CN104437500B - A kind of montmorillonite-base metal nickel nano piece catalyst and its preparation method and application - Google Patents
A kind of montmorillonite-base metal nickel nano piece catalyst and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of montmorillonite-base metal nickel nano piece catalyst and its preparation method and application, belong to chemical technology field.The catalyst carrier is montmorillonite, and active component is metallic nickel, and nickel quality is 5 30wt% of catalyst gross mass, and its preparation method is：Montmorillonite is thoroughly mixed with nickel salt, urea and water, it is the aqueous solution of individual layer montmorillonite nano piece to disperse to obtain being completely exfoliated by ultrasonic wave added, individual layer montmorillonite nano piece surface with the chemical liquid deposition precipitation method in the aqueous solution is scattered in introduces the homogeneous nickel species of distribution, and montmorillonite-base metal nickel nano piece catalyst is obtained through high temperature reduction.Montmorillonite-base metal nickel nano piece catalyst of the present invention has catalysis activity very high to aromatic compound hydrogenation reaction, while the method for preparing catalyst is simple, with low cost, is well suited for industrialized production.
Description
Technical field
The invention belongs to chemical technology field, and in particular to a kind of montmorillonite-base metal nickel nano piece catalyst, its ultrasound
The chemical liquid deposition of aid dispersion-precipitation preparation method and its application in terms of aromatic compound catalytic hydrogenation.
Background technology
Two-dimensional structure catalysis material with molecular sieve nanometer sheet as representative spreads because significantly shortening the mass transfer of reactant-product
Path, excellent catalytic performance is shown in numerous reactions more particularly, to bulky molecular catalysis.Therefore, New Two Dimensional structure is urged
The preparation and application study for changing material get more and more people's extensive concerning.Two-dimentional catalysis material generally has two building modes：One
Bar is the synthetic route of " bottom up " (" Bottom-up "), from the primary structure unitses of ZSM-5 molecular sieve, by spy
Determine the ZSM-5 nanometer sheets that dual function surface activating agent guide effect is directly synthesized be it is the most typical represent (Nature, 2009,
461:246-249.).The route has the complicated especially specific dual function surface activating agent of relatively costly, preparation process needs experiment
The deficiencies such as room self-control, it is difficult to realize batch production, be subject to certain restrictions in actual applications.Article 2 is " top down "
The structure route of (" Top-down "), i.e. post treatment method, to the precursor with layer structure such as lamellar zeolite, layered bi-metal
Hydroxide (LDHs) etc. carries out the treatment such as Delamination and forms ultra-thin molecular sieve (Chem.Rev., 2014,114 (9)：4807-
4837.) or LDHs nanometer sheets (catalysis journal, 2013,34 (1):225-234.) two-dimentional catalysis material.Post treatment method has cost
It is low, simple to operate and the advantages of large-scale production can be realized, but the extent of exfoliation of lamellar zeolite is often difficult to control to
(J.Am.Chem.Soc.,2011,133:3288-3291.Chem.Mater.,2011,23:5404-5408.), peel off
Generally there is (Angew.Chem.Int.Ed., 2011,50 in the form of colloidal solution in LDHs nanometer sheets:9171-9176.), limit
Its range of application is made.
Montmorillonite (MMT) is layer structure clay mineral, and its crystal structure is in 2 layers of 1 layer of silicon-oxy tetrahedron sandwich
Alumina octahedral, composition 2:1 phyllosilicate crystalline texture, tetrahedron is connected with octahedron by common oxygen atom, is formed
Thickness about 1nm, length and width are about 100nm, and the quasi- Three-dimensional wafer of high-sequential is the natural process factory of nano particle, when montmorillonite contains
Its layer structure can be even fully exfoliated as single crystal nanoplate is dispersed in water when amount is very low, be to prepare New Two Dimensional catalysis material
The ideal precursor of material.
The content of the invention
It is an object of the invention to provide a kind of montmorillonite-base metal nickel nano piece catalyst.
It is a further object of the present invention to provide a kind of cost is relatively low, process is simple method prepare above-mentioned catalyst.
It is a further object of the present invention to provide application of the above-mentioned catalyst in aromatic compound hydrogenation reaction.
To achieve the above object, the montmorillonite-base metal nickel nano piece catalyst that the present invention is provided, its carrier is montmorillonite,
Active component is metallic nickel, wherein：The quality of metallic nickel is the 5-30% of catalyst gross mass.
