CN105214686B - A kind of charcoal carries multicomponent catalyst and preparation method and application - Google Patents
A kind of charcoal carries multicomponent catalyst and preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of charcoals to carry multicomponent catalyst and preparation method thereof, and the catalyst is made of carrier and the metal active constituent being supported on carrier, and the carrier is activated carbon, and the metal active constituent is palladium, platinum and a kind of transition metal element auxiliary agent；Quality based on carrier active carbon, palladium load capacity are 0.5wt%~5.0wt%, and platinum load capacity is 0.5wt%~5.0wt%, and transition metal element auxiliary agent load capacity is 0.1wt%~2.5wt%；Meanwhile the mass ratio of palladium and platinum is 1：0.5~2.0；Catalyst of the present invention can be applied to catalytic hydrogenation synthesis benzotriazole ultraviolet absorber；Method for preparing catalyst provided by the invention is easy, and catalytic activity is high, and target product selectivity and high income, stability is good, and the three wastes generate few in Simultaneous hydrogenation process.
Description
(1) technical field
The present invention relates to a kind of charcoals to carry multicomponent catalyst and preparation method thereof, and the charcoal carries multicomponent catalyst and can apply
Benzotriazole ultraviolet absorber is synthesized in catalytic hydrogenation.
(2) background technology
Benzotriazole ultraviolet absorber is the principal item of Light Stabilizers for Plastics, has excellent ultraviolet radiation absorption energy
Power can absorb the ultraviolet light of 290~400nm wavelength.And its with shallower color, relatively low toxicity, do not allow it is volatile,
Oil resistivity is good, with polymer compatibility it is good the advantages that, be widely used in polypropylene, polyethylene, polyvinyl chloride, polyformaldehyde,
The photochemical modification of the various synthetic materials such as polyamide, polystyrene, polyurethane, alkyd resin.
The synthesis of benzotriazole ultraviolet absorber is a complicated multi-step reaction.It is even firstly the need of diazonium is passed through
Close reaction synthesize with the corresponding azo intermediate of product, then restore to obtain benzotriazole purple by azo intermediate again
Outer absorbent.
The reduction reaction of wherein azo intermediate is the committed step of its synthesis.Electronation technology is current industrial production
In widely used mature technology, such as：Zinc powder reduction, sodium hydrosulfite reduction, hydrazine hydrate-zinc powder reduction and glucose-zinc powder are also
Original etc..Although chemical reduction method synthesis benzotriazole ultraviolet absorber technology maturation, technique are relatively easy, exist more
The shortcomings of waste water and waste sludge discharge amount are big, atom economy efficiency is low and reducing agent is expensive.Such as：Zinc powder reduction can generate largely
Zinc mud and zinc-containing water, damage ratio are more serious；Sulfide reduction method needs to carry out a large amount of solvent recovery and processing depth pollution
Sulfur-containing waste water；When hydrazine hydrate is reducing agent, excessive hydrazine hydrate equally can cause environmental pollution, while the price of hydrazine hydrate
Also it is higher；Glucose equally has a large amount of high cod values waste water and generates when being reducing agent.In the shape that environmental protection is paid more and more attention
Under gesture, pollute more serious chemical reduction process and be faced with the severe survival pressure that may be eliminated at any time.Therefore, one is found
More green, economic reduction route replaces traditional handicraft to have important and urgent realistic meaning.
Catalytic hydrogenating reduction method synthesizes benzotriazole ultraviolet absorber as shown in reaction equation 1：First choice is by raw material azo
Intermediate (I) is reduced to hydrazine class compound under hydrogenation catalyst and hydrogen effect and by the generation of intramolecular dehydration annulation
Intermediate product nitrogen oxides (II), nitrogen oxides further add hydrogen to ultimately generate benzotriazole product (III).
Reaction equation 1
Catalytic hydrogenation method due to not can cause environmental pollution using hydrogen as reducing agent, and with wastewater discharge it is small,
The advantages that Atom economy is high is the green route that can replace traditional chemical reducing process.
But catalytic hydrogenation reaction process generates more by-product often with many side reactions occur.Such as：Azo compounds
Object hydrogenating reduction carries out that the fracture side reaction of hydrazine key easily occurs during intramolecular dehydration annulation for hydrazine class compound again,
Two molecule arylamine class by-products are generated, as shown in reaction equation 2.
Reaction equation 2
Further, since influenced by triazole ring to tend to conjugated diene structure with triazole ring and phenyl ring even,
So that being easier to be hydrogenated saturation with triazole ring and phenyl ring even, nitrogen oxides intermediate and benzotriazole product meeting are caused
Excessive hydrogenation side reaction, generation tetrahydrochysene by-product (IV, V) occurs.
The generation of these by-products not only reduces product yield and is unfavorable for separating-purifying, constrains Catalytic Hydrogenation Techniques
Commercial Application.
