CN105214686A - A kind of charcoal carries multicomponent catalyst and preparation method thereof and application - Google Patents
A kind of charcoal carries multicomponent catalyst and preparation method thereof and application Download PDFInfo
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Abstract
The invention provides a kind of charcoal and carry multicomponent catalyst and preparation method thereof, by carrier and load, the metal active constituent on carrier forms described catalyst, and described carrier is active carbon, and described metal active constituent is palladium, platinum and a kind of transition metal auxiliary agent; Based on the quality of carrier active carbon, palladium load capacity is 0.5wt% ~ 5.0wt%, and platinum load capacity is 0.5wt% ~ 5.0wt%, and transition metal 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 applicable to catalytic hydrogenation synthesis benzotriazole ultraviolet absorber; Method for preparing catalyst provided by the invention is easy, and catalytic activity is high, target product selectivity and yield high, good stability, in Simultaneous hydrogenation process, the three wastes produce few.
Description
(1) technical field
The present invention relates to a kind of charcoal and carry multicomponent catalyst and preparation method thereof, described charcoal carries multicomponent catalyst and can be applicable to catalytic hydrogenation synthesis benzotriazole ultraviolet absorber.
(2) background technology
Benzotriazole ultraviolet absorber is the principal item of Light Stabilizers for Plastics, has excellent ultraviolet absorption ability, can absorb the ultraviolet of 290 ~ 400nm wavelength.And it has more shallow color, lower toxicity, be not easy volatilization, oil resistivity is good, with the advantage such as polymer compatibility is good, be widely used in the photochemical modification of the various synthetic materials such as polypropylene, polyethylene, polyvinyl chloride, polyformaldehyde, polyamide, polystyrene, polyurethane, alkyd resins.
The synthesis of benzotriazole ultraviolet absorber is a complicated multi-step reaction.First need to synthesize the azo intermediate corresponding with product by diazo coupling, and then obtain benzotriazole ultraviolet absorber by azo intermediate reduction.
Wherein the reduction reaction of azo intermediate is the committed step of its synthesis.Electronation technology is the mature technology widely used in current industrial production, such as: zinc powder reduction, sodium hydrosulfite reduction, hydrazine hydrate-zinc powder reduction and glucose-zinc powder reduction etc.Although chemical reduction method synthesis benzotriazole ultraviolet absorber technology maturation, technique are relatively simple, the shortcoming such as there is waste water and waste sludge discharge amount is large, atom economy efficiency is low and reducing agent is expensive more.Such as: zinc powder reduction can produce a large amount of zinc mud and zinc-containing water, and damage ratio is more serious; Sulfide reducing process needs the sulfur-containing waste water carrying out a large amount of solvent recovery and treating depth pollution; When hydrazine hydrate is reducing agent, excessive hydrazine hydrate equally can to environment, and the price of hydrazine hydrate is also higher simultaneously; Have a large amount of high cod values waste water when glucose is reducing agent equally to produce.Under the situation that environmental protection comes into one's own day by day, pollute more serious chemical reduction process and be faced with the severe survival pressure that may be eliminated at any time.Therefore, the reduction route that searching one is more green, economic replaces traditional handicraft to have important and urgent realistic meaning.
Catalytic hydrogenating reduction method synthesis benzotriazole ultraviolet absorber is as shown in reaction equation 1: first-selection is reduced to hydrazine class compound by raw material azo intermediate (I) and generates intermediate product nitrogen oxide (II) through intramolecular dehydration annulation under hydrogenation catalyst and hydrogen effect, and nitrogen oxide further hydrogenation finally generates benzotriazole product (III).
Reaction equation 1
Catalytic hydrogenation method due to can not to environment using hydrogen as reducing agent, and has that wastewater discharge is little, Atom economy advantages of higher, is the green route that can replace traditional chemical reducing process.
But catalytic hydrogenation reaction process is normal with there is many side reactions, produces more accessory substance.Such as: azo-compound hydrogenating reduction is that hydrazine class compound carries out, in the process of intramolecular dehydration annulation, hydrazine bond fission side reaction easily occurs again, generates two molecule arylamine class accessory substances, as shown in reaction equation 2.
Reaction equation 2
In addition, due to triazole ring and the impact that the phenyl ring connected is subject to triazole ring more trends towards conjugated diene structure, make with triazole ring and the phenyl ring connected more easily by hydrotreated lube base oil, cause nitrogen oxide intermediate and benzotriazole product that excessive hydrogenation side reaction can occur, generate tetrahydrochysene accessory substance (IV, V).
The generation of these accessory substances not only reduces product yield and is unfavorable for separating-purifying, constrains the commercial Application of Catalytic Hydrogenation Techniques.