The method for preparing above-mentioned montmorillonite-base metal nickel nano piece catalyst that the present invention is provided, its step is：
A) by montmorillonite and water in mass ratio 1:20~100 mixing, are stirred at room temperature after 2~4h and obtain the illiteracy of abundant aquation and take off
The stone aqueous solution, is 3~8 according to montmorillonite mass ratio:1 and 2~5:1 is separately added into nickel salt and urine to the above-mentioned montmorillonite aqueous solution
Element is simultaneously stirred 0.5~1 hour, then ultrasonic 0.5~1 hour under 40% ultrasonic power in supersonic cell smashes instrument,
Obtain being completely exfoliated is the aqueous solution of individual layer montmorillonite nano piece；
B) it is completely exfoliated what step A was obtained for the aqueous solution of individual layer montmorillonite nano piece is placed in Hydrothermal Synthesiss kettle, 90
DEG C carry out chemical liquid deposition-precipitation reaction 1~8 hour, be cooled to centrifuge washing 3 times after room temperature, done at 100~120 DEG C
Montmorillonite-base nickel hydroxide nano piece catalyst precarsor is obtained after dry 8~16 hours；
C the logical hydrogen of montmorillonite-base nickel hydroxide nano piece catalyst precarsor for) obtaining step B is in 450~650 DEG C of reduction
3~6 hours, room temperature is cooled under an atmosphere of hydrogen, be passed through O2/N2Volume ratio be 0.5~1.0% gaseous mixture passivation it is 2~4 small
When, obtain the montmorillonite-base metal nickel nano piece catalyst that directly can be preserved in atmosphere.
Described preparation method, wherein, montmorillonite described in step A is preferably na-montmorillonite, and nickel salt used is nitric acid
Any one in nickel, nickel chloride, nickel sulfate, nickel acetate and nickel formate, preferably nickel nitrate.
Montmorillonite-base metal nickel nano piece catalyst of the present invention can be urged at aromatic compound (naphthalene or naphthane)
Change hydrogenation aspect to be applied.Aromatic hydrogenation reaction is carried out in 40mL stainless steel autoclaves.Specific steps and condition are as follows：
Successively to added in autoclave 0.125g montmorillonite-base metal nickel nano pieces catalyst, 10g mass concentrations be 10.0wt% naphthalenes just
Dodecane solution or 3g naphthanes, after sealing, first use H23 times are replaced to remove air in kettle, then by H in kettle2Needed for being adjusted to
Pressure, reacts 2.0h under 300 DEG C, 5.0MPa, and taking-up is analyzed with gas-chromatography after product is cooled to room temperature.
The montmorillonite-base metal nickel nano piece catalyst that the present invention is provided, by ultrasonic wave added disperse to obtain being completely exfoliated for
The aqueous solution of individual layer montmorillonite nano piece, the individual layer montmorillonite with chemical liquid deposition-precipitation method in the aqueous solution is scattered in is received
Rice piece surface introduces the homogeneous nickel species of distribution, and montmorillonite-base metal nickel nano piece catalyst is obtained through high temperature reduction.
Compared with prior art, the present invention has following technique effect：
1) being obtained as matrix with natural clay montmorillonite cheap and easy to get has two-dimensional structure load type metal Raney nickel；
2) method for preparing catalyst operating process is simple, is well suited for industrialized production；
3) not using noble metal can just prepare active height and with the aromatic hydrogenation of certain anti-sulfur poisonous performance
Catalyst.
Brief description of the drawings
Fig. 1 is the transmission electron microscope photo of montmorillonite-base metal nickel nano piece catalyst of the present invention.
Fig. 2 is the transmission electron microscope photo of montmorillonite-loaded Raney nickel prepared by infusion process.
Specific embodiment
In order to further illustrate the present invention, following examples are enumerated, but it is not intended to limit the defined hair of each claim
Bright scope.
