CN100431705C - Preparation method of Pd complex compound loading catalyst - Google Patents
Preparation method of Pd complex compound loading catalyst Download PDFInfo
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- CN100431705C CN100431705C CNB2005100162702A CN200510016270A CN100431705C CN 100431705 C CN100431705 C CN 100431705C CN B2005100162702 A CNB2005100162702 A CN B2005100162702A CN 200510016270 A CN200510016270 A CN 200510016270A CN 100431705 C CN100431705 C CN 100431705C
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Abstract
The present invention relates to a preparation method of a Pd complex compound supported catalyst and particularly relates to a preparation method for synthesizing the Pd complex compound supported catalyst by adopting an anchoring method. The preparation method of the Pd complex compound supported catalyst of the present invention comprises the following steps: firstly, lysine hydrochloride exchanges ions with a commutable inorganic carrier; then, the lysine hydrochloride carries out a complex reaction with H2PdCl4 to form a Pd-amino acid complex compound; after the Pd-amino acid complex compound is recovered, a PdO-amino acid / inorganic supported catalyst is obtained. The Pd complex compound supported catalyst of the present invention has the advantages of mild synthesis conditions, cheap and easily obtainable raw materials, capability of obtaining stable Pd complex compound catalysts of different inorganic carriers, and high hydrogenation reaction activation of the prepared supported catalyst.
Description
Technical field
The present invention relates to the preparation method of Pd complex compound supported catalyst, more particularly, relate to a kind of preparation method who adopts the synthetic load P d complex compound catalyst of anchorage method.
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.To have a specific surface big for active carbon in the inorganic carrier, the characteristics that particle is thin, and therefore adopting the Pd/C catalyst of immersion process for preparing is hydrogenation catalyst the most frequently used in the fine chemistry industry, it also is the higher catalyst of specific activity.
Adopt anchorage method, the method for preparing the high activity metal complex catalyst is practical method, sees the Ye Makefu work, and high taste waits " effect of load complex catalysis " of translating.General adopt the organo-metallic compound and the hydroxyl effect of carrier surface to carry out grappling, relatively harsher because of the preparation condition of organo-metallic compound, therefore adopt the cost of the metal complex catalyst that this method prepares higher, thereby limited its extensive use.
USP 4,313,018 and 4,238,358 have set forth Pd, Rh, Pt, Ru be anchored on the catalytic hydrogenation catalyst characteristic that the amino benzoic Acid on the polystyrene is carried out complexing.
Chen Yifei, Qiu Liyuan etc. are at CN 85103783, having set forth with the active carbon among CN 88105517 and the CN 88105542.5 is the protein-palladium complex catalyst of carrier, be used for the many nitro-derivative (P of fatty alkene derivatives and aromatic hydrocarbons, P`-dinitro benzene formyl piperazine, 3, the 4`-dinitro diphenyl ether) synthetic middle catalytic hydrogenation result of the test.It mainly is to utilize the suction-operated of active carbon to form protein-palladium complex catalyst.
Document Semikolenov V A, Likholobov V A, et al, Kinet Katal, 1980,21,420 and Zhang Zhen power, Yang Yongzheng, Liu Quanying, Sun Qiang, Northeast China Normal University's journal natural science edition 02, the palladium catalyst of having set forth magnesia-protein load in 46,1994 carries out the catalytic hydrogenation characteristics to castor oil, and has investigated the influence factors such as valence state of palladium.
Summary of the invention
The purpose of this invention is to provide the preparation method of the Pd complex compound supported catalyst that a kind of reaction condition gentleness, raw material cheaply be easy to get, it provides a kind of Pd complex catalyst, and this complex catalyst has high hydrogenation reaction activity.
A kind of preparation method of Pd complex compound supported catalyst, this method comprise at first FE-5 and the inorganic carrier that can exchange are carried out ion-exchange, and then and H
2PdCl
4Carry out complex reaction, form the Pd-amino acid complex, this complex compound promptly can obtain Pd through reduction
0-amino acid/inorganic carrier catalyst.
The preparation method of described Pd complex compound supported catalyst is characterized in that: described ion-exchange, its reaction condition are preferably 50-60 ℃ for the exchange reaction temperature is 20-90 ℃, and the exchange reaction time is 1-10 hour, is preferably 2-4 hour.
Vector contg is 0.5-10 weight % in the described ion-exchange reactions, is preferably 1-5 weight %; The lysine hydrochloric acid salinity is 0.5-10 weight %, is preferably 1-5 weight %; The weight ratio 1 of FE-5 and carrier: 2-1: 8, be preferably 1: 2-1: 5.
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.
Described tradable inorganic carrier is silica, aluminium oxide, molecular sieve or bentonite.
Described reducing condition is a room temperature to 80 ℃ for using hydrogen reducing, temperature, is preferably 40-60 ℃, and the reduction reaction time is 2-10 hour, is preferably 4-5 hour.
Beneficial effect of the present invention is a palladium complex supported catalyst synthesis condition gentleness, and raw material cheaply is easy to get, and can obtain the stable palladium complex catalyst of different inorganic carrier loads, and the supported catalyst that makes has higher hydrogenation reaction activity.
The specific embodiment
Below by embodiment the present invention is described
Embodiment 1
2g sodium type bentonite (Black Hills, Liaoning product) is suspended in the 100ml deionized water, stirred 1 hour,, carried out ion-exchange reactions 4 hours to wherein adding 1g solid FE-5 at 50-60 ℃.Filter, be washed till no Cl with deionized water
-This solid is dispersed in the 100ml deionized water again, stirred 1 hour at 50-60 ℃, to wherein dripping 0.5ml H
2PdCl
4Solution (Pd content is 20.035mg/ml) drips, and continues reaction 4 hours again, filters, and is washed till no Cl with deionized water
-The solid that obtains was dried 4 hours at 70-80 ℃.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 load P d complex compound catalyst A.