There are many research reports about catalytic hydrogenation synthesis benzotriazole ultraviolet absorber in recent years, as: (the Wang Li such as Wang Li, Li Keguo. the synthesis technique [J] of optimization of orthogonal test UV-327. synthetic chemistry, 2007, (5): 658-660.) have studied Raney's nickel catalyst hydrogenating reduction UV-327 nitrogen oxide (N-oxide) and synthesize UV-327, yield is 91%.Patent EP0380840A1 reports in toluene-isopropanol-water-NaOH system, and Raney's nickel is catalyst to catalyzing hydrogenating synthesis UV-328, yield 82%.But when taking Raney's nickel as hydrogenation catalyst, the selective and yield of benzotriazole product is not high; And Raney's nickel has inflammability, in use there is potential safety hazard.Also report is had to adopt charcoal supported noble metal to be hydrogenation catalyst synthesis benzotriazole product, to compare Raney's nickel catalyst, the security of charcoal supported noble metal catalyst is better, such as: CIBAGEIGY company (patent US5276161) adopts 5%Pt/C to be catalyst to catalyzing hydrogenating synthesis UV-P, and yield is 92%; Patent US5104992 adopts 5%Pd/C to be catalyst hydrogenation synthesis UV-320, yield 87.3%; Patent EP0794179A1 is that catalyst synthesizes UV-328 with 4%Pd/C+1%Pt/C, this patent in reduction system, add hypophosphorous acid or sulfuric acid can improve product yield, but need in reaction system, add a large amount of liquid acid (mol ratio of acid/raw material is 3.0), more spent acid can be produced to environment, the liquid acid simultaneously added easily remains in the product, affects product quality.
As can be seen here, though existing hydrogenation catalyst is Raney's nickel catalyst or Pd/C, Pt/C catalyst all exist selective not high or use the defect such as liquid acid.Therefore, research emphasis and the difficult point of catalytic hydrogenation synthesis BTA ultraviolet absorber are the generation suppressing side reaction, improve the selective and yield of target product, reduce the three wastes simultaneously and produce, and key technology is wherein the design and development of hydrogenation catalyst.
(3) summary of the invention
For the deficiencies in the prior art, the invention provides a kind of charcoal and carry multicomponent catalyst and preparation method thereof, described charcoal carries multicomponent catalyst and can be applicable to catalytic hydrogenation synthesis benzotriazole ultraviolet absorber, and has higher catalytic activity and target product selectivity.
The present invention adopts following technical scheme:
A kind of charcoal carries multicomponent catalyst, and by carrier and load, the metal active constituent on carrier forms, and described carrier is active carbon, and described metal active constituent is palladium, platinum and a kind of transition metal auxiliary agent; Based on the quality of carrier active carbon, palladium load capacity is 0.5wt% ~ 5.0wt%, and platinum load capacity is 0.5wt% ~ 5.0wt%, and transition metal auxiliary agent load capacity is 0.1wt% ~ 2.5wt%; Meanwhile, the mass ratio of palladium and platinum is 1:0.5 ~ 2.0; Described transition metal auxiliary agent is selected from one of following: 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 area of preferred vector active carbon is 800 ~ 1600m
2/ g; Preferred palladium load capacity is 1.0wt% ~ 2.0wt%, and platinum load capacity is 1.0wt% ~ 2.0wt%, and transition metal auxiliary agent load capacity is 0.5wt% ~ 1.0wt%; The mass ratio of preferred palladium and platinum is 1:1; Preferred described transition metal auxiliary agent is selected from one of following: Fe, Co, Ni, Cu, Zn or Mo, particularly preferably Cu.
Present invention also offers the preparation method that a kind of described charcoal carries multicomponent catalyst, described preparation method is:
By palladium presoma, platinum presoma, the presoma of transition metal auxiliary agent, citrate is dissolved in ethylene glycol (EG), stir formation precursor solution, carrier active carbon is added in precursor solution, impregnation process 1 ~ 6h is stirred in 0 ~ 50 DEG C of (preferably 25 DEG C) constant temperature, be 8 ~ 12 (preferably 9 ~ 10) by alkali lye adjust ph again, be warming up to 120 ~ 180 DEG C (preferably 160 DEG C) and continue constant temperature stirring 4 ~ 8h, question response system naturally cools to room temperature afterwards, filter, filter cake spends deionized water to neutral, vacuum drying 10 ~ 16h under 70 ~ 90 DEG C (preferably 90 DEG C), obtain described charcoal and carry multicomponent catalyst,
Described palladium presoma counts the 0.5wt% ~ 5.0wt% of carrier active carbon quality with palladium, described platinum presoma counts the 0.5wt% ~ 5.0wt% of carrier active carbon quality with platinum, the presoma of described transition metal auxiliary agent counts the 0.1wt% ~ 2.5wt% of carrier active carbon quality with transition metal auxiliary agent; Meanwhile, palladium presoma in palladium with platinum presoma in the mass ratio of platinum for 1:0.5 ~ 2.0; Described citrate add 0.5 ~ 5 times of quality summation that quality is palladium presoma, platinum presoma, transition metal auxiliary agent presoma; The volumetric usage of described ethylene glycol counts 10 ~ 100mL/g with the quality of carrier active carbon.
In described preparation method, usual described palladium presoma is palladium bichloride, palladium nitrate or palladium, preferred palladium bichloride.
Described platinum presoma can be chloroplatinic acid.
