CN110385145A - A kind of preparation method of Pt/C catalyst, Pt/C catalyst and its application - Google Patents
A kind of preparation method of Pt/C catalyst, Pt/C catalyst and its application Download PDFInfo
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- CN110385145A CN110385145A CN201910694605.8A CN201910694605A CN110385145A CN 110385145 A CN110385145 A CN 110385145A CN 201910694605 A CN201910694605 A CN 201910694605A CN 110385145 A CN110385145 A CN 110385145A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/18—One oxygen or sulfur atom
- C07D231/20—One oxygen atom attached in position 3 or 5
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
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Abstract
The present invention provides a kind of method for preparing modified Pt/C catalyst, comprising: by Pt/C catalyst soak in organic amine mixed solution, forms precursor mixture；The organic amine mixed solution includes component A and B component, and the component A is organic amine, and the B component is at least one solvent to dissolve each other with organic amine；Stir the precursor mixture；And it filters the precursor mixture and washs much filtrate to get modified Pt/C catalyst.
Description
Technical field
The present invention relates to a kind of methods for preparing Pt/C catalyst, especially with respect to one kind with organic amine-modified Pt/C catalyst
Method.
Background technique
Azanol aromatic hydrocarbons is a kind of organic intermediate for the important fine chemical product such as synthetic pesticide, medicine, is had wide
General market application prospect.Azanol aromatic hydrocarbons is generally using corresponding Nitro-aromatic Compounds in Different as raw material, through stoichiometric reaction, electrification
Learn reduction method or the synthesis of catalytic hydrogenation method.
Stoichiometric reaction includes metal deoxidization and sodium sulfide reducing method, and with metallic iron, tin and vulcanized sodium etc. are reduction
Agent restores nitro by stoichiometric reaction, simple process, but because environmental pollution is serious caused by the slag and effluent of generation, by
It is gradually disabled.Electrochemical reducing operating condition is mild, and product is controllable, but current utilization rate is not high, and high to equipment requirement,
There are certain difficulty for industrialization.Catalytic hydrogenation method becomes the mainstream of industrial nitro reduction at present with its cleaning, high financial profit
Technique.
And nitro-aromatic prepares azanol aromatic hydrocarbons method by catalytic hydrogenation and target product azanol aromatic hydrocarbons may be made further
Hydrogenation is more stable amido aromatic hydrocarbons.Therefore, expensive usually using activity higher Pt, Pd etc. in this kind of catalytic hydrogenation reaction
Metallic catalyst, to obtain the highly selective and high-recovery to azanol aromatic hydrocarbons, the prior art reported so far is all whole
Compound appropriate, such as DMSO, sulfur-containing compound or organic phosphorus compound are added in a reaction system your gold partially poisoned
Belong to, needed for being down to noble metal catalyst activity.
As United States Patent (USP) No.3694509 discloses a kind of addition DMSO raising in reaction system of the Pt/C as catalyst
To the method for the selectivity of N- phenylhydroxylamine, 86% rate of recovery can reach；United States Patent (USP) No.3927101 is then in reactant
Secondary, tertiary alkyl or cycloalkyl monoamines, piperidines, pyridine, alkyl pyridine, quinoline, the alkyl derivative of isoquinolin or N, C are added in system
Etc. the rate of recovery of azanol can be made to reach 58.6%；United States Patent (USP) No.5166435 discloses a kind of introducing N, P class in the reaction system
Compound, such as the method for phosphoric acid, dimethyl aminopyridine, triethyl phosphite, can make the azanol rate of recovery is up to 87%.In
Document " by loaded platinum catalyst to nitro-aromatic class row hydrogenation reaction with selectivity synthesis N- aryl hydroxylamine "
(Selective synthesis of N-aryl hydroxylamines by the hydrogenation of
nitroaromatics using supported platinum catalysts.2009.Y.Takenaka,T.Kiyosu,
J.-C.Choi, T.Sakakura and H.Yasuda.Green Chemistry.11:1385-1390) in, Takenaka etc.
People is with Pt/SiO2For catalyst, organic base, such as piperazine are added while adding DMSO as poisonous agent in entire reaction system
Pyridine, triethylamine, pyridine etc. are used as activating agent, and the conversion ratio of nitrobenzene connects while so that the selectivity of N-Phenylhydroxylamine is reached 99%
Nearly 100%.
However, though the above-mentioned method for adding poisonous agent reduction catalyst activity in entire reaction system is able to achieve azanol virtue
Hydrocarbon it is highly selective, but the catalyst partially poisoned usually will appear after an operation cycle activity decline even thoroughly lose
Phenomenon living, and then reuse catalyst can not.In addition, added poisonous agent may be with product azanol in reaction system
Aromatic hydrocarbons has intermiscibility, to keep subsequent processing difficult.
