CN101780406B - Nano metal catalyst and preparation method and application thereof - Google Patents

Nano metal catalyst and preparation method and application thereof Download PDF

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CN101780406B
CN101780406B CN200910077059XA CN200910077059A CN101780406B CN 101780406 B CN101780406 B CN 101780406B CN 200910077059X A CN200910077059X A CN 200910077059XA CN 200910077059 A CN200910077059 A CN 200910077059A CN 101780406 B CN101780406 B CN 101780406B
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catalyst
reaction
hydrogenation
carbon dioxide
reaction time
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CN101780406A (en
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吴天斌
韩布兴
姜涛
侯民强
樊红雷
张兆富
张建玲
杨冠英
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Institute of Chemistry CAS
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Abstract

The invention discloses a nano metal catalyst and a preparation method and an application thereof. The nano metal catalyst consists of nano Pd catalyst particles, carrier of nano Pd catalyst and a crosslink polymer coat which is wrapped on the surface of the nano Pd catalyst. The preparation method of the nano metal catalyst comprises the following steps: in the inert atmosphere, reaction monomer and comonomer are undertaken the copolymerization with the nano Pd catalyst loaded by the carrier to obtain the product. The reaction of the 2,4-dimethyl-1,3-pentylene and the propenol in the catalyzing supercritical carbon dioxide medium has high selectivity and reaction activity. The method has simple preparation process, and the metal catalyst is stable; and after the reaction is ended, the catalyst can be separated from the product through the centrifugal to be repeatedly used. By adequately integrating the steric effect of the polymer coat and the particular performance of the supercritical carbon dioxide, the nano metal catalyst has promising application prospect in the catalyzing reaction.

Description

A kind of metallic catalyst and preparation method thereof and application
Technical field
The present invention relates to a kind of metallic catalyst and preparation method thereof and application, the application during metallic catalyst that particularly relates to the load of a kind of cross-linked polymer coating coated carrier and preparation method thereof reacts with high-selective and hydrogenating in supercritical carbon dioxide.
Background technology
Prepare at hydrocarbon cracking in the monoolefines such as ethene, propylene, butylene, produced partly conjugated alkadienes.These conjugated dienes process behind alkene particularly in the olefin polymerization process that easy polymerization generates colloid under the effect of catalyst, and the blocking catalyst duct has influenced catalyst life.And effective method to remove these conjugated dienes be exactly that conjugated diene is selected to be hydrogenated to corresponding monoolefine and generation (the Munro S and ColmanP.Effect of Toluene-d8 on the Hydrogenation of 1 that do not have alkane; 3-Hexadiene over a Pd/SilicaCatalysts-Promoter and Poison; Langmuir 2000; 16,6519-6526).This selection hydrogenation to catalyst itself has proposed very high requirement: catalyst has very high selectivity, only diene hydrogenation is not lost monoolefine; Catalyst has good activity, under lower temperature, reacts, and reduces by the inactivation of olefin(e) oligomerization to catalyst; Catalyst has good recycle performance (Berhault G, Bisson L, Thomazeau C; VerdonC; Uzio D.Preparation of Nanostructured Pd Particles Using a Seeding SynthesisApproach-Application to the Selective Hydrogenation, Applied Catalysis A:General, 2007; 327,32-43).
Therefore; For the selective hydrogenation that can realize this type conjugated diene is a monoolefine; The inventor designs a kind of special catalyst, promptly uses polymer coating clad nano metallic catalyst, is intended to improve the selective hydrogenation to the two keys of conjugated diene end group through the steric effect of this polymer; And inner two keys are unaffected basically, and the general exposed metal nano catalyst of this type reactant employing is the hydrogenation that is difficult to its certain a pair of key of control.But, there are two problems to need to solve, problem is exactly the surface that how the polymer stabilizing coating is coated on the metallic catalyst of solid supported, and this has very big difficulty on Preparation of catalysts, has very big challenge.Another problem is exactly this polymer coating with general solvent is to be difficult to that reaction substrate is diffused into polymer coating contact with catalyst; This just needs a kind of special reaction medium to come this polymer coating of swelling; And with the supercritical carbon dioxide performance combine just can solve this problem; Because it is zero and to the characteristics such as expansion character of polymer that supercritical carbon dioxide has high diffusibility, interfacial tension, can the expanded polymer layer drive reactant with hydrogen arrival catalyst and catalytic reaction takes place.Therefore, we are the particular design and the properties of supercritical carbon dioxide of abundant combined catalyst, in the hope of reaching the reactivity that improves catalyst and the purpose of high-selective and hydrogenating.