The presoma of described transition metal auxiliary agent is the soluble-salt of transition metal auxiliary agent, as nitrate, chlorate, oxalates etc., and preferably nitrate or chlorate; Concrete preferred, the presoma of described transition metal auxiliary agent can be selected from one of following: Sc (NO
3)
3, TiCl
4, NH
4vO
3, Cr (NO
3)
3, Mn (NO
3)
2, FeCl
3, Co (NO
3)
2, Ni (NO
3)
2, Cu (NO
3)
2, ZnCl
2, Zr (NO
3)
4, (NH
4)
6mo
7o
24, RuCl
3, AgNO
3, (NH
4)
10w
12o
41or La (NO
3)
3, particularly preferably Cu (NO
3)
2, ZnCl
2, Co (NO
3)
2, Zr (NO
3)
4, FeCl
3or (NH
4)
6mo
7o
24.
Usual described citrate is potassium citrate or natrium citricum, optimization citric acid potassium; Preferred described citrate add 2 times of quality summation that quality is palladium presoma, platinum presoma, transition metal auxiliary agent presoma.
The volumetric usage of preferred described ethylene glycol counts 30 ~ 50mL/g with the quality of carrier active carbon.
Concrete, the alkali lye for adjust ph is NaOH, NaCO
3, NaHCO
3, KOH, KCO
3, KHCO
3, (NH
2)
2cO
3in the mixture of one or more arbitrary proportions be dissolved in the solution be made in ethylene glycol, and the mass concentration of described alkali lye is 0.1% ~ 30%, preferably 5%.
Charcoal of the present invention carries multicomponent catalyst and can be applicable to catalytic hydrogenation synthesis benzotriazole ultraviolet absorber, and the method for described application is:
Charcoal of the present invention is carried in azo intermediate shown in multicomponent catalyst, formula (I), solvent, alkaline assistant input autoclave, regulate Hydrogen Vapor Pressure 1 ~ 3MPa, stirring reaction 1 ~ 10h at 30 ~ 80 DEG C, reacting liquid filtering, get filtrate decompression evaporate to dryness, residue is dry, obtains benzotriazole ultraviolet absorber shown in target product formula (III);
Described solvent is the mixed solvent of one or more arbitrary proportions in toluene, dimethylbenzene, chlorobenzene, oxolane; Described alkaline assistant is diethylamine, n-butylamine, piperidines, ethylenediamine or monoethanolamine;
In formula (I) or formula (III),
R
1for H, C1 ~ C12 alkyl, C5 ~ C8 cycloalkyl, phenyl or (C1 ~ C4 alkyl) phenyl; Preferred H, the tert-butyl group, 1,1-dimethyl propyl or 1,1,3,3-tetramethyl butyl;
R
2for C1 ~ C12 alkyl, C5 ~ C8 cycloalkyl, phenyl or (C1-C4 alkyl) phenyl; Preferable methyl, the tert-butyl group, 1,1-dimethyl propyl or 1,1,3,3-tetramethyl butyl;
R
3for H, Cl or Br; Preferred H or Cl.
Further, more concrete, the method for described application is:
Charcoal of the present invention is carried multicomponent catalyst, azo intermediate shown in formula (I), solvent, alkaline assistant drops in autoclave, envelope still, after air in hydrogen exchange still, regulate Hydrogen Vapor Pressure 1 ~ 3MPa (preferred 1MPa), under 30 ~ 80 DEG C (preferably 50 ~ 65 DEG C), stir (speed 800 ~ 1200rpm) react 1 ~ 10h (preferably 3 ~ 5h), reaction system is filtered afterwards, get filtrate decompression evaporate to dryness, residue washs through deionized water respectively, dry after methanol wash, obtain benzotriazole ultraviolet absorber shown in target product formula (III),
The mass ratio that feeds intake that described charcoal carries azo intermediate shown in multicomponent catalyst and formula (I) is 0.5 ~ 5:100; Described solvent is the mixed solvent of one or more arbitrary proportions in toluene, dimethylbenzene, chlorobenzene, oxolane; The volumetric usage of described solvent counts 5 ~ 20mL/g with the quality of azo intermediate formula (I) Suo Shi; Described alkaline assistant is diethylamine, n-butylamine, piperidines, ethylenediamine or monoethanolamine; Shown in described alkaline assistant and formula (I), the mass ratio that feeds intake of azo intermediate is 1:1 ~ 5.
In described application process, the mass ratio that feeds intake that preferred described charcoal carries azo intermediate shown in multicomponent catalyst and formula (I) is 2:100; Preferred described solvent is toluene; The volumetric usage of preferred described solvent counts 10 ~ 15mL/g with the quality of azo intermediate formula (I) Suo Shi; Preferred described alkaline assistant is piperidines; Shown in preferred described alkaline assistant and formula (I), the mass ratio that feeds intake of azo intermediate is 1:2.5.
Compared with prior art, the present invention has the following advantages:
(1) charcoal of the present invention carries that the preparation method of multicomponent catalyst is easy, metal dispersity is high, catalytic activity good;
(2) charcoal of the present invention carries multicomponent catalyst in catalytic hydrogenation synthesis benzotriazole ultraviolet absorber, and the selective and yield of product benzotriazole ultraviolet absorber is high, and reaction system is simple, and the three wastes are few;
(3) charcoal of the present invention carries multicomponent catalyst good stability, can repeatedly use, and effectively reduces catalyst cost, and in use procedure simultaneously, security is high, has higher industrial application value.
