CN1827213A - Supported nano Au catalyst and method for preparing the same - Google Patents
Supported nano Au catalyst and method for preparing the same Download PDFInfo
- Publication number
- CN1827213A CN1827213A CN 200610050249 CN200610050249A CN1827213A CN 1827213 A CN1827213 A CN 1827213A CN 200610050249 CN200610050249 CN 200610050249 CN 200610050249 A CN200610050249 A CN 200610050249A CN 1827213 A CN1827213 A CN 1827213A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- type nano
- load type
- gold
- nano gold
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a carrier nanometer gold catalyst gold catalyst and relative preparing method. Said invention is formed by Au, Al, and Ti/Si, Ag, Cu, Ce, Fe, or Zn. Wherein, Au is the main active component of catalyst, whose mass percentage is 0.1-4.0%; Al is the carrier of catalyst, whose mass percentage is larger than 90%; Ti or Si is the agent of catalyst carrier, whose mass percentage is 0.01-1.0%; Ag, Cu, Ce, Fe, or Zn is used as the auxiliary active component of catalyst, whose mass percentage is 0.1-5.0%. The invention has the advantages that: the gold is distributed uniformly, and the graininess of attained gold particle can be adjusted easily; the catalyst has high stability; and it can apply the oxide carrier for carrying gold whose isoelectric point pH is less than 6 and made by coprecipitation method. The invention has be used to apply the cyclohexane to prepare the nadone and cyclohexanol, with better activity and selectivity, less used amount and recycle support.
Description
Technical field
The present invention relates to load type nano gold catalyst that is used for cyclohexane oxidation preparing cyclohexanone and cyclohexanol and preparation method thereof.
Background technology
Nano catalyst has good low-temperature catalytic oxidation activity, is one of great discovery of catalytic field in recent years.Found that at present Au catalyst is at CO and NO
xEliminate, hydrocarbon oxidation, the steam conversion, fields such as fuel cell have a good application prospect.The preparation method commonly used of nano catalyst has coprecipitation, deposition-precipitation method etc.In the catalyst that coprecipitation obtains, the golden suppressed by vector of part wraps up, and can not bring into play catalytic action, and the utilization rate of gold is low.Deposition-precipitation method is only applicable to the carrier of isoelectric pH 〉=6, and the catalyst of these two kinds of method preparations remains in the uppity shortcoming of gold grain granularity.Other preparation methods as chemical vapour deposition technique, because preparation cost is higher, are used for experimental study more, and industrial applications is worth not high.
Adopt oxygen-containing organic compounds such as oxygen or air oxidation hydro carbons preparation alcohol, ketone to have important industrial application value.Wherein, cyclohexanone is a kind of important chemical material and industrial solvent, and the air oxidation of cyclohexane rule is the main method of producing cyclohexanone both at home and abroad.The air oxidation of cyclohexane preparing cyclohexanone can be divided into two kinds of no catalysis method and catalysis methods.Wherein, no Catalytic processes is to adopt cyclohexane oxidation to produce the universal method of cyclohexanone at present both at home and abroad.Because the reaction condition of this arts demand HTHP, deep oxidation, poor selectivity can take place in target product cyclohexanone and cyclohexanol (both are called for short KA oil).Therefore, in the actual production, control usually cyclohexane conversion less than 4% to keep KA oil selectivity about 80%.In addition, intermediate product cyclohexyl hydroperoxide decomposition workshop section produces a large amount of spent lyes, environmental treatment expense height.Catalysis method mesoboric acid method is higher because of cost, almost eliminates.Catalysis of cobalt salt exists also that conversion ratio is low, the shortcoming of poor selectivity.Chinese patent CN 00113225.3 has the relative gentle and high advantage of selectivity of reaction condition with the disclosed bionic catalysis method of CN 1405131A, but has problems such as catalyst life is short, recovery difficulty.
