CN106179351B - A kind of Cu-Ni/Al2O3Preparation method of catalyst and products thereof and application - Google Patents
A kind of Cu-Ni/Al2O3Preparation method of catalyst and products thereof and application Download PDFInfo
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- 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
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/18—Reducing with gases containing free hydrogen
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- 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
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/36—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
Abstract
The present invention relates to a kind of Cu-Ni/Al2O3The preparation method of catalyst includes the following steps: the 1) ratio according to shared by each component in catalyst, prepares the mixed solution of copper, nickel and aluminium salt, is denoted as solvent A；Alkaline solution is configured, solution B is denoted as；2) solution A is add to deionized water with B, stirs and control pH=8~10, generate sediment；3) sediment is aged 3~7h；It is then centrifuged for cleaning at 100~130 DEG C of temperature, dry 10~15h；4) continue to roast 3~8h at 500~800 DEG C；Finally at 350~700 DEG C, 1~2h of hydrogen reducing obtains Cu-Ni/Al2O3Catalyst.The present invention also provides Cu-Ni/Al2O3Catalyst and its application in 2- methylfuran is prepared in furfural add in-place hydrogen.The catalyst is free of toxic metals Cr, reduces the pollution to environment and the harm of human body；Secondly, activity, selectivity and repeat performance with higher.
Description
Technical field
The present invention relates to the preparation fields of metallic catalyst, and in particular to a kind of Cu-Ni/Al2O3The preparation method of catalyst
And products thereof and application.
Background technique
2- methylfuran (2-MF) is a kind of important biomass platform chemicals, and organic solvent and basic chemical industry are former
Material, there is critically important application in pesticide, medicine, the field of polymers.2-MF can be by the non-cereal crops system such as jerusalem artichoke, corn stover
Take, raw material sources are abundant, and due to 2-MF octane number with higher, quality is low, calorific value relative to ethyl alcohol improves about 16%
Be slightly soluble in the advantages such as water, be considered as one of substitute Fuel of Internal Combustion Engine [Feng Dengquan, internal combustion engine journal, (2014) 340].
The method of industrial production 2-MF is mainly made by furfural (furfuryl alcohol) catalytic hydrogenation at present, and this method needs to consume
A large amount of hydrogen, higher requirements are also raised for reaction unit for the hydrogen of high pressure at the same time.And H2There are biggish
Safety and storage and transportation problem, and China has that energy consumption is high, dirty mainly with the fossil energies hydrogen manufacturing such as coal, natural gas, in hydrogen production process
The problems such as dye is serious and CO2 emission intensity is big.Furthermore industrially production 2-MF master's catalyst to be used is Cu-Cr body
Series catalysts, it is expensive, but also cause serious environmental pollution.Therefore replace hydrogen as hydrogen source using hydrogen supply agent,
Become the target of more and more researcher researchs using more cheap, environmental protection catalyst.
The related work for having there are some document reports to prepare 2-MF about furfural add in-place hydrogen at present, and obtain
Good achievement, Vlachos etc. (Applied Catalysis A:General, 2014,480,17-24) are reported with Ru/C
As catalyst, under conditions of isopropanol is as hydrogen supply agent, the 2-MF that yield is 61% can be obtained.Subsequent Vlachos etc.
(ACS Catalysis,2015,5,3988-3994) (Journal of Molecular Catalysis A:Chemical,
2014,392,223-228) a kind of difunctional Ru/RuOx/C catalyst is reported again, in 2- butanol and 2- amylalcohol as hydrogen source
When, furfural add in-place hydrogen can be catalyzed and obtain yield as 76% 2-MF, and give certain explanation in mechanism.
Hermans etc. (Chemsuschem, 2014,7,268-275) uses Pd/Fe2O3Catalyst, furfural add in-place hydrogen have obtained 2-
MF and 2- methyltetrahydrofuran (2-MTHF), gross production rate 62%.But during furfural add in-place hydrogen prepares 2-MF
The catalyst mainly used is still to concentrate on noble metal, and expensive price is that it is hindered to industrialize maximum obstacle.
