CN106582640A - Preparation method and application of copper/silicon oxide xerogel catalyst - Google Patents
Preparation method and application of copper/silicon oxide xerogel catalyst Download PDFInfo
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- CN106582640A CN106582640A CN201610943626.5A CN201610943626A CN106582640A CN 106582640 A CN106582640 A CN 106582640A CN 201610943626 A CN201610943626 A CN 201610943626A CN 106582640 A CN106582640 A CN 106582640A
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—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
Abstract
The invention belongs to the field of energy chemical industry and discloses a preparation method and an application of a copper/silicon oxide xerogel catalyst. The preparation method includes the steps of: 1) at room temperature, adding tetraethyl orthosilicate to anhydrous ethanol, and fully stirring and mixing the components; 2) adding a copper salt to deionized water, stirring the mixture uniformly, dropwise slowly adding the mixture to a silicon solution, magnetically stirring the mixed solution for 8-10 h and stopping stirring; 3) dropwise slowly adding nitric acid to the mixed solution, stirring the solution for 3-5 min, stopping stirring and allowing the solution to stand at room temperature to await gelatinization; 4) aging the gel in air, vacuum-drying and normal-pressure-drying the gel, calcining the gel in air and feeding H2/Ar mixed gas to reduce the gel to prepare the copper/silicon oxide xerogel catalyst. The method is simple, is low in raw material cost, is low in demand on equipment, is free of pollution during synthesis and is environment-friendly, and is suitable for industrial production. The catalyst can be used for catalytically reducing paranitrophenol to prepare p-aminophenol at room temperature with water as a solvent and sodium borohydride as a hydrogen source. The process is low in usage amount of catalyst, is short in reaction time, and is high in conversion rate.
Description
Technical field
The present invention relates to a kind of copper/silica xerogels and preparation method thereof, belong to derived energy chemical field.
Background technology
Paranitrophenol (PNP) is a kind of poisonous environmental contaminants of non-biodegradation, and p-aminophenol (PAP) is a kind of
Important industrial chemicals and medicine intermediate, with the increase of p-aminophenol demand, using the direct catalytic hydrogenation of paranitrophenol
P-aminophenol is prepared because its efficient, environmental protection becomes principal synthetic routes.
P-nitrophenol catalytic hydrogenation used catalyst generally comprises noble metal catalyst (Au, Pt, Pd, Ru, Rh), non-noble
Metal nickel-base catalyst (Ni).Noble metal catalyst has preferable catalysis activity and high-temperature stability, but production cost is high, and
And using process easy-sintering, the rate of recovery is low, it is impossible to realize industrialized production.Nano nickel is although stable chemical nature, cheap and height
Activity increasingly receives publicity, but nickel is also non-negligible to the carcinogenicity of human body.Therefore a kind of cheap, environmental protection catalysis is found
Agent is used to being catalyzed p-nitrophenol that to prepare para-aminophenol significant.
In recent years, Cu series catalysts are simply industrially used widely due to its low price, preparation method, wherein
With Cu-SiO2Research it is more, preparation method includes infusion process, ion-exchange, sol-gel process etc., wherein sol-gel
Method can effectively make Cu species enter SiO2Oxide framework, ion-oxygen compound network is combined to form with silica gel, so as to prepare
Go out there is the catalyst of higher stability and metal dispersity.And utilize the Cu-SiO of sol-gel process preparation2Xerogel is urged
Agent is used to being catalyzed the research of p-nitrophenol hydrogenation reaction still to show and has been reported that.
The content of the invention
It is an object of the invention to provide a kind of silica xerogels load the preparation method of nano copper particle, urged using acid
Change sol-gel process synthesis, the two-step method of calcining reduction and be prepared for copper/silica xerogels, wherein copper is even size distribution
Nano particle, with the xerogel catalyst paranitrophenol Hydrogenation for p-aminophenol, with preparation cost is low, technique stream
Journey is simple, catalysis activity is high, good stability advantage.
