CN100415367C - Method for preparing nano metal palladium/supporter catalyst - Google Patents
Method for preparing nano metal palladium/supporter catalyst Download PDFInfo
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- CN100415367C CN100415367C CNB2005100162717A CN200510016271A CN100415367C CN 100415367 C CN100415367 C CN 100415367C CN B2005100162717 A CNB2005100162717 A CN B2005100162717A CN 200510016271 A CN200510016271 A CN 200510016271A CN 100415367 C CN100415367 C CN 100415367C
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Abstract
The present invention relates to a preparation method of a nanometer metal Pd / supported catalyst and particularly relates to a preparation method of a nanometer metal Pd / supported catalyst synthesized by adopting a complex compound decomposition method. The preparation method of the nanometer metal Pd / supported catalyst of the present invention comprises the following steps: firstly, a complex reaction of lysine hydrochloride and H2PdCl4 is carried out; then, reactants immerge on an inorganic carrier or through ion exchange so that a Pd-amino acid complex compound is formed on the surface of the carrier; the complex compound is thermally decomposed and recovered, and the nanometer metal Pd / supported catalyst can be obtained. A Pd complex supported catalyst of the present invention has the advantages of mild synthesis conditions and cheap and easily obtained raw materials; thereby, the nanometer metal Pd catalyst synthesized by the complex compound has the same advantages as the Pd complex supported catalyst likewise; moreover, the nanometer metal Pd catalyst also has high hydrogenation reaction activation.
Description
Technical field
The present invention relates to the preparation method of nanometer metal palladium/carried catalyst, more particularly, relate to a kind of preparation method who adopts complex compound decomposition method synthesis of nano Metal Palladium/carried catalyst.
Background technology
Pt-supported catalyst is the hydrogenation catalyst of blanket gentleness, and the activated centre of hydrogenation reaction is Pd
0Adopt general dipping method, restore the Pd of preparation
0Catalyst, its metal Pd particle diameter is generally 10-30nm.Because have only the Pd of metal Pd particle surface
0Participate in catalytic reaction, therefore when the noble metal pickup was identical, the metal Pd particle was more little, and its reactivity is high more.
Nazimek and partner thereof were at (React.Kinet.Catal.Lett.1981 in 1981,17 (1-2), 169) at first propose with two immersion process for preparing high-dispersion loading type metallic catalysts, promptly at first use certain density EDTA solution impregnation oxide carrier, dry being lower than under the EDTA decomposition temperature, use the salt solution impregnation of concentration known subsequently, drying, calcination, the reduction catalyst that gets product.
Qi Caixia etc. in 278 pages of " Journal of Molecular Catalysis " the 8th the 4th phases of volume, discussed tenor lower (as,＜0.7wt%) time, adopt the palladium catalyst of two immersion process for preparing to have active component and focus mostly in carrier surface, decentralization height, advantage that crystal grain is little.This method mainly is the complexing center that EDTA and carrier surface bonding form metal ion of introducing earlier; During the palladium-impregnated salting liquid, the adsorption site of carrier and complexing center act on simultaneously again.
Scholar etc. (" catalysis journal " 11 (3), 188) adopts organic acid (acetate, maleic acid, citric acid) to prepare loaded palladium catalyst as competitive adsorbate and palladium salt solution impregnation in crossing.
(J.Mol.Catal.A such as Olgioly Dominguez-Quintero, Chemical 197 (2003), 185-191) set forth employing Pd (II) and prepared the palladium/monox nanometer catalyst with 1.9nm as maceration extract with bis-dibencylidene acetone complex compound.Concrete method for making is to adopt the THF solution of this palladium complex and carrier to react 24 hours, uses the hydrazine reductase 12 again 4 hours.This catalyst is catalysis 1-hexene under different condition, cyclohexene, benzene, methyl-n-butyl ketone, the hydrogenation reaction of cyclohexanone and benzene nitrile.
Summary of the invention
The purpose of this invention is to provide the preparation method of nanometer metal palladium/carried catalyst that a kind of reaction condition gentleness, raw material cheaply be easy to get, it provides a kind of nano metal palladium catalyst, and this catalyst has high hydrogenation reaction activity.
A kind of preparation method of nanometer metal palladium/carried catalyst, this method comprise at first with FE-5 and H
2PdCl
4Carry out complex reaction, dipping or ion-exchange are on inorganic carrier again, so form the Pd-amino acid complex at carrier surface, this complex compound is through thermal decomposition, and reduction promptly can obtain nano metal Pd/ carried catalyst.
