CN105664947B - A kind of NiAl-LDH/ γ-AlO (OH)/C composite catalysts and preparation method thereof - Google Patents
A kind of NiAl-LDH/ γ-AlO (OH)/C composite catalysts and preparation method thereof Download PDFInfo
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/007—Mixed salts
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- 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
- B01J23/74—Iron group metals
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/10—Heat treatment in the presence of water, e.g. steam
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Abstract
The invention discloses a kind of NiAl LDH/ γ AlO (OH)/C composite catalysts and preparation method thereof.The composite catalyst is using the inner shell membrane of birds, beasts and eggs as biological template, egg film is carbonized first and wraps up one layer of micro amorphous alumina, NiAl LDH/ γ AlO (the OH)/C composite catalysts for then in conjunction with hydro-thermal urea method being prepared for that there is unique fiber network structure on its surface.The present invention is easy to operate, egg film template source is extensive, and production cost is low, and pollution is few, the hydrotalcite good crystallinity of generation.
Description
Technical field
The present invention relates to the catalyst in terms of a kind of sewage disposal, and in particular to a kind of using egg film as the NiAl- of template
LDH/ γ-AlO (OH)/C composite catalysts and preparation method thereof.
Background technology
With progress of research, it is impossible to meet people to the multi-level of material, multi-functional, multidimensional for traditional material
The demand of degree, and it is very troublesome to remove to synthesize a kind of material of the microcosmic complexity oneself needed, is synthesized with biological template
Special pathway come the special and with unique properties material for preparing morphology controllable, structure be most directly, most efficient method.I
Described biological template method be one kind using natural biologic material as template, realize novel micro nanometer rice three using its unique texture
Tie up the porous inorganic material bionics method for preparation of scale.In biological template method, the micropore, mesoporous and macro in biological structure is transcribed
The target material of hole multilayer classifying porous structure, tempting foreground is shown in chemical catalysis, adsorbing separation, has been had
Many biomaterials are used as template, for example, microorganism, yeast, pollen, butterfly's wing etc..Multistage pore canal system
It can provide size different ducts simultaneously, promote the mass transfer of the gas phase or liquid phase in catalysis.
Shell membrane is divided into two layers：Periostracum（50–70 μm）It is one layer of opaque, structureless film, effect is avoided in egg
Tolerant moisture evaporation；Inner shell membrane（15 ~ 26 μm）, it is attached to the internal layer of periostracum, air can pass freely through this film.Inner shell membrane
It is tightly engaged into mostly with periostracum, is only detached in both blunt ends of egg and constitute gas chamber.The advantages of egg film is as biological template：（1）
With high-specific surface area, layering macroporous network structure.（2）Good water absorbing capacity.（3）Stability, ingredient are that protein is fine
Dimension, based on C and O.（4）It derives from a wealth of sources, it is cheap：Only in 2014, Chinese fresh egg yield was about 24,000,000 tons, if pressed
If eggshell quality is 10% calculation of egg quality, eggshell is about 2,400,000 tons, and egg film is about the 5% of eggshell quality, then egg film is 12
Ten thousand tons, not using egg film all thrown away as house refuse, certain injury is caused to environment.
Invention content
The purpose of the present invention is to provide a kind of NiAl-LDH/ γ-AlO (OH)/C composite catalysts and preparation method thereof.
The present invention uses following technical scheme：
A kind of NiAl-LDH/ γ-AlO (OH)/C composite catalysts, which is characterized in that it is made using egg film of biological template,
Active ingredient is NiAl-LDH nanometer rods, γ-AlO (OH) nanometer rods, amorphous carbon, amorphous alumina；The egg film is chicken
The inner shell membrane of the birds, beasts and eggs such as egg, duck's egg or goose egg.
The microstructure of the composite catalyst is the two-dimensional network structure that single fiber is woven into, the diameter of single fiber
It it is 1 ~ 1.4 μm, single fiber is by NiAl-LDH nanometer rods, γ-AlO (OH) nanometer rods, amorphous carbon, amorphous alumina structure
At.