It is reported in recent years there are many research about catalytic hydrogenation synthesis benzotriazole ultraviolet absorber, such as：Wang Li
Deng (synthesis technology [J] synthesis chemistry of Wang Li, Li Ke state optimization of orthogonal test UV-327,2007, (5):658-660.) grind
Raney's nickel catalyst hydrogenating reduction UV-327 nitrogen oxides (N-oxide) synthesis UV-327, yield 91% are studied carefully.Patent
EP0380840A1 is reported in toluene-isopropanol-water-NaOH systems, and Raney's nickel synthesizes UV- for catalyst to catalyzing hydrogenating
328, yield 82%.But during using Raney's nickel as hydrogenation catalyst, the selectivity and yield of benzotriazole product be not high；
And Raney's nickel has inflammability, and there are security risks in use.Also it has been reported that and uses charcoal supported noble metal as hydrogen is added to urge
Agent synthesizes benzotriazole product, and compare Raney's nickel catalyst, and the safety of charcoal supported noble metal catalyst is more preferable, than
Such as：CIBA GEIGY companies (patent US5276161) use 5%Pt/C to synthesize UV-P for catalyst to catalyzing hydrogenating, and yield is
92%；Patent US5104992 uses 5%Pd/C to synthesize UV-320, yield 87.3% for catalyst hydrogenation；Patent
EP0794179A1 using 4%Pd/C+1%Pt/C as catalyst synthesize UV-328, the patent added in reduction system hypophosphorous acid or
Sulfuric acid can improve product yield, but need to add a large amount of liquid acids in the reaction system (molar ratio of acid/raw material is
3.0) more spent acid, can be generated to pollute the environment, while easily residual in the product, influences product product to the liquid acid added in
Matter.
It can be seen that whether all there is choosing in Raney's nickel catalyst or Pd/C, Pt/C catalyst to existing hydrogenation catalyst
Not the defects of selecting property is not high or uses liquid acid.Therefore, the research emphasis of catalytic hydrogenation synthesis benzotriazole ultraviolet absorber
It is the generation of inhibition side reaction with difficult point, improves the selectivity and yield of target product, while reduces three wastes generation, and wherein
Key technology be the design and development of hydrogenation catalyst.
(3) invention content
In view of the deficiencies of the prior art, the present invention provides a kind of charcoals to carry multicomponent catalyst and preparation method thereof, described
Charcoal carries multicomponent catalyst and can be applied to catalytic hydrogenation synthesis benzotriazole ultraviolet absorber, and lives with higher catalysis
Property and target product selectivity.
The present invention adopts the following technical scheme that：
A kind of charcoal carries multicomponent catalyst, is made of carrier and the metal active constituent being supported on carrier, the carrier
For activated carbon, the metal active constituent is palladium, platinum and a kind of transition metal element auxiliary agent；Quality based on carrier active carbon,
Palladium load capacity be 0.5wt%~5.0wt%, platinum load capacity be 0.5wt%~5.0wt%, transition metal element auxiliary agent load capacity
For 0.1wt%~2.5wt%；Meanwhile the mass ratio of palladium and platinum is 1：0.5~2.0；The transition metal element auxiliary agent is selected from down
One of row：Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ru, Ag, W, La, Re or Os.
Charcoal of the present invention carries multicomponent catalyst, and the specific surface area of preferred vector activated carbon is 800~1600m2/g；It is excellent
Palladium load capacity is selected as 1.0wt%~2.0wt%, platinum load capacity is 1.0wt%~2.0wt%, and transition metal element auxiliary agent loads
It measures as 0.5wt%~1.0wt%；It is preferred that the mass ratio of palladium and platinum is 1：1；It is preferred that the transition metal element auxiliary agent is selected from following
One of：Fe, Co, Ni, Cu, Zn or Mo, particularly preferred Cu.
The present invention also provides the preparation method that a kind of charcoal carries multicomponent catalyst, the preparation method is：
Palladium presoma, platinum presoma, the presoma of transition metal element auxiliary agent, citrate are dissolved in ethylene glycol (EG)
In, it stirs evenly to form precursor solution, carrier active carbon is added in precursor solution, in 0~50 DEG C (preferably 25 DEG C) perseverance
Temperature stirring 1~6h of impregnation, then it is 8~12 (preferably 9~10) to adjust pH value with lye, is warming up to 120~180 DEG C (preferably
160 DEG C) continue constant temperature 4~8h of stirring, reaction system cooled to room temperature is treated later, is filtered, and filter cake is washed with deionized
To neutrality, 10~16h is dried in vacuo under 70~90 DEG C (preferably 90 DEG C) to get charcoal load multicomponent catalyst；
The palladium presoma is calculated as 0.5wt%~5.0wt% of carrier active carbon quality with palladium, and the platinum presoma is with platinum
0.5wt%~5.0wt% of carrier active carbon quality is calculated as, the presoma of the transition metal element auxiliary agent is with transition metal member
Plain auxiliary agent is calculated as 0.1wt%~2.5wt% of carrier active carbon quality；Meanwhile palladium presoma in terms of palladium with platinum presoma with platinum
The mass ratio of meter is 1：0.5~2.0；The addition quality of the citrate is palladium presoma, platinum presoma, transition metal element
0.5~5 times of the quality summation of auxiliary agent presoma；The volumetric usage of the ethylene glycol is calculated as 10 with the quality of carrier active carbon~
100mL/g。
In the preparation method, the usual palladium presoma is palladium bichloride, palladium nitrate or palladium, preferably palladium bichloride.
The platinum presoma can be chloroplatinic acid.