Therefore, ethylenediamine synthesis of ethylenediamine chelating Pt is added in old et al. one kind of delivering in 2016 in platinum precursor solution
The method of nano wire, p-nitrophenyl add hydrogen phenylhydroxylamine to have the selectivity (Interfacial for being up to 100%
electronic effects control the reaction.2016.G.Chen,C.Xu,X.Huang,J.Ye,L.Gu,
G.Li, Z.Tang,B.Wu,H.Yang,Z.Zhao,Z.Zhou,G.Fu,and N.Zheng.Nature Materials. 15:
564-569), those skilled in the art should know that organic amine will lead to Pt nanocatalyst and be poisoned and inhibitory activity, so will not be straight
Modification after carrying out directly to Pt nanocatalyst is connect, in addition, this method that organic amine-modified Pt nanocatalyst is prepared in situ,
Wherein noble metal precursor body acetylacetone,2,4-pentanedione platinum used is not easy to obtain, and preparation process is complicated, uses toxic gases such as CO, DMF and molten
Agent is unfavorable for industrialization large-scale production therefore, it is difficult to prepare in batches.
It can be seen from the above, industry, which still needs to one kind, is suitable for Nitro-aromatic Compounds in Different hydrogenation reaction, there is height to azanol aromatic hydrocarbons
Selectivity, and the catalyst that can continuously apply and keep activity, not influence subsequent product processing and can be mass produced.
Summary of the invention
First aspect present invention provides a kind of method for preparing modified Pt/C catalyst, comprising: by Pt/C catalyst
It is immersed in organic amine mixed solution, forms precursor mixture；Stir the organic amine mixed solution；And it filters described organic
Amine mixed solution simultaneously washs much filtrate to get modified Pt/C catalyst.
According to the present invention, the organic amine mixed solution includes component A and B component, and the component A is organic amine, the B
Group is divided at least one solvent to dissolve each other with organic amine
According to an embodiment of the invention, the molar ratio of the Pt of the organic amine and the Pt/C catalyst is 1:1 to 200:
1。
According to an embodiment of the invention, the organic amine in the organic amine mixed solution is selected from level-one amine, secondary amine, three
At least one of grade amine, heterocyclic amine.
According to an embodiment of the invention, the organic amine of the organic amine mixed solution is selected from the secondary amine being substituted, passes through
At least one of substituted tertiary amine, heterocyclic amine.
According to an embodiment of the invention, the organic amine of the organic amine mixed solution is selected from ethylenediamine, triethylamine, three
At least one of (2- aminoethyl) amine, N-methylmorpholine.
According to the present invention, stirring described in the preparation method, takes 1 to 3 hour.
According to the method for the present invention prepared modified Pt/C catalyst be used to be catalyzed the hydrogenation reaction of nitro-aromatic with
Prepare azanol aromatic hydrocarbons.
Second aspect of the present invention provides a kind of through organic amine-modified Pt/C catalyst, wherein the modified Pt/C
Catalyst is with the method preparation for preparing modified Pt/C catalyst of the invention.
Third aspect present invention provide it is a kind of be catalyzed nitro-aromatic hydrogenation reaction method, including by nitro-aromatic, with
Modified Pt/C catalyst, the solvent of method preparation provided by the invention sequentially add reaction kettle, form mixture；It is passed through N2
Replace air in the reaction kettle；It is passed through H again2To the reaction kettle；And the stirred under pressure mixture is until reaction completion.
According to an embodiment of the invention, the modified Pt/C catalyst is through organic amine-modified 2%Pt/C catalysis
Agent.
According to an embodiment of the invention, the temperature of the reaction is 30 DEG C or less.
Fourth aspect present invention provides a kind of for hydrogenating the set group of nitro-aromatic, which is characterized in that and the set group includes, with
The modified Pt/C catalyst of method preparation provided by the invention；Solvent；And H2。
Compared to prior art, the present invention provides a kind of method that Pt/C catalyst can be more precisely modified with organic amine,
Through it is organic it is amine-modified after Pt/C catalyst morphology it is complete, coverage and the uniformity of the organic amine in metal surface all can be controlled effectively
System, therefore can realize that 90% or more is highly selective, and have longer service life, it can repeat to apply, in addition, mentioning with the present invention
The method of confession is applicable to commercially available Pt/C catalyst, low in cost, is conducive to large-scale production.
Detailed description of the invention
Fig. 1 (a) is the TEM figure of the Pt/C catalyst before modification；Fig. 1 (b) through the method provided by the present invention prepare through modifying
EDA-2% Pt/C catalyst TEM figure.
