in a revolution dipping method at first and loading gold in a dipping-ammonia washing method. The invention has the advantages of simple preparation method, uniform dispersion of gold particles and high load efficiency. The catalyst provided by the invention has the advantages of good activity and selectivity and low consumption in preparation of cyclohexanone and cyclohexanol through cyclohexane oxidation.
Description
Technical field
The present invention relates to a kind of load type nano gold catalyst that is used for cyclohexane oxidation and preparation method thereof.
Background technology
The cyclohexane selective oxidation is a very important chemical process, oxidation product cyclohexanone and cyclohexanol (both mixtures are commonly called as KA oil) are the raw materials of producing caprolactam and adipic acid, and then both are important intermediate of industrial production nylon-6 and nylon-66.In addition, cyclohexanone and cyclohexanol have a wide range of applications in solvent, paint, coating and agrochemical field.At present, domestic and international cyclohexanone and cyclohexanol more than 90% is to adopt cyclohexane oxidation process production, and wherein 70% is cyclohexane non-catalyst oxidation method.But there are problems such as cyclohexane conversion low (one way molar yield 4～6%), keto-alcohol selectivity not high (about 80%), energy consumption height and three-waste pollution be serious in this technology.In order to improve conversion ratio and selectivity, Chinese scholars has been done number of research projects at the cyclohexane selective catalytic oxidation, has developed the catalyst of numerous species.A wherein important class is a nano catalyst.
Nano catalyst is a big important discovery of catalytic field in recent years.Found nano catalyst at present in the CO low-temperature oxidation, the elimination of nitrogen oxide, the liquid phase selective oxidation, fields such as Water gas shift/WGS have a good application prospect.Appropriate preparation method is closely related with the high performance nano catalyst of acquisition.The method that is commonly used to prepare nano catalyst mainly is the coprecipitation (CP method) and the deposition-precipitation method (DP method).The major defect of CP method is to have the gold particle of a great deal of to be embedded in carrier inside, has reduced golden utilization rate.Though the DP method can obtain the very little high-activity nano Au catalyst of particle diameter, this method is stronger to the dependence of carrier isoelectric point (IEP), generally only is applicable to the carrier of IEP＞6.Conventional infusion process is the industrial method for preparing catalyst that generally uses, and but is proved to be and is not suitable for preparing highly active nano catalyst.
Chinese patent CN 1827213A adopts the post-modification method to prepare load type nano gold catalyst, its weak point is that the high-temperature roasting in the post-modification process causes nm of gold to assemble easily and grows up, thereby reduce the activity of nano catalyst, and use poisonous organic matter such as benzene and toluene as solvent.Patent CNl01036887A employing order immersion process for preparing load type nano gold catalyst, the process of load gold uses NaOH solution to regulate the pH value of chlorauric acid solution.Gold chloride (HAuCl
44H
2O) in the aqueous solution, gold is with anion [AuCl
x(OH)
4-x] form of (x=0～4) exists.Along with the rising of pH value of solution, anion [AuCl
x(OH)
4-x] (x=0～4) progressively hydrolysis, reaching balance needs the long time.In addition, above-mentioned catalyst does not contain cobalt, and cobalt is a kind of component of oxidation reduction catalyst preferably.In sum, the nano catalyst performance that is used for cyclohexane oxidation haves much room for improvement.In addition, because preparation method's step is more, the preparation cost height is unfavorable for suitability for industrialized production.
Summary of the invention
The object of the present invention is to provide a kind of load type nano gold catalyst that is used for cyclohexane oxidation and preparation method thereof.
The load type nano gold catalyst that is used for cyclohexane oxidation is made up of Au, Al, Co, Zr and Ce, and wherein Au is as the main active of catalyst, and its quality percentage composition is 1.0%; Al is as the carrier of catalyst, its quality percentage composition 〉=90%; Co, Zr and Ce are as the auxiliary activity component of catalyst carrier, and its quality percentage composition is 1%～7%.
Described Au is the mixture of metal, metal oxide or metal and metal oxide.The grain diameter of described Au is 1～20nm.The carrier A l of described catalyst is a gama-alumina.Described Co, Zr and Ce are metal oxide.