The invention provides the preparation method of this copper/silica xerogels catalyst, specifically includes following steps：
(1) at room temperature, tetraethyl orthosilicate is added in absolute ethyl alcohol in proportion, is thoroughly mixed and uniformly obtains
Mixed solution A；
(2) mantoquita is added in deionized water in proportion, is stirred until homogeneous and obtains mixed solution B；
(3) mixed solution B is dropwise slowly added in mixed solution A, is reacted after 8～10h under magnetic agitation, stop stirring
Mix, obtain mixed solution C；Dropwise it is slowly added to nitric acid in mixed solution C again, stirs 3～5min, stop stirring, is placed in room
Middle benefit gas wait gel, obtain wet gel；
(4) wet gel for obtaining step (3) is aging in atmosphere, vacuum drying, and constant pressure and dry is calcined in air, then
It is passed through hydrogen-argon-mixed reduction, you can copper/silica xerogels catalyst is obtained.
In step (1), the tetraethyl orthosilicate is 0.9898～1.2249 with the mass ratio of absolute ethyl alcohol；
In step (2), the mantoquita is the one kind in copper nitrate, copper acetate or copper chloride, and the amount of the mantoquita is according to product
The quality 1～20% of copper is calculated in thing copper/zirconium oxide xerogel.
In step (3), in the mixed solution C, the body of the absolute ethyl alcohol in step (2) in deionized water and step (1)
Product is than being 5:9～15.
In step (3), the nitric acid is 2 with the volume ratio of absolute ethyl alcohol in mixed solution A:9～18；
In step (4), the ageing time is 10～12h, and vacuum drying temperature is 45～60 DEG C, vacuum drying time
For 24h.
In step (4), it is the step of the constant pressure and dry：First 4h is dried at 60 DEG C, then 80 DEG C are dried 2h, last 120
2h is dried at DEG C.
In step (4), the temperature of the calcining is 600～800 DEG C, and the time of calcining is 4～6h,
In step (4), the temperature of the hydrogen-argon-mixed reduction is 300～400 DEG C, and the recovery time is 2～4h.
In step (4), the volume fraction 5%～10% of the hydrogen-argon-mixed middle hydrogen；
Further, it is used to urge another object of the present invention is to provide described copper/silica xerogels nano material
Change paranitrophenol (PNP) and prepare p-aminophenol (PAP), comprise the following steps that：
(1) the paranitrophenol 50mL for preparing 0.1mM at room temperature is standby in volumetric flask；
(2) the sodium borohydride solution 25mL of 0.25M and standby in being stored in ice-water bath is prepared in ice-water bath；
(3) the paranitrophenol 20mL measured in step (1) is added in the beaker of 50mL, speed of agitator be maintained at 100 turns/
Minute；
(4) the sodium borohydride solution 1mL for measuring fresh preparation in step (2) is added in above-mentioned there-necked flask, stirs 10s
The sample for taking out 3mL afterwards does ultraviolet test；
(5) the bar-shaped xerogel catalyst of homemade copper/zirconium oxide is added in above-mentioned solution, in mechanical agitation rotating speed not
A sample is taken per 20s in the case of change, with ultraviolet specrophotometer the conversion situation of paranitrophenol is surveyed, test terminates rear sample and falls
In returning above-mentioned beaker.
(6) catalyst is reclaimed after the completion of reacting, is washed repeatedly, be dried, in case using when being catalyzed again.
Beneficial effects of the present invention are：
(1) compare with noble metal catalyst (Au, Pt, Pd, Ru, Rh) with base metal nickel-base catalyst (Ni), Cu systems urge
Agent price at a low price, environmental friendliness, for being catalyzed p-nitrophenol, to prepare para-aminophenol significant.
(2) active metal Cu is dispersed in into higher three-dimensional netted carrier S iO of sintering temperature2On, increased the dispersion of Cu
Spend, avoid reunion, improve specific surface area, increased chemical stability, and increased area of dissipation, be conducive to removing heat
Amount, improves the thermally-stabilised of Cu base catalyst.
(3) compared with conventional infusion process, coprecipitation, on the one hand the sol-gel process of employing can effectively make Cu things
Plant and enter SiO2Oxide framework, combine to form ion-oxygen compound network with silica gel, stablize with higher so as to prepare
The catalyst of property and metal dispersity, on the other hand enhances the decentralization of copper particle, reduces the particle diameter of copper particle.
(4) compared with freeze-drying, supercritical drying, not only reduces cost is vacuum dried, and avoids experimentation
Danger.
(5) the method process is simple, low for equipment requirements, building-up process pollution-free, environmental friendliness completely, it is adaptable to which industry is raw
Produce.