Fig. 2 is the thermogravimetric analysis for modifying front and back Pt/C catalyst with EDA with the method provided by the present invention.Before modification
Pt/C catalyst；AndFor the modified EDA-2%Pt/C catalyst prepared through the method provided by the present invention.
Fig. 3 repeats set for EDA-Pt/C catalyst provided by the invention and prepares phenylhydroxylamine for Catalytic Hydrogenation of Nitrobenzene
Selectivity.For corresponding hydroxylamine compound；For corresponding amine compound；For corresponding nitroso compound；With
AndFor corresponding azo-compound.
Fig. 4 repeats set for EDA-Pt/C catalyst provided by the invention and prepares phenylhydroxylamine for Catalytic Hydrogenation of Nitrobenzene
ACTIVITY CHANGE OF FT.TopIndicate each reaction time applied；And lower sectionReaction system when indicating to apply for each time
Hydrogen-consuming volume per minute when being reacted in system.
Specific embodiment
Illustrate embodiments of the present invention by particular specific embodiment below, people skilled in the art can be by this theory
The bright revealed content of book is understood other advantages and efficacy of the present invention easily.
It should be clear that this specification structure depicted in this specification institute accompanying drawings, ratio, size etc., only to cooperate specification to be taken off
The content shown is not intended to limit the invention enforceable qualifications for the understanding and reading of people skilled in the art,
Therefore not having technical essential meaning, the modification of any structure, the change of proportionate relationship or the adjustment of size are not influencing this hair
Under bright the effect of can be generated and the purpose that can reach, disclosed technology contents should all be fallen in and obtain the model that can cover
In enclosing.Meanwhile cited such as "upper" in this specification, "inner", "outside", "bottom", " one ", " in " term, be also only and be convenient for
Narration is illustrated, rather than to limit the scope of the invention, relativeness is altered or modified, without substantive change
Under technology contents, when being also considered as the enforceable scope of the present invention.
First aspect present invention provides a kind of method for preparing modified Pt/C catalyst, comprising: by Pt/C catalyst
It is immersed in organic amine mixed solution, forms precursor mixture；Stir the precursor mixture；And filter forerunner's mixing
Object simultaneously washs much filtrate to get modified Pt/C catalyst.
According to an embodiment of the invention, the organic amine mixed solution includes component A and B component, the component A is organic
Amine, the B component are at least one solvent to dissolve each other with organic amine.
According to an embodiment of the invention, the molar ratio of the Pt of the organic amine and the Pt/C catalyst is 1:1 to 200:
1.According to embodiments of the present invention, the mass percentage of the Pt of the Pt/C catalyst can be 1% to 5%, preferably, the Pt/C
The mass percentage of the Pt of catalyst can be 2%.
According to an embodiment of the invention, the organic amine of the organic amine mixed solution can be the amine for being substituted or being unsubstituted
Class and the amine can be level-one amine, secondary amine, tertiary amine or heterocyclic amine；Preferably, which can be for selected from level-one amine, two
At least one of grade amine, tertiary amine, heterocyclic amine.Wherein, the substituent group of the amine can for being substituted with 1 to 6 C atom or
The alkyl being unsubstituted；Preferably, the substituent group of the amine can be the alkyl for being substituted or being unsubstituted with 1 to 3 C atom.
Alternatively, the amine can be the heterocyclic compound with exotic atoms such as N, O for being substituted or being unsubstituted, such as morpholine or N- methyl
Quinoline etc..
According to an embodiment of the invention, the organic amine of the organic amine mixed solution is selected from ethylenediamine, triethylamine, three
At least one of (2- aminoethyl) amine, morpholine, N-methylmorpholine.
According to the present invention, at least one solvent to dissolve each other with organic amine, visual selected organic amine determine, should with it is organic
The solvent that amine dissolves each other can be, such as, but not limited to, water, methanol, ethyl alcohol etc..
According to the present invention, after by Pt/C catalyst soak in organic amine mixed solution, precursor mixture is formed, can be stirred
The precursor mixture 1 to 3 hour.
Prepared modified Pt/C catalyst can be used for being catalyzed the hydrogenation reaction of nitro-aromatic according to the method for the present invention
To prepare azanol aromatic hydrocarbons.
According to an embodiment of the invention, the nitro-aromatic can beWherein R1、R2And R3Respectively
Selected from H, halogen, it is substituted or the alkyl with 1 to 6 C atom being unsubstituted, the aromatic hydrocarbon for being substituted or being unsubstituted
Base, the naphthenic base for being substituted or being unsubstituted or heterocycle, NO2, one of CHO.