The presoma of the transition metal element auxiliary agent is the soluble-salt of transition metal element auxiliary agent, such as nitrate, chlorine
Salt dissolving, oxalates etc., preferably nitrate or chlorate；Specific preferred, the presoma of the transition metal element auxiliary agent can be with
Selected from one of following：Sc(NO3)3、TiCl4、NH4VO3、Cr(NO3)3、Mn(NO3)2、FeCl3、Co(NO3)2、Ni(NO3)2、Cu
(NO3)2、ZnCl2、Zr(NO3)4、(NH4)6Mo7O24、RuCl3、AgNO3、(NH4)10W12O41Or La (NO3)3, particularly preferred Cu
(NO3)2、ZnCl2、Co(NO3)2、Zr(NO3)4、FeCl3Or (NH4)6Mo7O24。
The usual citrate is potassium citrate or sodium citrate, optimization citric acid potassium；It is preferred that the citrate
Addition quality is palladium presoma, 2 times of quality summation of platinum presoma, transition metal element auxiliary agent presoma.
It is preferred that the volumetric usage of the ethylene glycol is calculated as 30~50mL/g with the quality of carrier active carbon.
Specifically, for adjusting the lye of pH value as NaOH, NaCO3、NaHCO3、KOH、KCO3、KHCO3、(NH2)2CO3In
The mixtures of one or more kinds of arbitrary proportions be dissolved in the solution being made into ethylene glycol, and the mass concentration of the lye
It is 0.1%~30%, preferably 5%.
Charcoal of the present invention carries multicomponent catalyst and can be applied to catalytic hydrogenation synthesis benzotriazole ultraviolet absorber,
The method of the application is：
Azo intermediate, solvent, alkaline assistant input high pressure shown in charcoal of the present invention load multicomponent catalyst, formula (I) is anti-
It answers in kettle, adjusts 1~3MPa of Hydrogen Vapor Pressure, 1~10h is stirred to react at 30~80 DEG C, reaction solution filtering takes filtrate decompression to steam
Dry, residue drying obtains benzotriazole ultraviolet absorber shown in target product formula (III)；
The solvent is that the mixing of one or more of toluene, dimethylbenzene, chlorobenzene, tetrahydrofuran arbitrary proportion is molten
Agent；The alkaline assistant is diethylamine, n-butylamine, piperidines, ethylenediamine or ethanol amine；
In formula (I) or formula (III),
R1For H, C1~C12 alkyl, C5~C8 cycloalkyl, phenyl or (C1~C4 alkyl) phenyl；It is preferred that H, tertiary butyl, 1,
1- dimethyl propyls or 1,1,3,3- tetramethyl butyls；
R2For C1~C12 alkyl, C5~C8 cycloalkyl, phenyl or (C1-C4 alkyl) phenyl；It is preferred that methyl, tertiary butyl, 1,
1- dimethyl propyls or 1,1,3,3- tetramethyl butyls；
R3For H, Cl or Br；It is preferred that H or Cl.
Further, more specifically, the method for the application is：
Azo intermediate, solvent, alkaline assistant input high pressure shown in charcoal of the present invention load multicomponent catalyst, formula (I) is anti-
It answers in kettle, seals kettle, after air in hydrogen displacement kettle, adjust 1~3MPa of Hydrogen Vapor Pressure (preferably 1MPa), it is (excellent at 30~80 DEG C
Select 50~65 DEG C) under stirring (800~1200rpm of rate) react 1~10h (preferably 3~5h), later reaction system filter, take
Filtrate decompression is evaporated, and residue is dry after deionized water is washed, methanol washs respectively, obtains shown in target product formula (III)
Benzotriazole ultraviolet absorber；
It is 0.5~5 that the charcoal, which carries multicomponent catalyst and the mass ratio that feeds intake of azo intermediate shown in formula (I),：100；Institute
State mixed solvent of the solvent for one or more of toluene, dimethylbenzene, chlorobenzene, tetrahydrofuran arbitrary proportion；It is described molten
The volumetric usage of agent is calculated as 5~20mL/g with the quality of azo intermediate shown in formula (I)；The alkaline assistant is diethylamine, just
Butylamine, piperidines, ethylenediamine or ethanol amine；The alkaline assistant and the mass ratio that feeds intake of azo intermediate shown in formula (I) are 1：1~
5。
In the application process, preferably described charcoal carries multicomponent catalyst and the matter that feeds intake of azo intermediate shown in formula (I)
Amount is than being 2：100；It is preferred that the solvent is toluene；It is preferred that the volumetric usage of the solvent is with azo intermediate shown in formula (I)
Quality is calculated as 10~15mL/g；It is preferred that the alkaline assistant is piperidines；It is preferred that shown in the alkaline assistant and formula (I) among azo
The mass ratio that feeds intake of body is 1：2.5.
Compared with prior art, the present invention has the following advantages：
(1) preparation method of charcoal load multicomponent catalyst of the present invention is easy, metal dispersity is high, catalytic activity is good；
(2) charcoal of the present invention carries multicomponent catalyst in catalytic hydrogenation synthesizes benzotriazole ultraviolet absorber, product
The selectivity and high income of benzotriazole ultraviolet absorber, reaction system is simple, and the three wastes are few；
(3) it is good to carry multicomponent catalyst stability for charcoal of the present invention, can repeatedly use, effectively reduce catalyst into
This, at the same it is safe during use, there is higher industrial application value.
(4) it illustrates
Fig. 1 is the transmission electron microscope phenogram (50nm scales) of catalyst made from the embodiment of the present invention 1；
Fig. 2 is the transmission electron microscope phenogram (5nm scales) of catalyst made from the embodiment of the present invention 1；
Fig. 3 is the particle size distribution figure of 100 particle specimens of catalyst made from the embodiment of the present invention 1.