Summary of the invention
The purpose of this invention is to provide a kind of metallic catalyst and preparation method thereof and application.
Metallic catalyst provided by the invention is made up of the carrier of nanometer Pd catalyst granules, said nanometer Pd catalyst and the cross-linked polymer coating that is coated on said nanometer Pd catalyst surface;
Wherein, carrier is SiO 2Particle; Cross-linked polymer is cross-linked (styrene-divinylbenzene).The particle diameter of nanometer Pd catalyst granules is the 2-5 nanometer, and the particle diameter of carrier is the 200-500 nanometer, and the degree of polymerization of cross-linked polymer is 2.5-12%.
The preparation method of above-mentioned metallic catalyst provided by the invention is in inert atmosphere, and reaction monomers and comonomer and carrier loaded nanometer Pd catalyst are carried out copolyreaction, obtains metallic catalyst provided by the invention.
In this method, reaction monomers is styrene and divinylbenzene, and comonomer is an allylamine, and carrier is SiO 2Particle, the reaction medium of copolyreaction are water, and styrene sulfonic acid is received and is that emulsifying agent, PVP are dispersion stabilizer, and potassium peroxydisulfate is an initator.The mol ratio of styrene, divinylbenzene and allylamine is 4.0-35.0: 0.1-3.0: 1.0-30, preferred 4.4-34.8: 0.35-2.8: 1.3-26.6.Various inert atmospheres commonly used such as nitrogen etc. all are applicable to this method.This copolyreaction temperature is 80 ℃, and the reaction time is 8-24 hour, preferred 12 hours.
Wherein, carrier loaded nanometer Pd metallic particles can prepare according to conventional method, and concrete preparation method can be: at SiO 2Particle as carrier through amine propyl-triethoxysilicane coupling agent functionalization back loading Pd 2+, then through 2-5MPa H 2Reduction, reduction temperature is 120-200 ℃, the recovery time is 4-8 hour, obtains SiO 2Carrier loaded nanometer Pd particle.
In addition, the present invention also provides above-mentioned metallic catalyst that catalysis 2 takes place in supercritical carbon dioxide, the application in the hydrogenation of 4-dimethyl-1,3-pentadiene and the propenyl hydrogenation.
Above-mentioned catalysis 2, the hydrogenation of 4-dimethyl-1,3-pentadiene, as shown in Figure 1, wherein, the pressure of carbon dioxide is 2-14MPa, preferred 8MPa.The pressure of hydrogen is 1-4MPa, preferred 3MPa, and reaction temperature is 30-50 ℃, preferred 40 ℃, the reaction time is 0.2-30 hour, preferred 16 hours; This reaction does not need to add in addition reaction dissolvent.
In the aforesaid propylene alcohol hydrogenation, the pressure of carbon dioxide is 2-14, preferred 8MPa, and the pressure of hydrogen is 1-4MPa, preferred 2MPa, reaction temperature is 30-50 ℃, preferred 40 ℃, the reaction time is 1-10 hour, preferred 5 hours; This reaction does not need to add in addition reaction dissolvent.
The present invention at first loads on monodispersed sub-micron SiO with nanometer Pd metallic particles 2Particle surface is realized crosslinked gathering (styrene-divinylbenzene) coating coated Si O through method of emulsion polymerization through the comonomer allylamine then 2Carrier loaded nanometer Pd metal granular catalyst.The resulting cross-linked of the present invention (styrene-divinylbenzene) coating coated Si O 2In the carrier loaded nanometer Pd metal granular catalyst catalysis supercritical CO 2 medium 2, the reaction of 4-dimethyl-1,3-pentadiene and propenyl has very high selectivity and reactivity.Relatively, the preparation process is simple with other cladded type catalyst (perhaps gathering dielectric clad metal nanocatalyst like tree-shaped polymer), and metallic catalyst is stable; After reaction finished, catalyst can separate with product through centrifugal, can reuse.The steric effect of the abundant conjugated polymer coating of the present invention and the property of supercritical carbon dioxide, this will have broad application prospects in catalytic reaction.