Wherein, halogen can be F, Cl, Br, I；The alkyl with 1 to 6 C atom for being substituted or being unsubstituted can be warp
Methyl, ethyl, propyl, the isopropyl for replacing or being unsubstituted；The aryl radical for being substituted or being unsubstituted can be substituted or
The phenyl being unsubstituted；And the naphthenic base or heterocycle for being substituted or being unsubstituted can be the different original for being substituted or being unsubstituted
Subring base.
According to an embodiment of the invention, the nitro-aromatic can beWherein R1、R2And R3Respectively
Selected from H, F, Cl, CH3、NO2, CHO, one of heterocycle.
According to an embodiment of the invention, the nitro-aromatic can be But
It is without being limited thereto.
According to the present invention, stirring precursor mixture, i.e. the organic amine mixed solution containing Pt/C catalyst is after 1 to 3 hour,
It can be further evacuated the filtering precursor mixture, give up filtrate, and much filtrate can be dried with milli-Q water much filtrate,
Up to modified Pt/C catalyst.
Second aspect of the present invention provides a kind of through organic amine-modified Pt/C catalyst, wherein the modified Pt/C
Catalyst is with the method preparation for preparing modified Pt/C catalyst of the invention.
According to the present invention, described through essence before organic amine-modified Pt/C catalyst, pattern and particle size and modification
It is upper identical.
According to the present invention, described through in organic amine-modified Pt/C catalyst, which is substantially adsorbed in Pt/C and urges
Agent surface.
According to the present invention, described to obtain Pt/C catalysis before specific surface area is at least modified through organic amine-modified Pt/C catalyst
At least the 75% of agent；Preferably, described to obtain Pt/C catalysis before specific surface area is at least modified through organic amine-modified Pt/C catalyst
At least the 80% of agent.
Third aspect present invention provide it is a kind of be catalyzed nitro-aromatic hydrogenation reaction method, including by nitro-aromatic, with
Modified Pt/C catalyst, the solvent of method preparation provided by the invention sequentially add reaction kettle, form mixture；It is passed through N2
Replace air in the reaction kettle；It is passed through H again2To the reaction kettle；And the stirred under pressure mixture is until reaction completion.
According to the present invention, shown in the hydrogenation reaction such as following formula (1).
According to an embodiment of the invention, the mass percentage of the Pt of the Pt/C catalyst can be 1% to 5%, preferably,
The mass percentage of the Pt of the Pt/C catalyst can be 2%.
According to an embodiment of the invention, the modified Pt/C catalyst is through organic amine-modified Pt/C catalyst.
According to the present invention, described through essence before organic amine-modified Pt/C catalyst, pattern and particle size and modification
It is upper identical.
According to the present invention, described through in organic amine-modified Pt/C catalyst, which is substantially adsorbed in Pt/C and urges
Agent surface.
According to the present invention, described to obtain Pt/C catalysis before specific surface area is at least modified through organic amine-modified Pt/C catalyst
At least the 75% of agent；Preferably, described to obtain Pt/C catalysis before specific surface area is at least modified through organic amine-modified Pt/C catalyst
At least the 80% of agent.
According to an embodiment of the invention, the solvent can be the analogs such as acetonitrile, ethyl alcohol, methanol, THF, but not limited to this.
According to an embodiment of the invention, described be passed through N2The step of replacing air in the reaction kettle can be to reaction kettle
It is passed through N interior continuous 3 times2To replace the air in kettle.
According to an embodiment of the invention, followed by H is passed through2To the reaction kettle.When the pressure of reaction kettle reaches 0.8MPa
Start to stir the mixture.According to the present invention, which can be 750rpm.
According to an embodiment of the invention, the temperature of the reaction can be 30 DEG C or less.
According to the present invention, the reaction is completed to determine for example, by observing hydrogen consumption situation per minute, for example, when anti-
It answers and can be considered that reaction is completed when pressure no longer changes in kettle.
According to an embodiment of the invention, the nitro-aromatic can beWherein R1、R2And R3Respectively
For selected from H, halogen, be substituted or the alkyl with 1 to 6 C atom being unsubstituted, the fragrance for being substituted or being unsubstituted
Alkyl, the naphthenic base for being substituted or being unsubstituted, aromatic radical or heterocycle, NO2, one of CHO.
Wherein, halogen can be F, Cl, Br, I；The alkyl with 1 to 6 C atom for being substituted or being unsubstituted can be warp
Methyl, ethyl, propyl, the isopropyl for replacing or being unsubstituted；The aryl radical for being substituted or being unsubstituted can be substituted or
The phenyl being unsubstituted；And naphthenic base, aromatic radical or the heterocycle for being substituted or being unsubstituted can be to be substituted or without taking
The exotic atom ring group in generation.