(5) specific embodiment
Technical scheme of the present invention is described further with specific embodiment below, but protection scope of the present invention is unlimited
In this.
Embodiment 1
Weigh 0.088g PdCl2、0.132g H2PtCl6·6H2O、0.088g Cu(NO3)2·2H2O and 0.6g citric acids
Potassium is put into three-necked flask；150ml ethylene glycol is added in into flask again and about 0.5h is stirred at room temperature, it is molten to obtain presoma
Liquid；5g activated carbons are added in into prepared precursor solution again, constant temperature stirring impregnation 4h is kept at 25 DEG C；Dipping is completed
Afterwards, 5wt.%KOH/EG solution is added dropwise, adjusts slurry pH value to 10；It is warming up to 160 DEG C again and keeps constant temperature stirring 6h；Deng its cooling
Afterwards, filtering, filter cake are washed with deionized to neutrality；About 12h is dried in vacuo at a temperature of 80 DEG C.Up to 1%Pd1%
Pt0.5%Cu/C catalyst 5.125g.
Fig. 1 is the transmission electron microscope phenogram of catalyst 50nm scales made from the present embodiment, from figure 1 it appears that golden
Belong to component particles size and distributing very evenly in carrier surface, the dispersion of metallic particles are very good.
Fig. 2 is the high resolution electron microscopy characterization result of catalyst 5nm scales made from the present embodiment, from figure 2 it can be seen that
The size of metallic particles is in 5nm or so, and granular size is also more uniformly.
By transmission electron microscope to the sampling statistics of 100 particle specimens of catalyst made from the present embodiment, particle ruler is obtained
Very little distribution is as shown in Figure 3.The average grain diameter of catalyst metal particles is for 5.3nm or so, and narrow distribution, illustrates the catalyst
Metallic particles is smaller and dispersion is highly uniform.The reason is that due to adding potassium citrate complexing in catalyst preparation process
Caused by agent.The addition of complexing agent prevents the reunion of the metallic during heating reduction.During preparing reduction simultaneously,
The reducing environment of strong basicity may cause the reducing power of ethylene glycol to enhance, and the rate of reduction of metal ion is accelerated, nucleation rate
Increase, results in formed metal and its alloy nanoparticle grain size is smaller.
Embodiment 2
Weigh 0.066g PdCl2、0.1g H2PtCl6·6H2O、0.088g Cu(NO3)2·2H2O and 0.5g potassium citrates
It is put into three-necked flask；150ml ethylene glycol is added in into flask again and about 0.5h is stirred at room temperature, obtains precursor solution；
5g activated carbons are added in into prepared precursor solution again, constant temperature stirring impregnation 4h is kept at 25 DEG C；After the completion of dipping,
5wt.%KOH/EG solution is added dropwise, adjusts slurry pH value to 10；It is warming up to 160 DEG C again and keeps constant temperature stirring 6h；After its cooling,
Filtering, filter cake are washed with deionized to neutrality；About 12h is dried in vacuo at a temperature of 80 DEG C.Up to 0.75%Pd0.75%
Pt0.5%Cu/C catalyst 5.1g.
Embodiment 3
Weigh 0.044g PdCl2、0.066g H2PtCl6·6H2O、0.088gCu(NO3)2·2H2O and 0.4g citric acids
Potassium is put into three-necked flask；150ml ethylene glycol is added in into flask again and about 0.5h is stirred at room temperature, it is molten to obtain presoma
Liquid；5g activated carbons are added in into prepared precursor solution again, constant temperature stirring impregnation 4h is kept at 25 DEG C；Dipping is completed
Afterwards, 5wt.%KOH/EG solution is added dropwise, adjusts slurry pH value to 10；It is warming up to 160 DEG C again and keeps constant temperature stirring 6h；It is cold Deng its
But after, filtering, filter cake are washed with deionized to neutrality；About 12h is dried in vacuo at a temperature of 80 DEG C.Up to 0.5%
Pd0.5%Pt0.5%Cu/C catalyst 5.075g.
Embodiment 4
Weigh 0.176g PdCl2、0.264g H2PtCl6·6H2O、0.088g Cu(NO3)2·2H2O and 1.0g citric acids
Potassium is put into three-necked flask；150ml ethylene glycol is added in into flask again and about 0.5h is stirred at room temperature, it is molten to obtain presoma
Liquid；5g activated carbons are added in into prepared precursor solution again, constant temperature stirring impregnation 4h is kept at 25 DEG C；Dipping is completed
Afterwards, 5wt.%KOH/EG solution is added dropwise, adjusts slurry pH value to 10；It is warming up to 160 DEG C again and keeps constant temperature stirring 6h；Deng its cooling
Afterwards, filtering, filter cake are washed with deionized to neutrality；About 12h is dried in vacuo at a temperature of 80 DEG C.Up to 2%Pd2%
Pt0.5%Cu/C catalyst 5.225g.
Embodiment 5
Weigh 0.44g PdCl2、0.66g H2PtCl6·6H2O、0.088g Cu(NO3)2·2H2O and 2.4g potassium citrates
It is put into three-necked flask；150ml ethylene glycol is added in into flask again and about 0.5h is stirred at room temperature, obtains precursor solution；
5g activated carbons are added in into prepared precursor solution again, constant temperature stirring impregnation 4h is kept at 25 DEG C；After the completion of dipping,
5wt.%KOH/EG solution is added dropwise, adjusts slurry pH value to 10；It is warming up to 160 DEG C again and keeps constant temperature stirring 6h；After its cooling,
Filtering, filter cake are washed with deionized to neutrality；About 12h is dried in vacuo at a temperature of 80 DEG C.Up to 5%Pd5%Pt0.5%
Cu/C catalyst 5.525g.