Chinese invention patent (104549319 A of CN), (105498787 A of CN), (101422731 A of CN), (CN
104368346 A) and (104383929 A of CN) disclose preparation by furfural gas phase hydrogenation for some techniques and catalyst system of 2-MF
It is standby, and some catalyst also use cheap non-precious metal catalyst.But these patents still need without exception
Consume the hydrogen of high pressure.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of Cu-Ni/Al2O3The preparation method of catalyst
And products thereof and application.Catalyst provided in the present invention is free of toxic metals Cr, reduces the pollution to environment and human body
Harm；Secondly, activity, selectivity and repeat performance with higher.
Technical solution provided by the present invention are as follows:
A kind of Cu-Ni/Al2O3The preparation method of catalyst, includes the following steps:
1) ratio according to shared by each component in catalyst prepares the mixed solution of copper, nickel and aluminium salt, is denoted as solvent A；Match
Alkaline solution is set, solution B is denoted as；
2) solution A is add to deionized water with B, stirs and control pH=8~10, generate sediment；
3) sediment is aged 3~7h；It is then centrifuged for cleaning at 100~130 DEG C of temperature, dry 10~15h；
4) continue to roast 3~8h at 500~800 DEG C；Finally at 350~700 DEG C, 1~2h of hydrogen reducing obtains Cu-
Ni/Al2O3Catalyst.
In above-mentioned preparation method, the cost of material of catalyst is cheap and preparation method is simple；Toxic gold is free of in catalyst
Belong to Cr, reduces to the pollution of environment and the harm of human body；And resulting Cu-Ni/Al2O3Active component is Cu, Ni conjunction in catalyst
Gold, carrier Al2O3, activity, selectivity and repeat performance with higher.
Preferably, the copper, nickel and aluminium salt are one of nitrate, chlorate or sulfate；Alkali is hydroxide
One or both of sodium, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate or ammonium hydroxide.
Further preferably, the copper, nickel and aluminium salt are respectively copper nitrate, nickel nitrate and aluminum nitrate；The alkali is hydrogen
The mixture of sodium oxide molybdena and sodium carbonate.
Further preferably, the mass ratio of the sodium hydroxide and sodium carbonate is 3.2~1:1.
Preferably, being stirred in the step 2) and controlling pH=9.3-9.7.Further preferably pH=9.5.
The present invention also provides a kind of Cu-Ni/Al that above-mentioned preparation method obtains2O3Catalyst, activity in the catalyst
Group is divided into Cu, Ni alloy, carrier Al2O3。
Preferably, the mass percentage of Cu, Ni alloy is 0.1~60% in the catalyst, surplus Al2O3。
Preferably, in the catalyst mass fraction of Cu be 20~40%, the mass fraction of Ni be 20~
40%, surplus Al2O3.Further preferably, the mass fraction that the mass fraction of Cu is 18~22%, Ni in the catalyst
It is 38~42%, surplus Al2O3。
The present invention also provides a kind of above-mentioned Cu-Ni/Al2O3Catalyst is prepared in 2- methylfuran in furfural add in-place hydrogen
Using.
Compared with the existing technology, the beneficial effects of the present invention are embodied in:
(1) the catalyst raw material in the present invention is cheap and preparation method is simple；
(2) catalyst in the present invention is free of toxic metals Cr, reduces the pollution to environment and the harm of human body；
(3) the catalyst activity and selectivity with higher and repeat performance in the present invention, such as at 230 DEG C,
The total moles yield that the conversion ratio of furfural reaches 100%, 2-MF can reach 75% or more.
Detailed description of the invention
Fig. 1 is 20%Cu-40%Ni/Al in the present invention2O3The experimental result of the STEM-EDS partial face surface sweeping of catalyst
Figure；
Fig. 2 is 20%Cu-40%Ni/Al in the present invention2O3The experimental result of the STEM-EDS local line surface sweeping of catalyst
Figure；
Fig. 3 is the XRD spectrum of the catalyst fines of difference Cu, Ni load capacity in the present invention, wherein a) 60%Cu/Al2O3；
B) 50%Cu-10%Ni/Al2O3；C) 40%Cu-20%Ni/Al2O3；D) 30% Cu-30%Ni/Al2O3；E) 20%Cu-
40%Ni/Al2O3；F) 10%Cu-50%Ni/Al2O3；G) 60% Ni/Al2O3；
Fig. 4 is the H of the catalyst fines of difference Cu, Ni load capacity in the present invention2- TPR map, wherein a) 60%Cu/
Al2O3；B) 50%Cu-10%Ni/Al2O3；C) 40%Cu-20%Ni/Al2O3；D) 30% Cu-30%Ni/Al2O3；E) 20%
Cu-40%Ni/Al2O3；F) 10%Cu-50%Ni/Al2O3；G) 60% Ni/Al2O3。
Specific embodiment
All raw materials involved in following embodiment are commercially available or simple process is passed through with regard to getable in laboratory.