According to an embodiment of the invention, the nitro-aromatic can beWherein R1、R2And R3Respectively
Selected from H, F, Cl, CH3、NO2, CHO, one of heterocycle.
According to an embodiment of the invention, the nitro-aromatic can be But
It is without being limited thereto.
The present invention further provides it is a kind of be catalyzed nitro-aromatic hydrogenation reaction method, including by nitro-aromatic, with this
Modified Pt/C catalyst, the solvent for the method preparation that invention provides sequentially add reaction kettle, form mixture；It is passed through N2It sets
Change air in the reaction kettle；It is passed through H again2To the reaction kettle；And the stirred under pressure mixture is until reaction completion；It takes out
Used modified Pt/C catalyst simultaneously adds the reaction after 1% fresh modified Pt/C catalyst to the reaction
In kettle；And the step of repeating the hydrogenation reaction of the catalysis nitro-aromatic.
According to the present invention, the modified Pt/C catalyst is to repair according to prepared by the method for the invention through organic amine
The Pt/C catalyst of decorations.
Fourth aspect present invention provide it is a kind of for hydrogenating the set group of nitro-aromatic, including with method system provided by the invention
Standby modified Pt/C catalyst；Solvent；And H2。
According to the present invention, described through essence before organic amine-modified Pt/C catalyst, pattern and particle size and modification
It is upper identical.
According to the present invention, described through in organic amine-modified Pt/C catalyst, which is substantially adsorbed in Pt/C and urges
Agent surface.
According to the present invention, described to obtain Pt/C catalysis before specific surface area is at least modified through organic amine-modified Pt/C catalyst
At least the 75% of agent；Preferably, described to obtain Pt/C catalysis before specific surface area is at least modified through organic amine-modified Pt/C catalyst
At least the 80% of agent.
According to an embodiment of the invention, the solvent can be the analogs such as acetonitrile, ethyl alcohol, methanol, THF, but not limited to this.
According to an embodiment of the invention, the nitro-aromatic can beWherein R1、R2And R3Respectively
Selected from H, halogen, it is substituted or the alkyl with 1 to 6 C atom being unsubstituted, the aromatic hydrocarbon for being substituted or being unsubstituted
Base, the naphthenic base for being substituted or being unsubstituted, aromatic radical or heterocycle, NO2, one of CHO.
Wherein, halogen can be F, Cl, Br, I；The alkyl with 1 to 6 C atom for being substituted or being unsubstituted can be warp
Methyl, ethyl, propyl, the isopropyl for replacing or being unsubstituted；The aryl radical for being substituted or being unsubstituted can be substituted or
The phenyl being unsubstituted；And naphthenic base, aromatic radical or the heterocycle for being substituted or being unsubstituted can be to be substituted or without taking
The exotic atom ring group in generation.
According to an embodiment of the invention, the nitro-aromatic can beWherein R1、R2And R3Respectively
Selected from H, F, Cl, CH3、NO2, CHO, one of heterocycle.
According to an embodiment of the invention, the nitro-aromatic can be But
It is without being limited thereto.
Compared to prior art, the present invention provides a kind of method that Pt/C catalyst can be more precisely modified with organic amine,
Through it is organic it is amine-modified after Pt/C catalyst morphology it is complete, coverage and the uniformity of the organic amine in metal surface all can be controlled effectively
System, the present invention use the solvent to dissolve each other with organic amine to prepare organic amine mixed solution, the concentration of strict control organic amine, and to repairing
Catalyst after decorations is washed, and extra organic amine is removed, so that organic amine molecule is in the specific number of plies of the surface Pt uniform fold,
Therefore it can realize that 90% or more is highly selective, and have longer service life, can repeat to apply.Due to warp provided by the invention
Organic amine-modified Pt/C catalyst be individually to organic amine-modified, it is subsequent to pass through washing, filtering and drying, extra is had
Machine amine aqueous solution filters, and when being accordingly used in hydrogenation reaction, keeps reaction system simpler, is not necessary to add other auxiliary agents, such as poisonous agent
Deng avoiding the complexity of reaction system, reduce by-product.In addition, being applicable to commercially available Pt/C in method provided by the invention
Catalyst, low in cost, simple process is conducive to large-scale production.