The preparation method who is used for the load type nano gold catalyst of cyclohexane oxidation comprises the steps:
1) the 2.50g gama-alumina is contained rotary dipping 1～2h in the aqueous solution of 0.09～0.68g cobalt nitrate, 0.09～0.27g zirconium nitrate or 0.07～0.20g cerous nitrate at 15mL, rotation is evaporated to dried under 50～60 ℃, 80～110 ℃ of drying 2～3h, 500 ℃ of roasting 3～4h obtain the alumina support after the modification;
2) get under the aqueous solution room temperature that alumina support after the above-mentioned modification of 2.00g and 100mL contain the 0.04g gold chloride and stir dipping 1～2h, supernatant inclines, spend deionised water earlier 2～3 times, filter after soaking 5～10min with 15mL 4M ammoniacal liquor again, spend deionised water 2～3 times at last again, with the solid dry 8～10h under 80～100 ℃ that obtain, 300 ℃ of roasting 3～4h obtain load type nano gold catalyst.
The beneficial effect that the present invention compared with prior art has:
1) simple to operate, and the load efficiency height of gold;
2) gold grain is uniformly dispersed, the catalytic activity height;
3) catalyst provided by the invention prepares cyclohexanone and cyclohexanol for cyclohexane oxidation and has characteristics active and that selectivity is good, catalyst amount is little.
The specific embodiment
Below be embodiments of the invention.
Embodiment 1
The preparation of catalyst A.Get 0.04g gold chloride (HAuCl
44H
2O) be dissolved in the 100mL deionized water, add 2.00g gama-alumina (γ-Al
2O
3) carrier, room temperature condition stirs dipping 1h down, supernatant inclines, the solid that obtains spends deionised water earlier 2 times, with filtering behind the 15mL 4M ammoniacal liquor immersion 5min, spends deionised water at last again 2 times again, with the solid dry 10h under 80 ℃ that obtains, 300 ℃ of roasting 3h get catalyst A, and its composition sees Table 1.
Embodiment 2
The preparation of catalyst B.With 2.50g gama-alumina (γ-Al
2O
3) contain 0.09g cobalt nitrate (Co (NO with 15mL
3)
26H
2O) rotary dipping 1h under the aqueous solution room temperature condition, then 60 ℃ down rotation be evaporated to dried, 110 ℃ of dry 2h, 500 ℃ of roasting 3h obtain the alumina support after the modification.Get 0.04g gold chloride (HAuCl
44H
2O) be dissolved in the 100mL deionized water, alumina support after the above-mentioned modification of adding 2.00g, room temperature condition stirs dipping 1h down, and the supernatant that inclines, the solid that obtains spend deionised water earlier 3 times, filter after soaking 8min with 15mL 4M ammoniacal liquor again, spend deionised water 2 times at last again, with the solid dry 8h under 100 ℃ that obtains, 300 ℃ of roasting 4h, get catalyst B, its composition sees Table 1.
Embodiment 3
The preparation of catalyst C.With 2.50g gama-alumina (γ-Al
2O
3) contain 0.28g cobalt nitrate (Co (NO with 15mL
3)
26H
2O) rotary dipping 2h under the aqueous solution room temperature condition, then 50 ℃ down rotation be evaporated to dried, 80 ℃ of dry 3h, 500 ℃ of roasting 4h obtain the alumina support after the modification.Get 0.04g gold chloride (HAuCl
44H
2O) be dissolved in the 100mL deionized water, alumina support after the above-mentioned modification of adding 2.00g, room temperature condition stirs dipping 2h down, and the supernatant that inclines, the solid that obtains spend deionised water earlier 2 times, filter after soaking 7min with 15mL 4M ammoniacal liquor again, spend deionised water 3 times at last again, with the solid dry 8h under 90 ℃ that obtains, 300 ℃ of roasting 4h, get catalyst C, its composition sees Table 1.
Embodiment 4
The preparation of catalyst D.With 2.50g gama-alumina (γ-Al
2O
3) contain 0.68g cobalt nitrate (Co (NO with 15mL
3)
26H
2O) rotary dipping 1h under the aqueous solution room temperature condition, then 60 ℃ down rotation be evaporated to dried, 110 ℃ of dry 2h, 500 ℃ of roasting 3h obtain the alumina support after the modification.Get 0.04g gold chloride (HAuCl
44H
2O) be dissolved in the 100mL deionized water, alumina support after the above-mentioned modification of adding 2.00g, room temperature condition stirs dipping 1h down, and the supernatant that inclines, the solid that obtains spend deionised water earlier 3 times, filter after soaking 5min with 15mL 4M ammoniacal liquor again, spend deionised water 3 times at last again, with the solid dry 10h under 80 ℃ that obtains, 300 ℃ of roasting 3h, get catalyst D, its composition sees Table 1.