(4) accompanying drawing explanation
Fig. 1 is the transmission electron microscope phenogram (50nm scale) of the catalyst that the embodiment of the present invention 1 obtains;
Fig. 2 is the transmission electron microscope phenogram (5nm scale) of the catalyst that the embodiment of the present invention 1 obtains;
Fig. 3 is the particle size distribution figure of catalyst 100 particle specimens that the embodiment of the present invention 1 obtains.
(5) detailed description of the invention
With specific embodiment, technical scheme of the present invention is described further below, but protection scope of the present invention is not limited thereto.
Embodiment 1
Take 0.088gPdCl
2, 0.132gH
2ptCl
66H
2o, 0.088gCu (NO
3)
22H
2there-necked flask put into by O and 0.6g potassium citrate; In flask, add 150ml ethylene glycol again and at room temperature stir about 0.5h, obtain precursor solution; In the precursor solution prepared, add 5g active carbon again, at 25 DEG C, keep constant temperature to stir impregnation process 4h; After having flooded, drip 5wt.%KOH/EG solution, regulate slurry pH value to 10; Being warming up to 160 DEG C again keeps constant temperature to stir 6h; After its cooling, filtration, filter cake spend deionized water to neutral; At 80 DEG C of temperature, vacuum drying is about 12h again.Obtain 1%Pd1%Pt0.5%Cu/C catalyst 5.125g.
Fig. 1 is the transmission electron microscope phenogram of the catalyst 50nm scale that the present embodiment obtains, and as can be seen from Figure 1, metal component particle size size and distributing very evenly at carrier surface, the dispersion of metallic particles is very good.
Fig. 2 is the high resolution electron microscopy characterization result of the catalyst 5nm scale that the present embodiment obtains, and as can be seen from Figure 2, the size of metallic particles is at about 5nm, and granular size is also comparatively even.
By the sampling statistics of transmission electron microscope to catalyst 100 particle specimens that the present embodiment obtains, obtain particle size distribution as shown in Figure 3.The average grain diameter of catalyst metal particles is about 5.3nm, and narrow distribution, illustrates that this catalyst metal particles is less and dispersion is very even.Its reason causes owing to adding potassium citrate complexing agent in catalyst preparation process.Complexing agent add the reunion preventing metallic in heating reduction process.Prepare in the process of reduction, alkaline reducing environment may make the reducing power of ethylene glycol strengthen simultaneously, and the rate of reduction of metal ion is accelerated, and nucleation rate increase, result in formed metal and alloy nanoparticle particle diameter is less.
Embodiment 2
Take 0.066gPdCl
2, 0.1gH
2ptCl
66H
2o, 0.088gCu (NO
3)
22H
2there-necked flask put into by O and 0.5g potassium citrate; In flask, add 150ml ethylene glycol again and at room temperature stir about 0.5h, obtain precursor solution; In the precursor solution prepared, add 5g active carbon again, at 25 DEG C, keep constant temperature to stir impregnation process 4h; After having flooded, drip 5wt.%KOH/EG solution, regulate slurry pH value to 10; Being warming up to 160 DEG C again keeps constant temperature to stir 6h; After its cooling, filtration, filter cake spend deionized water to neutral; At 80 DEG C of temperature, vacuum drying is about 12h again.Obtain 0.75%Pd0.75%Pt0.5%Cu/C catalyst 5.1g.
Embodiment 3
Take 0.044gPdCl
2, 0.066gH
2ptCl
66H
2o, 0.088gCu (NO
3)
22H
2there-necked flask put into by O and 0.4g potassium citrate; In flask, add 150ml ethylene glycol again and at room temperature stir about 0.5h, obtain precursor solution; In the precursor solution prepared, add 5g active carbon again, at 25 DEG C, keep constant temperature to stir impregnation process 4h; After having flooded, drip 5wt.%KOH/EG solution, regulate slurry pH value to 10; Being warming up to 160 DEG C again keeps constant temperature to stir 6h; After its cooling, filtration, filter cake spend deionized water to neutral; At 80 DEG C of temperature, vacuum drying is about 12h again.Obtain 0.5%Pd0.5%Pt0.5%Cu/C catalyst 5.075g.
Embodiment 4
Take 0.176gPdCl
2, 0.264gH
2ptCl
66H
2o, 0.088gCu (NO
3)
22H
2there-necked flask put into by O and 1.0g potassium citrate; In flask, add 150ml ethylene glycol again and at room temperature stir about 0.5h, obtain precursor solution; In the precursor solution prepared, add 5g active carbon again, at 25 DEG C, keep constant temperature to stir impregnation process 4h; After having flooded, drip 5wt.%KOH/EG solution, regulate slurry pH value to 10; Being warming up to 160 DEG C again keeps constant temperature to stir 6h; After its cooling, filtration, filter cake spend deionized water to neutral; At 80 DEG C of temperature, vacuum drying is about 12h again.Obtain 2%Pd2%Pt0.5%Cu/C catalyst 5.225g.
