CN104709932B - Gama-alumina nano material and the preparation method of nickel/gamma-alumina catalyst - Google Patents
Gama-alumina nano material and the preparation method of nickel/gamma-alumina catalyst Download PDFInfo
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- CN104709932B CN104709932B CN201510080468.0A CN201510080468A CN104709932B CN 104709932 B CN104709932 B CN 104709932B CN 201510080468 A CN201510080468 A CN 201510080468A CN 104709932 B CN104709932 B CN 104709932B
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Abstract
The invention discloses the synthetic method of a kind of gamma-alumina nano material: under room temperature, alum is added in deionized water with urea, cool down after hydro-thermal reaction, be centrifuged and washing precipitate；By dried hydrothermal product calcine after gamma-alumina nano material.The gamma-alumina that the method is prepared into has higher specific surface area and certain pore structure.Present invention also offers a kind of gamma-alumina nano material to use above-mentioned synthetic method to obtain as raw material, the method preparing nickel/gamma-alumina catalyst: gamma-alumina nano material be impregnated in the nickel salt solution of debita spissitudo, magnetic agitation is until solvent evaporates；Collect dried impregnation product grind into powder, heating reduction in reducing atmosphere, nickel/gamma-alumina catalyst.This catalyst can be used for catalytic methane dry method reforming reaction, has higher methane conversion, at high temperature carries out long-time catalytic reaction and remains to keep excellent stability and anti-carbon performance.
Description
Technical field
The present invention relates to the preparation of inorganic nano material, be specifically related to the synthesis of a kind of gama-alumina nano material and with this
Material is the method that nickel/gamma-alumina catalyst prepared by raw material.
Background technology
Nano aluminium oxide, owing to having the nano effects such as skin effect, quantum effect and bulk effect, is widely used
In every field.Nano aluminium oxide is little due to size, and its surface atom proportion is the highest and specific surface area big, high ratio
The high surface energy that surface area and Atomic coordinate bring the most entirely causes surface-active position to increase, it is easy to adsorbed gas or with
Gas reaction around；Secondly, and along with the reduction of particle diameter, nano alumina surface smooth degree is deteriorated, defines
Scraggly atomic steps, adds the contact surface of chemical reaction, therefore, the catalysis activity of nano aluminium oxide and choosing
Selecting property is much higher than traditional aluminium oxide catalyst, can be used as PETROLEUM PROCESSING, gas purification, catalysis burning, macromolecule
The catalyst of the reactions such as synthesis or carrier.
But, the preparation of nano aluminium oxide predominantly stays in laboratory stage the most at home, domestic not yet realizes industry
Metaplasia is produced, and one of chief reason is the nano aluminium oxide particle diameter wider distribution that most preparation method obtains, and
Preparation process is strict, poor repeatability, it is impossible to be widely applied.Additionally, during as carrier, nano aluminium oxide is deposited
The problem that at high temperature catalysis activity reduces.This is due at high temperature, due to the long-pending reduction of nano alumina surface, hole
Hold and shrink so that the catalyst blockage that loaded, come off, thus cause the activity decrease of catalyst.Therefore, exploitation
Preparation technology is simple, equipment requirement is relatively low, suitable for mass production and excellent performance gama-alumina nano material is modern
One of major tasks of rear research.
Therefore, those skilled in the art is devoted to develop a kind of raw material and is easy to get and gama-alumina nanometer simple to operate
The preparation method of material；Meanwhile, those skilled in the art also with the gama-alumina nano material that is prepared into as raw material,
Develop a kind of feasible method preparing nickel/gamma-alumina catalyst.
Summary of the invention
Because the drawbacks described above of prior art, the technical problem to be solved is to provide a kind of gama-alumina and receives
The preparation method of rice material；Meanwhile, the present invention is with the gama-alumina nano material that is prepared into as raw material, it is provided that a kind of
The feasible method preparing nickel/gamma-alumina catalyst, this catalyst is applied to methane dry method reforming reaction.