Embodiment 5
The preparation of catalyst E.With 2.50g gama-alumina (γ-Al
2O
3) contain 0.27g zirconium nitrate (Zr (NO with 15mL
3)
45H
2O) rotary dipping 1.5h under the aqueous solution room temperature condition, then 50 ℃ down rotation be evaporated to dried, 110 ℃ of dry 2h, 500 ℃ of roasting 4h obtain the alumina support after the modification.Get 0.04g gold chloride (HAuCl
44H
2O) be dissolved in the 100mL deionized water, alumina support after the above-mentioned modification of adding 2.00g, room temperature condition stirs dipping 1h down, and the supernatant that inclines, the solid that obtains spend deionised water earlier 3 times, filter after soaking 5min with 15mL 4M ammoniacal liquor again, spend deionised water 2 times at last again, with the solid dry 9h under 80 ℃ that obtains, 300 ℃ of roasting 4h, get catalyst E, its composition sees Table 1.
Embodiment 6
The preparation of catalyst F.With 2.50g gama-alumina (γ-Al
2O
3) contain 0.20g cerous nitrate (Ce (NO with 15mL
3)
36H
2O) rotary dipping 1.5h under the aqueous solution room temperature condition, then 60 ℃ down rotation be evaporated to dried, 110 ℃ of dry 2h, 500 ℃ of roasting 3h obtain the alumina support after the modification.Get 0.04g gold chloride (HAuCl
44H
2O) be dissolved in the 100mL deionized water, alumina support after the above-mentioned modification of adding 2.00g, room temperature condition stirs dipping 1h down, and the supernatant that inclines, the solid that obtains spend deionised water earlier 3 times, filter after soaking 10min with 15mL 4M ammoniacal liquor again, spend deionised water 2 times at last again, with the solid dry 9h under 80 ℃ that obtains, 300 ℃ of roasting 3h, get catalyst F, its composition sees Table 1.
Embodiment 7
The preparation of catalyst G.With 2.50g gama-alumina (γ-Al
2O
3) contain 0.19g cobalt nitrate (Co (NO with 15mL
3)
26H
2O) and 0.09g zirconium nitrate (Zr (NO
3)
45H
2O) rotary dipping 1h under the aqueous solution room temperature condition, then 55 ℃ down rotation be evaporated to dried, 85 ℃ of dry 3h, 500 ℃ of roasting 3h obtain the alumina support after the modification.Get 0.04g gold chloride (HAuCl
44H
2O) be dissolved in the 100mL deionized water, alumina support after the above-mentioned modification of adding 2.00g, room temperature condition stirs dipping 1.5h down, and the supernatant that inclines, the solid that obtains spend deionised water earlier 3 times, filter after soaking 6min with 15mL 4M ammoniacal liquor again, spend deionised water 2 times at last again, with the solid dry 8h under 85 ℃ that obtains, 300 ℃ of roasting 4h, get catalyst G, its composition sees Table 1.
Embodiment 8
The preparation of catalyst H.With 2.50g gama-alumina (γ-Al
2O
3) contain 0.19g cobalt nitrate (Co (NO with 15mL
3)
26H
2O) and 0.07g cerous nitrate (Ce (NO
3)
36H
2O) rotary dipping 1h under the aqueous solution room temperature condition, then 50 ℃ down rotation be evaporated to dried, 100 ℃ of dry 2h, 500 ℃ of roasting 3h obtain the alumina support after the modification.Get 0.04g gold chloride (HAuCl
44H
2O) be dissolved in the 100mL deionized water, alumina support after the above-mentioned modification of adding 2.00g, room temperature condition stirs dipping 2h down, and the supernatant that inclines, the solid that obtains spend deionised water earlier 3 times, filter after soaking 8min with 15mL 4M ammoniacal liquor again, spend deionised water 2 times at last again, with the solid dry 9h under 80 ℃ that obtains, 300 ℃ of roasting 4h, get catalyst H, its composition sees Table 1.
Embodiment 9
The catalytic performance test of catalyst A～H.Be reflected in the stainless steel autoclave that 100mL has the polytetrafluoroethylene (PTFE) liner and carry out.0.05g catalyst and 20mL cyclohexane are joined in the batch reactor, and after the sealing, the oil bath heating makes temperature in the kettle rise to 145～147 ℃ and feeds part oxygen, arrives 150 ℃ of supplemental oxygen to reaction pressure 1.5MPa, and the reaction timing begins; Lasting aerating oxygen is kept constant pressure, stirring reaction 3h.Reaction finishes, and is cooled to room temperature, centrifugation behind the adding amount of acetone lysate.Product mixed liquor GC-1690 gas chromatograph (SE-54 capillary chromatographic column, specification: 30m * 0.32mm * 0.5 μ m, fid detector) carry out quantitative analysis, normal heptane is as internal standard compound, wherein cyclohexyl hydroperoxide (CHHP) adopts the iodimetric titration quantitative analysis, and analysis result sees Table 2.
