CN1748860A - Loaded palladium catalyst and preparing method and its use - Google Patents
Loaded palladium catalyst and preparing method and its use Download PDFInfo
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- CN1748860A CN1748860A CN 200510014999 CN200510014999A CN1748860A CN 1748860 A CN1748860 A CN 1748860A CN 200510014999 CN200510014999 CN 200510014999 CN 200510014999 A CN200510014999 A CN 200510014999A CN 1748860 A CN1748860 A CN 1748860A
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Abstract
The present invention belongs to the field of the preparation of palladium catalyst, and is especially supported palladium catalyst and its preparation process and application. The supported palladium catalyst is noble metal palladium supported onto nanometer alumina fiber carrier and has the supported amount of palladium as the active component in 0.1-1 wt%. The nanometer alumina fiber carrier is gamma-alumina fiber, and the noble metal palladium is supported onto the nanometer alumina fiber carrier through equal volume soaking process. The high dispersive supported palladium catalyst is used in hydrogenating anthraquinone to prepare hydrogen peroxide solution, has high hydrogenating effect and mild reaction condition, and suitable for industrial production.
Description
Technical field
The invention belongs to the preparation of palladium catalyst, particularly a kind of load type palladium catalyst and preparation method and application thereof, novel high-dispersion loading type palladium catalyst is used for anthraquinone hydrogenation and prepares hydrogen peroxide.
Background technology
Noble metal catalyst is extensively approved with its excellent catalytic performance, but the noble metal resource-constrained, cost is higher.How to improve the noble metal catalyst utilization rate, reduce cost, become the focus that domestic and international researcher pays close attention to.Wherein, improve the dispersion situation at noble metal active center to greatest extent, reduce the activated centre size and become one of most important solution.Hydrogen peroxide is a kind of important chemical material.Owing to produce water and oxygen after the hydrogen peroxide decomposes, to the environment non-secondary pollution, belong to green chemical, make hydrogen peroxide be subjected to increasing attention as oxidant.At present, the main method of producing hydrogen peroxide is anthraquinone, and wherein, this reactions steps of anthraquinone hydrogenation needs the effect of catalyst.Chinese patent CN 1435277A discloses a kind of with process for prepairng hydrogen peroxide by anthraquinone load type palladium catalyst and preparation method thereof, the hydrogenation catalyst that alkyl-anthraquinone is produced hydrogen peroxide is to be carrier with coated rare earth oxide in advance and through the aluminium oxide of 900-1000 ℃ of high-temperature calcination, it is 0.1-15%wt that rare earth oxide is coated with complexor, with palladium is main active ingredient, and loading is 0.15-0.25%wt.CN1539737A discloses high purity nanometer alumina fiber powder preparation method, and to distilled water, the adding inorganic acid reaches to heat slightly and can promote its dissolving with the HV-1 catalyst dissolution; Metallic aluminium soaked in above-mentioned catalyst solution carried out activation processing in 1-30 minute, aluminium is taken out,, wash surface impurity off with its surface of distilled water flushing; Then aluminium is placed into the air-blowing air port, by air compressor to the metallic aluminium air-blowing; Place some hrs, this moment, the surface and the one solid reaction of airborne oxygen generation gas of aluminium generated nano-alumina fiber; Collect fibrous alumina powder jointed that the aluminium surface generates then, repeat above-mentioned steps.At last with the pressed powder that generates under the condition of 500 ℃ of left and right sides temperature, roasting 0.5-5 hour, catalyst flashed to gas, can make wherein catalyst and powder separation, and reclaimed catalyst.Above-mentioned load type palladium catalyst and preparation method thereof and high purity nanometer alumina fiber powder preparation method condition harshness, complex process, difficulty and large-scale production.The most frequently used catalyst is loaded palladium catalyst or raney nickel catalyst on the current industrial.Wherein the supported precious metal palladium catalyst activity is higher, but costs an arm and a leg, and there are shortcomings such as inflammable, that structure of reactor is complicated, environmental pollution is serious in raney nickel catalyst.Therefore, the novel anthraquinone hydrogenation catalyst of developing inexpensive environmental protection has crucial meaning.
Summary of the invention
The invention provides a kind of load type palladium catalyst and preparation method and application thereof, can overcome the shortcoming of prior art.It is carrier that the present invention selects the nano-scale fiber shape gama-alumina (called after TH) that is different from industrial gama-alumina for use, load P d.Support type high dispersive palladium catalyst is used for the reaction of anthraquinone hydrogenation producing hydrogen peroxide and demonstrates high hydrogenation activity, and the reaction condition gentleness, is easy to industry's enlarging production.