(6) catalytic reaction condition is gentle, and catalyst stability is good, because the carrier effect catalysis activity of silica is substantially carried
Height, the selectivity of catalyst is good, the recyclable recycling of catalyst, long service life.
Description of the drawings
Fig. 1 is the X-ray diffraction pattern of copper/silica xerogels catalyst that embodiments of the invention 1 are obtained；
Fig. 2 is the scanning electron microscope (SEM) photograph of the copper/silica xerogels catalyst shown in Fig. 1；
Fig. 3 is the transmission electron microscope picture a and high-resolution-ration transmission electric-lens figure of the copper/silica xerogels catalyst shown in Fig. 1
b；
Fig. 4 is the nitrogen adsorption-desorption curve a and graph of pore diameter distribution of the copper/silica xerogels catalyst shown in Fig. 1
b；
UV absorption spectrograms of the Fig. 5 for the copper/silica xerogels catalyst shown in Fig. 1 when paranitrophenol is catalyzed；
Circulation figures of the Fig. 6 for the copper/silica xerogels catalyst shown in Fig. 1 when paranitrophenol is catalyzed.
Specific embodiment
With reference to specific embodiment, the invention will be further described.
Embodiment 1：
(1) at room temperature, the eight water oxygen zirconium chlorides for weighing 7.9172g are added in 9mL absolute ethyl alcohols, are thoroughly mixed
Uniformly obtain mixed solution A；
(2) weigh 0.76g nitrate trihydrate copper to be added in the deionized water of 3mL, be stirred until homogeneous and obtain mixed solution B；
(3) mixed solution B is dropwise slowly added in mixed solution A, is reacted under magnetic agitation after 8h, stop stirring,
Obtain mixed solution C；
(4) nitric acid for measuring 1mL is dropwise slowly added in mixed solution C, stirs 5min, stops stirring, is placed in room temperature
Lower wait gel；
(5) wet gel for obtaining step (4) is placed in 60 DEG C of vacuum drying chambers after aging 10h is dried 24h in atmosphere,
Then constant pressure and dry：First 4h is dried at 60 DEG C, then 80 DEG C are dried 2h, and at last 120 DEG C 2h is dried；
(6) blocks of solid for obtaining step (5) calcines 4h in 800 DEG C in atmosphere, then is passed through body at a temperature of 300 DEG C
Fraction is 10% hydrogen-argon-mixed reductase 12 h, and heating rate is 4 DEG C/min, you can copper/silica xerogels catalysis is obtained
Agent.
Fig. 1 be gained copper/silica xerogels catalyst X-ray diffraction pattern, from figure line it is observed that 2 θ=
22 ° of SiO for disperse occur2Bao Feng, shows SiO2With amorphous state presence；In 2 θ=43.29 °, 50.43 ° corresponding with 74.13 °
(111), metallic copper (JCPDS 04-0836) diffraction maximum of (200) and (220) crystal face, shows that copper ion is successfully reduced into copper
Simple substance is supported on silica.
Fig. 2 is the copper/silica xerogels catalyst scanning electron microscope (SEM) photograph of gained, as can be seen from Figure 2 it is observed that whole
Individual Cu-SiO2Sample is formed by stacking by three-D nano-porous thin slice, there are nanovoids between layers.
Fig. 3 is the transmission electron microscope picture a and high-resolution-ration transmission electric-lens figure b of the copper/silica xerogels catalyst of gained, from figure
3 (a) is it is observed that the ball shaped nano copper particle (black round dot) of size uniform is highly dispersed at SiO2Surface, overcomes copper
Agglomeration；Fig. 3 (b) is the high-resolution-ration transmission electric-lens figure of nano spherical particle in Fig. 3 (a), can clearly measure lattice bar
Line spacing is 0.208nm, the metallic copper of corresponding crystal face (111).
Fig. 4 is the nitrogen adsorption-desorption isothermal curve a and graph of pore diameter distribution of the copper/silica xerogels catalyst of gained
B, the isothermal curve is typical IV class isothermal curve, illustrates the Cu-SiO for preparing2There is xerogel catalyst porous nano to tie
Structure, the specific surface area of the sample is 139.3918m2/ g, pore volume is 0.08714cm3/ g, pore-size distribution is put down between 0～8nm
Aperture is 1.3809nm.