Description of drawings
Fig. 1 cross-linked polymer coating coated Si O 2Carrier loaded Pd metallic particles and supercritical carbon dioxide (scCO thereof 2) middle catalysis 2, the sketch map of 4-dimethyl-1,3-pentadiene hydrogenation reaction.
The specific embodiment
Below in conjunction with specific embodiment the present invention is described further, but the present invention is not limited to following examples.
Embodiment 1, preparation metallic catalyst
One) preparation monodispersed submicron SiO 2Particle
The ethanolic solution of ethyl orthosilicate is joined rapidly in the ethanolic solution of ammoniacal liquor, and in final mixed solution, ammonia: water: the mol ratio of ethyl orthosilicate is 1: 11: 0.22.Formed mixed solution reacted 4 hours under magnetic agitation, and reaction temperature is 30 ℃.With the centrifugation of reacted suspension,,, obtain the monodispersed submicron SiO of 230nm 100 ℃ of dryings 12 hours respectively through ethanol and washing three times 2Particle.
Two) SiO 2The amino-functionalization of particle
With 3 gram SiO 2Particle and 3.6 donaxine propyl-triethoxysilicanes are dispersed in the 45ml toluene, and after ultrasonic dispersion, formed suspension refluxed 24 hours 110 ℃ of magnetic agitation.With the centrifugation of the suspension after refluxing, it is inferior to give a baby a bath on the third day after its birth through toluene and ethanol respectively, 100 ℃ of dryings 12 hours, obtains the SiO of amino-functionalization 2Particle.
Three) preparation SiO 2Particulate vector loaded with nano Pd metal granular catalyst
SiO with 1.2 donaxine functionalization 2Particle is ultrasonic to be scattered in the 40ml water, adds 32ml H 2PdCl 4Solution (2mmolL -1), formed suspension is in the room temperature magnetic agitation after 30 minutes, and suspension is washed three times through centrifugation, 100 ℃ of dryings 12 hours, obtains SiO 2Particulate load Pd 2+With SiO 2Particulate load Pd 2+Insert in the 6ml autoclave, feed 3MPa H 2, reduced 5 hours down at 150 ℃, obtain black SiO 2Particulate vector loaded with nano Pd metal granular catalyst.Through the ICP-AES analysis, Pd content is 0.47%.
Four) preparation crosslinked gathering (styrene-divinylbenzene) coating coated Si O 2Carrier loaded nanometer Pd metal granular catalyst
With the black SiO of 0.3 gram 2Particulate vector loaded with nano Pd metallic particles is ultrasonic to be scattered in the 35ml water, adds 0.5ml allylamine and 0.5 gram PVP, feeds protection gas nitrogen, and at room temperature magnetic agitation is 1 hour.Adding 0.25 gram styrene sulfonic acid in back is received, 0.15 gram potassium peroxydisulfate and 40ml water, stirs after 30 minutes, adds 2ml styrene and 0.2ml divinylbenzene, and last whole reaction system is warming up to 80 ℃, and polymerization process is at N 2Under the protection, condensing reflux 12 hours.After reaction finished, with the centrifugation of the suspension after the polymerization, it was inferior to give a baby a bath on the third day after its birth through water and ethanol respectively, 60 ℃ of vacuum drying 24 hours, obtains crosslinked gathering (styrene-divinylbenzene) coating coated Si O 2Carrier loaded nanometer Pd metal granular catalyst.Through the ICP-AES analysis, Pd content is 0.28%.
Embodiment 2, preparation metallic catalyst
One) preparation monodispersed submicron SiO 2Particle
The ethanolic solution of ethyl orthosilicate is joined rapidly in the ethanolic solution of ammoniacal liquor, and in final mixed solution, ammonia: water: the mol ratio of ethyl orthosilicate is 1: 11: 0.22.Formed mixed solution reacted 4 hours under magnetic agitation, and reaction temperature is 30 ℃.With the centrifugation of reacted suspension,,, obtain the monodispersed submicron SiO of 230nm 100 ℃ of dryings 12 hours respectively through ethanol and washing three times 2Particle.
