CN102728386B - Pd-Ni/Al2O3 catalyst, its preparation method and application thereof - Google Patents
Pd-Ni/Al2O3 catalyst, its preparation method and application thereof Download PDFInfo
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- CN102728386B CN102728386B CN201210210417.1A CN201210210417A CN102728386B CN 102728386 B CN102728386 B CN 102728386B CN 201210210417 A CN201210210417 A CN 201210210417A CN 102728386 B CN102728386 B CN 102728386B
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Abstract
The invention discloses a Pd-Ni/Al2O3 catalyst, its preparation method and an application thereof. With PdCl2 and Ni(NO3)2 being used as active components and Al2O3.H2O being used as a catalyst carrier, the Pd-Ni/Al2O3 catalyst is prepared by loading the active components onto the catalyst carrier, wherein the gross mass of PdCl2 and Ni(NO3)2 is 0.5-1 wt% of the weight of Al2O3.H2O and the mass ratio of Pd to Ni in the active components is 1:0.5-3. The Pd-Ni/Al2O3 catalyst can be used as a selective catalyst in cyclopentadiene selective hydrogenation for synthesis of cyclopentene. By the adoption of the catalyst, hydrogenation reaction can be conducted at normal temperature; the reaction condition is mild; conversion rate and selectivity are very good; the conversion rate is 98-99.5%; and the selectivity of cyclopentene also reaches 97-98.5%.
Description
One, technical field
The present invention relates to a kind of Pd-Ni/Al
2o
3catalysts and its preparation method and purposes are used as catalyst in cyclopentadiene catalytic hydrogenation is prepared cyclopentene.
Two, background technology
In recent years, along with the fast development of ethylene industry, the output of C 5 fraction sharply rises, and dicyclopentadiene accounts for 21% of C 5 fraction, makes dicyclopentadiene have very much researching value as the raw material of synthetic cyclopentene.Dicyclopentadiene cut generates cyclopentadiene through depolymerization, and then selective hydrogenation can obtain cyclopentene.In dicyclopentadiene downstream product, cyclopentene occupies very important position, due to the specific structure of cyclopentene, it is a kind of important Organic Chemicals, can be used for preparing the high added value intermediates such as cyclopentanol, cyclopentanone, glutaraldehyde, ring amyl methyl ether, bromocyclopentane, be widely used in the fields such as spices, medical industry and synthetic rubber.
The key of cyclopentadiene hydrogenating is the active of catalyst and selective, the report of existing multiple hydrogenation catalyst abroad, but these catalyst all exist shortcomings such as preparation is complicated, the life-span is short, poor selectivity.Cyclopentadiene can selective hydrogenation generate cyclopentene under suitable condition, and also hydrogenation generates pentamethylene entirely, and this depends primarily on catalyst and the condition of reaction etc. that reaction is used.Due to cyclopentene and pentamethylene boiling point comparatively approaching, be difficult to separate, the productive rate of therefore selecting suitable reaction condition and hydrogenation catalyst to improve target product is critical problem.In early literatures report, the selective hydrogenation catalyst of being prepared cyclopentene by cyclopentadiene hydrogenating more typically has Raney nickel, and the use Raney nickel of mentioning as US Patent No. 4108911 is as catalyst, and ethylene glycol is as solvent, under certain condition, the conversion ratio of cyclopentadiene reaches 90.7%.Cyclopentene be selectively 96.7%.Also have in the recent period bibliographical information, Pd salt as major catalyst effect under, taking cyclopentadiene as raw material, ethanol is as solvent, catalytic hydrogenation reaction has synthesized cyclopentene; The impact of the existence of having investigated different anions Pd salt in catalyst system and catalyzing and multiple co-catalyst on selective hydrogenation.But their catalyst is more difficult with separating of cyclopentene, and the conversion ratio of cyclopentadiene is lower, because the boiling point of cyclopentadiene and cyclopentene are very approaching, the purification of product will be more difficult like this.In prior art, also have and adopt taking Metal Palladium as main active component, Al
2o
3, active carbon etc. prepares the reaction of cyclopentene for Selective Hydrogenation of Cyclopentadiene as the solid supported of carrier, this solid catalyst can be more easily and product separation.If report in Chinese patent CN1911877A is with γ-Al
2o
3for carrier, Metal Palladium is active component, solvent is taken from any in toluene, cyclohexane etc., by adopting the heat-exchanger rig of settling a kind of injector in hydrogenation reactor, the comparatively ideal reaction heat of having removed the generation of cyclopentadiene hydrogenating process, make reaction obtain higher cyclopentene yield, but the method complicated operation, and cost is higher.For another example to have proposed a kind of active component be Pd-Zn to Deutsche Bundespatent, and carrier is Al
2o
3loaded catalyst for cyclopentadiene hydrogenating preparing cyclopentene.Although this scheme cyclopentene selectively can reach 96%, cyclopentadiene conversion ratio is only 86%.