Fig. 5 is UV absorption spectrogram of the copper/silica xerogels catalyst of gained when paranitrophenol is catalyzed, from the figure
It is observed that adding after catalyst, wavelength corresponding nitro absworption peak at 400nm is more and more weaker, while going out at 300nm
The absworption peak of amino is showed and has gradually strengthened, after 120s, nitro has been fully converted to amino.
Fig. 6 is the cyclic curve figure of the copper/silica xerogels catalyst in catalysis paranitrophenol of gained, can be with from the figure
Find out, after the copper/silica xerogels catalyst to preparing recycles five times, the conversion ratio of paranitrophenol still 83% with
On.
Embodiment 2：
(1) at room temperature, the eight water oxygen zirconium chlorides for weighing 8.709g are added in 9mL absolute ethyl alcohols, are thoroughly mixed
Uniformly obtain mixed solution A；
(2) weigh 0.076g nitrate trihydrate copper to be added in the deionized water of 3mL, be stirred until homogeneous and obtain mixed solution B；
(3) mixed solution B is dropwise slowly added in mixed solution A, is reacted under magnetic agitation after 8h, stop stirring,
Obtain mixed solution C；
(4) nitric acid for measuring 1mL is dropwise slowly added in mixed solution C, stirs 3min, stops stirring, is placed in room temperature
Lower wait gel；
(5) wet gel for obtaining step (4) is placed in 45 DEG C of vacuum drying chambers after aging 10h is dried 24h in atmosphere,
Then constant pressure and dry：First 4h is dried at 60 DEG C, then 80 DEG C are dried 2h, and at last 120 DEG C 2h is dried；
(6) blocks of solid for obtaining step (5) calcines 4h in 600 DEG C in atmosphere, then is passed through body at a temperature of 400 DEG C
Fraction is 10% hydrogen-argon-mixed reductase 12 h, and heating rate is 4 DEG C/min, you can copper/silica xerogels catalysis is obtained
Agent.
Embodiment 3：
(1) at room temperature, the eight water oxygen zirconium chlorides for weighing 7.4774g are added in 9mL absolute ethyl alcohols, are thoroughly mixed
Uniformly obtain mixed solution A；
(2) 0.8048g copper chloride dihydrates are weighed to be added in the deionized water of 5mL, is stirred until homogeneous and is obtained mixed solution
B；
(3) mixed solution B is dropwise slowly added in mixed solution A, is reacted under magnetic agitation after 10h, stop stirring,
Obtain mixed solution C；
(4) nitric acid for measuring 1.5mL is dropwise slowly added in mixed solution C, stirs 5min, stops stirring, is placed in room
Temperature is lower to wait gel；
(5) wet gel for obtaining step (4) is placed in 60 DEG C of vacuum drying chambers after aging 12h is dried 24h in atmosphere,
Then constant pressure and dry：First 4h is dried at 60 DEG C, then 80 DEG C are dried 2h, and at last 120 DEG C 2h is dried；
(6) blocks of solid for obtaining step (5) calcines 5h in 800 DEG C in atmosphere, then is passed through body at a temperature of 400 DEG C
Fraction is 10% hydrogen-argon-mixed reduction 4h, and heating rate is 4 DEG C/min, you can copper/silica xerogels catalysis is obtained
Agent.
Embodiment 4：
((1) at room temperature, the eight water oxygen zirconium chlorides for weighing 7.0376g are added in 9mL absolute ethyl alcohols, are sufficiently stirred for mixing
Conjunction uniformly obtains mixed solution A；
(2) the water copper acetates of 1.2567g mono- are weighed to be added in the deionized water of 5mL, is stirred until homogeneous and is obtained mixed solution
B；
(3) mixed solution B is dropwise slowly added in mixed solution A, is reacted under magnetic agitation after 10h, stop stirring,
Obtain mixed solution C；
(4) nitric acid for measuring 2mL is dropwise slowly added in mixed solution C, stirs 5min, stops stirring, is placed in room temperature
Lower wait gel；
(5) wet gel for obtaining step (4) is placed in 60 DEG C of vacuum drying chambers after aging 12h is dried 24h in atmosphere,
Then constant pressure and dry：First 4h is dried at 60 DEG C, then 80 DEG C are dried 2h, and at last 120 DEG C 2h is dried；
(6) blocks of solid for obtaining step (5) calcines 6h in 800 DEG C in atmosphere, then is passed through body at a temperature of 400 DEG C
Fraction is 5% hydrogen-argon-mixed reduction 4h, and heating rate is 4 DEG C/min, you can copper/silica xerogels catalysis is obtained
Agent.