The invention provides a kind of gama-alumina preparation method of nano material, comprise the steps:
Step one, under room temperature, adds alum in deionized water with urea, and magnetic agitation makes solid dissolve in 10 minutes；
Gained solution is transferred to carry out in reactor hydro-thermal reaction；After hydro-thermal reaction terminates, the reactant of gained is cooled to
20～30 DEG C, the sediment after centrifugation cooling, replace washing precipitate by absolute ethyl alcohol and deionized water,
It is vacuum dried at 60 DEG C, obtains AlOOH presoma；
Step 2, is placed in AlOOH presoma in corundum porcelain boat, calcines in atmosphere, i.e. can get gama-alumina
Nano material.
Preferably, in step one, alum and urea weigh in molar ratio, and the urea of addition and the mol ratio of alum are
8:1～1:1, overall solution volume is the 1/2～3/4 of reactor volume.
Preferably, in step one, the temperature of hydro-thermal reaction is 140～200 DEG C, and the reaction time is 10～20 hours.
Preferably, in step 2, calcining heat 400～900 DEG C, calcination time is 2～10 hours.
Present invention also offers and synthesize, according to said method, the gama-alumina nano material obtained, it is characterised in that: outward appearance
For the multilevel hierarchy nano-hollow ball of sunflower shape, its surface is that alumina nano-sheet is connected with each other and assembles.
Preferably, a diameter of 10～50 μm of gama-alumina hollow ball, shell thickness is 50～500nm, cavity diameter
For: 10～50 μm.
Further, gama-alumina applications to nanostructures of the present invention is: as catalyst or catalyst carrier.
Present invention also offers a kind of gama-alumina nano material using above-mentioned synthetic method to obtain is raw material, prepares nickel
The method of/gamma-alumina catalyst, specifically comprises the following steps that
Step one, impregnated in the nickel salt solution of debita spissitudo by gama-alumina nano material, while heating, and magnetic force
Stirring is until solvent evaporates；
Step 2, collects dried impregnation product grind into powder, is placed in corundum porcelain boat and heats up in reducing atmosphere
Reduction, nickel/gamma-alumina catalyst；
Preferably, in step one, nickel salt includes anhydrous or nitric hydrate nickel, nickel sulfate, nickel chloride and nickel acetate, molten
Agent includes water, ethanol and other organic or inorganic solution.
Preferably, in step one, nickel salt and gama-alumina nano material example in molar ratio weigh, the nickel salt of addition and γ
The mol ratio of-aluminum oxide is 2:1～1:5.
Preferably, in step one, magnetic agitation temperature is room temperature or 20～80 DEG C, and heating means are water-bath or oil bath.
Preferably, in step 2, reducing atmosphere includes the hydrogen-argon-mixed of hydrogen and various concentration.
Preferably, in step 2, reduction temperature is 400～800 DEG C, and the recovery time is 2～8 hours.
The present invention prepares gama-alumina nano material by hydro-thermal method and follow-up calcination process, and advantage is as follows:
1. the raw material of this preparation method is alum and urea, is common industrial production raw material, cheap is easy to get；
This method technique is simple, low for equipment requirements, and building-up process is entirely without pollution, environmental friendliness, it is adaptable to industrial production；
2. the gama-alumina being prepared into is nano material, has higher specific surface area and certain pore structure, available
Make catalyst or catalyst carrier.
The present invention has prepared nickel/gamma-alumina catalyst also by infusion process, and this catalyst is applied to methane dry method
There is during reforming reaction higher methane conversion, at high temperature carry out long-time catalytic reaction and remain to keep excellent steady
Qualitative and anti-carbon performance.
