CN110075851A - A kind of application of nickel-base catalyst and its catalysis furfural hydrogenation reaction - Google Patents
A kind of application of nickel-base catalyst and its catalysis furfural hydrogenation reaction Download PDFInfo
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- CN110075851A CN110075851A CN201910395410.3A CN201910395410A CN110075851A CN 110075851 A CN110075851 A CN 110075851A CN 201910395410 A CN201910395410 A CN 201910395410A CN 110075851 A CN110075851 A CN 110075851A
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- nickel
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- intercalation
- aluminum hydrotalcite
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- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
- B01J27/25—Nitrates
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
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Abstract
The invention discloses a kind of nickel-base catalyst and its applications of catalysis furfural hydrogenation reaction.The method comprises the steps of firstly, preparing the hydrotalcite precursors of the nickel aluminum hydrotalcite of nitrate anion intercalation and carbonate intercalation, have then obtained the evenly dispersed novel nickel-base catalyst of Ni particle height by topology conversion.Furfural hydrogenation can be catalyzed by the nickel-base catalyst that the nickel aluminum hydrotalcite precursor of nitrate anion intercalation is prepared and prepare furfuryl alcohol；Furfural hydrogenation can be catalyzed by the nickel-base catalyst that the nickel aluminum hydrotalcite precursor of carbonate intercalation is prepared and prepare tetrahydrofurfuryl alcohol.The catalyst system can regulate and control final product by regulating and controlling hydrotalcite precursor interlayer anion, and realize catalyst performance facilitates conversion.And the present invention regulates and controls catalyst surface pattern by regulation hydrotalcite layers anion, and will have a direct impact on reaction process using the exquisite difference for demonstrating this surface topography of a series of means in situ to change reaction product.
Description
Technical field
The invention belongs to metallic catalyst preparation technical field, in particular to a kind of nickel-base catalyst and its catalysis chaff
The application of aldehyde hydrogenation reaction.
Background technique
Furfural has its special research significance as a kind of α, the biomass molecule of β unsaturated aldehyde.With resource and ring
Border problem is on the rise, and biomass energy and obtains more and more extensive concern in recent years with biomass plateform molecules.Chaff
Aldehyde adds the response path of hydrogen complicated, and product is varied, how to select suitable reaction system and catalyst, highly selective
Target product is obtained, in the course of the research always one challenge.The product of furfural hydrogenation first is that furfuryl alcohol (FOL), percent
60 or so furfural is all used as the preparation of furfuryl alcohol, has huge demand, and production lysine, dimension in resin industry
Raw element, the important source material of lubricating oil.Tetrahydrofurfuryl alcohol (THFOL) is the product of furfuryl alcohol deep hydrogenation, is that a kind of important green is molten
Agent in agricultural, press, and industrially has important application.The selective hydrogenation of α, β unsaturated aldehyde is research all the time
Hot spot, because its selective hydrogenation product and complete hydrogenation product all play an important role in every field, in general, mistake
Metal such as Rh, Ir, Ni are crossed, Pd and Pt have a wide range of applications in heterogeneous hydrogenation system, and particularly, nickel is excellent due to its
Hydrogenation and relative moderate price, be the emphasis of research all the time, but these metals are all more likely to C=C double bond
Plus hydrogen rather than C=O, people are often through being added bimetallic doping (Sn, In, Cu, Fe) etc. or utilize difference
Carrier and intermetallic interaction, to change its electronic structure and surface texture, to achieve the purpose that selective hydrogenation.
It is Cu-Cr catalyst that furfural hydrogenation, which prepares furfuryl alcohol and industrially leads to be applied, and due to its toxicity, everybody develops difference one after another
Catalyst, wherein with Cu, Ni, Co and noble metal such as Ru, Pd, Rh, based on Pt etc..It is calculated according to DFT, due to Furfural Molecule
It is so furfuryl alcohol is more readily formed, and to be η 2- (C, O) absorption with η 1- (O) absorption, be easy on Cu on Ni, the metals such as Pd
C=C double bond plus hydrogen and C-O key fracture occurs.Particularly, due to the highdensity electronics of Ni, add hydrogen so that crossing and take off
The reactions such as carbonyl are easier to occur, so now to the research of copper-based catalysts catalysis furfural furfuryl alcohol using more, and Ni-based phase
To less.The preparation of tetrahydrofurfuryl alcohol, catalyst are noble metal catalyst (Pd, Pt, Rh) and load type metal catalyst mostly.