Two) SiO 2The amino-functionalization of particle
With 3 gram SiO 2Particle and 3.6 donaxine propyl-triethoxysilicanes are dispersed in the 45ml toluene, and after ultrasonic dispersion, formed suspension refluxed 24 hours 110 ℃ of magnetic agitation.With the centrifugation of the suspension after refluxing, it is inferior to give a baby a bath on the third day after its birth through toluene and ethanol respectively, 100 ℃ of dryings 12 hours, obtains the SiO of amino-functionalization 2Particle.
Three) preparation SiO 2Particulate vector loaded with nano Pd metal granular catalyst
SiO with 1.2 donaxine functionalization 2Particle is ultrasonic to be scattered in the 40ml water, adds 32ml H 2PdCl 4Solution (2mmolL -1), formed suspension is in the room temperature magnetic agitation after 30 minutes, and suspension is washed three times through centrifugation, 100 ℃ of dryings 12 hours, obtains SiO 2Particulate load Pd 2+With SiO 2Particulate load Pd 2+Insert in the 6ml autoclave, feed 2MPa H 2, reduced 6 hours down at 120 ℃, obtain black SiO 2Particulate vector loaded with nano Pd metal granular catalyst.Through the ICP-AES analysis, Pd content is 0.46%.
Four) preparation crosslinked gathering (styrene-divinylbenzene) coating coated Si O 2Carrier loaded nanometer Pd metal granular catalyst
With the black SiO of 0.3 gram 2Particulate vector loaded with nano Pd metallic particles is ultrasonic to be scattered in the 35ml water, adds 0.25ml allylamine and 0.5 gram PVP, feeds protection gas nitrogen, and at room temperature magnetic agitation is 1 hour.Adding 0.25 gram styrene sulfonic acid in back is received, 0.15 gram potassium peroxydisulfate and 40ml water, stirs after 30 minutes, adds 1ml styrene and 0.1ml divinylbenzene, and last whole reaction system is warming up to 80 ℃, and polymerization process is at N 2Under the protection, condensing reflux 12 hours.After reaction finished, with the centrifugation of the suspension after the polymerization, it was inferior to give a baby a bath on the third day after its birth through water and ethanol respectively, 60 ℃ of vacuum drying 24 hours, obtains crosslinked gathering (styrene-divinylbenzene) coating coated Si O 2Carrier loaded nanometer Pd metal granular catalyst.Through the ICP-AES analysis, Pd content is 0.32%.
Embodiment 3, preparation metallic catalyst
One) preparation monodispersed submicron SiO 2Particle
The ethanolic solution of ethyl orthosilicate is joined rapidly in the ethanolic solution of ammoniacal liquor, and in final mixed solution, ammonia: water: the mol ratio of ethyl orthosilicate is 2: 11: 0.22.Formed mixed solution reacted 4 hours under magnetic agitation, and reaction temperature is 30 ℃.With the centrifugation of reacted suspension,,, obtain the monodispersed submicron SiO of 500nm 100 ℃ of dryings 12 hours respectively through ethanol and washing three times 2Particle.
Two) SiO 2The amino-functionalization of particle
With 3 gram SiO 2Particle and 3.6 donaxine propyl-triethoxysilicanes are dispersed in the 45ml toluene, and after ultrasonic dispersion, formed suspension refluxed 24 hours 110 ℃ of magnetic agitation.With the centrifugation of the suspension after refluxing, it is inferior to give a baby a bath on the third day after its birth through toluene and ethanol respectively, 100 ℃ of dryings 12 hours, obtains the SiO of amino-functionalization 2Particle.
Three) preparation SiO 2Particulate vector loaded with nano Pd metal granular catalyst
SiO with 1.2 donaxine functionalization 2Particle is ultrasonic to be scattered in the 40ml water, adds 32ml H 2PdCl 4Solution (2mmolL -1), formed suspension is in the room temperature magnetic agitation after 30 minutes, and suspension is washed three times through centrifugation, 100 ℃ of dryings 12 hours, obtains SiO 2Particulate load Pd 2+With SiO 2Particulate load Pd 2+Insert in the 6ml autoclave, feed 5MPaH 2,, obtain black SiO at 180 ℃ of following reductase 12s hour 2Particulate vector loaded with nano Pd metal granular catalyst.Through the ICP-AES analysis, Pd content is 0.45%.