Three, summary of the invention
The present invention is intended to for the synthetic cyclopentene of cyclopentadiene selective hydrogenation provides a kind of catalysts selective, to improve the conversion ratio of selective and product of reaction.
The catalyst that the present invention uses is easy to and separation of products, there is good reusing, the use of mixed solvent also effectively reduces the amount of heat producing in course of reaction, and simultaneous reactions condition is also gentleer, can effectively solve some defects of prior art scheme.
Pd-Ni/Al of the present invention
2o
3catalyst, is characterized in that: with PdCl
2and Ni (NO
3)
2for active component, with Al
2o
3h
2o is catalyst carrier, the catalyst obtaining after active component is carried in catalyst carrier;
PdCl
2and Ni (NO
3)
2gross mass be Al
2o
3h
2the 0.5-1% of O quality;
In active component, the mass ratio of Pd and Ni is 1:0.5-3.
Pd-Ni/Al of the present invention
2o
3the preparation method of catalyst, comprises load and the each unit process of activation:
Described load is by PdCl
2and Ni (NO
3)
2be dissolved in the acetum of mass concentration 25-35%, after stirring and dissolving, add again Al
2o
3h
2o, stirs and standing 1.5-2.5h, subsequently in 100-120 DEG C of dry 8-10h, then in 540-560 DEG C of roasting 2.5-3.5h; PdCl
2and Ni (NO
3)
2gross mass be Al
2o
3h
2the 0.5-1% of O quality, Pd and Ni mass ratio are 1:0.5-3;
Described activation is after roasting, to pass into hydrogen to carry out catalyst activation, activation temperature 240-260 DEG C, and activation pressure 0.1-0.2MPa, hydrogen flowing quantity 40-50ml/min, soak time 40-50 hour, makes Pd-Ni/Al
2o
3catalyst.
Pd-Ni/Al of the present invention
2o
3the purposes of catalyst, is characterized in that: in cyclopentadiene liquid phase catalytic hydrogenation reduction reaction is prepared cyclopentene as the application of catalyst.
The detailed process that cyclopentadiene catalytic hydrogenation is prepared cyclopentene is as follows:
Taking cyclopentadiene as raw material, taking ethanol and acetonitrile as mixed solvent, in hydrogen atmosphere, Pd-Ni/Al
2o
3under the existence of catalyst, in 25-40 DEG C of reaction 1.5-3 hour, Hydrogen Vapor Pressure is controlled at 0.8-1.5MPa, Pd-Ni/Al
2o
3the addition of catalyst is the 3-7% of cyclopentadiene quality; In mixed solvent, the volume ratio of ethanol and acetonitrile is 1:0.2-1; The addition of mixed solvent is 5-10 times of cyclopentadiene quality.
Utilize the reaction scheme of catalyst to catalyzing hydrogenating of the present invention as follows:
The present invention selects the bimetallic catalyst of Pd and Ni, Ni active component add the activity decreased that makes catalyst, suppressed cyclopentadiene excessive hydrogenation and generated pentamethylene, better selective thereby the synthetic cyclopentene of cyclopentadiene selective hydrogenation has.Because the cost of the Ni salt Pd salt of comparing is much lower, Ni catalyst is as also reducing reaction cost adding of co-catalyst.