U.S. Pat 6160183 adopts deposition-precipitation method to prepare loaded catalyst Au/Al
2O
3, under 160～180 ℃, 3.4MPa condition, be oxidant with the air, reaction 45～55min, cyclohexane conversion is between 1.80～4.95%, and the KA selectivity is 86～97%.World patent WO 2004071998-A2 is fixed on nm of gold and obtains a series of catalyst on sial and the phosphate aluminium molecular sieve, as adopt Au/ total silicon ZSM-5 catalyst to carry out air oxidation of cyclohexane, 170 ℃ of reaction temperatures, under pressure 0.88～0.95MPa condition, KA and cyclohexyl hydroperoxide overall selectivity 91.4%, cyclohexane conversion 3.39%.Have the advantage that need not reaction dissolvent and other additives though above-mentioned load type gold catalyst is used for cyclohexane oxidation, reaction temperature generally about 170 ℃, obtains high conversion ratio and selectivity simultaneously and remains a challenge under high-temperature and high-pressure conditions like this.
Summary of the invention
The object of the present invention is to provide a kind of load type nano gold catalyst and preparation method thereof.
Load type nano gold catalyst is made up of Au, Al and Ti or Si and Ag, Cu, Ce, Fe or Zn, and wherein, Au is as the main active component of catalyst, and its quality percentage composition is 0.1～4.0%; Al is as the carrier of catalyst, its quality percentage composition 〉=90%; Ti or Si are as the auxiliary agent of catalyst carrier, and its quality percentage composition is 0.01～1.0%; Ag, Cu, Ce, Fe or Zn are as the auxiliary activity component of catalyst, and its quality percentage composition is 0.1～5.0%.
Described Au is the mixture of metal, metal oxide or metal and metal oxide, and the grain diameter of Au is 1～30nm;
The carrier A l of catalyst is an aluminium oxide; The auxiliary agent Ti of catalyst carrier and Si are silica, titanium oxide or their mixture;
Ag, Cu, Ce, Fe or Zn are metal or metal oxide.
Load type nano gold catalyst preparation method's step is as follows:
1) 1.0g solid alumina and the reactant aqueous solution 2～8h that contains 0.002～0.09g gold chloride, the temperature of reaction is 20～90 ℃, the pH value is 3.0～6.0, the filter cake that filtration or centrifugation obtain 1～4M ammonia scrubbing of 30mL, behind 60～200 ℃ of drying 4～8h, obtain the aluminium oxide of load gold;
2) aluminium oxide with above-mentioned load gold contains 0.002～0.1g silver nitrate with 2mL, 0.003～0.15g nitric acid ketone, 0.003～0.15g cerous nitrate, 0.005 the aqueous solution room temperature of～0.25g ferric nitrate or 0.004～0.2g zinc nitrate dipping 10～20h, 60～200 ℃ of drying 4～8h then, 200～500 ℃ of roasting 4～8h, contain 0.055～5.5mL ethyl orthosilicate with 20mL again, 0.04 the organic solvent of～4.0mL butyl titanate or their mixture reaction 2～8h, the filter cake that filtration obtains is at first used 30～60mL absolute ethanol washing, wash with 50～100mL deionized water then, 60～200 ℃ of drying 4～8h, 200～500 ℃ of roasting 4～8h obtain load type nano gold catalyst.
Described organic solvent is the mixture of benzene, toluene and methyl alcohol or ethanol.
Advantage of the present invention:
The granularity of 1) being uniformly dispersed of gold, and gained gold component particles is regulated easily;
2) stability of catalyst is high;
3) be particularly useful for the oxide carrier that those isoelectric pH values are difficult to the load gold less than 6 employing co-precipitation or deposition-precipitation method;
4) catalyst provided by the invention prepares cyclohexanone for cyclohexane oxidation and cyclohexanol has the advantages that reaction condition gentleness, activity and selectivity are good, catalyst amount is little, be easy to recycle.
The specific embodiment
Below be embodiments of the invention.
Embodiment 1
The preparation of catalyst A.Get 0.03g gold chloride HAuCl
44H
2O is dissolved in the 100mL deionized water, and regulating the pH value with the sodium hydroxide solution of 1M is 5.0.In above-mentioned solution, add 1.0g Al
2O
3, in 70 ℃ of following stirring reaction 2h, filtering, solid product behind 80 ℃ of dry 4h, floods 10h, 80 ℃ of dry 4h with the 0.008g liquor argenti nitratis ophthalmicus room temperature that contains of 2mL with the 1M ammonia scrubbing of 30mL again.Resulting solid product is joined in the mixture that contains 0.55mL ethyl orthosilicate, 10mL benzene, 10mL ethanol, stirring reaction 2h under the room temperature condition, filter, wash with 30mL ethanol, then with the washing of 50mL deionized water, 80 ℃ of dry 4h, 400 ℃ of roasting 4h, get catalyst A, its composition sees Table 1.