Below with reference to accompanying drawing, the technique effect of design, concrete structure and the generation of the present invention is described further, with
It is fully understood from the purpose of the present invention, feature and effect.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of the gama-alumina nano material of preferred embodiment 1 acquisition of the present invention；
Fig. 2 is the SEM electron microscopic picture of gama-alumina nano material shown in Fig. 1；
Fig. 3 is the TEM electron microscopic picture of gama-alumina nano material shown in Fig. 1；
Fig. 4 is the nitrogen adsorption-desorption curve of gama-alumina nano material shown in Fig. 1；
Fig. 5 is the graph of pore diameter distribution of gama-alumina nano material shown in Fig. 1；
Fig. 6 is the TEM electron microscopic picture of nickel/gamma-alumina catalyst；
Fig. 7 is the methane conversion curve at different temperatures of nickel/gamma-alumina catalyst shown in Fig. 6；
Fig. 8 is that the methane conversion at 750 DEG C of nickel/gamma-alumina catalyst shown in Fig. 6 is bent with the relation in reaction time
Line；
Fig. 9 be nickel/gamma-alumina catalyst shown in Fig. 6 at 750 DEG C through 50 hours methane dry method reforming reactions
After TEM electron microscopic picture.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate this
Bright rather than limit the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, ability
The present invention can be made various changes or modifications by field technique personnel, and these equivalent form of values fall within right appended by the application equally
Claim limited range.
Embodiment 1
(1) synthesis of gama-alumina nano material
At room temperature, by 0.8000g alum and 0.4000g urea, add in 25ml deionized water, add magnetic force and stir
Mixing sub-stirring makes solid be completely dissolved in 10 minutes；Transfer to this solution, in 50ml reactor, carry out at 180 DEG C
Hydro-thermal reaction, during reaction a length of 15 hours.After hydro-thermal reaction terminates to be down to room temperature, reacted product is taken out, from
Heart sediment separate out, with absolute ethyl alcohol and deionized water alternately washing, is vacuum dried at 60 DEG C, obtains AlOOH
Presoma.Being placed in corundum porcelain boat by AlOOH presoma, be fired to 800 DEG C in atmosphere, calcination time is 5
Hour, i.e. can get gama-alumina nano material.
(2) preparation of nickel/gamma-alumina catalyst
The gama-alumina nano material being prepared into by 1.075g impregnated in the Ni (NO that 100ml concentration is 0.1M3)2·
6H2In O solution, at room temperature magnetic agitation is until solvent evaporates；Collect dried impregnation product grind into powder,
It is placed in corundum porcelain boat at H2Being warming up to 700 DEG C in/Ar gaseous mixture, the recovery time is 2 hours, nickel/γ-
Aluminium oxide catalyst；
Fig. 1 is the X-ray diffractogram of gained sample, as can be seen from Figure 1 in 2 θ=19.4 °, 31.9 °, 37.6 °,
39.5 °, 45.9 °, 60.9 °, 67.0 ° and 85.0 ° have obvious Al2O3Peak position, and do not observe other
What peak position, this proves that all of aluminium element exists with gama-alumina structure, and does not contains any impurity phase.
Fig. 2 is the SEM electron microscopic picture of gained sample, it is evident that this material is chondritic from Fig. 2, and table
Face is assembled by alumina nano-sheet, there is obvious hole.The diameter distribution of ball is about 2～4 μm.
Fig. 3 is the TEM electron microscopic picture of above-mentioned gama-alumina nano material, can find out that this sample is from Fig. 3
In the hollow-core construction of sunflower shape, surface is assembled by alumina nano-sheet, and the diameter of hollow ball is about 3～3.5 μm,
Cavity inside diameter is about 2～3 μm, and wall thickness is about 300～500nm.
Fig. 4, Fig. 5 are nitrogen adsorption-desorption curve and the graph of pore diameter distribution of above-mentioned gama-alumina nano material, this sample
Specific surface area be up to 104.1m2/ g, pore-size distribution is 4～4.5nm.
Fig. 6 is the TEM electron microscopic picture of nickel/gamma-alumina catalyst, as can be seen from Figure 6 γ after dipping
-aluminum oxide still maintains original pattern, and nickel metallic particles is supported on alumina nano-sheet surface, and metallic particles more divides
Dissipate, obvious clustering phenomena does not occur.