Four) preparation crosslinked gathering (styrene-divinylbenzene) coating coated Si O 2Carrier loaded nanometer Pd metal granular catalyst
With the black SiO of 0.3 gram 2Particulate vector loaded with nano Pd metallic particles is ultrasonic to be scattered in the 35ml water, adds 1.0ml allylamine and 0.5 gram PVP, feeds protection gas nitrogen, and at room temperature magnetic agitation is 1 hour.Adding 0.25 gram styrene sulfonic acid in back is received, 0.15 gram potassium peroxydisulfate and 40ml water, stirs after 30 minutes, adds 3ml styrene and 0.15ml divinylbenzene, and last whole reaction system is warming up to 80 ℃, and polymerization process is at N 2Under the protection, condensing reflux 12 hours.After reaction finished, with the centrifugation of the suspension after the polymerization, it was inferior to give a baby a bath on the third day after its birth through water and ethanol respectively, 60 ℃ of vacuum drying 24 hours, obtains crosslinked gathering (styrene-divinylbenzene) coating coated Si O 2Carrier loaded nanometer Pd metal granular catalyst.Through the ICP-AES analysis, Pd content is 0.25%.
Embodiment 4,2, the hydrogenation reaction of 4-dimethyl-1,3-pentadiene
In the 6ml autoclave, add 2.0mmol 2, crosslinked the gathering of gained (styrene-divinylbenzene) coating coated Si O among 4-dimethyl-1,3-pentadiene and the 0.0136 gram embodiment 1 2Carrier loaded nanometer Pd metal granular catalyst.Air in the still with carbon dioxide replacement three times after, be heated to 40 ℃, feed 3MPa hydrogen and 8MPa carbon dioxide, under magnetic agitation, react after 16 hours, the mixture of ice and water cooling, the slow venting, ultracentrifugation, supernatant liquor is used gas chromatographic analysis.Corresponding product 2,4-dimethyl-2-amylene productive rate is 80.1%, 2, and 4-dimethyl-1-amylene productive rate is 19.8%, 2, and 4-dimethyl pentane productive rate is 0.1%.
Comparative Examples 1
In the 6ml autoclave, add 2.0mmol 2, the SiO of 4-dimethyl-1,3-pentadiene and 0.0081 gram embodiment, 1 preparation 2Particulate vector loaded with nano Pd metal granular catalyst.Air in the still with carbon dioxide replacement three times after, be heated to 40 ℃, feed 3MPa hydrogen, under magnetic agitation, react after 20 minutes, the mixture of ice and water cooling is slowly exitted, ultracentrifugation, supernatant liquor is used gas chromatographic analysis.Corresponding product 2,4-dimethyl-2-amylene productive rate is 51.2%, 2, and 4-dimethyl-1-amylene productive rate is 48.4%, 2, and 4-dimethyl pentane productive rate is 0.4%.
The hydrogenation reaction of embodiment 5, propenyl
In the 6ml autoclave, add 2mmol propenyl and 0.0100 gram crosslinked the gathering of embodiment 1 gained (styrene-divinylbenzene) coating coated Si O 2Carrier loaded nanometer Pd metal granular catalyst.Air in the still with carbon dioxide replacement three times after, be heated to 40 ℃, feed 2MPa hydrogen and 8MPa carbon dioxide, under magnetic agitation, react after 5 hours, the mixture of ice and water cooling, the slow venting, ultracentrifugation, supernatant liquor is used gas chromatographic analysis.Corresponding product 1-propyl alcohol productive rate is 93.1%, and the propionic aldehyde productive rate is 6.9%.
Comparative Examples 2
Adding 2mmol propenyl and 0.0060 gram embodiment, 1 gained prepare SiO in the 6ml autoclave 2Particulate vector loaded with nano Pd metal granular catalyst.Air in the still with carbon dioxide replacement three times after, be heated to 40 ℃, feed 2MPa hydrogen, under magnetic agitation, react after 1 hour, the mixture of ice and water cooling is slowly exitted, ultracentrifugation, supernatant liquor is used gas chromatographic analysis.Corresponding product 1-propyl alcohol productive rate is 75.3%, and the propionic aldehyde productive rate is 24.7%.