Embodiment 2
The preparation of catalyst B.Get 0.02g gold chloride HAuCl
44H
2O is dissolved in the 100mL deionized water, and regulating the pH value with the sodium hydroxide solution of 1M is 6.0.In above-mentioned solution, add 1.0g Al
2O
3,, filter the solid product 4M ammonia scrubbing of 30mL, 200 ℃ of dry 4h in 90 ℃ of following stirring reaction 2h.This solid product contains 0.02g nitric acid ketone Cu (NO with 2mL
3)
26H
2200 ℃ of dry 4h behind the aqueous solution room temperature dipping 10h of O, 500 ℃ of roasting 4h, resulting solid product joined contain in 1.6mL butyl titanate, 10mL toluene, the 10mL methanol mixture, stirring reaction 2h under the room temperature condition filters, wash with 60mL ethanol, then with the washing of 100mL deionized water, 200 ℃ of dry 4h, 500 ℃ of roasting 4h, get catalyst B, its composition sees Table 1.
Embodiment 3
The preparation of catalyst C.Get 0.02g gold chloride HAuCl
44H
2O is dissolved in the 100mL deionized water, and regulating the pH value with the sodium hydroxide solution of 1M is 3.0.In above-mentioned solution, add 1.0g Al
2O
3,, filter the solid product 1M ammonia scrubbing of 30mL, 60 ℃ of dry 8h in 20 ℃ of following stirring reaction 8h.This solid product contains 0.01g cerous nitrate Ce (NO with 2mL
3)
36H
260 ℃ of dry 8h behind the aqueous solution room temperature dipping 20h of O, 200 ℃ of roasting 8h, resulting solid product is joined in the mixture that contains 2.2mL ethyl orthosilicate, 10mL toluene, 10mL ethanol, and stirring reaction 8h under the room temperature condition filters, wash with 30mL ethanol, then with the washing of 50mL deionized water, 60 ℃ of dry 8h, 200 ℃ of roasting 8h, get catalyst C, its composition sees Table 1.
Embodiment 4
The preparation of catalyst D.Get 0.02g gold chloride HAuCl
44H
2O is dissolved in the 100mL deionized water, and regulating the pH value with the sodium hydroxide solution of 1M is 4.0.In above-mentioned solution, add 1.0g Al
2O
3,, filter the solid product 1M ammonia scrubbing of 30mL, 120 ℃ of dry 4h in 50 ℃ of following stirring reaction 2h.This solid product contains 0.02g ferric nitrate Fe (NO with 2mL
3)
39H
280 ℃ of dry 6h behind the aqueous solution room temperature dipping 10h of O, 300 ℃ of roasting 4h, resulting solid product is joined in the mixture that contains 2.4mL butyl titanate, 10mL toluene, 10mL ethanol, and stirring reaction 2h under the room temperature condition filters, wash with 30mL ethanol, then with the washing of 50mL deionized water, 80 ℃ of dry 4h, 400 ℃ of roasting 4h, get catalyst D, its composition sees Table 1.
Embodiment 5
The preparation of catalyst E.Get 0.02g gold chloride HAuCl
44H
2O is dissolved in the 100mL deionized water, and regulating the pH value with the sodium hydroxide solution of 1M is 4.0.In above-mentioned solution, add 1.0g Al
2O
3,, filter the solid product 4M ammonia scrubbing of 30mL, 80 ℃ of dry 4h in 80 ℃ of following stirring reaction 2h.This solid product contains 0.03g zinc nitrate Zn (NO with 2mL
3)
26H
280 ℃ of dry 6h behind the aqueous solution room temperature dipping 20h of O, 400 ℃ of roasting 4h, resulting solid product is joined in the mixture that contains 1.1mL ethyl orthosilicate, 1.6mL butyl titanate, 10mL toluene, 10mL ethanol, and stirring reaction 2h under the room temperature condition filters, wash with 30mL ethanol, then with the washing of 50mL deionized water, 80 ℃ of dry 4h, 400 ℃ of roasting 4h, get catalyst E, its composition sees Table 1.