A kind of preparation method of NiAl-LDH/ γ-AlO (OH)/C composite catalysts, which is characterized in that it includes following step
Suddenly：
（1）Egg film pre-processes：Inner shell membrane in egg film is removed to clean, 5 min of ultrasound in deionized water, washing and drying
For use；
（2）The immersion of egg film：The soluble salt solutions for preparing a certain concentration aluminium, the egg film handled well is put into solution and is soaked
Steep 8 h, 50oC is dried；
（3）Above-mentioned egg film is put into 450 in Muffle furnaceoC calcines 1 h, and the amorphous carbon for retaining egg film macro morphology is made
And amorphous alumina；
（4）By metal ion soluble-salt according to Ni2+With Al3+Molar ratio is 1:1 ~3:1 prepares mixing salt solution, to
0.3g steps are wherein added（3）Gained egg film and appropriate urea, it is 3 to make the molar ratio of urea and metal ion:1, then add again
Enter 60 mL distilled water, mixed liquor is transferred in reaction kettle, in 190oC reacts 18h；
（5）It gained sediment will be filtered after reaction with filter paper funnel, and be washed and filtered using deionized water, repeat two
It is secondary, by filtered solid 80oC is drying to obtain final catalyst prod.
The egg film is the inner shell membrane of the birds, beasts and eggs such as egg, duck's egg or goose egg.
The step（2）The soluble-salt of middle aluminium is Al (NO3)3Or AlCl3, the mol/L of a concentration of 0.05mol/L ~ 0.3.
The step（4）Middle Ni2+Soluble-salt is Ni (NO3)2Or NiCl2；The Al3+Soluble-salt is Al (NO3)3Or
AlCl3。
AlO (OH) has double-layer structure, is that Al-O is keyed the reticular structure to be formed inside layer, interlayer is formed by hydroxyl
Hydrogen bond be connected.The interface AlO (OH) energy is high, porosity is big, specific surface is big, good dispersion.AlO (OH) is 450~750oC
Between roasting can be prepared into γ-Al2O3, and the process has " memory effect ", gained γ-Al2O3It keeps and AlO (OH) forerunner
The consistent pattern of body；Have document report AlO (OH) can be used as adsorbent use, while may be used as catalyst carrier load Pd,
Au, Ru isoreactivity component are used for low temperature（120-145oC）Organic synthesis.
Layered double hydroxide (abbreviation LDHs), also known as hydrotalcite-based compound, including hydrotalcite and class neatly
Stone compound, it is made of two or more metallic element and the hydroxide with hydrotalcite laminar crystalline structure
Object.Hydrotalcite and houghite due to its exchangeability with unique structure and anion and its memory effect make it
Absorption, catalysis, pharmaceutical carrier etc. show good application prospect in fields.
The present invention is with egg film in order to prepare the NiAl-LDH with special appearance, high-specific surface area, using one kind
The method of biological template growth, this method are that egg film is carbonized first and wraps up one layer of Al on its surface2O3, then use urea water
The method for the hydrotalcite that hot method prepares high-specific surface area, is evenly distributed.
The beneficial effects of the invention are as follows：The present invention is using egg film as template growth NiAl-LDH, and NiAl-LDH is as catalyst
It is all demonstrated by good catalytic performance in fields such as ethanol decomposition, CO conversions, improves its specific surface area, Neng Gouti on this basis
For more activated centres, be conducive to improve its catalysis, in preparation process temperature, time can be very good to control, pass through adjusting
Different metal ratios obtains different layer structures, can regulate and control to the number and arrangement mode of interlayer anion, into
And controllable adjustment is carried out to its catalytic performance, hydro-thermal method one-step synthesis is easy to operate, at low cost, and pollution is few, the NiAl-LDH of generation
Good crystallinity.
Description of the drawings
Fig. 1（a）For step of the present invention（3）The unformed Al of gained after calcining2O3The XRD diagram of/C（b）It is urged for final product is compound
The XRD diagram of agent NiAl-LDH/ γ-AlO (OH)/C；
Fig. 2 (a) is that the macrograph (b) of the made egg film of step 2 of the present invention is the high power SEM figures of egg film；
Fig. 3（a）~（c）For the low power and high power SEM figures of NiAl-LDH/ γ-AlO (OH)/C that the present invention synthesizes；（d）For
NiAl-LDH/ γ-the AlO (OH) of synthesis/C composite catalyst macrographs.
Specific implementation mode
Technical scheme of the present invention and effect are further described with reference to embodiment.But it is used specific
Method, formula and explanation are not limitation of the present invention.
Embodiment 1
A kind of NiAl-LDH/ γ-AlO (OH)/C composite catalysts, preparation method are as follows：
（1）It is for use that inner shell membrane in egg film is removed into 5 min of ultrasound, washing and drying in deionized water；
（2）Prepare the Al (NO of 0.05 mol/L of 100 mL3)3The egg film handled well is put into solution and impregnates 8 by solution
H, 50oC is dried.