Embodiment 6
Weigh 0.088g PdCl2、0.132g H2PtCl6·6H2O、0.044g Cu(NO3)2·2H2O and 0.5g citric acids
Potassium is put into three-necked flask；150ml ethylene glycol is added in into flask again and about 0.5h is stirred at room temperature, it is molten to obtain presoma
Liquid；5g activated carbons are added in into prepared precursor solution again, constant temperature stirring impregnation 4h is kept at 25 DEG C；Dipping is completed
Afterwards, 5wt.%KOH/EG solution is added dropwise, adjusts slurry pH value to 10；It is warming up to 160 DEG C again and keeps constant temperature stirring 6h；Deng its cooling
Afterwards, filtering, filter cake are washed with deionized to neutrality；About 12h is dried in vacuo at a temperature of 80 DEG C.Up to 1%Pd1%
Pt0.25%Cu/C catalyst 5.113g.
Embodiment 7
Weigh 0.088g PdCl2、0.132g H2PtCl6·6H2O、0.176g Cu(NO3)2·2H2O and 0.8g citric acids
Potassium is put into three-necked flask；150ml ethylene glycol is added in into flask again and about 0.5h is stirred at room temperature, it is molten to obtain presoma
Liquid；5g activated carbons are added in into prepared precursor solution again, constant temperature stirring impregnation 4h is kept at 25 DEG C；Dipping is completed
Afterwards, 5wt.%KOH/EG solution is added dropwise, adjusts slurry pH value to 10；It is warming up to 160 DEG C again and keeps constant temperature stirring 6h；Deng its cooling
Afterwards, filtering, filter cake are washed with deionized to neutrality；About 12h is dried in vacuo at a temperature of 80 DEG C.Up to 1%Pd1%
Pt1%Cu/C catalyst 5.15g.
Embodiment 8
Weigh 0.088g PdCl2、0.132g H2PtCl6·6H2O、0.052gZnCl2Three mouthfuls are put into 0.6g potassium citrates
In flask；150ml ethylene glycol is added in into flask again and about 0.5h is stirred at room temperature, obtains precursor solution；Again to preparation
5g activated carbons are added in good precursor solution, constant temperature stirring impregnation 4h is kept at 25 DEG C；After the completion of dipping, it is added dropwise
5wt.%KOH/EG solution adjusts slurry pH value to 10；It is warming up to 160 DEG C again and keeps constant temperature stirring 6h；After its cooling, mistake
Filter, filter cake are washed with deionized to neutrality；About 12h is dried in vacuo at a temperature of 80 DEG C.Up to 1%Pd1%Pt0.5%
Zn/C catalyst 5.125g.
Embodiment 9
Weigh 0.088g PdCl2、0.132g H2PtCl6·6H2O、0.123g Co(NO3)2·6H2O and 0.7g citric acids
Potassium is put into three-necked flask；150ml ethylene glycol is added in into flask again and about 0.5h is stirred at room temperature, it is molten to obtain presoma
Liquid；5g activated carbons are added in into prepared precursor solution again, constant temperature stirring impregnation 4h is kept at 25 DEG C；Dipping is completed
Afterwards, 5wt.%KOH/EG solution is added dropwise, adjusts slurry pH value to 10；It is warming up to 160 DEG C again and keeps constant temperature stirring 6h；Deng its cooling
Afterwards, filtering, filter cake are washed with deionized to neutrality；About 12h is dried in vacuo at a temperature of 80 DEG C.Up to 1%Pd1%
Pt0.5%Co/C catalyst 5.125g.
Embodiment 10
Weigh 0.088g PdCl2、0.132g H2PtCl6·6H2O、0.118g Zr(NO3)4·5H2O and 0.7g citric acids
Potassium is put into three-necked flask；150ml ethylene glycol is added in into flask again and about 0.5h is stirred at room temperature, it is molten to obtain presoma
Liquid；5g activated carbons are added in into prepared precursor solution again, constant temperature stirring impregnation 4h is kept at 25 DEG C；Dipping is completed
Afterwards, 5wt.%KOH/EG solution is added dropwise, adjusts slurry pH value to 10；It is warming up to 160 DEG C again and keeps constant temperature stirring 6h；Deng its cooling
Afterwards, filtering, filter cake are washed with deionized to neutrality；About 12h is dried in vacuo at a temperature of 80 DEG C.Up to 1%Pd1%
Pt0.5%Zr/C catalyst 5.125g.
Embodiment 11
Weigh 0.088g PdCl2、0.132g H2PtCl6·6H2O、0.073g FeCl3Three are put into 0.6g potassium citrates
In mouth flask；150ml ethylene glycol is added in into flask again and about 0.5h is stirred at room temperature, obtains precursor solution；Again to
5g activated carbons are added in the precursor solution made, constant temperature stirring impregnation 4h is kept at 25 DEG C；After the completion of dipping, it is added dropwise
5wt.%KOH/EG solution adjusts slurry pH value to 10；It is warming up to 160 DEG C again and keeps constant temperature stirring 6h；After its cooling, mistake
Filter, filter cake are washed with deionized to neutrality；About 12h is dried in vacuo at a temperature of 80 DEG C.Up to 1%Pd1%Pt0.5%
Fe/C catalyst 5.125g.