Described complex reaction condition is that reaction temperature is 30-80 ℃, is preferably 50-60 ℃, and the reaction time is 1-10 hour, is preferably 4-6 hour.
H in the described complex reaction
2PdCl
4Concentration be 10mg/ml-50mg/ml, be preferably 20mg/ml-40mg/ml; The lysine hydrochloric acid salinity is 0.5-10 weight %, is preferably 1-5 weight %; H
2PdCl
4With the mol ratio of FE-5 be 1: 1.
Described dipping or ion-exchange reactions condition are that reaction temperature is 20-80 ℃, are preferably 50-60 ℃, and dipping or ion-exchange time are 1-10 hour, are preferably 2-4 hour.
Vector contg is 50-90 weight % in the described dipping reaction, is preferably 60-70 weight %; The weight ratio 1 of FE-5 and carrier: 2-1: 8, be preferably 1: 2-1: 5.
Described inorganic carrier that can flood or ion-exchange is silica, aluminium oxide, molecular sieve or bentonite.
Described thermal decomposition condition is 100-500 ℃, preferably 120-350 ℃.
Described reducing condition is a room temperature to 80 ℃ for using hydrogen reducing, temperature, and the reduction reaction time is 2-10 hour.
Beneficial effect of the present invention is a palladium complex supported catalyst synthesis condition gentleness, raw material cheaply is easy to get, the synthetic nano Pd catalyst of complex compound has the synthesis condition gentleness equally thus, the advantage that raw material cheaply is easy to get, and this catalyst also has higher hydrogenation reaction activity.
The specific embodiment
Below by embodiment the present invention is described
Embodiment 1
1g solid FE-5 is dissolved in the 50ml deionized water, is warming up to 50-60 ℃ and stirred 10 minutes, to wherein dripping 30ml H
2PdCl
4Solution (Pd content is 20.035mg/ml) dropwises, and continues reaction 4 hours again.
In 2g sodium type Y molecular sieve (Zhou village, Shandong product), add the 3ml deionized water, stirred 1 hour, mix, carried out stirring reaction simultaneously 4 hours, evaporate to dryness in 80-100 ℃ of water-bath with the above-mentioned complex compound for preparing at 50-60 ℃.The solid that obtains was dried 20 hours at 120 ℃.Dried solid porphyrize to＜200 orders, is dispersed in the 100ml deionized water again,, filters, be washed till no Cl with deionized water 40-50 ℃ of logical hydrogen reducing 2 hours
-, promptly obtain loaded with nano metal palladium/carried catalyst A.
Embodiment 2
1g solid FE-5 is dissolved in the 50ml deionized water, is warming up to 50-60 ℃ and stirred 10 minutes, to wherein dripping 30ml H
2PdCl
4Solution (Pd content is 20.035mg/ml) dropwises, and continues reaction 4 hours again.
In 2g sodium type Y molecular sieve (Zhou village, Shandong product), add the 3ml deionized water, stirred 1 hour, mix, carried out stirring reaction simultaneously 4 hours, evaporate to dryness in 80-100 ℃ of water-bath with the above-mentioned complex compound for preparing at 50-60 ℃.300 ℃ of calcinations 2 hours, promptly obtain loaded with nano metal palladium/carried catalyst B with embodiment 1 solid that different is will make.
Embodiment 3
With embodiment 2, different is to select for use 2 hours aluminium oxide of 600 ℃ of calcinations of 2g as carrier, promptly obtains loaded with nano metal palladium/carried catalyst C.
Embodiment 4
With embodiment 2, different is to stir 1 hour at 30 ℃, to wherein dripping 30ml H
2PdCl
4Solution (Pd content is 20.035mg/ml) drips, and continues reaction 10 hours again, makes nanometer metal palladium/carried catalyst D.
Embodiment 5
With embodiment 2, different is that 1g solid FE-5 is dissolved in the 20ml deionized water, adds the 6ml deionized water in 4g sodium type Y molecular sieve (Zhou village, Shandong product), makes catalyst E.
Embodiment 6
With implementing 2, different is to lead to hydrogen reducing 5 hours in room temperature, makes catalyst F.