First, the preparation of montmorillonite-base metal nickel nano piece catalyst
Embodiment 1
Weigh 2g na-montmorillonites to be placed in 200ml beakers, add 100ml water to be stirred at room temperature 3 hours and acquire abundant water
The montmorillonite aqueous solution of change, takes 7g nickel nitrates (Ni (NO respectively3)2·6H2O), 4g urea is added to above-mentioned montmorillonite aqueous solution stirring
1 hour, in ultrasonic power be then that 40% time ultrasonic to obtain being completely exfoliated within 0.5 hour be individual layer in supersonic cell smashes instrument
The aqueous solution of montmorillonite nano piece.To be completely exfoliated as the aqueous solution of individual layer montmorillonite nano piece is placed in 100ml Hydrothermal Synthesiss kettles,
Chemical liquid deposition-precipitation reaction being carried out at 90 DEG C 4 hours, being cooled to centrifuge washing 3 times after room temperature, 12 are dried at 100 DEG C
Hour after 550 DEG C of logical hydrogen reducings 4 hours, room temperature is cooled under an atmosphere of hydrogen, be passed through O2/N2Volume ratio be 1.0% it is mixed
Close gas to be passivated 3 hours, obtain the montmorillonite-base metal nickel nano piece catalyst that directly can be preserved in atmosphere.Received with Ni/MMT-
Rice piece 4 is represented.
Using transmission electron microscope (Jeol Ltd., JEM-1200EX (120KV)), to montmorillonite-base metal nickel nano
The catalyst of piece Ni/MMT- nanometer sheets 4 is characterized, and sees Fig. 1.In order to contrast, while montmorillonite is prepared to conventional impregnation method bearing
Carrying metallic nickel Ni/MMT catalyst has carried out transmission electron microscope sign, sees Fig. 2.Ni/MMT- nanometer sheets 4 can be observed by Fig. 1 to be catalyzed
What metallic Ni particles were very uniform is distributed in the whole surface of montmorillonite in agent, also be can be clearly seen that from the photo of partial enlargement
The montmorillonite single-layer wafers being completely exfoliated, and single-layer wafers are uniformly distributed in single-layer wafers two in certain curly, metallic nickel
Face.And in Fig. 2 the upper metal nickel particles of Ni/MMT catalyst do not scatter, reunite it is more serious；The metal Ni at middle part compared with
It is few, and nickel particles size and difference very heterogeneity；Bottom montmorillonite is stacked layer by layer, and surface texture is irregular, Ji Huwei
Carried metal nickel.Nickel particles number is few in this explanation Ni/MMT catalyst and size and size distribution all unusual heterogeneities, also not
It was observed that the presence of montmorillonite single-layer wafers.
Embodiment 2
Weigh 1g na-montmorillonites to be placed in 200ml beakers, add 100ml water to be stirred at room temperature 2 hours and acquire abundant water
The montmorillonite aqueous solution of change, takes 7g nickel formates (Ni (HCO respectively2)2·2H2O), 4g urea is added to the above-mentioned montmorillonite aqueous solution and stirs
Mix 1 hour, in ultrasonic power be then that 40% time ultrasonic to obtain being completely exfoliated within 0.5 hour be list in supersonic cell smashes instrument
The aqueous solution of layer montmorillonite nano piece.To be completely exfoliated as the aqueous solution of individual layer montmorillonite nano piece is placed in 100ml Hydrothermal Synthesiss
Kettle, chemical liquid deposition-precipitation reaction is carried out 2 hours at 90 DEG C, is cooled to centrifuge washing 3 times after room temperature, is dried at 100 DEG C
After 450 DEG C of logical hydrogen reducings 3 hours, room temperature is cooled under an atmosphere of hydrogen within 12 hours, be passed through O2/N2Volume ratio is 1.0%
Gaseous mixture is passivated 3 hours, obtains the montmorillonite-base metal nickel nano piece catalyst that directly can be preserved in atmosphere.With Ni/MMT-
Nanometer sheet 2 is represented.
Embodiment 3
Weigh 3g na-montmorillonites to be placed in 200ml beakers, add 100ml water to be stirred at room temperature 3 hours and acquire abundant water
The montmorillonite aqueous solution of change, takes 7g nickel chlorides (NiCl respectively2·6H2O), to be added to the stirring 1 of the above-mentioned montmorillonite aqueous solution small for 4g urea
When, in ultrasonic power be then that 40% time ultrasound obtains being completely exfoliated for 0.5 hour in supersonic cell smashes instrument it is individual layer illiteracy
The aqueous solution of de- stone nanometer sheet.To be completely exfoliated as the aqueous solution of individual layer montmorillonite nano piece is placed in 100ml Hydrothermal Synthesiss kettles,
90 DEG C carry out chemical liquid deposition-precipitation reaction 6 hours, are cooled to centrifuge washing 3 times after room temperature, 12 are dried at 100 DEG C small
When after 550 DEG C of logical hydrogen reducings 4 hours, room temperature is cooled under an atmosphere of hydrogen, be passed through O2/N2Volume ratio is 1.0% mixing
Gas is passivated 3 hours, obtains the montmorillonite-base metal nickel nano piece catalyst that directly can be preserved in atmosphere.With Ni/MMT- nanometers
Piece 6 is represented.