Fig. 7 is this catalyst methane conversion curve at different temperatures, as can be seen from Figure 7 this catalyst
Catalysis activity with temperature rises and increases, and at high temperature remains to keep catalysis activity, and conversion ratio is higher.
Fig. 8 be this catalyst at 750 DEG C during catalytic methane dry method reforming reaction, the time dependent curve of conversion ratio.
This sample is at 750 DEG C during catalytic reaction, and methane conversion fluctuates 75%；When experienced by 50 hours long
Between after pyroreaction, the catalysis activity of this catalyst does not decline, and this illustrates the stability that this sample is excellent
With anti-caking power.
Fig. 9 is this TEM electron microscopic picture after 50 hours methane dry method reforming reactions at 750 DEG C, from Fig. 9
In can find out that this sample experiences metallic after long-time pyroreaction and the phenomenon of sintering do not occurs, the most instead
Only observed the formation of small carbon filament in sample after should in local, this illustrates that this sample has excellent anti-sintering
Ability and certain anti-carbon performance.
Embodiment 2
(1) synthesis of gama-alumina nano material
At room temperature, by 0.8000g alum and 0.1012g urea, add in 25ml deionized water, add magnetic force and stir
Mixing sub-stirring makes solid be completely dissolved in 10 minutes；Transfer to this solution, in 50ml reactor, carry out at 180 DEG C
Hydro-thermal reaction, during reaction a length of 15 hours.After hydro-thermal reaction terminates to be down to room temperature, reacted product is taken out, from
Heart sediment separate out, with absolute ethyl alcohol and deionized water alternately washing, is vacuum dried at 60 DEG C, obtains AlOOH
Presoma.Being placed in corundum porcelain boat by AlOOH presoma, be fired to 800 DEG C in atmosphere, calcination time is 5
Hour, i.e. can get gama-alumina nano material.
(2) preparation of nickel/gamma-alumina catalyst
The gama-alumina nano material being prepared into by 0.510g impregnated in the Ni (NO that 100ml concentration is 0.1M3)2·
6H2In O solution, at room temperature magnetic agitation is until solvent evaporates；Collect dried impregnation product grind into powder,
It is placed in corundum porcelain boat at H2Being warming up to 700 DEG C in/Ar gaseous mixture, the recovery time is 2 hours, nickel/γ-
Aluminium oxide catalyst；
Embodiment 3
(1) synthesis of gama-alumina nano material
At room temperature, by 0.8000g alum and 0.8101g urea, add in 25ml deionized water, add magnetic force and stir
Mixing sub-stirring makes solid be completely dissolved in 10 minutes；Transfer to this solution, in 50ml reactor, carry out at 180 DEG C
Hydro-thermal reaction, during reaction a length of 15 hours.After hydro-thermal reaction terminates to be down to room temperature, reacted product is taken out, from
Heart sediment separate out, with absolute ethyl alcohol and deionized water alternately washing, is vacuum dried at 60 DEG C, obtains AlOOH
Presoma.Being placed in corundum porcelain boat by AlOOH presoma, be fired to 800 DEG C in atmosphere, calcination time is 5
Hour, i.e. can get gama-alumina nano material.