The present invention is with Al
2o
3h
2o, as catalyst carrier, under the same conditions, uses Al
2o
3h
2o is as catalyst carrier and γ-Al
2o
3compare as carrier, the output of cyclopentene can improve 10-20%, and this is because the former has a large amount of constitution waters, and the surface of catalyst exists a large amount of hydrophilic hydroxyls, has greatly improved the selective of its catalysis.
Cyclopentadiene hydrogenating reaction is a strong exothermal reaction, in order to reduce the thermal discharge of reaction, the present invention selects ethanol and acetonitrile mixed solvent, the use of mixed solvent has increased the selective of cyclopentene, and can effectively stop in course of reaction because of excess Temperature, cyclopentadiene self-polymerization generates dicyclopentadiene, and the application of mixed solvent is simultaneously extended the activity of catalyst.
Use catalyst hydrogenation reaction of the present invention to carry out at normal temperatures, reaction condition gentleness, the load catalyst using is easy to and separation of products, and the synthetic cyclopentene of cyclopentadiene selective hydrogenation has extraordinary conversion ratio with selective, conversion ratio is 98-99.5%, cyclopentene selectively also reach 97-98.5%.
Conversion ratio of the present invention and optionally computational methods are as follows:
Four, detailed description of the invention
Non-limiting examples of the present invention is described below:
1, the preparation of catalyst
By PdCl
2and Ni (NO
3)
2add in the acetum of mass concentration 30%, Pd and Ni mass ratio are 1:0.5-3, add Al after stirring and dissolving again
2o
3h2O, stir and standing 2h, subsequently in 100-120 DEG C of dry 8-10h, again in 540-560 DEG C of roasting 2.5-3.5h, after roasting, pass into hydrogen and carry out catalyst activation, the Reduction of Oxide that makes Ni is the activated Ni of tool, and 250 DEG C of activation temperatures, pressure 0.1MPa, hydrogen flowing quantity 45ml/min, soak time 48 hours, make Pd-Ni/Al
2o
3catalyst, wherein PdCl
2and Ni (NO
3)
2gross mass be Al
2o
3h
2the 0.5-1% of O quality;
2, liquid phase catalytic hydrogenation
Pd-Ni/Al prepared by step 1
2o
3catalyst and 50g cyclopentadiene (derive from dicyclopentadiene cracking, dicyclopentadiene content is at 85-95wt%) add a built-in cooling coil and be equipped with in the reactor of agitating device, add ethanol and acetonitrile mixed solvent, after good seal, first use nitrogen replacement 3 times, then use hydrogen exchange 3 times, be warming up to 25-40 DEG C and start stirring reaction, and Hydrogen Vapor Pressure is controlled to 0.8-1.5MPa, Pd-Ni/Al
2o
3the addition of catalyst is the 3-7% of cyclopentadiene quality, in mixed solvent, the volume ratio of ethanol and acetonitrile is 1:0.2-1, the addition of mixed solvent be cyclopentadiene quality 5-10 doubly, reach 98% until cyclopentadiene conversion ratio and stop reaction when above, reactant liquor taking-up is carried out to rectification and purification.Products therefrom utilizes gas-chromatography analysis.
The preparation parameter of embodiment 1-10 arranges in table 1, the conversion ratio of cyclopentadiene and selectively in table 2.As can be seen from Table 2, synthesize taking cyclopentadiene as raw material selective hydrogenation in the reaction of cyclopentene, select ethanol and acetonitrile as mixed solvent, be raw material cyclopentadiene quality 3-7% at catalyst amount, catalyst activity component Pd/Ni mass ratio is at 1:0.5-3, when active component accounts between the 0.5-1.0% of loaded catalyst gross mass, Hydrogen Vapor Pressure is between 0.8-1.5MPa, and temperature is reacted between 30-35 DEG C has good conversion ratio for 1.5-3 hour with selective.The conversion ratio of the cyclopentadiene that wherein preparation condition of embodiment 2 makes and selectively the highest.