Embodiment 5
Take 0.44gPdCl
2, 0.66gH
2ptCl
66H
2o, 0.088gCu (NO
3)
22H
2there-necked flask put into by O and 2.4g potassium citrate; In flask, add 150ml ethylene glycol again and at room temperature stir about 0.5h, obtain precursor solution; In the precursor solution prepared, add 5g active carbon again, at 25 DEG C, keep constant temperature to stir impregnation process 4h; After having flooded, drip 5wt.%KOH/EG solution, regulate slurry pH value to 10; Being warming up to 160 DEG C again keeps constant temperature to stir 6h; After its cooling, filtration, filter cake spend deionized water to neutral; At 80 DEG C of temperature, vacuum drying is about 12h again.Obtain 5%Pd5%Pt0.5%Cu/C catalyst 5.525g.
Embodiment 6
Take 0.088gPdCl
2, 0.132gH
2ptCl
66H
2o, 0.044gCu (NO
3)
22H
2there-necked flask put into by O and 0.5g potassium citrate; In flask, add 150ml ethylene glycol again and at room temperature stir about 0.5h, obtain precursor solution; In the precursor solution prepared, add 5g active carbon again, at 25 DEG C, keep constant temperature to stir impregnation process 4h; After having flooded, drip 5wt.%KOH/EG solution, regulate slurry pH value to 10; Being warming up to 160 DEG C again keeps constant temperature to stir 6h; After its cooling, filtration, filter cake spend deionized water to neutral; At 80 DEG C of temperature, vacuum drying is about 12h again.Obtain 1%Pd1%Pt0.25%Cu/C catalyst 5.113g.
Embodiment 7
Take 0.088gPdCl
2, 0.132gH
2ptCl
66H
2o, 0.176gCu (NO
3)
22H
2there-necked flask put into by O and 0.8g potassium citrate; In flask, add 150ml ethylene glycol again and at room temperature stir about 0.5h, obtain precursor solution; In the precursor solution prepared, add 5g active carbon again, at 25 DEG C, keep constant temperature to stir impregnation process 4h; After having flooded, drip 5wt.%KOH/EG solution, regulate slurry pH value to 10; Being warming up to 160 DEG C again keeps constant temperature to stir 6h; After its cooling, filtration, filter cake spend deionized water to neutral; At 80 DEG C of temperature, vacuum drying is about 12h again.Obtain 1%Pd1%Pt1%Cu/C catalyst 5.15g.
Embodiment 8
Take 0.088gPdCl
2, 0.132gH
2ptCl
66H
2o, 0.052gZnCl
2there-necked flask is put into 0.6g potassium citrate; In flask, add 150ml ethylene glycol again and at room temperature stir about 0.5h, obtain precursor solution; In the precursor solution prepared, add 5g active carbon again, at 25 DEG C, keep constant temperature to stir impregnation process 4h; After having flooded, drip 5wt.%KOH/EG solution, regulate slurry pH value to 10; Being warming up to 160 DEG C again keeps constant temperature to stir 6h; After its cooling, filtration, filter cake spend deionized water to neutral; At 80 DEG C of temperature, vacuum drying is about 12h again.Obtain 1%Pd1%Pt0.5%Zn/C catalyst 5.125g.
Embodiment 9
Take 0.088gPdCl
2, 0.132gH
2ptCl
66H
2o, 0.123gCo (NO
3)
26H
2there-necked flask put into by O and 0.7g potassium citrate; In flask, add 150ml ethylene glycol again and at room temperature stir about 0.5h, obtain precursor solution; In the precursor solution prepared, add 5g active carbon again, at 25 DEG C, keep constant temperature to stir impregnation process 4h; After having flooded, drip 5wt.%KOH/EG solution, regulate slurry pH value to 10; Being warming up to 160 DEG C again keeps constant temperature to stir 6h; After its cooling, filtration, filter cake spend deionized water to neutral; At 80 DEG C of temperature, vacuum drying is about 12h again.Obtain 1%Pd1%Pt0.5%Co/C catalyst 5.125g.
Embodiment 10
Take 0.088gPdCl
2, 0.132gH
2ptCl
66H
2o, 0.118gZr (NO
3)
45H
2there-necked flask put into by O and 0.7g potassium citrate; In flask, add 150ml ethylene glycol again and at room temperature stir about 0.5h, obtain precursor solution; In the precursor solution prepared, add 5g active carbon again, at 25 DEG C, keep constant temperature to stir impregnation process 4h; After having flooded, drip 5wt.%KOH/EG solution, regulate slurry pH value to 10; Being warming up to 160 DEG C again keeps constant temperature to stir 6h; After its cooling, filtration, filter cake spend deionized water to neutral; At 80 DEG C of temperature, vacuum drying is about 12h again.Obtain 1%Pd1%Pt0.5%Zr/C catalyst 5.125g.