Embodiment 6
The catalytic performance test of catalyst A～E.With the 100mL cyclohexane, 0.2g a kind of the joining in the 500mL autoclave among catalyst A～I, be warmed up to the oxygen that feeds 1.0MPa after 130 ℃, stirring reaction 90min under this temperature and pressure condition, reaction finishes, filter or centrifugation recovery catalyst, cyclohexane oxidation product adopts gas chromatography to analyze, and analysis result sees Table 2.
The composition of table 1 catalyst
| Catalyst | Catalyst is formed and content, wt.% | ||
| Active component | Carrier | Auxiliary agent | |
| A | Au 1.4，Ag 0.5 | Al 2O 3 98.0 | SiO 2 0.1 |
| B | Au 0.9，CuO 0.6 | Al 2O 3 98.1 | TiO 2 0.4 |
| C | Au 0.9，Ce 2O 3 0.4 | Al 2O 3 98.3 | SiO 2 0.4 |
| D | Au 0.9，Fe 2O 3 0.4 | Al 2O 3 98.1 | TiO 2 0.6 |
| E | Au 0.9，ZnO 0.8 | Al 2O 3 97.7 | SiO 2 0.2，TiO 2 0.4 |
The catalytic performance test of table 2 catalyst A～E
| Catalyst | Conversion ratio mol% | Selectivity, mol% | |
| Cyclohexanone and cyclohexanol | Cyclohexanone, cyclohexanol and cyclohexyl hydroperoxide | ||
| A | 10.2 | 87.7 | 92.0 |
| B | 7.8 | 81.5 | 93.2 |
| C | 4.7 | 71.4 | 95.6 |
| D | 7.5 | 83.7 | 94.4 |
| E | 6.8 | 85.4 | 93.7 |
Cyclohexane oxidation condition: cyclohexane 100mL, catalyst 0.20g, 130 ℃ of temperature, pressure 1.0MPa, time 90min.
Claims (8)
1. a load type nano gold catalyst is characterized in that, it is made up of Au, Al and Ti or Si and Ag, Cu, Ce, Fe or Zn, and wherein, Au is as the main active component of catalyst, and its quality percentage composition is 0.1～4.0%; Al is as the carrier of catalyst, its quality percentage composition 〉=90%; Ti or Si are as the auxiliary agent of catalyst carrier, and its quality percentage composition is 0.01～1.0%; Ag, Cu, Ce, Fe or Zn are as the auxiliary activity component of catalyst, and its quality percentage composition is 0.1～5.0%.
2. a kind of load type nano gold catalyst 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 according to claim 1, the grain diameter that it is characterized in that described Au is 1～30nm.
4. a kind of load type nano gold catalyst according to claim 1, the carrier A l that it is characterized in that described catalyst is an aluminium oxide.
5. a kind of load type nano gold catalyst according to claim 1 is characterized in that the auxiliary agent Ti of described catalyst carrier and Si are silica, titanium oxide or their mixture.
6. a kind of load type nano gold catalyst according to claim 1 is characterized in that described Ag, Cu, Ce, Fe or Zn are metal or metal oxide.
7. the preparation method of a load type nano gold catalyst as claimed in claim 1 is characterized in that, the step of method is as follows:
1) 1.0g solid alumina and the reactant aqueous solution 2～8h that contains 0.002～0.09g gold chloride, the temperature of reaction is 20～90 ℃, the pH value is 3.0～6.0, the filter cake that filtration or centrifugation obtain 1～4M ammonia scrubbing of 30mL, behind 60～200 ℃ of drying 4～8h, obtain the aluminium oxide of load gold;
2) aluminium oxide with above-mentioned load gold contains 0.002～0.1g silver nitrate with 2mL, 0.003～0.15g nitric acid ketone, 0.003～0.15g cerous nitrate, 0.005 the aqueous solution room temperature of～0.25g ferric nitrate or 0.004～0.2g zinc nitrate dipping 10～20h, 60～200 ℃ of drying 4～8h then, 200～500 ℃ of roasting 4～8h, contain 0.055～5.5mL ethyl orthosilicate with 20mL again, 0.04 the organic solvent of～4.0mL butyl titanate or their mixture reaction 2～8h, the filter cake that filtration obtains is at first used 30～60mL absolute ethanol washing, wash with 50～100mL deionized water then, 60～200 ℃ of drying 4～8h, 200～500 ℃ of roasting 4～8h obtain load type nano gold catalyst.