Embodiment 1
Preparation is through organic amine-modified Pt/C catalyst(organic amine is 100:1 with Pt molar ratio)
Provided method according to the present invention takes 2g 2%Pt/C catalyst in 250mL beaker, and 100mL ethyl alcohol is added,
Stirring is uniformly dispersed to Pt/C, 1.23g ethylenediamine (Ethylenediamine, EDA) is added dropwise into the beaker, ethylenediamine: Pt
=100:1 (mole ratio) forms precursor mixture；Continue the precursor mixture to stir 3 hours；Filter forerunner's mixing
Object and to dry after milli-Q water 3 times, obtains organic amine-modified Pt/C catalyst of the invention, the modification that the present embodiment obtains
Rear catalyst is EDA-2%Pt/C (100:1).
Fig. 1 (a) is the TEM figure of the Pt/C catalyst (comparative example 1) before modification；Fig. 1 (b) is prepared through the method provided by the present invention
Modified EDA-2%Pt/C catalyst TEM figure.Fig. 2 is to modify front and back Pt/C catalysis with the method provided by the present invention with EDA
The thermogravimetric analysis of agent.Table 1 indicates EDA modification front and back, the specific surface area variation of Pt/C catalyst.It can be found from Fig. 1 (a) and (b)
EDA modifies the pattern and particle for having no effect on Pt/C catalyst.And ethylenediamine can be seen that by thermogravimetric analysis and be adsorbed on Pt/C
Surface.Also shown in table 1 it is ethylene diamine-modified after the specific surface area of Pt/C catalyst is influenced less, this is exactly of the invention through having
One of the reason of amine-modified Pt/C catalyst of machine can be applied continuously and keep excellent activity.
The specific surface area of table 1, EDA modification front and back Pt/C catalyst
Hydrogenation catalyst efficiency
Performance evaluation is carried out to catalyst prepared by the present invention.By 10g nitrobenzene, the EDA-2%Pt/ of 0.15g embodiment 1
C, 100mL acetonitrile sequentially add reaction kettle, air in the continuous 3 displacement kettles of nitrogen are passed through into kettle, then hydrogen is passed through into kettle
Gas, pressure opens stirring, revolving speed 750rpm in 0.8MPa in kettle, and maintaining reaction temperature is not higher than 30 DEG C, and observation is per minute
Hydrogen consumption situation uses liquid-phase chromatographic analysis until stopping reacting there is no change in pressure drop after reaction.
Catalyst is repeatedly applied
The EDA-2%Pt/C for continuously applying embodiment 1 under the same conditions with the test of above-mentioned hydrogenation efficiency, applies benefit every time
Add 1% fresh EDA-2%Pt/C, the selective data and ACTIVITY CHANGE OF FT after applying are as shown in Figure 3 and Figure 4.
As can be seen that the selection of EDA-2%Pt/C of the invention after continuous several times are applied, to azanol aromatic hydrocarbons in Fig. 3
Property is maintained at about 80% to 90%, wherein when applying the 5th batch and the 11st batch occurred data floating, thus it is speculated that be corresponding
Azo increases and the selectivity of azanol is caused to decline, this is because sample connects with air in the detection process of liquid-phase chromatographic analysis
Overlong time is touched, unstable azanol is caused to be oxidized, and the hydrogenation reaction of non-present invention selectively declines.
Fig. 4 is recycled and reused for Catalytic Hydrogenation of Nitrobenzene for EDA-Pt/C catalyst provided by the invention and prepares the anti-of phenylhydroxylamine
Activity change is answered, to be gradually recovered after batch increases activity and first slightly reduces be first with applying from hydrogen content and from the point of view of the reaction time
Beginning state leads to the reduction of initial reaction rate, with additional amount this is because the amount of catalyst is lost during applying
Increase, the amount of catalyst is slowly restored, and reactivity is also restored to original state, illustrates provided by the present invention through organic amine-modified
Pt/C catalyst will not with apply batch increase and cause it to be poisoned.And apply that only to add 1% fresh every time
EDA-2%Pt/C catalyst is applied 10 selectivity and is still kept, and the ethylenediamine after illustrating modification exists in Pt surface-stable.
Embodiment 2
Preparation is through organic amine-modified Pt/C catalyst(organic amine is 100:1 with Pt molar ratio)
For the present embodiment using the reaction condition for preparing similar to Example 1, difference from Example 1 is only that reaction institute
It is three (2- aminoethyl) amine [Tris (2-aminoethyl) amine, TAEA] with organic amine, organic amine mixed solution is water-soluble
Liquid, obtains organic amine-modified Pt/C catalyst of the invention, and the modification rear catalyst that the present embodiment obtains is TAEA-2%Pt/C
(100:1).The catalytic reaction condition of the present embodiment is also same as Example 1.