The recycling of catalyst is by simply filtering and drying steps in following embodiment.
Pass through GC-FID quantitative analysis furfural and 2-MTHF in following embodiment.Concrete analysis condition is as follows: chromatographic column is
Agilent HP-5 capillary column (30m × 0.32mm × 0.25 μm), injector temperature: 300 DEG C；Sample volume: 1 μ L；Split ratio:
10:1；FID detection temperature: 320 DEG C；Temperature programming: 30 DEG C are kept for 4 minutes, are warming up to later with 10 DEG C of speed per minute
140 DEG C, 300 DEG C then are raised to 20 DEG C per minute.
2-MF carries out quantitative analysis by high performance liquid chromatography, and specific analytical method is as follows: chromatographic column Phenomenex
Gemini 5u C18 110A (250 × 4.60mm, 5 μm), detector are UV detector, and eluant, eluent is 60% water and 40% second
Nitrile mixed liquor, eluant, eluent flow velocity are 0.6mL/min, and column temperature is 30 DEG C, and sample injection volume is 1 μ L.
The calculation method of relevant parameter is as follows:
Embodiment 1:
Weigh copper nitrate (Cu (NO3)2·3H2O) 9.664g, aluminum nitrate (Al (NO3)3·9H2O) 12.47g dissolves in 400mL
In deionized water, 6g NaOH and 5.299g Na are weighed2CO3It is dissolved in 400mL deionized water, is added in conical flask first
100mL deionized water, and be stirred continuously.Two solution are added dropwise in conical flask respectively, and are stirred continuously, control reaction pH
9.5, the temperature of simultaneous reactions liquid is controlled at 30 DEG C value, after solution drips, is continued to stir 3h, is then stood aging 4h,
Filtering, 110 DEG C of dry 12h, then 600 DEG C of roasting 4h in Muffle furnace, finally in tube furnace 650 DEG C of reductase 12 h to get arriving
Catalyst 60%Cu/Al2O3。
By 0.1g furfural, 0.025g catalyst 60%Cu/Al2O314mL high temperature and pressure is added after mixing with 7mL isopropanol
In reaction kettle, 230 DEG C, reaction time 4h are heated to, reaction product is cooling, carries out GC- respectively after organic solvent dissolution
FID and efficient liquid phase chromatographic analysis, reaction result such as table 1:
Table 1, furfural conversion ratio and 2-MF yield under the differential responses time
| Reaction time/h | Furfural conversion ratio (%) | 2-MF yield (%) |
| 1 | 60 | 24 |
| 2 | 92 | 37 |
| 4 | 100 | 43 |
| 8 | 100 | 41 |
Embodiment 2:
Weigh copper nitrate (Cu (NO3)2·3H2O) 9.664g, nickel nitrate (Ni (NO3)2·6H2O) 2.508g and aluminum nitrate
(Al(NO3)3·9H2O) 15g dissolves in 400mL deionized water, weighs 8g NaOH and 3.180g Na2CO3Be dissolved in 400mL go from
In sub- water, 100mL deionized water is added first in conical flask, and be stirred continuously.Triangle is added dropwise in two solution respectively
It in flask, and is stirred continuously, 9.5, the temperature of simultaneous reactions liquid is controlled at 30 DEG C control pH value in reaction, is dripped to solution
Afterwards, continue to stir 3h, then stand aging 4h, filter, 110 DEG C of dry 12h, then 600 DEG C of roasting 4h in Muffle furnace, finally
In tube furnace 650 DEG C of reductase 12 h to get arrive catalyst 50%Cu-10% Ni/Al2O3。
By 0.1g furfural, 0.025g catalyst 50%Cu-10%Ni/Al2O314mL high is added after mixing with 7mL isopropanol
In warm autoclave, be heated to 230 DEG C, reaction time 4h, reaction product is cooling, after organic solvent dissolution respectively into