Table 1
* active component addition refers to PdCl
2and Ni (NO
3)
2gross mass account for Al
2o
3h
2the percentage of O quality.
Table 2
| Cyclopentadiene conversion ratio/% | Cyclopentene is selective/% | |
| Implement 1 | 98.1 | 97.8 |
| Implement 2 | 99.5 | 98.5 |
| Implement 3 | 98.5 | 97.1 |
| Implement 4 | 98.0 | 97.5 |
| Implement 5 | 99.1 | 97.2 |
| Implement 6 | 98.1 | 98.1 |
| Implement 7 | 98.4 | 97.9 |
| Implement 8 | 98.7 | 97.2 |
| Implement 9 | 98.1 | 98.3 |
| Implement 10 | 98.6 | 97.0 |
Claims (1)
1. a Pd-Ni/Al
2o
3the purposes of catalyst, is characterized in that: in cyclopentadiene liquid phase catalytic hydrogenation reduction reaction is prepared cyclopentene as the application of catalyst;
Described Pd-Ni/Al
2o
3catalyst prepares by the following method:
By PdCl
2and Ni (NO
3)
2add in the acetum of mass concentration 25-35%, after stirring and dissolving, add again Al
2o
3h
2o, stirs and standing 1.5-2.5h, subsequently in 100-120 DEG C of dry 8-10h, then in 540-560 DEG C of roasting 2.5-3.5h; PdCl
2and Ni (NO
3)
2gross mass be Al
2o
3h
2the 0.5-1% of O quality, Pd and Ni mass ratio are 1:0.5-3; After roasting, pass into hydrogen and carry out catalyst activation, activation temperature 240-260 DEG C, activation pressure 0.1-0.2MPa, hydrogen flowing quantity 40-50ml/min, soak time 40-50 hour.
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| CN103433059B (en) * | 2013-09-16 | 2014-12-10 | 陈卓杰 | Catalyst used in hydrogenation reaction of m-dinitrobenzene to synthesize m-phenylenediamine and application of catalyst |
| CN104549560A (en) * | 2013-10-10 | 2015-04-29 | 中国石油化工股份有限公司 | Method for activating hydrogenation catalyst |
| CN103894209B (en) * | 2014-03-18 | 2016-04-13 | 巨化集团技术中心 | A kind of catalyst for chlorination aromatic hydrocarbon dechlorination hydrogenation and preparation and application |
| CN105413707B (en) * | 2015-10-30 | 2017-10-31 | 南京理工大学 | The bimetallic Pd Ni/CeO reduced for nitrosodimethylamine2‑TiO2Catalyst and preparation method thereof |
| CN106673951B (en) * | 2015-11-09 | 2019-07-12 | 中国石油化工股份有限公司 | A method of cyclopentene is produced by cyclopentadiene |
| CN108689790B (en) * | 2017-04-07 | 2021-07-30 | 中国石油化工股份有限公司 | Method for preparing cyclopentene by selective hydrogenation of cyclopentadiene |
| CN108689791B (en) * | 2017-04-07 | 2021-08-03 | 中国石油化工股份有限公司 | Method for preparing cyclopentene by selective hydrogenation of cyclopentadiene |
| CN109865519B (en) * | 2017-12-01 | 2021-11-30 | 中国石化扬子石油化工有限公司 | Ruthenium modified activated carbon supported nickel catalyst, preparation method and application thereof |
| CN115806477A (en) * | 2021-09-14 | 2023-03-17 | 中国科学院大连化学物理研究所 | Method and device for producing cyclopentanone product |
| CN114225945B (en) * | 2021-12-31 | 2022-07-12 | 北京化工大学 | Preparation method, product and application of PdNi alloy catalyst |
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