CN1424145A - Carrier style palladium amorphous alloy catalyst for hydrogenation of anthraquinone - Google Patents
Carrier style palladium amorphous alloy catalyst for hydrogenation of anthraquinone Download PDFInfo
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- CN1424145A CN1424145A CN 02158531 CN02158531A CN1424145A CN 1424145 A CN1424145 A CN 1424145A CN 02158531 CN02158531 CN 02158531 CN 02158531 A CN02158531 A CN 02158531A CN 1424145 A CN1424145 A CN 1424145A
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Abstract
A carried non-crystal Pd alloy catalyst for hydrogenating anthraquinone to prepare H2O2 is prepared from the carrier which is one or two of gamma-Al2O3, alpha-Al2O3, MgO, activated carbon, molecular sieve and mullite, non-crystal PdB alloy and RE element through immersing the carrier in the solution of RE metal's nitrate under ultrasonic condition, calcining at 400-700 deg.C for 2-5 hr, immersing in PdCl2 solution, dropping KBH4 solution in ice water bath, and washing. Its advantages are high catalytic activity and low cost.
Description
Technical field
The present invention relates to a kind of anthraquinone hydrogenation load type palladium series non-crystalline state alloy catalyst and preparation method thereof.Belong to catalyst preparation technology.
Background technology
Hydrogen dioxide solution production by anthraquinone process is a kind of method that generally adopts both at home and abroad, accounts for more than 95% of total output.Wherein, hydrogenation catalyst is one of key technology of hydrogen dioxide solution production by anthraquinone process, and the quality of its performance directly affects the carrying out of whole process of production.The catalyst of high activity and high selectivity can improve the circulation H of unit
2O
2Productive rate and reduce the degraded of anthraquinone, thereby simplify technological process, improve working solution cyclic utilization rate, reduce production costs, improve product quality.So this field is one of focus of research both at home and abroad always.
The hydrogenation catalyst that hydrogen dioxide solution production by anthraquinone process is commonly used has two classes at present: a class is the metallic nickel catalyst, and another kind of is with γ-Al
2O
3, α-Al
2O
3Or SiO
2Deng the palladium catalyst that is carrier, palladium content is between 0.15-0.18wt%.This catalyst activity height (hydrogenation efficiency of industrial catalyst is generally 7-8g/L), stable performance.Yet costing an arm and a leg of palladium, the load capacity of palladium is big again, has increased the production cost of hydrogen peroxide, causes anthraquinone hydrogenation to prepare hydrogen peroxide production and has been subjected to certain restriction.
Summary of the invention
The object of the invention is to provide a kind of anthraquinone hydrogenation load type palladium series non-crystalline state alloy catalyst and preparation method thereof.This catalyst has active high, and production cost is low, the simple characteristics of technology.
The present invention adopts γ-Al
2O
3, α-Al
2O
3, among the MgO, active carbon, molecular sieve, mullite one or both are carrier, on it load quality be catalyst quality 0.01-0.15% the PdB amorphous alloy and account for the rare earth element of the 0-1% of total catalyst weight.
Above-mentioned rare earth element is selected from one or both among La, Nd, Sm, Ce, the Eu.
Above-mentioned Preparation of catalysts method, its process comprise preliminary treatment, dipping, the KBH of carrier
4Electronation and washing.Carrier floods down in the 20-40kHz ultrasound condition in 0.01-0.1mol/L rare-earth metal nitrate solution, afterwards in 400-700 ℃ of roasting 2-5h, uses the PdCl of 5-15mmol/L then
2The solution incipient impregnation, the KBH of dropping 1M in ice-water bath
4Solution when waiting not have the gas generation, is used deionized water, absolute ethanol washing respectively, places absolute ethyl alcohol to preserve.
The advantage of catalyst of the present invention is load P d-B amorphous alloy on carrier, and it is active high, and its load capacity is low, and the cost that catalyst is made is low and preparation technology is simple, can be widely used in anthraquinone hydrogenation preparing hydrogen peroxide.
The specific embodiment
Catalyst of the present invention has very high hydrogenation activity, can be embodied from following embodiment.