(2) preparation of nickel/gamma-alumina catalyst
The gama-alumina nano material being prepared into by 5.098g impregnated in the Ni (NO that 100ml concentration is 0.1M3)2·
6H2In O solution, at room temperature magnetic agitation is until solvent evaporates；Collect dried impregnation product grind into powder,
It is placed in corundum porcelain boat at H2Being warming up to 700 DEG C in/Ar gaseous mixture, the recovery time is 2 hours, nickel/γ-
Aluminium oxide catalyst；
Embodiment 4
(1) synthesis of gama-alumina nano material
At room temperature, by 0.8000g alum and 0.4000g urea, add in 25ml deionized water, add magnetic force and stir
Mixing sub-stirring makes solid be completely dissolved in 10 minutes；Transfer to this solution, in 50ml reactor, carry out at 140 DEG C
Hydro-thermal reaction, during reaction a length of 20 hours.After hydro-thermal reaction terminates to be down to room temperature, reacted product is taken out, from
Heart sediment separate out, with absolute ethyl alcohol and deionized water alternately washing, is vacuum dried at 60 DEG C, obtains AlOOH
Presoma.Being placed in corundum porcelain boat by AlOOH presoma, be fired to 400 DEG C in atmosphere, calcination time is 10
Hour, i.e. can get gama-alumina nano material.
(2) preparation of nickel/gamma-alumina catalyst
The gama-alumina nano material being prepared into by 1.075g impregnated in the Ni (NO that 100ml concentration is 0.1M3)2·
6H2In O solution, at room temperature magnetic agitation is until solvent evaporates；Collect dried impregnation product grind into powder,
It is placed in corundum porcelain boat at H2Being warming up to 400 DEG C in/Ar gaseous mixture, the recovery time is 2 hours, nickel/γ-
Aluminium oxide catalyst；
Embodiment 5
(1) synthesis of gama-alumina nano material
At room temperature, by 0.8000g alum and 0.4000g urea, add in 25ml deionized water, add magnetic force and stir
Mixing sub-stirring makes solid be completely dissolved in 10 minutes；Transfer to this solution, in 50ml reactor, carry out at 200 DEG C
Hydro-thermal reaction, during reaction a length of 10 hours.After hydro-thermal reaction terminates to be down to room temperature, reacted product is taken out, from
Heart sediment separate out, with absolute ethyl alcohol and deionized water alternately washing, is vacuum dried at 60 DEG C, obtains AlOOH
Presoma.Being placed in corundum porcelain boat by AlOOH presoma, be fired to 900 DEG C in atmosphere, calcination time is 2
Hour, i.e. can get gama-alumina nano material.
(2) preparation of nickel/gamma-alumina catalyst
The gama-alumina nano material being prepared into by 1.075g impregnated in the Ni (NO that 100ml concentration is 0.1M3)2·
6H2In O solution, at room temperature magnetic agitation is until solvent evaporates；Collect dried impregnation product grind into powder,
It is placed in corundum porcelain boat at H2Being warming up to 800 DEG C in/Ar gaseous mixture, the recovery time is 8 hours, nickel/γ-
Aluminium oxide catalyst；
Embodiment 6
(1) synthesis of gama-alumina nano material
At room temperature, by 0.8000g alum and 0.4000g urea, add in 25ml deionized water, add magnetic force and stir
Mixing sub-stirring makes solid be completely dissolved in 10 minutes；Transfer to this solution, in 50ml reactor, carry out at 200 DEG C
Hydro-thermal reaction, during reaction a length of 6 hours.After hydro-thermal reaction terminates to be down to room temperature, reacted product is taken out, from
Heart sediment separate out, with absolute ethyl alcohol and deionized water alternately washing, is vacuum dried at 60 DEG C, obtains AlOOH
Presoma.Being placed in corundum porcelain boat by AlOOH presoma, be fired to 400 DEG C in atmosphere, calcination time is 10
Hour, i.e. can get gama-alumina nano material.
(2) preparation of nickel/gamma-alumina catalyst
The gama-alumina nano material being prepared into by 1.075g impregnated in the Ni (NO that 100ml concentration is 0.1M3)2·
6H2In O solution, at room temperature magnetic agitation is until solvent evaporates；Collect dried impregnation product grind into powder,
It is placed in corundum porcelain boat at H2Being warming up to 400 DEG C in/Ar gaseous mixture, the recovery time is 8 hours, nickel/γ-
Aluminium oxide catalyst；
The preferred embodiment of the present invention described in detail above.Should be appreciated that those of ordinary skill in the art without
Need creative work just can make many modifications and variations according to the design of the present invention.Therefore, all in the art
Technical staff the most on the basis of existing technology can by logical analysis, reasoning, or a limited experiment
With the technical scheme obtained, all should be in the protection domain being defined in the patent claims.