（3）Above-mentioned egg film is put into 450 in Muffle furnaceoC calcines 1 h, obtains the unformed Al of calcined product2O3/C。
（4）Weigh 1 mmol Ni (NO3)2·9H2O and 0. 5 mmol Al (NO3)3·9H2O, 0.3 g steps（3）Institute
Egg film, 4.5 mmol urea are obtained, is added in 60 mL distilled water, is put into reaction kettle, in 190 after mixingoC places 18 h.
（5）Sediment filter paper funnel is filtered, is washed and is filtered using deionized water, is repeated twice, it will be filtered solid
Body is 80oC is drying to obtain final catalyst product.
Embodiment 2
A kind of NiAl-LDH/ γ-AlO (OH)/C composite catalysts, preparation method are as follows：
（1）It is for use that inner shell membrane in egg film is removed into 5 min of ultrasound, washing and drying in deionized water；
（2）Prepare the AlCl of 0.05 mol/L of 100 mL3The egg film handled well is put into solution and impregnates 8 by solution
H, 50oC is dried.
（3）Above-mentioned egg film is put into 450 in Muffle furnaceoC calcines 1 h, obtains the unformed Al of calcined product2O3/C。
（4）Weigh 1 mmol NiCl2·6H2O and 0.5 mmol AlCl3·6H2O, 0.3 g steps（3）Gained egg film,
4.5 mmol urea are added in 60 mL distilled water after mixing, are put into reaction kettle, in 190oC places 18 h.
（5）Sediment filter paper funnel is filtered, is washed and is filtered using deionized water, is repeated twice, it will be filtered solid
Body is 800oC is drying to obtain final catalyst product.
Embodiment 3
A kind of NiAl-LDH/ γ-AlO (OH)/C composite catalysts, preparation method are as follows：
（1）It is for use that inner shell membrane in egg film is removed into 5 min of ultrasound, washing and drying in deionized water；
（2）Prepare the Al (NO of 0.05 mol/L of 100 mL3)3The egg film handled well is put into solution and impregnates 8 by solution
H, 50oC is dried.
（3）Above-mentioned egg film is put into 450 in Muffle furnaceoC calcines 1 h, obtains the unformed Al of calcined product2O3/C。
（4）Weigh 1.5 mmol Ni (NO3)2·9H2O and 0. 5 mmol Al (NO3)3·9H2O, 0.3 g steps（3）
Gained egg film, 6 mmol urea, are added in 60 mL distilled water after mixing, are put into reaction kettle, in 190oC places 18 h.
（5）Sediment filter paper funnel is filtered, is washed and is filtered using deionized water, is repeated twice, it will be filtered solid
Body is 80oC is drying to obtain final catalyst product.
Embodiment 4
A kind of NiAl-LDH/ γ-AlO (OH)/C composite catalysts, preparation method are as follows：
（1）It is for use that inner shell membrane in egg film is removed into 5 min of ultrasound, washing and drying in deionized water；
（2）3 solution of Al (NO3) for preparing 0.05 mol/L of 100 mL, the egg film handled well is put into solution and is impregnated
8 h, 50oC is dried.
（3）Above-mentioned egg film is put into 450 oC in Muffle furnace and calcines 1 h, obtains the unformed Al of calcined product2O3/C。
（4）Weigh 1 mmol Ni (NO3)2•9H2O and 1 mmol Al (NO3)3•9H2O, 0.3 g steps（3）Gained egg
Film, 6 mmol urea, are added in 60 mL distilled water after mixing, are put into reaction kettle, in 190oC places 18 h.
（5）Sediment filter paper funnel is filtered, is washed and is filtered using deionized water, is repeated twice, it will be filtered solid
Body is 80oC is drying to obtain final catalyst product.
Embodiment 5
A kind of NiAl-LDH/ γ-AlO (OH)/C composite catalysts, preparation method are as follows：
（1）It is for use that inner shell membrane in egg film is removed into 5 min of ultrasound, washing and drying in deionized water；
（2）Prepare 0.1 mol/L of 100 mL（Or 0.3 mol/L）Al (NO3)3Solution puts the egg film handled well
Enter and impregnates 8 h in solution, 50oC is dried.
（3）Above-mentioned egg film is put into 450 in Muffle furnaceoC calcines 1 h, obtains the unformed Al of calcined product2O3/C。
（4）Weigh 1 mmol Ni (NO3)2·9H2O and 0. 5 mmol Al (NO3)3·9H2O, 0.3 g steps（3）Institute
Egg film, 4.5 mmol urea are obtained, is added in 60 mL distilled water, is put into reaction kettle, in 190 after mixingoC places 18 h.