8. the preparation method of a kind of load type nano gold catalyst according to claim 7 is characterized in that described organic solvent is the mixture of benzene, toluene and methyl alcohol or ethanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100502499A CN100364663C (en) | 2006-04-07 | 2006-04-07 | Supported nano Au catalyst and method for preparing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100502499A CN100364663C (en) | 2006-04-07 | 2006-04-07 | Supported nano Au catalyst and method for preparing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1827213A true CN1827213A (en) | 2006-09-06 |
| CN100364663C CN100364663C (en) | 2008-01-30 |
Family
ID=36945889
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100502499A Expired - Fee Related CN100364663C (en) | 2006-04-07 | 2006-04-07 | Supported nano Au catalyst and method for preparing the same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100364663C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100435944C (en) * | 2007-03-13 | 2008-11-26 | 浙江大学 | Load type nano-au catalyst and the preparing method |
| CN101259423B (en) * | 2008-04-10 | 2010-06-16 | 杭州电子科技大学 | Method for preparing multicomponent co-synergistic effect synergistic effect photocatalytic material composite nano tube |
| CN101804347A (en) * | 2010-04-02 | 2010-08-18 | 浙江大学 | Preparation method and purpose of supported nano-gold catalyst for cyclohexene oxide |
| CN102553586A (en) * | 2010-12-28 | 2012-07-11 | 北京化工大学 | Cerium-containing composite metal oxide loaded nano-gold and preparation method and application thereof |
| CN104587993B (en) * | 2013-11-03 | 2016-11-16 | 中国石油化工股份有限公司 | A kind of preparation method of Hydrobon catalyst |
| CN108855063A (en) * | 2018-05-31 | 2018-11-23 | 云南大学 | A kind of nano catalyst and the preparation method and application thereof |
| CN109806863A (en) * | 2017-11-20 | 2019-05-28 | 中国科学院大连化学物理研究所 | The preparation of Au catalyst and its application in oxidative dehydrogenation of cyclonexane reaction |
| CN110051837A (en) * | 2019-04-08 | 2019-07-26 | 南京师范大学 | A kind of CuO/ZnO/Au nanoparticle and its preparation method and application |
| CN110372555A (en) * | 2019-08-19 | 2019-10-25 | 万华化学集团股份有限公司 | A kind of method that electro-catalysis oxygen oxidation of beta-carrotene prepares canthaxanthin |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR9815441B1 (en) * | 1997-02-11 | 2009-12-01 | improved process for decomposition of a hydroperoxide. | |
| US6160183A (en) * | 1998-02-10 | 2000-12-12 | E. I. Du Pont De Nemours And Company | Direct oxidation of cycloalkanes |
| DE19832016A1 (en) * | 1998-07-16 | 2000-01-20 | Studiengesellschaft Kohle Mbh | Selective oxidation of cyclohexane to cyclohexanol and cyclohexanone comprises reaction with oxygen on a micro- or meso-porous mixed oxide catalyst in a heated reactor with an inert lining |
| WO2000053550A1 (en) * | 1999-03-10 | 2000-09-14 | E.I. Du Pont De Nemours And Company | Hydroperoxide decomposition process |
| FR2824322A1 (en) * | 2001-05-04 | 2002-11-08 | Rhodia Polyamide Intermediates | PROCESS FOR HYDROCARBON OXIDATION |
| CN1611476A (en) * | 2003-10-30 | 2005-05-04 | 中国科学院兰州化学物理研究所 | Method for preparing cyclohexanone by selective odixation of cyclohexane |
-
2006
- 2006-04-07 CN CNB2006100502499A patent/CN100364663C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100435944C (en) * | 2007-03-13 | 2008-11-26 | 浙江大学 | Load type nano-au catalyst and the preparing method |
| CN101259423B (en) * | 2008-04-10 | 2010-06-16 | 杭州电子科技大学 | Method for preparing multicomponent co-synergistic effect synergistic effect photocatalytic material composite nano tube |
| CN101804347A (en) * | 2010-04-02 | 2010-08-18 | 浙江大学 | Preparation method and purpose of supported nano-gold catalyst for cyclohexene oxide |
| CN102553586A (en) * | 2010-12-28 | 2012-07-11 | 北京化工大学 | Cerium-containing composite metal oxide loaded nano-gold and preparation method and application thereof |