Load type palladium catalyst provided by the invention, it is a supported precious metal palladium on the nano-alumina fiber carrier, wherein the active component palladium load capacity is 0.1wt%～1wt% (quality), described nano-alumina fiber be diameter at 2～3nm, length is at the gama-alumina fiber of 50～80nm.
Active component palladium load capacity described in the described load type palladium catalyst is preferably 0.3wt%.
Described load type palladium catalyst is the load type palladium catalyst of gama-alumina fiber carrier load P d, PdO, Pd-beta-schardinger dextrin-or Pd-hexamethylenetetramine.
Described load type palladium catalyst PdO/ gama-alumina fiber preparation method comprises the steps:
Adopt equi-volume impregnating that the carrier nano-alumina fiber be impregnated in PdCl
2In the solution, filter behind the stirring 4h under the room temperature, filter cake dries in air, 120 ℃ of oven dry 3h, and 600 ℃ of roasting 3h make PdO/ nano-alumina fiber catalyst.
Described load type palladium catalyst Pd/ gama-alumina fiber preparation method comprises the steps:
1) adopt equi-volume impregnating that the carrier nano-alumina fiber be impregnated in PdCl
2In the solution, filter behind the stirring 4h under the room temperature, filter cake dries in air, 120 ℃ of oven dry 3h;
2) place cryosel to bathe, under the Ar gas shiled, add KBH
4Solution reduction no longer includes gas release to system, obtain black solid, behind the distilled water cyclic washing, is stored in the ethanolic solution, makes Pd/ nano-alumina fiber catalyst.KBH
4With PdCl
2The ratio of quality is 1～10: 1.
Described load type palladium catalyst Pd-beta-schardinger dextrin-/gama-alumina fiber preparation method comprises the steps: at room temperature to H
2PdCl
4Add NaOH solution in the complex solution, regulate this salting liquid pH value to 5, add the beta-schardinger dextrin-powder, stir 4h under the room temperature and make Pd-β-CD colloidal solution, in this colloidal solution, add the nano-alumina fiber support powder, suction filtration behind the stirring 2h, filter cake dries in air naturally, 100 ℃ of oven dry 3h make Pd-β-bad dextrin/nano-alumina fiber catalyst, described β-CD and PdCl
2Mass ratio is 1～10: 1.
Described load type palladium catalyst Pd-hexamethylenetetramine/gama-alumina fiber preparation method comprises the steps: the nano-alumina fiber carrier is placed acid PdCl
2Stir suction filtration behind the dipping 4h in the solution under the room temperature, in filter cake, add hexamethylenetetramine solution, continue to stir 1h, suction filtration, filter cake dries in air naturally, 100 ℃ of oven dry 3h, make Series P d-hexamethylenetetramine/nano-alumina fiber catalyst, described hexamethylenetetramine and PdCl
2Mass ratio is 1～10: 1.
Catalyst of the present invention is used for the anthraquinone hydrogenation reaction, carries out in the compressive reaction still, and reaction condition is as follows: the catalyst and the anthraquinone of industrial acceptable amount are added in the pressure reaction still, vacuumize after the sealing and remove air in the still, heating feeds hydrogen to 0.3Mpa in the time of 50 ℃, stir.Reaction is carried out finishing behind the 2h, the catalyst in the centrifugation hydride, and hydride obtains oxidation liquid in 45 ℃ through dioxygen oxidation 0.5-1h, this oxidation liquid water extraction.At last, in acid medium, use KMnO
4The solution titration.Catalyst: anthraquinone=3: 8 (mass ratio)
Catalyst of the present invention is used for the reaction of anthraquinone hydrogenation producing hydrogen peroxide and has high hydrogenation activity, obtains higher hydrogenation effect, and reaction condition is gentle relatively, suitable easy industry's enlarging production.
Substantive distinguishing features of the present invention and remarkable result can be embodied from following embodiment, but they are not that the present invention is imposed any restrictions.
The specific embodiment
Embodiment 1
Get the PdCl that Pd content is 0.01g/ml
2(one-level PdCl
2Last Haixing County luxurious metal factory) solution 6ml with distilled water diluting to 70ml, add 10g TH (production of Tianjin chemical research institute) carrier, stir dipping 4h under the room temperature, suction filtration, filter cake dries in air naturally, again through 120 ℃ of oven dry 3h, 600 ℃ of roasting 3h in Muffle furnace make the PdO/TH catalyst at last.This catalyst is used for anthraquinone hydrogenation reaction, reaction condition as mentioned above, reaction result sees Table 1.