Embodiment 11
Take 0.088gPdCl
2, 0.132gH
2ptCl
66H
2o, 0.073gFeCl
3there-necked flask is put into 0.6g potassium citrate; In flask, add 150ml ethylene glycol again and at room temperature stir about 0.5h, obtain precursor solution; In the precursor solution prepared, add 5g active carbon again, at 25 DEG C, keep constant temperature to stir impregnation process 4h; After having flooded, drip 5wt.%KOH/EG solution, regulate slurry pH value to 10; Being warming up to 160 DEG C again keeps constant temperature to stir 6h; After its cooling, filtration, filter cake spend deionized water to neutral; At 80 DEG C of temperature, vacuum drying is about 12h again.Obtain 1%Pd1%Pt0.5%Fe/C catalyst 5.125g.
Embodiment 12
Take 0.088gPdCl
2, 0.132gH
2ptCl
66H
2o, 0.047g (NH
4)
6mo
7o
244H
2there-necked flask put into by O and 0.55g potassium citrate; In flask, add 150ml ethylene glycol again and at room temperature stir about 0.5h, obtain precursor solution; In the precursor solution prepared, add 5g active carbon again, at 25 DEG C, keep constant temperature to stir impregnation process 4h; After having flooded, drip 5wt.%KOH/EG solution, regulate slurry pH value to 10; Being warming up to 160 DEG C again keeps constant temperature to stir 6h; After its cooling, filtration, filter cake spend deionized water to neutral; At 80 DEG C of temperature, vacuum drying is about 12h again.Obtain 5%Pd5%Pt0.5%Mo/C catalyst 5.125g.
Application Example 1-12
In 500mL autoclave, the charcoal adding one of 0.2g embodiment 1-12 preparation successively carries multicomponent catalyst, 10gUV-P azo intermediate, about 120mL toluene and 4g piperidines, envelope still, repeatedly replacing in still air with hydrogen to regulate for 5 times in still Hydrogen Vapor Pressure to 1MPa afterwards, start after being heated to 50 DEG C again to stir (stir speed (S.S.) is about 1000rpm), reaction 3h; After reaction terminates, filtering catalyst, isolate organic layer (sampling adopts hydrogenation products composition in efficient liquid phase chromatographic analysis filtrate), evaporated under reduced pressure, spends deionized water and methanol wash respectively, obtains target product UV-P after drying.
Application Example 13
In 500mL autoclave, the charcoal adding 0.2g embodiment 1 preparation successively carries multicomponent catalyst, 10gUV-P azo intermediate, about 120mL toluene and 4g diethylamine, envelope still, repeatedly replacing in still air with hydrogen to regulate for 5 times in still Hydrogen Vapor Pressure to 1MPa afterwards, start after being heated to 50 DEG C again to stir (stir speed (S.S.) is about 1000rpm), reaction 3h; After reaction terminates, filtering catalyst, isolate organic layer (sampling adopts hydrogenation products composition in efficient liquid phase chromatographic analysis filtrate), evaporated under reduced pressure, spends deionized water and methanol wash respectively, obtains target product UV-P after drying.
Application Example 14
In 500mL autoclave, the charcoal adding 0.2g embodiment 1 preparation successively carries multicomponent catalyst, 10gUV-P azo intermediate, about 120mL toluene and 4g n-butylamine, envelope still, repeatedly replacing in still air with hydrogen to regulate for 5 times in still Hydrogen Vapor Pressure to 1MPa afterwards, start after being heated to 50 DEG C again to stir (stir speed (S.S.) is about 1000rpm), reaction 3h; After reaction terminates, filtering catalyst, isolate organic layer (sampling adopts hydrogenation products composition in efficient liquid phase chromatographic analysis filtrate), evaporated under reduced pressure, spends deionized water and methanol wash respectively, obtains target product UV-P after drying.
Application Example 15
In 500mL autoclave, the charcoal adding 0.2g embodiment 1 preparation successively carries multicomponent catalyst, 10gUV-326 azo intermediate, about 120mL toluene and 4g piperidines, envelope still, repeatedly replacing in still air with hydrogen to regulate for 5 times in still Hydrogen Vapor Pressure to 1MPa afterwards, start after being heated to 50 DEG C again to stir (stir speed (S.S.) is about 1000rpm), reaction 3h; After reaction terminates, filtering catalyst, isolate organic layer (sampling adopts hydrogenation products composition in efficient liquid phase chromatographic analysis filtrate), evaporated under reduced pressure, spends deionized water and methanol wash respectively, obtains target product UV-326 after drying.
Application Example 16
In 500mL autoclave, the charcoal adding 0.2g embodiment 1 preparation successively carries multicomponent catalyst, 10gUV-327 azo intermediate, about 120mL solvent and 4g piperidines, envelope still, repeatedly replacing in still air with hydrogen to regulate for 5 times in still Hydrogen Vapor Pressure to 1MPa afterwards, start after being heated to 50 DEG C again to stir (stir speed (S.S.) is about 1000rpm), reaction 3h; After reaction terminates, filtering catalyst, isolate organic layer (sampling adopts hydrogenation products composition in efficient liquid phase chromatographic analysis filtrate), evaporated under reduced pressure, spends deionized water and methanol wash respectively, obtains target product UV-327 after drying.