Row GC-FID and efficient liquid phase chromatographic analysis.Reaction result such as table 2:
Table 2, furfural conversion ratio and 2-MF yield under the differential responses time
| Reaction time/h | Furfural conversion ratio (%) | 2-MF yield (%) |
| 1 | 60 | 21 |
| 2 | 92 | 35 |
| 4 | 100 | 41 |
| 8 | 100 | 39 |
Embodiment 3:
Weigh copper nitrate (Cu (NO3)2·3H2O) 9.664g, nickel nitrate (Ni (NO3)2·6H2O) 6.281g and aluminum nitrate
(Al(NO3)3·9H2O) 18.756g dissolves in 400mL deionized water, weighs 9.2g NaOH and 5.299g Na2CO3It is dissolved in
In 400mL deionized water, 100mL deionized water is added first in conical flask, and be stirred continuously.By two solution respectively by
It is added dropwise in conical flask, and is stirred continuously, 9.5, the temperature of simultaneous reactions liquid is controlled at 30 DEG C, to molten control pH value in reaction
After drop adds, continue to stir 3h, then stands aging 4h, filtering, 110 DEG C of dry 12h, then 600 DEG C of roastings in Muffle furnace
Burn 4h, finally in tube furnace 650 DEG C of reductase 12 h to get arrive catalyst 40%Cu-20% Ni/Al2O3。
By 0.1g furfural, 0.025g catalyst 40%Cu-20%Ni/Al2O314mL high is added after mixing with 7mL isopropanol
In warm autoclave, be heated to 230 DEG C, reaction time 4h, reaction product is cooling, after organic solvent dissolution respectively into
Row GC-FID and efficient liquid phase chromatographic analysis.Reaction result such as table 3:
Table 3, furfural conversion ratio and 2-MF yield under the differential responses time
| Reaction time/h | Furfural conversion ratio (%) | 2-MF yield (%) |
| 1 | 60 | 25 |
| 2 | 92 | 39 |
| 4 | 100 | 45 |
| 8 | 100 | 41 |
Embodiment 4:
Weigh copper nitrate (Cu (NO3)2·3H2O) 4.832g, nickel nitrate (Ni (NO3)2·6H2O) 6.281g and aluminum nitrate
(Al(NO3)3·9H2O) 12.470g dissolves in 400mL deionized water, weighs 6.4g NaOH and 3.18g Na2CO3It is dissolved in
In 400mL deionized water, 100mL deionized water is added first in conical flask, and be stirred continuously.Respectively dropwise by two solution
It is added in conical flask, and is stirred continuously, 9.5, the temperature of simultaneous reactions liquid is controlled at 30 DEG C, to solution control pH value in reaction
After dripping, continue to stir 3h, then stands aging 4h, filtering, 110 DEG C of dry 12h, then 600 DEG C of roastings in Muffle furnace
4h, finally in tube furnace 650 DEG C of reductase 12 h to get arrive catalyst 30%Cu-30% Ni/Al2O3。
By 0.1g furfural, 0.025g catalyst 30%Cu-30%Ni/Al2O314mL high is added after mixing with 7mL isopropanol
In warm autoclave, be heated to 230 DEG C, reaction time 4h, reaction product is cooling, after organic solvent dissolution respectively into
Row GC-FID and efficient liquid phase chromatographic analysis.Reaction result such as table 4:
Table 4, furfural conversion ratio and 2-MF yield under the differential responses time
| Reaction time/h | Furfural conversion ratio (%) | 2-MF yield (%) |
| 1 | 60 | 36 |
| 2 | 92 | 48 |
| 4 | 100 | 55 |
| 8 | 100 | 50 |
Embodiment 5:
Weigh copper nitrate (Cu (NO3)2·3H2O) 4.832g, nickel nitrate (Ni (NO3)2·6H2O) 12.533 g and aluminum nitrate
(Al(NO3)3·9H2O) 18.756g dissolves in 400mL deionized water, weighs 10g NaOH and 3.18g Na2CO3It is dissolved in 400mL