Embodiment 2
According to preparation process among the embodiment 1, sample dropwise adds KBH through making beating in cryosel is bathed after 120 ℃ of oven dry under the Ar gas shiled
4Solution, KBH
4With the ratio of Pd amount of substance be 5: 1.When no longer including gas in the slurries and discharge, the black solid that obtains through the distilled water cyclic washing, is stored in the ethanol, make the Pd/TH catalyst.Its catalytic performance sees Table 1.
Embodiment 3
Get the H that Pd content is 0.01g/ml
2PdCl
4Complex solution 3ml to 70ml, dropwise adds the NaOH solution regulator solution pH value to 5 of 0.2mol/L through distilled water diluting, adds and PdCl
2Mass ratio is β-CD powder of 1: 1, makes Pd-β-CD colloidal solution behind the stirring 4h under the room temperature.In this colloidal solution, add 10g TH carrier, suction filtration behind the stirring 2h.Filter cake dries in air naturally, and 100 ℃ of oven dry 3h make Pd-β-CD/TH-1 catalyst.Corresponding reaction result sees Table 1.
Embodiment 4
Catalyst is with embodiment 3, with β-CD and PdCl among the embodiment 3
2Mass ratio changes 2: 1 into, and all the other conditions are with embodiment 3.Make Pd-β-CD/TH-2 catalyst.Reaction result sees Table 1.
Embodiment 5
Catalyst is with embodiment 3, with β-CD and PdCl among the embodiment 3
2Mass ratio changes 3: 1 into, and all the other conditions are with embodiment 3.Make Pd-β-CD/TH-3 catalyst.Reaction result sees Table 1.
Embodiment 6
Catalyst is with embodiment 3, with β-CD and PdCl among the embodiment 3
2Mass ratio changes 4: 1 into, and all the other conditions are with embodiment 3.Make Pd-β-CD/TH-4 catalyst.Reaction result sees Table 1.
Embodiment 7
Catalyst is with embodiment 3, with β-CD and PdCl among the embodiment 3
2Mass ratio changes 5: 1 into, and all the other conditions are with embodiment 3.Make Pd-β-CD/TH-5 catalyst.Reaction result sees Table 1.
Embodiment 8
Get the PdCl that Pd content is 0.01g/ml
2Solution 6ml to 70ml, adds 10g TH carrier through distilled water diluting, stirs dipping 4h under the room temperature, suction filtration, and the filter cake making beating dropwise splashes into the HMT aqueous solution, HMT and PdCl in slurries
2Mass ratio is 1: 1.Dropwise the back and continue to stir 1h, suction filtration, filter cake dries in air, 100 ℃ of oven dry 3h.Make the Pd-HMT/TH-1 catalyst.Reaction result sees Table 1.
Embodiment 9
Catalyst is with embodiment 8, with HMT among the embodiment and PdCl
2Mass ratio changes 5: 1 into, and all the other conditions are with embodiment 8.Make the Pd-HMT/TH-5 catalyst.Reaction result sees Table 1.
Embodiment 10
The anthraquinone hydrogenation reaction
In the compressive reaction still, carry out.Reaction condition is as follows: 1.5g catalyst and 40ml (including 4g 2-EAQ, 30ml carbon 9 aromatic hydrocarbons, 10ml tributyl phosphate) are added in the 100ml pressure reaction still, vacuumize after the sealing and remove air in the still, begin heating subsequently.When temperature reaches 50 ℃, feed hydrogen to 0.3MPa and unlatching stirring.Reaction is carried out finishing behind the 2h, the catalyst in the centrifugation hydride, and hydride obtains oxidation liquid in 45 ℃ through dioxygen oxidation 0.5h, and this oxidation liquid is through distilled water extraction 3～4 times.At last, in acid medium, use KMnO
4The solution titration.Table 1 different catalysts is used for the reaction result of anthraquinone hydrogenation
Table 1 different catalysts is used for the reaction result of anthraquinone hydrogenation
| Catalyst | Hydrogenation efficiency B *(g/L) |
| Industrial catalyst | 6.8 |
| PdO/TH | 7.8 |
| Pd/TH | 10.5 |
| Pd-β-CD/TH-1 | 7.8 |
| Pd-β-CD/TH-2 | 8.4 |
| Pd-β-CD/TH-3 | 9.7 |
| Pd-β-CD/TH-4 | 8.9 |
| Pd-β-CD/TH-5 | 8.5 |
| Pd-HMT/TH-1 | 8.8 |
| Pd-HMT/TH-5 | 9.5 |
*Annotate:
(anthraquinone working solution of a certain amount of catalyst hydrogenation unit volume prepares 100%H to hydrogenation efficiency B
2O
2Ability, g/L): B=17 * 5MV
1/ V
2
M is KMnO in the formula
4The concentration of solution (mol/L), V
1Be KMnO
4Solution usage (ml), V
2Be oxidation liquid long-pending (ml).