Embodiment 3
Preparation is through organic amine-modified Pt/C catalyst(organic amine is 100:1 with Pt molar ratio)
For the present embodiment using the reaction condition for preparing similar to Example 1, difference from Example 1 is only that reaction institute
It is N-methylmorpholine (N-Methylmorpholine, NMM) with organic amine, organic amine mixed solution is ethanol solution, obtains this
Organic amine-modified Pt/C catalyst of invention, the modification rear catalyst that the present embodiment obtains are NMM-2%Pt/C (100:1).This
The catalytic reaction condition of embodiment is also same as Example 1.
Embodiment 4 (organic amine is 1:1 with Pt molar ratio)
Preparation is through organic amine-modified Pt/C catalyst and hydrogenation catalyst efficiency
For this comparative example using the reaction condition for preparing similar to Example 1, difference from Example 1 is only that reaction institute
Molar ratio with organic amine EDA and Pt is 1:1, and organic amine mixed solution is ethanol solution, is obtained of the invention organic amine-modified
Pt/C catalyst, the modification rear catalyst that the present embodiment obtains are EDA-2%Pt/C (1:1).Item is reacted in the catalysis of the present embodiment
Part is also same as Example 1.
Comparative example 1
Unmodified Pt/C catalyst and hydrogenation catalyst efficiency
This comparative example uses business 2%Pt/C (unmodified), and catalytic reaction condition is same as Example 1, catalysis substrate
Using the nitrobenzene of embodiment 1.
Comparative example 2
Preparation is through organic amine-modified Pt/C catalyst and hydrogenation catalyst efficiency
For this comparative example using the reaction condition for preparing similar to Example 1, difference from Example 1 is that Pt/C impregnates
In pure ethylenediamine (EDA) solution, EDA is much excessive, obtains to be catalyzed made from immersion way through organic amine-modified Pt/C
Agent, the catalyst that this comparative example obtains are EDA-2%Pt/C (pure EDA solution).The catalytic reaction condition of the present embodiment also with reality
It is identical to apply example 1.
Table 2, embodiment 1 to 4 and comparative example 1 to 2 add hydrogen azanol aromatic hydrocarbons data for nitro-aromatic
| Catalyst | Conversion ratio | Phenylhydroxylamine selectivity | Aniline selectivity | Other impurities | |
| Embodiment 1 | EDA-2%Pt/C (100:1) | 100% | 91.52% | 3.4% | 5.08% |
| Embodiment 2 | TAEA-2%Pt/C (100:1) | 99.82% | 91.29% | 4.232% | 4.478% |
| Embodiment 3 | NMM-2%Pt/C (100:1) | 98.93% | 90.28% | 4.5% | 5.22% |
| Embodiment 4 | EDA-2%Pt/C (1:1) | 96.57% | 85.6% | 8.84% | 5.56% |
| Comparative example 1 | 2%Pt/C (unmodified) | 95.32% | 66.3% | 27.5% | 6.2% |
| Comparative example 2 | EDA-2%Pt/C (pure EDA solution) | 86.7% | 75% | 14.8% | 10.2% |
From Table 2, it can be seen that the embodiment of the present invention through organic amine-modified Pt/C Catalyst Conversion all up to 98%,
Phenylhydroxylamine selectivity is also up to 90%, very excellent, and wherein optimal with EDA-2%Pt/C catalytic selectivity and conversion ratio
It is different.There are apparent differences with the selectivity through organic amine-modified Pt/C to azanol by unmodified Pt/C.And EDA and Pt
Molar ratio is different, and also different to the selective effect of azanol, EDA ratio is too low, can make the covering of the surface Pt not exclusively, so as to cause
Nitro-aromatic deep hydrogenation be amido aromatic hydrocarbons, and Pt/C bubble in pure EDA solution when, EDA is significantly excessive at this time, reaction live
Property reduce, and the selectivity of azanol is also reduced, this is because excessive EDA some Pt under pulling when being coordinated with Pt, lead
Cause the loss of noble metal.
Embodiment 5
The hydrogenation catalyst efficiency and selectivity of the embodiment of the present invention
For the present embodiment using the reaction condition for preparing similar to Example 1, difference from Example 1 is only that reaction institute
Molar ratio with organic amine EDA and Pt is 200:1, and the catalyst that the present embodiment obtains is EDA-2%Pt/C (200:1)；Catalysis
Reaction condition is also same as Example 1, and difference from Example 1 is only that reaction substrate used is ortho-methylnitrobenzene, as a result
As shown in table 3.
Embodiment 6
The hydrogenation catalyst efficiency and selectivity of the embodiment of the present invention
For the present embodiment using the reaction condition for preparing similar to Example 1, difference from Example 1 is only that reaction institute
Molar ratio with organic amine EDA and Pt is 200:1, and the catalyst that the present embodiment obtains is EDA-2%Pt/C (200:1)；Catalysis
Reaction condition is also same as Example 1, and difference from Example 1 is only that reaction substrate used is 2- [(N- rubigan)-
3- pyrazoles oxygroup methyl] nitrobenzene, the results are shown in Table 3.