In deionized water, 100mL deionized water is added first in conical flask, and be stirred continuously.Two solution are added dropwise respectively
It in conical flask, and is stirred continuously, 9.5, the temperature of simultaneous reactions liquid is controlled at 30 DEG C control pH value in reaction, is added dropwise to solution
After complete, continue to stir 3h, then stand aging 4h, filter, 110 DEG C of dry 12h, then 600 DEG C of roasting 4h in Muffle furnace, most
Afterwards in tube furnace 650 DEG C of reductase 12 h to get arrive catalyst 20%Cu-40% Ni/Al2O3。
By 0.1g furfural, a certain amount of catalyst 20%Cu-40%Ni/Al2O314mL is added after mixing with 7mL isopropanol
In high-temperature high-pressure reaction kettle, it is heated to 190-250 DEG C, the reaction time is 1~8h, and reaction product is cooling, and organic solvent is molten
GC-FID and efficient liquid phase chromatographic analysis are carried out after solution respectively.Reaction result such as table 5:
Furfural conversion ratio and 2-MF yield under table 5, differential responses temperature, reaction time and catalyst dosage
| Reaction temperature/DEG C | Catalyst dosage/g | Reaction time/h | Furfural conversion ratio/% | 2-MF yield/% |
| 190 | 0.025 | 2 | 88 | 11 |
| 190 | 0.025 | 9 | 100 | 59 |
| 230 | 0.025 | 4 | 100 | 67 |
| 210 | 0.025 | 1 | 91 | 18 |
| 210 | 0.025 | 6 | 100 | 61 |
| 230 | 0.025 | 9 | 100 | 52 |
| 230 | 0.025 | 0.5 | 81 | 19 |
| 250 | 0.025 | 2 | 100 | 41 |
| 250 | 0.025 | 6 | 100 | 1 |
| 230 | 0.017 | 4 | 100 | 75 |
| 230 | 0.1 | 4 | 100 | 0 |
| 230 | 0.005 | 4 | 60 | 19 |
| 230 | 0.05 | 4 | 100 | 4 |
| 210 | 0.017 | 9 | 100 | 68 |
Embodiment 6:
Weigh copper nitrate (Cu (NO3)2·3H2O) 2.416g, nickel nitrate (Ni (NO3)2·6H2O) 15.674 g and aluminum nitrate
(Al(NO3)3·9H2O) 18.721g dissolves in 400mL deionized water, weighs 10g NaOH and 5.299g Na2CO3It is dissolved in
In 400mL deionized water, 100mL deionized water is added first in conical flask, and be stirred continuously.By two solution respectively by
It is added dropwise in conical flask, and is stirred continuously, 9.5, the temperature of simultaneous reactions liquid is controlled at 30 DEG C, to molten control pH value in reaction
After drop adds, continue to stir 3h, then stands aging 4h, filtering, 110 DEG C of dry 12h, then 600 DEG C of roastings in Muffle furnace
Burn 4h, finally in tube furnace 650 DEG C of reductase 12 h to get arrive catalyst 10%Cu-50% Ni/Al2O3。
By 0.1g furfural, 0.025g catalyst 10%Cu-50%Ni/Al2O314mL high is added after mixing with 7mL isopropanol
In warm autoclave, be heated to 230 DEG C, reaction time 4h, reaction product is cooling, after organic solvent dissolution respectively into
Row GC-FID and efficient liquid phase chromatographic analysis.Reaction result such as table 6:
Table 6, furfural conversion ratio and 2-MF yield under the differential responses time
| Reaction time/h | Furfural conversion ratio (%) | 2-MF yield (%) |
| 1 | 60 | 14 |
| 2 | 92 | 17 |
| 4 | 100 | 20 |
| 8 | 100 | 18 |
Embodiment 7:
Weigh nickel nitrate (Ni (NO3)2·6H2O) 11.632g and aluminum nitrate (Al (NO3)3·9H2O) 11.569 g dissolve in
In 400mL deionized water, 6g NaOH and 5.299g Na are weighed2CO3It is dissolved in 400mL deionized water, first in conical flask
100mL deionized water is added, and is stirred continuously.Two solution are added dropwise in conical flask respectively, and are stirred continuously, control is anti-