Embodiment 4
Weigh 5g na-montmorillonites to be placed in 200ml beakers, add 100ml water to be stirred at room temperature 3 hours and acquire abundant water
The montmorillonite aqueous solution of change, takes 14g nickel sulfates (NiSO respectively4·6H2O), 7g urea is added to above-mentioned montmorillonite aqueous solution stirring 1
Hour, in ultrasonic power it is then that 40% time ultrasonic to obtain being completely exfoliated within 0.5 hour be individual layer in supersonic cell smashes instrument
The aqueous solution of montmorillonite nano piece.To be completely exfoliated as the aqueous solution of individual layer montmorillonite nano piece is placed in 100ml Hydrothermal Synthesiss kettles,
Chemical liquid deposition-precipitation reaction being carried out at 90 DEG C 8 hours, being cooled to centrifuge washing 3 times after room temperature, 12 are dried at 100 DEG C
Hour after 600 DEG C of logical hydrogen reducings 6 hours, room temperature is cooled under an atmosphere of hydrogen, be passed through O2/N2Volume ratio be 1.0% it is mixed
Close gas to be passivated 3 hours, obtain the montmorillonite-base metal nickel nano piece catalyst that directly can be preserved in atmosphere.Received with Ni/MMT-
Rice piece 8 is represented.
Comparative example 1
Conventional impregnation method prepares montmorillonite-loaded metalNicatalyst.2g montmorillonites are weighed, is by metal nickel loading
10.0wt% takes Ni (NO3)2·6H2O is dissolved in 60m water, and montmorillonite is slowly added thereto, and 1 hour, Ran Hou is stirred at room temperature
Stirring is evaporated at 85 DEG C, gained sample in 100 DEG C of dryings 12 hours after 550 DEG C of logical hydrogen reducings 4 hours, under an atmosphere of hydrogen
Room temperature is cooled to, O is passed through2/N2Volume ratio be 1.0% gaseous mixture be passivated 3 hours, obtain the illiteracy that directly can be preserved in atmosphere
De- stone supported nickel catalyst.Represented with Ni/MMT.
Comparative example 2
Ultrasonic wave added dispersion infusion process prepares montmorillonite-loaded metalNicatalyst.2g na-montmorillonites are weighed to be placed in
In 200ml beakers, add 100ml water that the montmorillonite aqueous solution for acquiring abundant aquation for 3 hours is stirred at room temperature, by metal Ni
Measure as 10.0wt% takes Ni (NO3)2·6H2O is added to the above-mentioned montmorillonite aqueous solution and stirs 1 hour, and instrument is smashed then at supersonic cell
In in ultrasonic power be that to obtain within 0.5 hour being completely exfoliated be the aqueous solution of individual layer montmorillonite nano piece, Ran Hou to 40% time ultrasound
Stirring is evaporated at 85 DEG C, gained sample in 100 DEG C of dryings 12 hours after 550 DEG C of logical hydrogen reducings 4 hours, under an atmosphere of hydrogen
Room temperature is cooled to, O is passed through2/N2Volume ratio be 1.0% gaseous mixture be passivated 3 hours, obtain the illiteracy that directly can be preserved in atmosphere
De- stone supported nickel catalyst.Catalyst is expressed as Ni/MMT- ultrasounds.
2nd, catalytic hydrogenation of the montmorillonite-base metal nickel nano piece catalyst of the present invention to aromatic hydrocarbons
Embodiment 5
The naphthalene hydrogenation activity of the catalyst of Ni/MMT- nanometer sheets 4 is evaluated：The naphthalene Hydrogenation evaluation of Ni/MMT-4 catalyst is
Carried out in 40mL stainless steel autoclaves.Specific steps and condition are as follows：Successively to addition 0.125g Ni/MMT-4 in autoclave
Catalyst, 10g mass concentrations are 10.0wt% naphthalene n-dodecane solution, after sealing, first use H23 times are replaced to remove sky in kettle
Gas, then by H in kettle2Required pressure is adjusted to, 2.0h is reacted under 300 DEG C, 5.0MPa, product takes after being cooled to room temperature
Go out and be analyzed with gas-chromatography.