Embodiment 2
With embodiment 1, different is to use sodium type Y zeolite, makes catalyst B.
Embodiment 3
With embodiment 1, different is to use 2 hours aluminium oxide of 500 ℃ of calcination process, makes catalyst C.
Embodiment 4
With embodiment 1, different was stirring at room 1 hour, to wherein adding 1g solid FE-5, carried out ion-exchange reactions 10 hours, made catalyst D.
Embodiment 5
With embodiment 1, different is to stir 1 hour at 30 ℃, to wherein dripping 0.5ml H
2PdCl
4Solution (Pd content is 20.035mg/ml) drips, and continues reaction 10 hours again, makes catalyst E.
Embodiment 6
With embodiment 1, different is that 4g sodium type bentonite (Black Hills, Liaoning product) is suspended in the 100ml deionized water, to wherein adding 3g solid FE-5.To wherein dripping 1.5ml H
2PdCl
4Solution (Pd content is 20.035mg/ml) makes catalyst F.
Embodiment 7
With implementing 1, different is to lead to hydrogen reducing 5 hours in room temperature, makes catalyst G.
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.
(R can be C to select the R substituted-nitrobenzene
1-C
3Alkyl, trifluoromethyl, chlorine) as the hydrogenation reaction raw material, in 1 liter of autoclave, add reaction raw materials 100ml, catalyst 2g.Reaction condition is temperature 40-50 ℃, and Hydrogen Vapor Pressure is 0.1-0.5Mpa, and speed of agitator is 1000 rev/mins, reacts 4 hours, and reaction result sees Table 1.
| The catalyst numbering | Reaction raw materials | Reaction condition temperature ℃, pressure Mpa | The hydrogenation reaction principal product | Reaction conversion ratio (weight %) | Reaction selectivity (%) |
| A | Parachloronitrobenzene | 50，0.1 | Parachloroanilinum | 25.5 | 98.8 |
| A | Parachloronitrobenzene | 50，0.4 | Parachloroanilinum | 43.5 | 90.2 |
| B | Parachloronitrobenzene | 50，0.4 | Parachloroanilinum | 35.4 | 88.3 |
| C | Parachloronitrobenzene | 50，0.4 | Parachloroanilinum | 5.2 | 99.5 |
| D | Parachloronitrobenzene | 50，0.4 | Parachloroanilinum | 44.3 | 91.0 |
| E | Parachloronitrobenzene | 50，0.4 | Parachloroanilinum | 40.7 | 92.1 |
| F | Parachloronitrobenzene | 50，0.4 | Parachloroanilinum | 40.3 | 91.4 |
| G | Parachloronitrobenzene | 50，0.4 | Parachloroanilinum | 44.5 | 89.2 |
| Pd/C (containing 5%Pd) | Parachloronitrobenzene | 50，0.4 | Parachloroanilinum | 90.8 | 81.1 |
When the catalyst use amount is identical, it is 5mg/g that prepared Pd complex compound catalyst contains Pd, and the Pd/C catalyst contains Pd is 50mg/g, the hydrogenation activity of prepared Pd complex compound catalyst is 1/2 of Pd/C under identical reaction condition, but by actual Pd cubage (hydrogenation activity of Unit Weight Pd), the hydrogenation activity of then prepared catalyst is 5 times of Pd/C catalyst.This catalyst has a hydrogenation nitro, the characteristics of not dechlorination under the mitigation condition simultaneously.Therefore Pd complex compound catalyst its bullion content when reaching same catalytic activity is low, so the cost of catalyst is also low.
Claims (8)
1, a kind of preparation method of Pd complex compound supported catalyst, this method comprise at first FE-5 and the inorganic carrier that can exchange are carried out ion-exchange, and then and H
2PdCl
4Carry out complex reaction, form the Pd-amino acid complex, this complex compound promptly can obtain Pd through reduction
0-amino acid/inorganic carrier catalyst.
2, the preparation method of Pd complex compound supported catalyst according to claim 1 is characterized in that: described ion-exchange, and its reaction condition is 20-90 ℃ for the exchange reaction temperature, the exchange reaction time is 1-10 hour.
3, the preparation method of Pd complex compound supported catalyst according to claim 1 is characterized in that: inorganic carrier content is 0.5-10 weight % in ion-exchange reactions; The lysine hydrochloric acid salinity is 0.5-10 weight %; The weight ratio 1 of FE-5 and inorganic carrier: 2-1: 8.
4, the preparation method of Pd complex compound supported 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.
5, the preparation method of Pd complex compound supported catalyst according to claim 1 is characterized in that: H in the described complex reaction
2PdCl
4Concentration be 10mg/ml-50mg/ml.
6, the preparation method of Pd complex compound supported catalyst according to claim 1 is characterized in that: the described inorganic carrier that can exchange is silica, aluminium oxide, molecular sieve or bentonite.
7, the preparation method of Pd complex compound supported 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.
8, the preparation method of Pd complex compound supported catalyst according to claim 1 is characterized in that: described ion-exchange, and its reaction condition is 50-60 ℃ for the exchange reaction temperature, the exchange reaction time is 2-4 hour; Inorganic carrier content is 1-5 weight % in ion-exchange reactions; The lysine hydrochloric acid salinity is 1-5 weight %; The weight ratio of FE-5 and inorganic carrier is 1: 2-1: 5; 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; Described reducing condition is 40-60 ℃ for using hydrogen reducing, temperature, and the reduction reaction time is 4-5 hour.
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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 |
-
2005
- 2005-03-07 CN CNB2005100162702A patent/CN100431705C/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 * |
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