Answer pH value 9.5, the temperature of simultaneous reactions liquid is controlled at 30 DEG C, after solution drips, is continued to stir 3h, is then stood aging
4h, filtering, 110 DEG C of dry 12h, then 600 DEG C of roasting 4h in Muffle furnace, finally in tube furnace 650 DEG C of reductase 12 h to get
To catalyst 60%Ni/Al2O3。
By 0.1g furfural, 0.025g catalyst 60%Ni/Al2O314 mL high temperature and pressure are added after mixing with 7mL isopropanol
In reaction kettle, 230 DEG C, reaction time 4h are heated to, reaction product is cooling, carries out GC- respectively after organic solvent dissolution
FID and efficient liquid phase chromatographic analysis.Reaction result such as table 7:
Table 7, furfural conversion ratio and 2-MF yield under the differential responses time
| Reaction time/h | Furfural conversion ratio (%) | 2-MF yield (%) |
| 1 | 60 | 15 |
| 2 | 92 | 19 |
| 4 | 100 | 22 |
| 8 | 100 | 19 |
Catalyst characterization
It is as shown in Figure 1 catalyst 20%Cu-40%Ni/Al2O3STEM-EDS figure, Cu, Ni element in derived sample
It is evenly distributed on same specific position in figure, and Al, O element are generally evenly distributed in the entire Electronic Speculum visual field.
And obtained from the line total number evidence of Fig. 2 individual particle and EDS quantitative analysis results (Cu:Ni=1:2.3), each
The content of Ni is similar to 2 times of Cu on grain, i.e., the catalyst that this method prepares is the mass ratio of a kind of Cu, Ni close to 1:2
CuNi2Alloy catalyst, i.e. 20%Cu-40%Ni/Al2O3.The analysis method of the catalyst of other load capacity and the catalyst
Analysis method it is consistent.
Table 8 is different catalysts { a) 60%Cu/Al2O3；B) 50%Cu-10%Ni/Al2O3；C) 40% Cu-20%Ni/
Al2O3；D) 30%Cu-30%Ni/Al2O3；E) 20%Cu-40%Ni/Al2O3；F) 10% Cu-50%Ni/Al2O3；G) 60%
Ni/Al2O3ICP-OES characterization result, it can be deduced that catalyst 20%Cu-40%Ni/Al2O3Actual Cu, Ni mass is
1:1.73, the result gap obtained with EDS is little, and possible one of the reason of error therein is because EDS determines element
Amount analysis has only taken a panel region of wherein very little, may and actual result somewhat deviation；In addition may be by
It is inconsistent in the settling rate of different metal in the solution, and without 100% completely precipitating, result in actually obtained Cu with
The content of Ni is more slightly lower than theoretical value.
The ICP-OES characterization result of 8. different catalysts of table
aContent < 0.1% shared by metal
The characterize data of XRD shown in Fig. 3, a, b, c, d, e, f, g respectively indicate a) 60%Cu/Al2O3；B) 50%Cu-
10%Ni/Al2O3；C) 40%Cu-20%Ni/Al2O3；D) 30%Cu-30%Ni/Al2O3；E) 20%Cu-40%Ni/Al2O3；
F) 10%Cu-50%Ni/Al2O3；G) 60%Ni/Al2O3。
Wherein in catalyst a three main peaks be belonging respectively to Ni (JCPDS 04-0850) (111), (200) and (220) it is brilliant
Face, and Cu (the JCPDS 65-9743) of (111), (200) and (220) be respectively belonging to to(for) three main peaks of catalyst g are brilliant
Face.And the 2 θ values of Ni are greater than Cu, from Fig. 3 it can be seen that as the 2 θ values that are gradually increased of the content of Ni become larger, more
Carry out the 2 θ values closer to Ni, also demonstrates a kind of presence of the Cu-Ni alloy of different ratio.