Following embodiment adopts following activity rating condition to estimate:
The present invention reacts and adopts homemade small-sized fluidized bed reaction unit.Reaction condition: normal pressure, 60 ℃, H
2Flow velocity 20ml/min.After hydrogenation finishes, at room temperature use dioxygen oxidation, extract, use the KMnO of 0.1N at last
4Hydrogenation efficiency is obtained in the acid solution titration.
Embodiment 1
Amorphous alloy catalyst Pd-B/ γ-Al
2O
3Preparation: the γ-Al that takes by weighing 0.88g
2O
3, at 600 ℃ of following roasting 3h, with the PdCl of 15mmol/L
2Solution is at 40 ℃ of incipient impregnations, makes the content of palladium account for the 0.01-0.15% of catalyst gross mass, and drying at room temperature 24h drips the KBH of 1M in ice-water bath
4Solution, when waiting not have the gas generation, water, absolute ethanol washing are four times respectively, place absolute ethyl alcohol to preserve.The activity rating result shows that its hydrogenation efficiency can reach more than the 8g/L.
Embodiment 2
Amorphous alloy catalyst Pd-B/ γ-Al
2O
3The preparation of+mullite: with γ-Al
2O
3With the mullite mechanical mixture, mullite content is between 10%, at 700 ℃ of following roasting 3h, takes by weighing the carrier of 0.88g, with the PdCl of 10mmol/L
2Solution is at 50 ℃ of incipient impregnations, and all the other steps are with embodiment 1, and hydrogenation efficiency is more than the 7g/L.
Embodiment 3
Amorphous alloy catalyst Pd-B-La/ γ-Al
2O
3Preparation: with the La (NO of 0.01mol/L
3)
3Solution impregnation γ-Al
2O
3, make the content of La account for 0.5% of gross mass, dry back takes by weighing the carrier of 0.88g in 700 ℃ of roasting 3h, and all the other steps are with embodiment 2, and hydrogenation efficiency is more than the 8g/L.
Claims (3)
1. an anthraquinone hydrogenation is characterized in that: with γ-Al with load type palladium series non-crystalline state alloy catalyst
2O
3, α-Al
2O
3, among the MgO, active carbon, molecular sieve, mullite one or both are carrier, on it load quality be catalyst quality 0.01-0.15% the PdB amorphous alloy and account for the rare earth element of the 0-1% of total catalyst weight.
2. by the described anthraquinone hydrogenation of claim 1 load type palladium series non-crystalline state alloy catalyst, it is characterized in that: rare earth element is selected from one or both among La, Nd, Sm, Ce, the Eu.
3. one kind prepares by the method for the described anthraquinone hydrogenation of claim 1 with load type palladium series non-crystalline state alloy catalyst, and this method preparation process comprises preliminary treatment, dipping, the KBH of carrier
4Electronation and washing is characterized in that: carrier floods down in the 20-40kHz ultrasound condition in 0.01-0.1mol/L rare-earth metal nitrate solution, afterwards in 400-700 ℃ of roasting 2-5h, uses the PdCl of 5-15mmol/L then
2The solution incipient impregnation, the KBH of dropping 1M in ice-water bath
4Solution when waiting not have the gas generation, is used deionized water, absolute ethanol washing respectively, places absolute ethyl alcohol to preserve.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021585318A CN1172744C (en) | 2002-12-25 | 2002-12-25 | Carrier style palladium amorphous alloy catalyst for hydrogenation of anthraquinone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021585318A CN1172744C (en) | 2002-12-25 | 2002-12-25 | Carrier style palladium amorphous alloy catalyst for hydrogenation of anthraquinone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1424145A true CN1424145A (en) | 2003-06-18 |
| CN1172744C CN1172744C (en) | 2004-10-27 |
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ID=4753120
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021585318A Expired - Fee Related CN1172744C (en) | 2002-12-25 | 2002-12-25 | Carrier style palladium amorphous alloy catalyst for hydrogenation of anthraquinone |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004026474A1 (en) * | 2002-09-19 | 2004-04-01 | Beijing University Of Chemical Technology | The highly dispersing catalyst from layed precursor and the process for preparing it |
| CN100387335C (en) * | 2004-10-26 | 2008-05-14 | 福州大学 | Palladium-aluminium oxide catalyst and its preparation process |
| CN101007275B (en) * | 2007-01-25 | 2010-04-07 | 南京工业大学 | Catalyst for p-nitrophenol hydrogenation and preparation method thereof |