The most common catalyst in laboratory is loading type nickel-based catalyst.
Summary of the invention
The object of the present invention is to provide a kind of nickel-base catalyst and its applications of catalysis furfural hydrogenation reaction.The present invention is first
The nickel aluminum hydrotalcite of nitrate anion intercalation and the hydrotalcite precursor of carbonate intercalation are prepared, has then obtained Ni by topology conversion
Grain high uniformity dispersion novel nickel-base catalyst (NiAl-MMO), the catalyst system by regulation hydrotalcite precursor interlayer yin from
Son can regulate and control final product, and realize catalyst performance facilitates conversion.And the present invention passes through regulation hydrotalcite layers yin
Ion regulates and controls catalyst surface pattern, and using a series of means in situ it is exquisite demonstrate the difference of this surface topography
It is different to will have a direct impact on reaction process to change reaction product.
Nickel-base catalyst of the present invention the preparation method is as follows:
(1) aluminum oxide bead is added in nickel nitrate solution, NH is then added4NO3As precipitating reagent, by mixed liquor
It is transferred in autoclave, crystallization 12-72h at 70-120 DEG C, centrifuge washing, drying are to get the nickel aluminum water for arriving nitrate anion intercalation
Talcum precursor；
(2) Na is added in the nickel aluminum hydrotalcite precursor of nitrate anion intercalation2CO3In solution, it is stirred to react 4-12h, centrifugation is washed
It washs, dry to get the nickel aluminum hydrotalcite precursor of carbonate intercalation is arrived；
(3) by the hydrotalcite precursor of the nickel aluminum hydrotalcite precursor of nitrate anion intercalation and carbonate intercalation respectively in reproducibility gas
It is heated to 400-600 DEG C in atmosphere and keeps the temperature 2-8h, heating rate is 2-10 DEG C/min, finally obtains nickel-base catalyst.
The above-mentioned nickel-base catalyst catalysis furfural hydrogenation preparation being prepared by the nickel aluminum hydrotalcite precursor of nitrate anion intercalation
The application of furfuryl alcohol.Catalysis furfural hydrogenation prepares the reaction condition of furfuryl alcohol are as follows: is prepared by the nickel aluminum hydrotalcite precursor of nitrate anion intercalation
Obtained nickel-base catalyst and furfural mixing, isopropanol is solvent, reacts 2-5h at 100-120 DEG C in nitrogen atmosphere.
The above-mentioned nickel-base catalyst catalysis furfural hydrogenation preparation being prepared by the nickel aluminum hydrotalcite precursor of carbonate intercalation
The application of tetrahydrofurfuryl alcohol.Catalysis furfural hydrogenation prepares the reaction condition of tetrahydrofurfuryl alcohol are as follows: by the nickel aluminum hydrotalcite of carbonate intercalation
The mixing of nickel-base catalyst and furfural that precursor is prepared, isopropanol are solvent, react 2-5h at 100-120 DEG C in nitrogen atmosphere.
The characterization of the surface topography of two kinds of catalyst: high power transmission electron microscope (HRTEM) combines Extended X-ray in situ to absorb essence
Fine texture spectrum (in situ EXAFS) demonstrates NiAl-NO3In-LDHs catalyst, nickel has the sudden and violent of a variety of low coordination crystal faces
Dew；Then unrestrained anti-using the original position under diffusing reflection Infrared Fourier Transform spectrum (in situ DRIFTS) in situ and reaction condition
It penetrates Infrared Fourier Transform spectrum (operandoFTIR) to demonstrate on the catalyst of two kinds of different surface morphologies, reactant has
Different suction types, to produce different reaction products.
The present invention innovatively utilizes the surface topography of the interlayer anion regulation catalyst of catalyst precarsor hydrotalcite, from
And achieve the purpose that conveniently regulating and controlling catalytic performance, never there is correlative study to prove that regulation interlayer anion can influence before this
Change and influence the reactivity worth of catalyst to catalyst topology.