（5）Sediment filter paper funnel is filtered, is washed and is filtered using deionized water, is repeated twice, it will be filtered solid
Body is 80oC is drying to obtain final catalyst product.
To further determine that the design feature of composite catalyst of the invention, to phase made in embodiment in the present invention 1
It closes product and has carried out XRD and SEM researchs.Concrete outcome is as shown in Figs. 1-3.(a) is gained after step 3 of the present invention calcining in Fig. 1
Unformed Al2O3The XRD diagram of/C；As can be seen from the figure calcined product is Al2O3And C, Al2O3The very disperse of its diffraction maximum, says
Bright Al2O3It is amorphous, its thermal stability is good, large specific surface area, LDH is prepared using it as carrier is conducive to improve it and urge
Change performance；Fig. 1 (b) is the XRD diagram of final product composite catalyst NiAl-LDH/ γ-AlO (OH)/C, can by comparing PDF cards
There are NiAl-LDH and γ-AlO (OH) with the final product found out.Fig. 2 (a) is the macrograph of the made egg film of step 2； (b)
For the high power SEM figures of the made egg film of step 2；From Figure 2 it can be seen that egg film be layering macroporous network structure, individual fiber diameter be 1 ~
1.4 μm or so.In Fig. 3（a）~（c）For the low power and high power SEM of NiAl-LDH/ γ-AlO (OH)/C composite catalysts of synthesis
Figure；（d）For the macrograph of NiAl-LDH/ γ-AlO (OH)/C composite catalysts of synthesis.As can be seen from Figure 3 in egg film
Portion's fiber equably grows NiAl-LDH and γ-AlO (OH) nanometer rods.
Claims (5)
1. a kind of NiAl-LDH/ γ-AlO (OH)/C composite catalysts, which is characterized in that used using egg film as made of biological template
In the composite catalyst that ethanol decomposition or CO are converted, active ingredient is NiAl-LDH nanometer rods, γ-AlO (OH) nanometer rods, nothing
Shape carbon, amorphous alumina；The preparation method of NiAl-LDH/ γ-AlO (the OH)/C composite catalysts is as follows：
（1）Egg film pre-processes：Inner shell membrane in egg film is removed clean, 5 min of ultrasound, washing and drying wait in deionized water
With；
（2）The immersion of egg film：The soluble salt solutions for preparing a certain concentration aluminium, the egg film handled well is put into solution and impregnates 8
H, 50oC is dried；
（3）Above-mentioned egg film is put into 450 in Muffle furnaceoC calcines 1 h, and the amorphous carbon and nothing for retaining egg film macro morphology is made
Shape aluminium oxide；
（4）By metal ion soluble-salt according to Ni2+With Al3+Molar ratio is 1:1 ~3:1 prepares mixing salt solution, adds thereto
Enter 0.3g steps（3）Gained egg film and appropriate urea, it is 3 to make the molar ratio of urea and metal ion:1, then add 60 mL
Mixed liquor is transferred in reaction kettle by distilled water, in 190oC reacts 18h；
（5）It gained sediment will be filtered after reaction with filter paper funnel, and be washed and filtered using deionized water, is repeated twice, it will
Filtered solid is 80oC is drying to obtain final catalyst prod.
2. NiAl-LDH/ γ-AlO (OH)/C composite catalysts according to claim 1, which is characterized in that described compound
The microstructure of catalyst is the two-dimensional network structure that single fiber is woven into, a diameter of 1 ~ 1.4 μm of single fiber, single
Fiber is made of NiAl-LDH nanometer rods, γ-AlO (OH) nanometer rods, amorphous carbon, amorphous alumina.
3. NiAl-LDH/ γ-AlO (OH)/C composite catalysts according to claim 1, which is characterized in that the egg film
For the inner shell membrane of egg, duck's egg or goose egg.
4. NiAl-LDH/ γ-AlO (OH)/C composite catalysts according to claim 1, which is characterized in that the step
（2）The soluble-salt of middle aluminium is Al (NO3)3Or AlCl3, the mol/L of a concentration of 0.05mol/L ~ 0.3.
5. NiAl-LDH/ γ-AlO (OH)/C composite catalysts according to claim 1, which is characterized in that the step
（4）Middle Ni2+Soluble-salt is Ni (NO3)2Or NiCl2；The Al3+Soluble-salt is Al (NO3)3Or AlCl3。
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