Embodiment 12
Weigh 0.088g PdCl2、0.132g H2PtCl6·6H2O、0.047g(NH4)6Mo7O24·4H2O and 0.55g lemons
Lemon acid potassium is put into three-necked flask；150ml ethylene glycol is added in into flask again and about 0.5h is stirred at room temperature, obtains presoma
Solution；5g activated carbons are added in into prepared precursor solution again, constant temperature stirring impregnation 4h is kept at 25 DEG C；It has impregnated
5wt.%KOH/EG solution is added dropwise in Cheng Hou, adjusts slurry pH value to 10；It is warming up to 160 DEG C again and keeps constant temperature stirring 6h；It is cold Deng its
But after, filtering, filter cake are washed with deionized to neutrality；About 12h is dried in vacuo at a temperature of 80 DEG C.Up to 5%Pd5%
Pt0.5%Mo/C catalyst 5.125g.
Application Example 1-12
In 500mL autoclaves, sequentially add one of 0.2g embodiments 1-12 preparation charcoal carry multicomponent catalyst,
10g UV-P azo intermediates, about 120mL toluene and 4g piperidines seal kettle, and kettle is adjusted after replacing in kettle air 5 times repeatedly with hydrogen
Interior Hydrogen Vapor Pressure starts to stir (stir speed (S.S.) about 1000rpm) after being again heated to 50 DEG C, reacts 3h to 1MPa；After reaction,
Organic layer (sampling is formed using hydrogenation products in efficient liquid phase chromatographic analysis filtrate) is isolated in filtration catalytic agent, evaporated under reduced pressure,
It is washed with deionized and is washed with methanol respectively, target product UV-P is obtained after dry.
Application Example 13
In 500mL autoclaves, the charcoal for sequentially adding the preparation of 0.2g embodiments 1 carries multicomponent catalyst, 10g UV-
P azo intermediates, about 120mL toluene and 4g diethylamine seal kettle, and hydrogen in kettle is adjusted after replacing in kettle air 5 times repeatedly with hydrogen
Atmospheric pressure starts to stir (stir speed (S.S.) about 1000rpm) after being again heated to 50 DEG C, reacts 3h to 1MPa；After reaction, it filters
Catalyst isolates organic layer (sampling is formed using hydrogenation products in efficient liquid phase chromatographic analysis filtrate), evaporated under reduced pressure, difference
It is washed with deionized and is washed with methanol, target product UV-P is obtained after dry.
Application Example 14
In 500mL autoclaves, the charcoal for sequentially adding the preparation of 0.2g embodiments 1 carries multicomponent catalyst, 10g UV-
P azo intermediates, about 120mL toluene and 4g n-butylamines seal kettle, and hydrogen in kettle is adjusted after replacing in kettle air 5 times repeatedly with hydrogen
Atmospheric pressure starts to stir (stir speed (S.S.) about 1000rpm) after being again heated to 50 DEG C, reacts 3h to 1MPa；After reaction, it filters
Catalyst isolates organic layer (sampling is formed using hydrogenation products in efficient liquid phase chromatographic analysis filtrate), evaporated under reduced pressure, difference
It is washed with deionized and is washed with methanol, target product UV-P is obtained after dry.
Application Example 15
In 500mL autoclaves, the charcoal for sequentially adding the preparation of 0.2g embodiments 1 carries multicomponent catalyst, 10g UV-
326 azo intermediates, about 120mL toluene and 4g piperidines seal kettle, and hydrogen in kettle is adjusted after replacing in kettle air 5 times repeatedly with hydrogen
Atmospheric pressure starts to stir (stir speed (S.S.) about 1000rpm) after being again heated to 50 DEG C, reacts 3h to 1MPa；After reaction, it filters
Catalyst isolates organic layer (sampling is formed using hydrogenation products in efficient liquid phase chromatographic analysis filtrate), evaporated under reduced pressure, difference
It is washed with deionized and is washed with methanol, target product UV-326 is obtained after dry.
Application Example 16
In 500mL autoclaves, the charcoal for sequentially adding the preparation of 0.2g embodiments 1 carries multicomponent catalyst, 10g UV-
327 azo intermediates, about 120mL solvents and 4g piperidines seal kettle, and hydrogen in kettle is adjusted after replacing in kettle air 5 times repeatedly with hydrogen
Atmospheric pressure starts to stir (stir speed (S.S.) about 1000rpm) after being again heated to 50 DEG C, reacts 3h to 1MPa；After reaction, it filters
Catalyst isolates organic layer (sampling is formed using hydrogenation products in efficient liquid phase chromatographic analysis filtrate), evaporated under reduced pressure, difference
It is washed with deionized and is washed with methanol, target product UV-327 is obtained after dry.
Application Example 17
In 500mL autoclaves, the charcoal for sequentially adding the preparation of 0.2g embodiments 1 carries multicomponent catalyst, 10g UV-
328 azo intermediates, about 120mL toluene and 4g piperidines seal kettle, and hydrogen in kettle is adjusted after replacing in kettle air 5 times repeatedly with hydrogen
Atmospheric pressure starts to stir (stir speed (S.S.) about 1000rpm) after being again heated to 50 DEG C, reacts 3h to 1MPa；After reaction, it filters
Catalyst isolates organic layer (sampling is formed using hydrogenation products in efficient liquid phase chromatographic analysis filtrate), evaporated under reduced pressure, difference
It is washed with deionized and is washed with methanol, target product UV-328 is obtained after dry.