The aromatic hydrocarbons of the Ni/MMT- ultrasonically catalyzing agent of the Ni/MMT and comparative example 2 of Ni/MMT- nanometer sheets 2 and comparative example 1 adds
Hydrogen activity is evaluated as Ni/MMT- nanometer sheets 4.
Reaction result is shown in Table 1.
The naphthalene Hydrogenation of the different montmorillonite-base metal nickel nano piece catalyst of table 1 compares
Nickel loading is determined according to hydrogen temperature programmed reduction in a catalyst.
Reaction condition：10.0g naphthalene n-dodecanes solution (10.0wt%), 0.125g catalyst, 300 DEG C, 5.0MPa H2,
2.0h。
The result of table 1 shows that the montmorillonite-base metal nickel nano piece catalyst prepared by the present invention is made with conventional impregnation method
Ni/MMT is compared with the ultrasonic wave added dispersion made Ni/MMT- ultrasonically catalyzings agent of infusion process, and naphthalene hydrogenation activity is significantly improved, Ni/MMT
With the naphthalene turn that the naphthalene conversion ratio of Ni/MMT- ultrasonically catalyzing agent is respectively 26.3% and the catalyst of 36.6%, Ni/MMT- nanometer sheet 2
Rate is improved to 87.7%, and the catalyst of Ni/MMT- nanometer sheets 4 is more up to 100%, and decahydronaphthalene is selectively also up to
85.4%.
Embodiment 6
The naphthane hydrogen activity of the catalyst of Ni/MMT- nanometer sheets 4 is evaluated：The naphthane Hydrogenation of Ni/MMT-4 catalyst
Evaluation is carried out in 40mL stainless steel autoclaves.Specific steps and condition are as follows：Successively to adding 0.125g in autoclave
Ni/MMT-4 catalyst, 3g naphthanes, after sealing, first use H23 times are replaced to remove air in kettle, then by H in kettle2It is adjusted to
Required pressure, reacts 2.0h under 300 DEG C, 5.0MPa, and taking-up is analyzed with gas-chromatography after product is cooled to room temperature.
The Ni/MMT of Ni/MMT- nanometer sheets 2, Ni/MMT- nanometer sheets 6 and Ni/MMT- nanometer sheets 8 and comparative example 1 and right
The naphthane hydrogenation activity of the Ni/MMT- ultrasonically catalyzing agent of ratio 2 is evaluated as Ni/MMT- nanometer sheets 4.
Reaction result is shown in Table 2.
The naphthane Hydrogenation of the different montmorillonite-base metal nickel nano piece catalyst of table 2 compares
Nickel loading is determined according to hydrogen temperature programmed reduction in a catalyst.
B TON are that the naphthane quality converted based on unit mass metallic nickel in catalyst is calculated.
Reaction condition：3g naphthanes, 0.125g catalyst, 300 DEG C, 5.0MPa H2,2.0h。
The result of table 2 shows that the montmorillonite-base metal nickel nano piece catalyst prepared by the present invention is made with conventional impregnation method
Ni/MMT is compared with the ultrasonic wave added dispersion made Ni/MMT- ultrasonically catalyzings agent of infusion process, and naphthane hydrogenation activity is significantly improved, no
It is different to catalyst activity increase rate with nickel loading, wherein, increase rate it is minimum be the He of Ni/MMT- nanometer sheets 2
The catalyst of Ni/MMT- nanometer sheets 8, TON respectively reaches 119.5 and 119.6, compared to Ni/MMT and Ni/MMT- ultrasonically catalyzings agent point
7.6 and 4.3 times are not improve；Nickel loading be the naphthane hydrogenation activity of 18.5% catalyst of Ni/MMT- nanometer sheets 6 most
Height, TON is up to 251.1, and 17 and 9.3 times have been respectively increased compared to Ni/MMT and Ni/MMT- ultrasonically catalyzing agent.