Comparative Examples
The Pd/C Preparation of catalysts
With 2g, 90% active carbon by 200 mesh sieves adds in the 10%50ml salpeter solution, handles 2 hours at 50 ℃, filters and is washed till no Cl
-Again in 50ml water, pull an oar Dropwise 5 ml H under 40 ℃ of stirrings
2PdCl
4Solution (Pd content is 20.035mg/ml) dropwises, and continues reaction 4 hours again, is neutralized to PH=8 with 5% sodium hydroxide solution, leads to hydrogen reducing 2 hours in room temperature.
Embodiment 7
The hydrogenation reaction activity rating.
Select benzoic acid as the hydrogenation reaction raw material, in 1 liter of autoclave, add reaction raw materials 100g, ethanol 50ml, catalyst 2g.Reaction condition is temperature 100-110 ℃, and Hydrogen Vapor Pressure is 0.5-1.0Mpa, and speed of agitator is 1000 rev/mins, reacts 4 hours, and reaction result sees Table 1 (product is carried out gas chromatographic analysis).
| The catalyst numbering | Metal Palladium average grain diameter nm | Reaction temperature ℃, pressure Mpa | Hydrogenation reaction product | Reaction conversion ratio (weight %) | Reaction selectivity (%) |
| A | ＜2 | 110，0.8 | Hexahydrobenzene formic acid | 85.5 | 96.8 |
| B | 4-6 | 120，1.0 | Hexahydrobenzene formic acid | 87.4 | 88.3 |
| C | 4-6 | 120，1.0 | Hexahydrobenzene formic acid | 85.2 | 95.5 |
| D | 4-5 | 120，1.0 | Hexahydrobenzene formic acid | 85.1 | 96.5 |
| E | 3-5 | 120，1.0 | Hexahydrobenzene formic acid | 86.3 | 88.5 |
| F | 3-5 | 120，1.0 | Hexahydrobenzene formic acid | 89.7 | 95.7 |
| Pd/C (containing 5%Pd) | ＞10 | 140，1.0 | Hexahydrobenzene formic acid | 90.8 | 92.5 |
When the catalyst use amount was identical with year palladium amount, the metal particle diameter of the catalyst of the inventive method preparation was obviously less, therefore has under lower reaction temperature and similar reactivity of Pd/C catalyst and selectivity.
Claims (9)
1. the preparation method of a nanometer metal palladium/carried catalyst, this method comprises at first with FE-5 and H
2PdCl
4Carry out complex reaction, dipping or ion-exchange are on inorganic carrier again, so form the Pd-amino acid complex on the inorganic carrier surface, this complex compound is through thermal decomposition, and reduction promptly can obtain nano metal Pd/ carried catalyst.
2. the preparation method of nanometer metal palladium/carried catalyst according to claim 1 is characterized in that, described complex reaction condition is that reaction temperature is 30-80 ℃, and the reaction time is 1-10 hour.
3. the preparation method of nanometer metal palladium/carried catalyst according to claim 1 is characterized in that, H in the described complex reaction
2PdCl
4Concentration be 10mg/ml-50mg/ml; The lysine hydrochloric acid salinity is 0.5-10 weight %; H
2PdCl
4With the mol ratio of FE-5 be 1: 1.
4. the preparation method of nanometer metal palladium/carried catalyst according to claim 1 is characterized in that, described dipping or ion-exchange reactions condition are that reaction temperature is 20-80 ℃, and dipping or ion-exchange time are 1-10 hour.
5. the preparation method of nanometer metal palladium/carried catalyst according to claim 1 is characterized in that, inorganic carrier content is 50-90 weight % in the dipping reaction; The weight ratio 1 of FE-5 and inorganic carrier: 2-1: 8.
6. the preparation method of nanometer metal palladium/carried catalyst according to claim 1 is characterized in that, described inorganic carrier is silica, aluminium oxide, molecular sieve or bentonite.
7. the preparation method of nanometer metal palladium/carried catalyst according to claim 1 is characterized in that, described thermal decomposition condition is 100-500 ℃.
8. the preparation method of nanometer metal palladium/carried catalyst according to claim 1 is characterized in that, described reducing condition is a room temperature to 80 ℃ for using hydrogen reducing, temperature, and the reduction reaction time is 2-10 hour.