Table 3, the present invention are applied to the comparison of different substrates through organic amine-modified Pt/C catalyst
From table 3 it is observed that be directed to different nitro-aromatics substrate, organic amine-modified Pt/C to azanol aromatic hydrocarbons according to
So there is good selectivity.
Above-described embodiment is only to be illustrated the principle of the present invention and its effect, and is not intended to limit the present invention.Appoint
What those skilled in the art without departing from the spirit and scope of the present invention, modifies to above-described embodiment.Cause
This scope of the present invention, should be as listed in the claims.
Claims (16)
1. a kind of method for preparing modified Pt/C catalyst, which is characterized in that this method comprises:
By Pt/C catalyst soak in organic amine mixed solution, precursor mixture is formed；The organic amine mixed solution includes A
Component and B component, the component A are organic amine, and the B component is at least one solvent to dissolve each other with organic amine；
Stir the precursor mixture；And
It filters the precursor mixture and washs much filtrate to get modified Pt/C catalyst.
2. the method as described in claim 1, which is characterized in that the molar ratio of the Pt of the organic amine and the Pt/C catalyst
For 1:1 to 200:1.
3. the method as described in claim 1, which is characterized in that organic amine in the organic amine mixed solution be level-one amine,
At least one of secondary amine, tertiary amine, heterocyclic amine.
4. method as claimed in claim 3, which is characterized in that organic amine in the organic amine mixed solution be ethylenediamine,
At least one of triethylamine, three (2- aminoethyl) amine, morpholine, N-methylmorpholine.
5. the method as described in claim 1, which is characterized in that the solvent to dissolve each other with organic amine is water, in methanol, ethyl alcohol
At least one.
6. the method as described in claim 1, which is characterized in that the time of the stirring is 1 to 3 hour.
7. the method as described in claim 1, which is characterized in that the modified Pt/C catalyst is for being catalyzed nitro-aromatic
Hydrogenation reaction to prepare azanol aromatic hydrocarbons.
8. the method for claim 7, which is characterized in that the nitro-aromatic isWherein R1、R2
And R3It is respectively selected from H, halogen, the alkyl with 1 to 6 C atom for being substituted or being unsubstituted, is substituted or is unsubstituted
Aryl radical, the heterocycle, the NO that are substituted or are unsubstituted2, one of CHO.
9. the method for claim 7, which is characterized in that the nitro-aromatic isWherein R1、R2
And R3Respectively it is selected from H, F, Cl, CH3、NO2, CHO, one of heterocycle.
10. a kind of through organic amine-modified Pt/C catalyst, which is characterized in that the modified Pt/C catalyst is such as to weigh
Benefit requires any one of 1 to 9 the method preparation.
11. a kind of method for the hydrogenation reaction for being catalyzed nitro-aromatic, which is characterized in that this method comprises:
Nitro-aromatic, modified Pt/C catalyst, solvent are sequentially added into reaction kettle, mixture is formed, wherein described through repairing
The Pt/C catalyst of decorations is the modified Pt/C catalyst as prepared by any one of claim 1 to 9 the method；
It is passed through N2Replace air in the reaction kettle；
It is passed through H again2To the reaction kettle；And
The stirred under pressure mixture is completed until reaction.
12. method as claimed in claim 11, which is characterized in that the modified Pt/C catalyst is through organic amine-modified
2%Pt/C catalyst.
13. method as claimed in claim 11, which is characterized in that the temperature of the reaction is 30 DEG C or less.
14. method as claimed in claim 11, which is characterized in that the nitro-aromatic isWherein R1、
R2And R3It is respectively selected from H, halogen, the alkyl with 1 to 6 C atom for being substituted or being unsubstituted, is substituted or without taking
The aryl radical in generation, the heterocycle for being substituted or being unsubstituted, NO2, one of CHO.
15. method as claimed in claim 14, which is characterized in that the nitro-aromatic isWherein
R1、R2And R3Respectively it is selected from H, F, Cl, CH3、NO2, CHO, one of heterocycle.
16. method as claimed in claim 11, which is characterized in that it is described after the reaction was completed, further includes:
It takes out used modified Pt/C catalyst and adds 1% fresh modified Pt/C catalyst to the reaction
In reaction kettle afterwards, wherein the modified Pt/C catalyst is as prepared by any one of claim 1 to 9 the method
Modified Pt/C catalyst；And
Repeat step as claimed in claim 11.
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