| CN102553586B (en) * | 2010-12-28 | 2014-02-19 | 北京化工大学 | Cerium-containing composite metal oxide loaded nano-gold and preparation method and application thereof |
| CN104587993B (en) * | 2013-11-03 | 2016-11-16 | 中国石油化工股份有限公司 | A kind of preparation method of Hydrobon catalyst |
| CN109806863A (en) * | 2017-11-20 | 2019-05-28 | 中国科学院大连化学物理研究所 | The preparation of Au catalyst and its application in oxidative dehydrogenation of cyclonexane reaction |
| CN108855063A (en) * | 2018-05-31 | 2018-11-23 | 云南大学 | A kind of nano catalyst and the preparation method and application thereof |
| CN110051837A (en) * | 2019-04-08 | 2019-07-26 | 南京师范大学 | A kind of CuO/ZnO/Au nanoparticle and its preparation method and application |
| CN110051837B (en) * | 2019-04-08 | 2021-05-11 | 南京师范大学 | CuO/ZnO/Au nano-particles and preparation method and application thereof |
| CN110372555A (en) * | 2019-08-19 | 2019-10-25 | 万华化学集团股份有限公司 | A kind of method that electro-catalysis oxygen oxidation of beta-carrotene prepares canthaxanthin |
| CN110372555B (en) * | 2019-08-19 | 2021-09-07 | 万华化学集团股份有限公司 | Method for preparing canthaxanthin by oxidizing beta-carotene through electrocatalytic oxygen |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100364663C (en) | 2008-01-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100364663C (en) | Supported nano Au catalyst and method for preparing the same | |
| CN103157471B (en) | Deoxidation catalyst for olefin gas, preparation method and application thereof | |
| CN107999116B (en) | Catalyst for catalyzing selective hydrogenation of chloro-aromatic nitro compound | |
| CN102206147B (en) | Method for oxidizing cyclohexane | |
| CN103272601B (en) | A kind of preparation method of the catalyst for By Catalytic Hydrogenation of Nitrobenzene synthesis aniline | |
| CN103406121B (en) | A kind of charcoal carries palladium oxide catalyst and its preparation method and application | |
| CN104492429A (en) | Catalyst and method for synthesizing methyl glycollate and ethylene glycol by virtue of dimethyl oxalate hydrogenation | |
| CN102295524B (en) | Method for preparing cyclohexanol and cyclohexanone by selective oxidation of cyclohexane | |
| CN111153768B (en) | Synthesis method of isohexide | |
| CN102513151A (en) | Method for preparing high-performance nano gold catalyst | |
| CN111269086A (en) | Application method of atomic-level dispersed ruthenium catalyst in catalytic hydrogenation | |
| CN101747152B (en) | Citral liquid-phase hydrogenation method for synthesizing unsaturated alcohols | |
| US20060224020A1 (en) | Method for manufacturing cycloalkanol and/or cycloalkanone | |
| CN100435944C (en) | Load type nano-au catalyst and the preparing method | |
| CN103111293B (en) | A kind of Catalysts and its preparation method for the preparation of acetparaminosalol cyclohexanol | |
| CN103965014A (en) | Method for preparing cyclohexanol and cyclohexanone through selective oxidation of cyclohexane | |
| CN103537301A (en) | Catalyst for coproduction of methylal and methyl formate from methanol through oxidization as well as preparation method and application of catalyst | |
| CN101157677B (en) | Method for catalytic preparation of delta-valerolactone by using supported nano-gold catalyst | |
| DE102007047430A1 (en) | catalyst | |
| CN110694632A (en) | Preparation method and application of cobalt-cerium composite oxide catalyst | |
| CN1193973C (en) | Method for synthesizing beta-ionone | |
| CN110368953A (en) | A kind of composite oxide supported platinum catalyst and its preparation and application | |
| CN108137464B (en) | Method for producing acrylic acid | |
| CN109174120A (en) | Loading type Pd-Ni duplex metal nano granule catalyst and its preparation method and application | |
| CN1583263A (en) | Catalyst for reversible hydrogen storing and releasing by organic liquid hydride and its preparation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080130 Termination date: 20110407 |