Application Example 17
In 500mL autoclave, the charcoal adding 0.2g embodiment 1 preparation successively carries multicomponent catalyst, 10gUV-328 azo intermediate, about 120mL toluene and 4g piperidines, envelope still, repeatedly replacing in still air with hydrogen to regulate for 5 times in still Hydrogen Vapor Pressure to 1MPa afterwards, start after being heated to 50 DEG C again to stir (stir speed (S.S.) is about 1000rpm), reaction 3h; After reaction terminates, filtering catalyst, isolate organic layer (sampling adopts hydrogenation products composition in efficient liquid phase chromatographic analysis filtrate), evaporated under reduced pressure, spends deionized water and methanol wash respectively, obtains target product UV-328 after drying.
Application Example 18
In 500mL autoclave, the charcoal adding 0.2g embodiment 1 preparation successively carries multicomponent catalyst, 10gUV-329 azo intermediate, about 120mL toluene and 4g piperidines, envelope still, repeatedly replacing in still air with hydrogen to regulate for 5 times in still Hydrogen Vapor Pressure to 1MPa afterwards, start after being heated to 50 DEG C again to stir (stir speed (S.S.) is about 1000rpm), reaction 3h; After reaction terminates, filtering catalyst, isolate organic layer (sampling adopts hydrogenation products composition in efficient liquid phase chromatographic analysis filtrate), evaporated under reduced pressure, spends deionized water and methanol wash respectively, obtains target product UV-329 after drying.
Application Example 19 (comparative example)
The catalyst adopted according to patent US5276161 and reaction condition contrast:
In 500mL autoclave, add 1.2g5%Pt/C catalyst, 60gUV-P azo intermediate, about 80g dimethylbenzene and 20g diethylenetriamine successively, envelope still, repeatedly replacing in still air with hydrogen to regulate for 5 times in still Hydrogen Vapor Pressure to 1MPa afterwards, start after being heated to 60 DEG C again to stir (stir speed (S.S.) is about 1000rpm), reaction 3h; After reaction terminates, filtering catalyst, isolate organic layer (sampling adopts hydrogenation products composition in efficient liquid phase chromatographic analysis filtrate), evaporated under reduced pressure, spends deionized water and methanol wash respectively, obtains target product UV-P after drying.
Application Example result is as shown in table 1:
Table 1 Application Example 1-19 catalyst performance result
Embodiment 1-20 applied mechanically by catalyst
In 2000mL autoclave, add 1.0g1%Pd1%Pt0.5%Cu/C catalyst, 50gUV-P azo intermediate, about 750mL toluene and 20g piperidines successively, envelope still, repeatedly replacing in still air with hydrogen to regulate for 5 times in still Hydrogen Vapor Pressure to 1MPa afterwards, start after being heated to 50 DEG C again to stir (stir speed (S.S.) is about 1000rpm), reaction 3h; After reaction terminates, filtering catalyst, isolate organic layer (sampling adopts hydrogenation products composition in efficient liquid phase chromatographic analysis filtrate), evaporated under reduced pressure, spends deionized water and methanol wash respectively, obtains target product UV-P after drying;
Catalyst cake is applied to after spending deionized water and methanol wash respectively again and applies mechanically experiment next time; Apply mechanically experimental result as shown in table 2:
Embodiment 1-20 catalyst performance result applied mechanically by table 2
a)
A) applying mechanically embodiment use catalyst is: 1%Pd1%Pt0.5%Cu/C catalyst
In above-described embodiment, the structural formula of UV-P, UV-326, UV-327, UV-328, UV-329 and azo intermediate thereof is as follows respectively:
。
Claims (10)
1. charcoal carries a multicomponent catalyst, and by carrier and load, the metal active constituent on carrier forms, and it is characterized in that, described carrier is active carbon, and described metal active constituent is palladium, platinum and a kind of transition metal auxiliary agent; Based on the quality of carrier active carbon, palladium load capacity is 0.5wt% ~ 5.0wt%, and platinum load capacity is 0.5wt% ~ 5.0wt%, and transition metal auxiliary agent load capacity is 0.1wt% ~ 2.5wt%; Meanwhile, the mass ratio of palladium and platinum is 1:0.5 ~ 2.0; Described transition metal auxiliary agent is selected from one of following: Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ru, Ag, W, La, Re or Os.
2. charcoal as claimed in claim 1 carries multicomponent catalyst, and it is characterized in that, the specific area of described carrier active carbon is 800 ~ 1600m
2/ g.
3. charcoal as claimed in claim 1 carries multicomponent catalyst, and it is characterized in that, described palladium load capacity is 1.0wt% ~ 2.0wt%, and platinum load capacity is 1.0wt% ~ 2.0wt%, and transition metal auxiliary agent load capacity is 0.5wt% ~ 1.0wt%.
4. charcoal as claimed in claim 1 carries multicomponent catalyst, it is characterized in that, described transition metal auxiliary agent is selected from one of following: Fe, Co, Ni, Cu, Zn or Mo.