| CN102430406A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method thereof |
| CN102441410A (en) * | 2010-10-15 | 2012-05-09 | 上海欣年石化助剂有限公司 | Catalyst for storing hydrogen by organic matter carrier and preparation method of catalyst |
| CN101804346B (en) * | 2009-11-03 | 2013-04-17 | 厦门大学 | Nanometer palladium catalyst for hydrogenation of anthraquinone and preparation method thereof |
| CN103706356A (en) * | 2014-01-10 | 2014-04-09 | 中国天辰工程有限公司 | Preparation method of eggshell type anthraquinone hydrogenation fixed bed catalyst |
| CN103769186A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst for anthraquinone hydrogenation and preparation method thereof |
| CN103769180A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Anthraquinone hydrogenation catalyst, preparation method and application thereof |
| CN103769093A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Anthraquinone hydrogenation catalyst and preparation method thereof |
| CN104549236A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Hydrogenation catalyst and application thereof |
| CN105268433A (en) * | 2014-06-13 | 2016-01-27 | 中国科学院大连化学物理研究所 | Highly-dispersed catalyst for hydrogen peroxide synthesis and preparation method thereof |
| CN105734457A (en) * | 2016-02-29 | 2016-07-06 | 天津大学 | Method for preparing Pd-Cu-S amorphous material by using amorphous alloy and application thereof |
| CN106669854A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Anthraquinone hydrogenation nonuniform porous channel zonal monolithic catalyst and preparation method thereof |
-
2002
- 2002-12-25 CN CNB021585318A patent/CN1172744C/en not_active Expired - Fee Related
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004026474A1 (en) * | 2002-09-19 | 2004-04-01 | Beijing University Of Chemical Technology | The highly dispersing catalyst from layed precursor and the process for preparing it |
| CN100387335C (en) * | 2004-10-26 | 2008-05-14 | 福州大学 | Palladium-aluminium oxide catalyst and its preparation process |
| CN101007275B (en) * | 2007-01-25 | 2010-04-07 | 南京工业大学 | Catalyst for p-nitrophenol hydrogenation and preparation method thereof |
| CN101804346B (en) * | 2009-11-03 | 2013-04-17 | 厦门大学 | Nanometer palladium catalyst for hydrogenation of anthraquinone and preparation method thereof |
| CN102430406A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method thereof |
| CN102441410A (en) * | 2010-10-15 | 2012-05-09 | 上海欣年石化助剂有限公司 | Catalyst for storing hydrogen by organic matter carrier and preparation method of catalyst |
| CN103769180A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Anthraquinone hydrogenation catalyst, preparation method and application thereof |
| CN103769186A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst for anthraquinone hydrogenation and preparation method thereof |
| CN103769093A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Anthraquinone hydrogenation catalyst and preparation method thereof |
| CN103769093B (en) * | 2012-10-24 | 2015-08-12 | 中国石油化工股份有限公司 | A kind of anthraquinone hydrogenation catalyst and preparation method thereof |
| CN103769186B (en) * | 2012-10-24 | 2015-09-02 | 中国石油化工股份有限公司 | Anthraquinone hydrogenation catalyst and preparation method thereof |
| CN104549236A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Hydrogenation catalyst and application thereof |
| CN104549236B (en) * | 2013-10-22 | 2017-03-01 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst and its application |
| CN103706356A (en) * | 2014-01-10 | 2014-04-09 | 中国天辰工程有限公司 | Preparation method of eggshell type anthraquinone hydrogenation fixed bed catalyst |
| CN105268433A (en) * | 2014-06-13 | 2016-01-27 | 中国科学院大连化学物理研究所 | Highly-dispersed catalyst for hydrogen peroxide synthesis and preparation method thereof |
| CN106669854A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Anthraquinone hydrogenation nonuniform porous channel zonal monolithic catalyst and preparation method thereof |
| CN106669854B (en) * | 2015-11-11 | 2019-04-12 | 中国石油化工股份有限公司 | A kind of non-homogeneous duct subregion monolithic catalyst of anthraquinone hydrogenation and preparation method thereof |
| CN105734457A (en) * | 2016-02-29 | 2016-07-06 | 天津大学 | Method for preparing Pd-Cu-S amorphous material by using amorphous alloy and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1172744C (en) | 2004-10-27 |
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