The composition of table 1 catalyst A～H
The catalytic performance test of table 2 catalyst A～H
Cyclohexane oxidation condition: 20mL cyclohexane, 0.05g catalyst, 150 ℃, 1.5MPa, 3h
Claims (6)
1. a load type nano gold catalyst that is used for cyclohexane oxidation is characterized in that, it is made up of Au, Al, Co, Zr and Ce, and wherein Au is as the main active of catalyst, and its quality percentage composition is 1.0%; Al is as the carrier of catalyst, its quality percentage composition 〉=90%; Co, Zr and Ce are as the auxiliary activity component of catalyst carrier, and its quality percentage composition is 1%～7%.
2. a kind of load type nano gold catalyst that is used for cyclohexane oxidation according to claim 1 is characterized in that described Au is the mixture of metal, metal oxide or metal and metal oxide.
3. a kind of load type nano gold catalyst that is used for cyclohexane oxidation according to claim 1, the grain diameter that it is characterized in that described Au is 1～20nm.
4. a kind of load type nano gold catalyst that is used for cyclohexane oxidation according to claim 1, the carrier A l that it is characterized in that described catalyst is a gama-alumina.
5. a kind of load type nano gold catalyst that is used for cyclohexane oxidation according to claim 1 is characterized in that described Co, Zr and Ce are metal oxide.
6. a preparation method who is used for the load type nano gold catalyst of cyclohexane oxidation as claimed in claim 1 is characterized in that comprising the steps:
1) the 2.50g gama-alumina is contained rotary dipping 1～2h in the aqueous solution of 0.09～0.68g cobalt nitrate, 0.09～0.27g zirconium nitrate or 0.07～0.20g cerous nitrate at 15mL, rotation is evaporated to dried under 50～60 ℃, 80～110 ℃ of drying 2～3h, 500 ℃ of roasting 3～4h obtain the alumina support after the modification;
2) get under the aqueous solution room temperature that alumina support after the above-mentioned modification of 2.00g and 100mL contain the 0.04g gold chloride and stir dipping 1～2h, supernatant inclines, spend deionised water earlier 2～3 times, filter after soaking 5～10min with 15mL 4M ammoniacal liquor again, spend deionised water 2～3 times at last again, with the solid dry 8～10h under 80～100 ℃ that obtain, 300 ℃ of roasting 3～4h obtain load type nano gold catalyst.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102199415A (en) * | 2010-12-27 | 2011-09-28 | 中国人民解放军空军油料研究所 | Preparation method of graphene oxide/nano-gold particulate composite material with mono-atomic thickness |
| CN104998643A (en) * | 2015-06-30 | 2015-10-28 | 浙江大学 | Au/BW11/Al2O3 catalyst and its preparation method and use |
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| JP2005081283A (en) * | 2003-09-10 | 2005-03-31 | Sumitomo Metal Mining Co Ltd | Oxidation catalyst for removing harmful gas |
| CN101036887A (en) * | 2007-03-13 | 2007-09-19 | 浙江大学 | Load type nano-au catalyst and the preparing method |
| CN101204662A (en) * | 2006-12-22 | 2008-06-25 | 中国科学院大连化学物理研究所 | Cyclohexane liquid-phase oxidation nanometer catalyst and preparation thereof |
-
2010
- 2010-04-02 CN CN 201010140045 patent/CN101822990A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005081283A (en) * | 2003-09-10 | 2005-03-31 | Sumitomo Metal Mining Co Ltd | Oxidation catalyst for removing harmful gas |
| CN101204662A (en) * | 2006-12-22 | 2008-06-25 | 中国科学院大连化学物理研究所 | Cyclohexane liquid-phase oxidation nanometer catalyst and preparation thereof |
| CN101036887A (en) * | 2007-03-13 | 2007-09-19 | 浙江大学 | Load type nano-au catalyst and the preparing method |
Non-Patent Citations (1)
| Title |
|---|
| 《高校化学工程学报》 20090430 许立信等 锆改性氧化铝负载的纳米金催化剂上环己烷氧化研究 第310页第2节 5 第23卷, 第2期 2 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102199415A (en) * | 2010-12-27 | 2011-09-28 | 中国人民解放军空军油料研究所 | Preparation method of graphene oxide/nano-gold particulate composite material with mono-atomic thickness |
| CN102199415B (en) * | 2010-12-27 | 2014-04-16 | 中国人民解放军空军油料研究所 | Preparation method of graphene oxide/nano-gold particulate composite material with mono-atomic thickness |
| CN104998643A (en) * | 2015-06-30 | 2015-10-28 | 浙江大学 | Au/BW11/Al2O3 catalyst and its preparation method and use |
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