Application Example 18
In 500mL autoclaves, the charcoal for sequentially adding the preparation of 0.2g embodiments 1 carries multicomponent catalyst, 10g UV-
329 azo intermediates, about 120mL toluene and 4g piperidines seal kettle, and hydrogen in kettle is adjusted after replacing in kettle air 5 times repeatedly with hydrogen
Atmospheric pressure starts to stir (stir speed (S.S.) about 1000rpm) after being again heated to 50 DEG C, reacts 3h to 1MPa；After reaction, it filters
Catalyst isolates organic layer (sampling is formed using hydrogenation products in efficient liquid phase chromatographic analysis filtrate), evaporated under reduced pressure, difference
It is washed with deionized and is washed with methanol, target product UV-329 is obtained after dry.
Application Example 19 (comparative example)
It is compared according to the patent US5276161 catalyst used and reaction condition：
In 500mL autoclaves, 1.2g 5%Pt/C catalyst, 60g UV-P azo intermediates, about are sequentially added
80g dimethylbenzene and 20g diethylenetriamines seal kettle, replaced repeatedly with hydrogen in kettle adjust after air 5 times in kettle Hydrogen Vapor Pressure to
1MPa starts to stir (stir speed (S.S.) about 1000rpm) after being again heated to 60 DEG C, reacts 3h；After reaction, filtration catalytic agent,
Isolate organic layer (sampling is formed using hydrogenation products in efficient liquid phase chromatographic analysis filtrate), evaporated under reduced pressure, spend respectively from
Sub- water washing is washed with methanol, and target product UV-P is obtained after dry.
The results are shown in Table 1 for Application Example：
1 Application Example 1-19 catalyst performance results of table
Catalyst applies mechanically embodiment 1-20
In 2000mL autoclaves, 1.0g 1%Pd1%Pt0.5%Cu/C catalyst, 50g UV-P are sequentially added
Azo intermediate, about 750mL toluene and 20g piperidines seal kettle, and hydrogen in kettle is adjusted after replacing in kettle air 5 times repeatedly with hydrogen
Pressure starts to stir (stir speed (S.S.) about 1000rpm) after being again heated to 50 DEG C, reacts 3h to 1MPa；After reaction, filtering is urged
Agent isolates organic layer (sampling is formed using hydrogenation products in efficient liquid phase chromatographic analysis filtrate), and evaporated under reduced pressure is used respectively
Deionized water is washed washs with methanol, and target product UV-P is obtained after dry；
Catalyst cake is washed with deionized respectively washed with methanol after reapply in applying mechanically experiment next time；Apply mechanically reality
Test that the results are shown in Table 2：
Table 2 applies mechanically embodiment 1-20 catalyst performance resultsa)
A) apply mechanically embodiment is using catalyst：1%Pd1%Pt0.5%Cu/C catalyst
In above-described embodiment, the structural formula point of UV-P, UV-326, UV-327, UV-328, UV-329 and its azo intermediate
It is not as follows：
。
Claims (8)
1. a kind of charcoal carries multicomponent catalyst, it is made of carrier and the metal active constituent being supported on carrier, which is characterized in that
The carrier is activated carbon, and the metal active constituent is palladium, platinum and a kind of transition metal element auxiliary agent；Based on carrier active carbon
Quality, palladium load capacity be 0.5wt%~5.0wt%, platinum load capacity be 0.5wt%~5.0wt%, transition metal element auxiliary agent
Load capacity is 0.1wt%~2.5wt%；Meanwhile the mass ratio of palladium and platinum is 1：0.5~2.0；The transition metal element auxiliary agent
Selected from one of following：Fe、Co、Cu、Zn、Zr、Mo；
The charcoal carries multicomponent catalyst and is made as follows：
Palladium presoma, platinum presoma, the presoma of transition metal element auxiliary agent, citrate are dissolved in ethylene glycol, stirred
Be formed uniformly precursor solution, carrier active carbon added in precursor solution, in 0~50 DEG C of constant temperature stirring impregnation 1~
6h, then it is 8~12 to adjust pH value with lye, is warming up to 120~180 DEG C and continues constant temperature 4~8h of stirring, treats reaction system certainly later
It is so cooled to room temperature, filters, filter cake is washed with deionized to neutrality, and 10~16h is dried in vacuo at 70~90 DEG C to get institute
It states charcoal and carries multicomponent catalyst；
The palladium presoma is palladium bichloride, palladium nitrate or palladium；The platinum presoma is chloroplatinic acid；The transition metal element
The presoma of auxiliary agent is the soluble-salt of transition metal element auxiliary agent；The addition quality of the citrate is palladium presoma, platinum
0.5~5 times of quality summation of presoma, transition metal element auxiliary agent presoma；The volumetric usage of the ethylene glycol is with carrier
The quality of activated carbon is calculated as 10~100mL/g.