The polymolecularity and and carrier that the catalyst that the hydrotalcite topology of specific morphology changes in the present invention has
Between interaction so that active sites activity improves, so that reaction system is reacted under conditions of relatively mild,
2- methyl furan is generated so as to avoid nickel-base catalyst C-O key fracture common under furfurol reaction high temperature and the fracture of C-C key
It mutters and furans.In range known to us, this is for the first time using the change of hydrotalcite layers anion to catalyst spy
Property carry out accuracy controlling research, obtained the chemical product of two kinds of high added values of furfuryl alcohol and tetrahydrofurfuryl alcohol, while nitric acid root cutting
The nickel aluminum hydrotalcite of the layer selectivity and stability excellent for C=O are catalyzed α for nickel-base catalyst, and β unsaturated aldehyde adds hydrogen
New thinking is provided, and interlayer anion regulation hydrotalcite topology transformation is also excavated all for the further of hydrotalcite material characteristic
Provide new direction.
Detailed description of the invention
Fig. 1 is the XRD diffraction pattern of the NiAl hydrotalcite precursor prepared in embodiment 1；(a)NiAl-NO3-LDH(b)NiAl-
CO3-LDH。
Fig. 2 is the nickel aluminum hydrotalcite precursor prepared in embodiment 1 and the scanning electron microscope (SEM) photograph of corresponding nickel-base catalyst；(a)
NiAl-NO3-LDH(b)NiAl-CO3Nickel-base catalyst (d) the carbonic acid root cutting that-LDH (c) nitrate anion intercalation nickel aluminum hydrotalcite obtains
The nickel-base catalyst that layer nickel aluminum hydrotalcite obtains.
Fig. 3 is the HRTEM electron microscope of the nickel-base catalyst obtained in embodiment 1 by nitrate anion intercalation nickel aluminum hydrotalcite.
Fig. 4 is the HRTEM electron microscope of the nickel-base catalyst obtained in embodiment 1 by carbonate intercalation nickel aluminum hydrotalcite.
Fig. 5 is that the furfural hydrogenation reaction of the nickel-base catalyst obtained in embodiment 1 by nitrate anion intercalation nickel aluminum hydrotalcite is urged
Change activity rating figure.
Fig. 6 is that the furfural hydrogenation reaction of the nickel-base catalyst obtained in embodiment 1 by carbonate intercalation nickel aluminum hydrotalcite is urged
Change activity rating figure.
Fig. 7 is the in situCO-DRIFT of the nickel-base catalyst obtained in embodiment 1 by carbonate intercalation nickel aluminum hydrotalcite
Figure.
Fig. 8 is the in situ of the nickel-base catalyst obtained in embodiment 1 by carbonate intercalation nickel aluminum hydrotalcite
EXAFSNiL3- edge figure.
Fig. 9 is the reactant molecule for preparing in embodiment 1 in the nickel catalyst obtained by carbonate intercalation nickel aluminum hydrotalcite
The operando of the adsorption of agent schemes.
Specific embodiment
[embodiment 1]
A: 0.25g aluminum oxide bead is put into wide-mouth bottle, and nitric acid nickel salt solution (nickel nitrate is then added
0.1mol, 250ml), add 0.2mol NH4NO3As precipitating reagent, raw material mixed liquor is obtained；Mixed liquor is transferred to high pressure
In reaction kettle, 90 DEG C of crystallization 48h；Before centrifugation, washing, drying are to get the nickel aluminum hydrotalcite of the perfect nitrate anion intercalation of crystal form is arrived
Body；
B: the nickel aluminum hydrotalcite precursor 0.1g of nitrate anion intercalation is put into three-necked flask, and 0.1gNa is added2CO3And 100ml
Water stirs 5h, and centrifuge washing, drying are to get the nickel aluminum hydrotalcite precursor for arriving carbonate intercalation；
C: the hydrotalcite precursor of the nickel aluminum hydrotalcite precursor of nitrate anion intercalation and carbonate intercalation is respectively placed in high temperature resistant
In porcelain boat, and it is placed in hydrogen and nitrogen mixture atmosphere kiln roasting 4h that volume ratio is 1:10, obtains nickel-base catalyst, atmosphere
The maturing temperature of furnace is 450 DEG C, and heating rate is 5 DEG C/min.
It is carried out using surface of the HRTEM to the nickel-base catalyst being prepared by the nickel aluminum hydrotalcite precursor of nitrate anion intercalation
Characterization, analyzes obtained lattice fringe, it can be seen that has diversified crystal face exposure.
It is carried out using surface of the HRTEM to the nickel-base catalyst being prepared by the nickel aluminum hydrotalcite precursor of carbonate intercalation
Characterization, analyzes obtained lattice fringe, it can be seen that only a kind of crystal face exposure.