Claims (9)
1. the preparation method of nickel/gamma-alumina catalyst, it is characterised in that use gama-alumina nano material is
Raw material, specifically comprises the following steps that
Step one, impregnated in nickel salt solution by described gama-alumina nano material, and heating uses magnetic agitation to mix simultaneously
Closing solution until solvent evaporation, the temperature of described magnetic agitation is 20～80 DEG C, and the method for described heating is water-bath
Or oil bath；
Step 2, collects dried impregnation product grind into powder, is placed in corundum porcelain boat and heats up in reducing atmosphere
Reduction, described nickel/gamma-alumina catalyst；
Wherein, the preparation method of described gama-alumina nano material comprises the steps:
Step 3, under room temperature, adds alum in deionized water with urea, and magnetic agitation makes solid in 10 minutes
Dissolving, wherein, described alum and described urea weigh in molar ratio, the described urea of addition and described alum
Mol ratio is 8:1～1:1；Gained solution is transferred to carry out in reactor hydro-thermal reaction, and wherein, described solution is total
Volume is the 1/2～3/4 of described reactor volume；After described hydro-thermal reaction terminates, the reactant of gained is cooled to
20～30 DEG C, the sediment after centrifugation cooling, alternately washs described precipitation by absolute ethyl alcohol and deionized water
Thing, is vacuum dried at 60 DEG C, obtains AlOOH presoma；
Step 4, is placed in described AlOOH presoma in corundum porcelain boat, calcines in atmosphere, the most available
Gama-alumina nano material.
2. the preparation method of nickel/gamma-alumina catalyst as claimed in claim 1, it is characterised in that described step
In one, described nickel salt includes anhydrous or nitric hydrate nickel, nickel sulfate, nickel chloride and nickel acetate, described solvent bag
Include water, ethanol and other organic or inorganic solution.
3. the preparation method of nickel/gamma-alumina catalyst as claimed in claim 1, it is characterised in that described step
In one, described nickel salt and described gama-alumina nano material example in molar ratio weigh, the described nickel salt of addition and institute
The mol ratio stating gama-alumina is 2:1～1:5.
4. the preparation method of nickel/gamma-alumina catalyst as claimed in claim 1, it is characterised in that described step
In two, described reducing atmosphere includes the hydrogen-argon-mixed of hydrogen and various concentration, and the temperature of described reduction is
400～800 DEG C, the time of described reduction is 2～8 hours.
5. the preparation method of nickel/gamma-alumina catalyst as claimed in claim 1, it is characterised in that described step
In three, the temperature of described hydro-thermal reaction is 140～200 DEG C, and the reaction time of described hydro-thermal reaction is 10～20 little
Time.
6. the preparation method of nickel/gamma-alumina catalyst as claimed in claim 1, it is characterised in that described step
In four, the temperature of described calcining is 400～900 DEG C, and the time of described calcining is 2～10 hours.
7. the preparation method of nickel/gamma-alumina catalyst as claimed in claim 1, it is characterised in that described γ-
Aluminum oxide is the multilevel hierarchy nano-hollow ball of sunflower shape, and the surface of described nano-hollow ball is aluminium oxide nano
Sheet is connected with each other and assembles.
8. the preparation method of nickel/gamma-alumina catalyst as claimed in claim 7, it is characterised in that described γ-
Aluminum oxide is hollow ball, and a diameter of 10～50 μm of described hollow ball, the shell thickness of described hollow ball is
50～500nm, the cavity diameter of described hollow ball is 10～50 μm.
9. the preparation method of nickel/gamma-alumina catalyst as claimed in claim 7, it is characterised in that described γ-
Aluminium oxide nano material is used as catalyst or catalyst carrier.
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