2. charcoal as described in claim 1 carries multicomponent catalyst, which is characterized in that the specific surface area of the carrier active carbon is
800~1600m2/g。
3. charcoal as described in claim 1 carries multicomponent catalyst, which is characterized in that the palladium load capacity for 1.0wt%~
2.0wt%, platinum load capacity are 1.0wt%~2.0wt%, and transition metal element auxiliary agent load capacity is 0.5wt%~1.0wt%.
4. charcoal as described in claim 1 carries multicomponent catalyst, which is characterized in that the forerunner of the transition metal element auxiliary agent
Body is selected from one of following：FeCl3、Co(NO3)2、Cu(NO3)2、ZnCl2、Zr(NO3)4、(NH4)6Mo7O24。
5. charcoal as described in claim 1 carries multicomponent catalyst in catalytic hydrogenation synthesizes benzotriazole ultraviolet absorber
Application.
6. application as claimed in claim 5, which is characterized in that the method for the application is：
Azo intermediate, solvent, alkaline assistant input shown in charcoal described in claim 1 load multicomponent catalyst, formula (I) is high
It presses in reaction kettle, adjusts 1~3MPa of Hydrogen Vapor Pressure, 1~10h is stirred to react at 30~80 DEG C, reaction solution filtering takes filtrate to subtract
Pressure is evaporated, and residue drying obtains benzotriazole ultraviolet absorber shown in target product formula (III)；
The solvent is the mixed solvent of one or more of toluene, dimethylbenzene, chlorobenzene, tetrahydrofuran arbitrary proportion；
The alkaline assistant is diethylamine, n-butylamine, piperidines, ethylenediamine or ethanol amine；
In formula (I) or formula (III),
R1For H, C1~C12 alkyl, C5~C8 cycloalkyl, phenyl or (C1~C4 alkyl) phenyl；
R2For C1~C12 alkyl, C5~C8 cycloalkyl, phenyl or (C1-C4 alkyl) phenyl；
R3For H, Cl or Br.
7. application as claimed in claim 6, which is characterized in that the R1For H, tertiary butyl, 1,1- dimethyl propyls or 1,1,3,
3- tetramethyl butyls；R2For methyl, tertiary butyl, 1,1- dimethyl propyls or 1,1,3,3- tetramethyl butyls；R3For H or Cl.
8. application as claimed in claim 6, which is characterized in that the method for the application is：
Azo intermediate, solvent, alkaline assistant input shown in charcoal described in claim 1 load multicomponent catalyst, formula (I) is high
It presses in reaction kettle, seals kettle, after air in hydrogen displacement kettle, adjust 1~3MPa of Hydrogen Vapor Pressure, be stirred to react at 30~80 DEG C
1~10h, reaction system filtering, takes filtrate decompression to be evaporated later, and residue is done after deionized water is washed, methanol washs respectively
It is dry, obtain benzotriazole ultraviolet absorber shown in target product formula (III)；
It is 0.5~5 that the charcoal, which carries multicomponent catalyst and the mass ratio that feeds intake of azo intermediate shown in formula (I),：100；It is described molten
Agent is the mixed solvent of one or more of toluene, dimethylbenzene, chlorobenzene, tetrahydrofuran arbitrary proportion；The solvent
Volumetric usage is calculated as 5~20mL/g with the quality of azo intermediate shown in formula (I)；The alkaline assistant for diethylamine, n-butylamine,
Piperidines, ethylenediamine or ethanol amine；The alkaline assistant and the mass ratio that feeds intake of azo intermediate shown in formula (I) are 1：1~5.
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| CN106179400A (en) * | 2016-06-30 | 2016-12-07 | 浙江工业大学 | Activated carbon supported type composite metal catalyst and preparation method and application |
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| CN109529820B (en) * | 2018-12-19 | 2021-11-30 | 利安隆科润(浙江)新材料有限公司 | Preparation method of catalyst for preparing benzotriazole ultraviolet absorber by catalytic hydrogenation |
| CN112295569B (en) * | 2019-07-26 | 2023-05-12 | 中国石油化工股份有限公司 | Catalyst for preparing aniline by one-step ammoniation of benzene and preparation method thereof |
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| CN114345328A (en) * | 2021-12-30 | 2022-04-15 | 利安隆科润(浙江)新材料有限公司 | Catalyst, preparation method and application thereof |
| CN114797870B (en) * | 2022-04-14 | 2023-06-09 | 浙江师范大学 | Catalyst for preparing m-xylylenediamine by hydrogenation of m-phthalonitrile, and preparation method and application thereof |
| CN115178257B (en) * | 2022-06-13 | 2024-06-07 | 浙江工业大学 | Preparation method and application of Pt-Ru-La/C multi-metal catalyst |
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| CN115920975B (en) * | 2022-12-29 | 2024-06-07 | 浙江工业大学 | Preparation method and application of defect MOFs material encapsulated noble metal Pt catalyst |
| CN117210167B (en) * | 2023-11-08 | 2024-01-09 | 广东鑫瑞新材料有限公司 | Nanofiber ceramic high-heat-insulation sun-shading adhesive film and preparation method and application thereof |
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| EP0794179A1 (en) * | 1996-03-07 | 1997-09-10 | Eastman Kodak Company | Process for the preparation of benzotriazole derivatives |
| CN101703935A (en) * | 2009-11-19 | 2010-05-12 | 浙江工业大学 | Load type metal catalyst and preparation method thereof |
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| EP0794179A1 (en) * | 1996-03-07 | 1997-09-10 | Eastman Kodak Company | Process for the preparation of benzotriazole derivatives |
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