Claims (9)
1, a kind of load type palladium catalyst, it is characterized in that it is a supported precious metal palladium on the nano-alumina fiber carrier, wherein the active component palladium load capacity is 0.1wt%～1wt%, described nano-alumina fiber be diameter at 2～3nm, length is at the gama-alumina fiber of 50～80nm.
2, load type palladium catalyst according to claim 1 is characterized in that described active component palladium load capacity is 0.3wt%.
3, load type palladium catalyst according to claim 1 is characterized in that described load type palladium catalyst is the load type palladium catalyst of gama-alumina fiber carrier load P d, PdO, Pd-beta-schardinger dextrin-or Pd-hexamethylenetetramine.
4, the described load type palladium catalyst PdO/ of claim 3 gama-alumina fiber preparation method is characterized in that comprising the steps:
Adopt equi-volume impregnating that the carrier nano-alumina fiber be impregnated in PdCl
2In the solution, filter behind the stirring 4h under the room temperature, filter cake dries in air, 120 ℃ of oven dry 3h, and 600 ℃ of roasting 3h make PdO/ nano-alumina fiber catalyst.
5, the described load type palladium catalyst Pd/ of claim 3 gama-alumina fiber preparation method is characterized in that comprising the steps:
1) adopt equi-volume impregnating that the carrier nano-alumina fiber be impregnated in PdCl
2In the solution, filter behind the stirring 4h under the room temperature, filter cake dries in air, 120 ℃ of oven dry 3h;
2) place cryosel to bathe, under the Ar gas shiled, add KBH
4Solution reduction no longer includes gas release to system, obtain black solid, behind the distilled water cyclic washing, is stored in the ethanolic solution, makes Pd/ nano-alumina fiber catalyst.KBH
4With PdCl
2The ratio of quality is 0.5～10: 1.
6, the described load type palladium catalyst Pd-beta-schardinger dextrin-of claim 3/gama-alumina fiber preparation method is characterized in that comprising the steps: at room temperature to H
2PdCl
4Add NaOH solution in the complex solution, regulate this salting liquid pH value to 5, add the beta-schardinger dextrin-powder, stir 4h under the room temperature and make Pd-β-CD colloidal solution, in this colloidal solution, add the nano-alumina fiber support powder, suction filtration behind the stirring 2h, filter cake dries in air naturally, 100 ℃ of oven dry 3h make Pd-beta-schardinger dextrin-/nano-alumina fiber catalyst, described β-CD and PdCl
2Mass ratio is 0.5～10: 1.
7, the described load type palladium catalyst Pd-hexamethylenetetramine of claim 3/gama-alumina fiber preparation method is characterized in that comprising the steps: the nano-alumina fiber carrier is placed acid PdCl
2Stir suction filtration behind the dipping 4h in the solution under the room temperature, in filter cake, add hexamethylenetetramine solution, continue to stir 1h, suction filtration, filter cake dries in air naturally, 100 ℃ of oven dry 3h, make Series P d-hexamethylenetetramine/nano-alumina fiber catalyst, described hexamethylenetetramine and PdCl
2Mass ratio is 0.5～10: 1.
8, the application of the described load type palladium catalyst of claim 1, it is as follows to it is characterized in that this catalyst is used for the reaction condition of anthraquinone hydrogenation reaction: the catalyst and the anthraquinone of industrial acceptable amount are added in the pressure reaction still, vacuumize after the sealing and remove air in the still, heating, feed hydrogen in the time of 50 ℃ to 0.3Mpa, stir, reaction is carried out finishing behind the 2h, catalyst in the centrifugation hydride, hydride obtains oxidation liquid in 45 ℃ through dioxygen oxidation 0.5-1h, KMnO is used in this oxidation liquid water extraction in acid medium
4The solution titration.