9. the preparation method of nanometer metal palladium/carried catalyst according to claim 1 is characterized in that, described complex reaction condition is that reaction temperature is 50-60 ℃, and the reaction time is 4-6 hour; H in the described complex reaction
2PdCl
4Concentration be 20mg/ml-40mg/ml; The lysine hydrochloric acid salinity is 1-5 weight %; Described dipping or ion-exchange reactions condition are that reaction temperature is 50-60 ℃, and dipping or ion-exchange time are 2-4 hour; Inorganic carrier content is 60-70 weight % in the dipping reaction; The weight ratio of FE-5 and inorganic carrier is 1: 2-1: 5; Described thermal decomposition condition is 120-350 ℃.
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| CNB2005100162717A CN100415367C (en) | 2005-03-07 | 2005-03-07 | Method for preparing nano metal palladium/supporter catalyst |
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| CNB2005100162717A CN100415367C (en) | 2005-03-07 | 2005-03-07 | Method for preparing nano metal palladium/supporter catalyst |
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| CN100415367C true CN100415367C (en) | 2008-09-03 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107356685A (en) * | 2017-07-06 | 2017-11-17 | 北京英力精化技术发展有限公司 | A kind of product content detection method that cyclohexanecarboxylic acid is produced using benzoic acid as raw material |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101497041B (en) * | 2009-02-12 | 2010-11-03 | 凯瑞化工有限责任公司 | Method for preparing palladium-carrying catalyst with nano Pd by suspension polymerization |
| CN102794204B (en) * | 2011-05-23 | 2014-11-26 | 中国石油天然气股份有限公司 | Reduction method of palladium catalyst |
| CN104549240B (en) * | 2013-10-28 | 2018-01-09 | 中国石油化工股份有限公司 | Hydrofining crude terephthalic acid catalyst and preparation method thereof |
| CN105268434B (en) * | 2014-07-24 | 2018-07-13 | 中国石油化工股份有限公司 | Hydrofining crude terephthalic acid catalyst |
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| US4313018A (en) * | 1977-04-14 | 1982-01-26 | Western Kentucky University | Heterogeneous catalytic hydrogenation |
| CN85103783A (en) * | 1985-05-08 | 1986-03-10 | 上海师范大学 | The manufacturing of egg albumin-palladium complex catalyst, purposes and using method |
| CN1366468A (en) * | 2000-04-20 | 2002-08-28 | 日本碍子株式会社 | Method for preparing decomposition catalyst for organic halide and method for manufacturing filter for use in decomposing organic halide |
| CN1380837A (en) * | 2000-05-15 | 2002-11-20 | 日本碍子株式会社 | Adsorbent having capability of decomposing organic halogen compound and method for producing the same |
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2005
- 2005-03-07 CN CNB2005100162717A patent/CN100415367C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4313018A (en) * | 1977-04-14 | 1982-01-26 | Western Kentucky University | Heterogeneous catalytic hydrogenation |
| CN85103783A (en) * | 1985-05-08 | 1986-03-10 | 上海师范大学 | The manufacturing of egg albumin-palladium complex catalyst, purposes and using method |
| CN1366468A (en) * | 2000-04-20 | 2002-08-28 | 日本碍子株式会社 | Method for preparing decomposition catalyst for organic halide and method for manufacturing filter for use in decomposing organic halide |
| CN1380837A (en) * | 2000-05-15 | 2002-11-20 | 日本碍子株式会社 | Adsorbent having capability of decomposing organic halogen compound and method for producing the same |
Non-Patent Citations (4)
| Title |
|---|
| 含氨基酸侧链的有机硅高分子催化剂VI.聚γ-(赖氨酸基)丙基硅氧烷钯催化剂的合成及加氢活性. 刘基万等.应用化学，第8卷第6期. 1991 |
| 含氨基酸侧链的有机硅高分子催化剂VI.聚γ-(赖氨酸基)丙基硅氧烷钯催化剂的合成及加氢活性. 刘基万等.应用化学，第8卷第6期. 1991 * |
| 聚γ-(赖氨酸基)丙基-γ-(组氨酸基)丙基硅氧烷钯催化剂的合成及其催化加氢活性. 王西新.河北化工，第1期. 1998 |
| 聚γ-(赖氨酸基)丙基-γ-(组氨酸基)丙基硅氧烷钯催化剂的合成及其催化加氢活性. 王西新.河北化工，第1期. 1998 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107356685A (en) * | 2017-07-06 | 2017-11-17 | 北京英力精化技术发展有限公司 | A kind of product content detection method that cyclohexanecarboxylic acid is produced using benzoic acid as raw material |
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