5. charcoal carries a preparation method for multicomponent catalyst as claimed in claim 1, it is characterized in that, described preparation method is:
Palladium presoma, platinum presoma, the presoma of transition metal auxiliary agent, citrate are dissolved in ethylene glycol, stir formation precursor solution, carrier active carbon is added in precursor solution, impregnation process 1 ~ 6h is stirred in 0 ~ 50 DEG C of constant temperature, be 8 ~ 12 by alkali lye adjust ph again, be warming up to 120 ~ 180 DEG C and continue constant temperature stirring 4 ~ 8h, question response system naturally cools to room temperature afterwards, filter, filter cake spends deionized water to neutral, vacuum drying 10 ~ 16h at 70 ~ 90 DEG C, obtains described charcoal and carries multicomponent catalyst;
Described palladium presoma is palladium bichloride, palladium nitrate or palladium; Described platinum presoma is chloroplatinic acid; The presoma of described transition metal auxiliary agent is the soluble-salt of transition metal auxiliary agent; Described palladium presoma counts the 0.5wt% ~ 5.0wt% of carrier active carbon quality with palladium, described platinum presoma counts the 0.5wt% ~ 5.0wt% of carrier active carbon quality with platinum, the presoma of described transition metal auxiliary agent counts the 0.1wt% ~ 2.5wt% of carrier active carbon quality with transition metal auxiliary agent; Meanwhile, palladium presoma in palladium with platinum presoma in the mass ratio of platinum for 1:0.5 ~ 2.0; Described citrate add 0.5 ~ 5 times of quality summation that quality is palladium presoma, platinum presoma, transition metal auxiliary agent presoma; The volumetric usage of described ethylene glycol counts 10 ~ 100mL/g with the quality of carrier active carbon.
6. preparation method as claimed in claim 5, is characterized in that, the presoma of described transition metal auxiliary agent is selected from one of following: Sc (NO
3)
3, TiCl
4, NH
4vO
3, Cr (NO
3)
3, Mn (NO
3)
2, FeCl
3, Co (NO
3)
2, Ni (NO
3)
2, Cu (NO
3)
2, ZnCl
2, Zr (NO
3)
4, (NH
4)
6mo
7o
24, RuCl
3, AgNO
3, (NH
4)
10w
12o
41or La (NO
3)
3.
7. charcoal as claimed in claim 1 carries the application of multicomponent catalyst in catalytic hydrogenation synthesis benzotriazole ultraviolet absorber.
8. application as claimed in claim 7, is characterized in that, the method for described application is:
Charcoal according to claim 1 is carried in azo intermediate shown in multicomponent catalyst, formula (I), solvent, alkaline assistant input autoclave, regulate Hydrogen Vapor Pressure 1 ~ 3MPa, stirring reaction 1 ~ 10h at 30 ~ 80 DEG C, reacting liquid filtering, get filtrate decompression evaporate to dryness, residue is dry, obtains benzotriazole ultraviolet absorber shown in target product formula (III);
Described solvent is the mixed solvent of one or more arbitrary proportions in toluene, dimethylbenzene, chlorobenzene, oxolane; Described alkaline assistant is diethylamine, n-butylamine, piperidines, ethylenediamine or monoethanolamine;
In formula (I) or formula (III),
R
1for H, C1 ~ C12 alkyl, C5 ~ C8 cycloalkyl, phenyl or (C1 ~ C4 alkyl) phenyl;
R
2for C1 ~ C12 alkyl, C5 ~ C8 cycloalkyl, phenyl or (C1-C4 alkyl) phenyl;
R
3for H, Cl or Br.
9. apply as claimed in claim 8, it is characterized in that, described R
1for H, the tert-butyl group, 1,1-dimethyl propyl or 1,1,3,3-tetramethyl butyl; R
2for methyl, the tert-butyl group, 1,1-dimethyl propyl or 1,1,3,3-tetramethyl butyl; R
3for H or Cl.
10. apply as claimed in claim 8, it is characterized in that, the method for described application is:
Charcoal according to claim 1 is carried in azo intermediate shown in multicomponent catalyst, formula (I), solvent, alkaline assistant input autoclave, envelope still, after air in hydrogen exchange still, regulate Hydrogen Vapor Pressure 1 ~ 3MPa, stirring reaction 1 ~ 10h at 30 ~ 80 DEG C, reaction system is filtered afterwards, gets filtrate decompression evaporate to dryness, residue is dry after deionized water washing, methanol wash respectively, obtains benzotriazole ultraviolet absorber shown in target product formula (III);
The mass ratio that feeds intake that described charcoal carries azo intermediate shown in multicomponent catalyst and formula (I) is 0.5 ~ 5:100; Described solvent is the mixed solvent of one or more arbitrary proportions in toluene, dimethylbenzene, chlorobenzene, oxolane; The volumetric usage of described solvent counts 5 ~ 20mL/g with the quality of azo intermediate formula (I) Suo Shi; Described alkaline assistant is diethylamine, n-butylamine, piperidines, ethylenediamine or monoethanolamine; Shown in described alkaline assistant and formula (I), the mass ratio that feeds intake of azo intermediate is 1:1 ~ 5.
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