The nickel-base catalyst being prepared by the nickel aluminum hydrotalcite precursor of nitrate anion intercalation is subjected to furfural hydrogenation reaction
Activity rating: after catalyst 0.1g, furfural 1ml, isopropanol 30ml are mixed at 110 DEG C, 3h, hydrogen pressure are reacted in nitrogen atmosphere
Power is 3MPa；Reaction obtains furfuryl alcohol FOL, the selectivity 97% of furfuryl alcohol, conversion ratio 100%.
The nickel-base catalyst being prepared by the nickel aluminum hydrotalcite precursor of carbonate intercalation is subjected to furfural hydrogenation reaction
Activity rating: after catalyst 0.1g, furfural 1ml, isopropanol 30ml are mixed at 110 DEG C, 3h, hydrogen pressure are reacted in nitrogen atmosphere
Power is 3MPa；Reaction obtains tetrahydrofurfuryl alcohol FOL, the selectivity 99% of tetrahydrofurfuryl alcohol, conversion ratio 100%.
Claims (5)
1. a kind of preparation method of nickel-base catalyst, which is characterized in that specific step is as follows for this method:
(1) aluminum oxide bead is added in nickel nitrate solution, NH is then added4NO3As precipitating reagent, mixed liquor is transferred to
In autoclave, crystallization 12-72h at 70-120 DEG C, centrifuge washing, drying are to get the nickel aluminum hydrotalcite for arriving nitrate anion intercalation
Precursor；
(2) Na is added in the nickel aluminum hydrotalcite precursor of nitrate anion intercalation2CO3In solution, it is stirred to react 4-12h, centrifuge washing is done
It is dry to get arrive carbonate intercalation nickel aluminum hydrotalcite precursor；
(3) in reducing atmosphere by the hydrotalcite precursor of the nickel aluminum hydrotalcite precursor of nitrate anion intercalation and carbonate intercalation difference
It is heated to 400-600 DEG C and keeps the temperature 2-8h, heating rate is 2-10 DEG C/min, finally obtains nickel-base catalyst.
2. the nickel-base catalyst catalysis according to claim 1 being prepared by the nickel aluminum hydrotalcite precursor of nitrate anion intercalation
Furfural hydrogenation prepares the application of furfuryl alcohol.
3. application according to claim 2, which is characterized in that the catalysis furfural hydrogenation prepares the reaction condition of furfuryl alcohol
Are as follows: nickel-base catalyst and the furfural mixing be prepared by the nickel aluminum hydrotalcite precursor of nitrate anion intercalation, isopropanol is solvent, hydrogen
2-5h is reacted at 100-120 DEG C in atmosphere.
4. the nickel-base catalyst catalysis according to claim 1 being prepared by the nickel aluminum hydrotalcite precursor of carbonate intercalation
Furfural hydrogenation prepares the application of tetrahydrofurfuryl alcohol.
5. application according to claim 4, which is characterized in that the catalysis furfural hydrogenation prepares the reaction item of tetrahydrofurfuryl alcohol
Part are as follows: nickel-base catalyst and the furfural mixing be prepared by the nickel aluminum hydrotalcite precursor of carbonate intercalation, isopropanol is solvent,
2-5h is reacted at 100-120 DEG C in nitrogen atmosphere.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114653372A (en) * | 2022-03-07 | 2022-06-24 | 国网综合能源服务集团有限公司 | Preparation method of high-dispersion nickel-based catalyst and application of high-dispersion nickel-based catalyst in catalyzing high-temperature water gas shift reaction |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107413344A (en) * | 2017-05-18 | 2017-12-01 | 北京化工大学 | A kind of preparation method of confinement structure hexahedron pattern nano nickel base catalyst and its application of catalytic hydrogenation |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107413344A (en) * | 2017-05-18 | 2017-12-01 | 北京化工大学 | A kind of preparation method of confinement structure hexahedron pattern nano nickel base catalyst and its application of catalytic hydrogenation |
Non-Patent Citations (2)
| Title |
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| 蒲勇: "NiO-WO3/γ-Al2O3复合材料的原位制备及表征", 《中国优秀硕士学位论文全文数据库 工程科技 I辑》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114653372A (en) * | 2022-03-07 | 2022-06-24 | 国网综合能源服务集团有限公司 | Preparation method of high-dispersion nickel-based catalyst and application of high-dispersion nickel-based catalyst in catalyzing high-temperature water gas shift reaction |
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