9, according to the application of the described load type palladium catalyst of claim 8, it is characterized in that described catalyst: anthraquinone=3: 8, mass ratio.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2008118097A1 (en) * | 2007-03-23 | 2008-10-02 | Agency For Science, Technology And Research | Palladium catalysts |
| CN100564244C (en) * | 2006-07-21 | 2009-12-02 | 东莞理工学院 | A kind of preparation method of palladium nanometer wire oldered array material |
| CN101173187B (en) * | 2006-11-01 | 2010-05-12 | 中国石油化工股份有限公司 | Method for producing hydrogenation catalyst with fluidized bed |
| 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 |
| US8921612B2 (en) | 2007-04-12 | 2014-12-30 | Evonik Degussa Gmbh | Supported noble metal catalyst |
| CN104667911A (en) * | 2013-11-30 | 2015-06-03 | 大连隆星新材料有限公司 | Liquid wax hydrogenation catalyst |
| CN106390999A (en) * | 2016-09-18 | 2017-02-15 | 中国天辰工程有限公司 | Novel anthraquinone hydrogenation slurry bed catalyst, and preparation method thereof |
| CN108299015A (en) * | 2017-05-19 | 2018-07-20 | 上海柯瑞冶金炉料有限公司 | Using the method for circulatory maceration coated aluminum oxide base alumina-silicate ceramic fibre |
| CN109967132A (en) * | 2018-12-28 | 2019-07-05 | 东莞东阳光科研发有限公司 | The preparation methods of modified aluminium oxide supports, palladium catalyst and preparation method thereof |
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| US4061598A (en) * | 1976-06-25 | 1977-12-06 | E. I. Du Pont De Nemours And Company | Catalyst for hydrogenating anthraquinones |
| US5772977A (en) * | 1994-12-14 | 1998-06-30 | E. I. Du Pont De Nemours And Company | Anthraquinone process |
| JP4411740B2 (en) * | 2000-04-21 | 2010-02-10 | 三菱瓦斯化学株式会社 | Supported catalyst and method for producing the same |
| US6908873B2 (en) * | 2000-12-22 | 2005-06-21 | Headwaters Nanokinetix, Inc. | Regeneration of spent supported metal catalysts |
| FI110427B (en) * | 2001-03-28 | 2003-01-31 | Kemira Chemicals Oy | Hydration of a working solution in a hydrogen in a hydrogen peroxide production process |
| CN1175931C (en) * | 2003-02-21 | 2004-11-17 | 福州大学 | Supported palladium catalyst for producing hydrogen peroxide by anthraquinone process and preparing method thereof |
| CN1312042C (en) * | 2003-10-24 | 2007-04-25 | 南京大学 | Method of preparing fibre powder body of nano alumina in high purity |
| CN1226257C (en) * | 2003-12-15 | 2005-11-09 | 南开大学 | Catalyst for hydrogenation of styrene oxide to beta-phenethyl alcohol, preparation and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100564244C (en) * | 2006-07-21 | 2009-12-02 | 东莞理工学院 | A kind of preparation method of palladium nanometer wire oldered array material |
| CN101173187B (en) * | 2006-11-01 | 2010-05-12 | 中国石油化工股份有限公司 | Method for producing hydrogenation catalyst with fluidized bed |
| WO2008118097A1 (en) * | 2007-03-23 | 2008-10-02 | Agency For Science, Technology And Research | Palladium catalysts |
| US8227640B2 (en) | 2007-03-23 | 2012-07-24 | Institute Of Bioengineering And Nanotechnology | Palladium catalysts |
| US8921612B2 (en) | 2007-04-12 | 2014-12-30 | Evonik Degussa Gmbh | Supported noble metal catalyst |
| CN104667911A (en) * | 2013-11-30 | 2015-06-03 | 大连隆星新材料有限公司 | Liquid wax hydrogenation catalyst |
| 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 |
| CN106390999A (en) * | 2016-09-18 | 2017-02-15 | 中国天辰工程有限公司 | Novel anthraquinone hydrogenation slurry bed catalyst, and preparation method thereof |
| CN108299015A (en) * | 2017-05-19 | 2018-07-20 | 上海柯瑞冶金炉料有限公司 | Using the method for circulatory maceration coated aluminum oxide base alumina-silicate ceramic fibre |
| CN109967132A (en) * | 2018-12-28 | 2019-07-05 | 东莞东阳光科研发有限公司 | The preparation methods of modified aluminium oxide supports, palladium catalyst and preparation method thereof |
| CN109967132B (en) * | 2018-12-28 | 2022-04-26 | 东莞东阳光科研发有限公司 | Preparation method of modified alumina carrier, palladium catalyst and preparation method thereof |
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