Claims (9)
1. the preparation method of a kind of copper/silica xerogels catalyst, it is characterised in that comprise the steps：
(1) at room temperature, tetraethyl orthosilicate is added in absolute ethyl alcohol in proportion, is thoroughly mixed and uniformly mixed
Solution A；
(2) mantoquita is added in deionized water in proportion, is stirred until homogeneous and obtains mixed solution B；
(3) mixed solution B is dropwise slowly added in mixed solution A, is reacted under magnetic agitation after 8～10h, stop stirring,
Obtain mixed solution C；Dropwise it is slowly added to nitric acid in mixed solution C again, stirs 3～5min, stops stirring, in being placed in room temperature
Gel is waited, wet gel is obtained；
(4) wet gel for obtaining step (3) is aging in atmosphere, vacuum drying, and constant pressure and dry is calcined in air, then is passed through
Hydrogen-argon-mixed reduction, you can copper/silica xerogels catalyst is obtained.
2. the preparation method of the bar-shaped xerogel catalyst of a kind of copper/zirconium oxide according to claim 1, it is characterised in that
In step (1), the tetraethyl orthosilicate is 0.9898～1.2249 with the mass ratio of absolute ethyl alcohol.
3. the preparation method of the bar-shaped xerogel catalyst of a kind of copper/zirconium oxide according to claim 1, it is characterised in that
In step (2), the mantoquita is the one kind in copper nitrate, copper acetate or copper chloride, and the amount of the mantoquita is according to product copper/oxidation
The quality 10～20% of copper is calculated in zirconium xerogel.
4. the preparation method of the bar-shaped xerogel catalyst of a kind of copper/zirconium oxide according to claim 1, it is characterised in that
In step (3), in the mixed solution C, the volume ratio of the absolute ethyl alcohol in step (2) in deionized water and step (1) is 5:9
～15.
5. the preparation method of the bar-shaped xerogel catalyst of a kind of copper/zirconium oxide according to claim 1, it is characterised in that
In step (3), the nitric acid is 2 with the volume ratio of absolute ethyl alcohol in mixed solution A:9～18.
6. the preparation method of the bar-shaped xerogel catalyst of a kind of copper/zirconium oxide according to claim 1, it is characterised in that
In step (4), the ageing time is 10～12h, and vacuum drying temperature is 45～60 DEG C, and vacuum drying time is
24h；The step of constant pressure and dry is：First 4h is dried at 60 DEG C, then 80 DEG C are dried 2h, and at last 120 DEG C 2h is dried.
7. the preparation method of the bar-shaped xerogel catalyst of a kind of copper/zirconium oxide according to claim 1, it is characterised in that
In step (4), the temperature of the calcining is 600～800 DEG C, and the time of calcining is 4～6h.
8. the preparation method of the bar-shaped xerogel catalyst of a kind of copper/zirconium oxide according to claim 1, it is characterised in that
In step (4), the temperature of the hydrogen-argon-mixed reduction is 300～400 DEG C, and the recovery time is 2～4h；The hydrogen argon
The volume fraction 5%～10% of hydrogen in gaseous mixture.
9. the application of copper obtained in preparation method described in any one of claim 1～8/silica xerogels catalyst, its feature
It is that the copper/silica xerogels catalyst is prepared into p-aminophenol for being catalyzed paranitrophenol.
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| CN108380246A (en) * | 2018-01-23 | 2018-08-10 | 湖北大学 | A kind of Cu（0）The preparation method and applications of@ZIF-8 catalyst |
| CN111633217A (en) * | 2020-06-08 | 2020-09-08 | 内蒙古工业大学 | Metal composite nano material and preparation method and application thereof |
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| CN108380246A (en) * | 2018-01-23 | 2018-08-10 | 湖北大学 | A kind of Cu（0）The preparation method and applications of@ZIF-8 catalyst |
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Application publication date: 20170426 |