3rd, the active contrast test of aromatic hydrocarbon hydrogenation catalyst
With with the identical method for preparing catalyst of comparative example 1, respectively with mesostructured material and commercial oxidation
Aluminium prepares Ni/MCM-41 the and Ni/ γ-Al that metal nickel loading is 10.0wt% for carrier2O3Catalyst, and contrast is implemented
The Ni/MMT- ultrasonically catalyzings agent of the Ni/MMT, comparative example 2 of example 1 catalyst as a comparison.
Embodiment 7
Except catalyst is with addition to Ni/MMT, remaining is same as Example 5, and reaction result is shown in Table 3.
Embodiment 8
Except catalyst is with addition to Ni/MMT- ultrasounds, remaining is same as Example 5, and reaction result is shown in Table 3.
Embodiment 9
Except catalyst is with addition to Ni/MCM-41, remaining is same as Example 5, and reaction result is shown in Table 3.
Embodiment 10
Except catalyst Ni/ γ-Al2O3Outward, remaining is same as Example 5, and reaction result is shown in Table 3.
Several catalyst naphthalene Hydrogenation comparing results of table 3
A TON are that the quality of the naphthalene+naphthane converted based on unit mass metallic nickel in catalyst is calculated
Reaction condition：10.0g naphthalene n-dodecanes solution (10.0wt%), 0.125g catalyst, 300 DEG C, 5.0MPa H2,
2.0h。
The result of table 3 shows that under identical reaction conditions, the montmorillonite-base metal nickel nano piece prepared by the present invention is catalyzed
Agent, compared with the made Ni/MMT of conventional impregnation method, aromatic hydrogenation activity improves 4.2 times；With ultrasonic wave added dispersion infusion process institute
Ni/MMT- ultrasonically catalyzings agent processed is compared, and aromatic hydrogenation activity improves 2.3 times；Compared with commercial oxidation aluminium supported nickel catalyst,
Aromatic hydrogenation activity improves 2.1 times；Compared with mesostructured material supported nickel catalyst, aromatic hydrogenation activity improves
32%.Experiment shows：Such catalyst be aromatic hydrogenation saturation with reduce coal tar, coal liquefaction oil product, light cycle and
Ideal catalyst of the made oil product arene content of biomass.
Claims (4)
1. a kind of preparation method of montmorillonite-base metal nickel nano piece catalyst, its step is as follows：
A) by montmorillonite and water in mass ratio 1:20~100 mixing, are stirred at room temperature after 2~4h and obtain the montmorillonite water of abundant aquation
Solution, is 3~8 according to montmorillonite mass ratio:1 and 2~5:1 is separately added into nickel salt and urea simultaneously to the above-mentioned montmorillonite aqueous solution
Stirring 0.5~1 hour, it is then ultrasonic 0.5~1 hour under 40% ultrasonic power in supersonic cell smashes instrument, obtain
It is the aqueous solution of individual layer montmorillonite nano piece to be completely exfoliated；
B) it is completely exfoliated what step A was obtained as the aqueous solution of individual layer montmorillonite nano piece is placed in Hydrothermal Synthesiss kettle, is entered at 90 DEG C
Row chemical liquid deposition-precipitation reaction 1~8 hour, is cooled to centrifuge washing 3 times after room temperature, dry 8 at 100~120 DEG C~
Montmorillonite-base nickel hydroxide nano piece catalyst precarsor is obtained after 16 hours；
C the logical hydrogen of montmorillonite-base nickel hydroxide nano piece catalyst precarsor for) obtaining step B reduces 3~6 in 450~650 DEG C
Hour, room temperature is cooled under an atmosphere of hydrogen, it is passed through O2/N2Volume ratio be 0.5~1.0% gaseous mixture be passivated 2~4 hours, obtain
To the montmorillonite-base metal nickel nano piece catalyst that directly can be preserved in atmosphere.
2. the preparation method of montmorillonite-base metal nickel nano piece catalyst as claimed in claim 1, it is characterised in that the step
Montmorillonite in rapid A is na-montmorillonite.
3. the preparation method of montmorillonite-base metal nickel nano piece catalyst as claimed in claim 1, it is characterised in that the step
Nickel salt in rapid A is any one in nickel nitrate, nickel chloride, nickel sulfate, nickel acetate and nickel formate.
4. the preparation method of montmorillonite-base metal nickel nano piece catalyst as claimed in claim 3, it is characterised in that the step
Nickel salt in rapid A is nickel nitrate.
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