All do not feed carbon dioxide in above-mentioned two Comparative Examples; Can know by the foregoing description 4,5 and Comparative Examples; Utilize metallic catalyst provided by the invention in catalysis 2, hydrogenation takes place in 4-dimethyl-1,3-pentadiene and propenyl in supercritical carbon dioxide; Reaction time obviously shortens, and has good catalytic effect.

Claims (18)

1. metallic catalyst is made up of the carrier of nanometer Pd catalyst granules, said nanometer Pd catalyst and the cross-linked polymer coating that is coated on said nanometer Pd catalyst surface;
Wherein, said carrier is SiO 2Particle; Said cross-linked polymer is cross-linked (styrene-divinylbenzene).
2. catalyst according to claim 1 is characterized in that: the particle diameter of said nanometer Pd catalyst granules is the 2-5 nanometer, and the particle diameter of said carrier is the 200-500 nanometer, and the degree of polymerization of said cross-linked polymer is 2.5-12%.
3. a method for preparing the described metallic catalyst of claim 1 is in inert atmosphere, and reaction monomers and comonomer and carrier loaded nanometer Pd catalyst are carried out copolyreaction, obtains said metallic catalyst;
Wherein, said reaction monomers is styrene and divinylbenzene; Said comonomer is an allylamine; Said carrier is SiO 2Particle.
4. method according to claim 3 is characterized in that: the reaction medium of said copolyreaction is a water; Used initator is a potassium peroxydisulfate in the said copolyreaction, and used emulsifying agent is a SSS, and used dispersion stabilizer is a PVP.
5. according to claim 3 or 4 described methods, it is characterized in that: the mol ratio of said styrene, divinylbenzene and allylamine is 4.0-35.0: 0.1-3.0: 1.0-30.
6. method according to claim 5 is characterized in that: the mol ratio of said styrene, divinylbenzene and allylamine is 4.4-34.8: 0.35-2.8: 1.3-26.6.
7. according to the arbitrary described method of claim 3-4, it is characterized in that: said copolyreaction temperature is 80 ℃, and the reaction time is 8-24 hour; Said inert atmosphere is a nitrogen.
8. method according to claim 7 is characterized in that: the reaction time is 12 hours.
9. method according to claim 5 is characterized in that: said copolyreaction temperature is 80 ℃, and the reaction time is 8-24 hour; Said inert atmosphere is a nitrogen.
10. method according to claim 9 is characterized in that: the reaction time is 12 hours.
11. method according to claim 6 is characterized in that: said copolyreaction temperature is 80 ℃, and the reaction time is 8-24 hour; Said inert atmosphere is a nitrogen.
12. method according to claim 11 is characterized in that: the reaction time is 12 hours.
13. the method for hydrogenation takes place in supercritical carbon dioxide for a catalysis 2,4-dimethyl-1,3-pentadiene, it is characterized in that: said 2, in 4-dimethyl-1,3-pentadiene hydrogenation, catalyst is the described metallic catalyst of claim 1.
14. method according to claim 13 is characterized in that: said 2, in 4-dimethyl-1,3-pentadiene hydrogenation, the pressure of carbon dioxide is 2-14MPa; The pressure of hydrogen is 1-4MPa; Reaction temperature is 30-50 ℃; Reaction time is 0.2-30 hour.
15. method according to claim 14 is characterized in that: said 2, in 4-dimethyl-1,3-pentadiene hydrogenation, the pressure of carbon dioxide is 8MPa; The pressure of hydrogen is 3MPa; Reaction temperature is 40 ℃; Reaction time is 16 hours.
16. the method for hydrogenation takes place in supercritical carbon dioxide a catalyzing propone alcohol, it is characterized in that: in the said propenyl hydrogenation, catalyst is the described metallic catalyst of claim 1.
17. method according to claim 16 is characterized in that: in the said propenyl hydrogenation, the pressure of carbon dioxide is 2-14MPa; The pressure of hydrogen is 1-4MPa; Reaction temperature is 30-50 ℃; Reaction time is 1-10 hour.
18. method according to claim 17 is characterized in that: in the said propenyl hydrogenation, the pressure of carbon dioxide is 8MPa; The pressure of hydrogen is 2MPa; Reaction temperature is 40 ℃; Reaction time is 5 hours.
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CN103752237B (en) * 2014-01-10 2015-12-30 陕西师范大学 The preparation method of the responsive microgel supported nano-gold of a kind of pH
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