Fig. 4 is the H of different catalysts2- TPR, wherein a, b, c, d, e, f, g respectively indicate a) 60% Cu/Al2O3；b)
50%Cu-10%Ni/Al2O3；C) 40%Cu-20%Ni/Al2O3；D) 30%Cu-30% Ni/Al2O3；E) 20%Cu-40%
Ni/Al2O3；F) 10%Cu-50%Ni/Al2O3；G) 60%Ni/Al2O3。
By scheming it can be concluded that 60%Ni/Al2O3The precursor reduction temperature of catalyst is very high, illustrates may there is Ni/ at this time
Al2O4Presence, and 60%Cu/Al2O3The precursor reduction temperature of catalyst is lower.But for Cu-Ni/Al2O3Catalyst,
In addition to 10%Cu-50%Ni/Al2O3Catalyst substantially only one corresponding reduction of outer others Cu, Ni ratio of catalyst
Peak also further illustrates the presence of Cu-Ni alloy.As for 10%Cu-50%Ni/Al2O3The corresponding high temperature of catalyst and low temperature
The reduction peak of the reduction peak in stage, hot stage can be construed to Ni/Al caused by excessive Ni2O3There are the reason of, low temperature rank
Section is the corresponding Cu-Ni alloy of a certain ratio.The explanation of other comparison catalysts and 20%Cu-40% Ni/Al2O3Phase
Seemingly.
Claims (9)
1. a kind of Cu-Ni/Al2O3The preparation method of catalyst, which comprises the steps of:
1) ratio according to shared by each component in catalyst prepares the mixed solution of copper, nickel and aluminium salt, is denoted as solvent A；Configure alkali
Property solution, is denoted as solution B；Copper, nickel and the aluminium salt is one of nitrate, chlorate or sulfate；
2) solution A is add to deionized water with B, stirs and control pH=8~10, generate sediment；
3) sediment is aged 3~7h；It is then centrifuged for cleaning, at 100~130 DEG C of temperature, dry 10~15h；
4) continue to roast 3~8h at 500~800 DEG C；Finally at 350~700 DEG C, 1~2h of hydrogen reducing obtains Cu-Ni/
Al2O3Catalyst.
2. Cu-Ni/Al according to claim 12O3The preparation method of catalyst, which is characterized in that the alkali is hydrogen-oxygen
Change one or both of sodium, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate or ammonium hydroxide.
3. Cu-Ni/Al according to claim 22O3The preparation method of catalyst, which is characterized in that the copper, nickel and
Aluminium salt is respectively copper nitrate, nickel nitrate and aluminum nitrate；The alkali is the mixture of sodium hydroxide and sodium carbonate.
4. Cu-Ni/Al according to claim 32O3The preparation method of catalyst, which is characterized in that the sodium hydroxide
Mass ratio with sodium carbonate is 3.2~1:1.
5. Cu-Ni/Al according to claim 12O3The preparation method of catalyst, which is characterized in that in the step 2)
It stirs and controls pH=9.3-9.7.
6. a kind of Cu-Ni/Al that the preparation method as described in Claims 1 to 5 is any obtains2O3Catalyst, which is characterized in that
Active component is Cu, Ni alloy, carrier Al in the catalyst2O3。
7. Cu-Ni/Al according to claim 62O3Catalyst, which is characterized in that Cu, Ni alloy in the catalyst
Mass percentage be 0.1~60%, surplus Al2O3。
8. Cu-Ni/Al according to claim 62O3Catalyst, which is characterized in that the quality of Cu point in the catalyst
Number is 20~40%, the mass fraction of Ni is 20~40%, surplus Al2O3。
9. a kind of Cu-Ni/Al as described in claim 6~8 is any2O3Catalyst prepares 2- methyl furan in furfural add in-place hydrogen
Application in muttering.
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| CN106861702A (en) * | 2017-02-28 | 2017-06-20 | 山西大学 | It is a kind of that the catalyst and its preparation method and application for being directly synthesized succinic acid are mutually hydrogenated with for cis-butenedioic anhydride water |
| CN108579747A (en) * | 2018-02-28 | 2018-09-28 | 浙江工业大学 | A kind of preparation method of fructose hydrogenation copper base catalyst |
| FR3091657B1 (en) * | 2019-01-15 | 2023-04-14 | Ifp Energies Now | Process for the preparation of a selective hydrogenation catalyst comprising a step of forming a NiCu alloy in pre-impregnation |
| CN110508287A (en) * | 2019-09-02 | 2019-11-29 | 吉林大学 | Ni-Cu/Al2O3Bimetallic catalyst, preparation method and its preparing the application in tert-butylamine base oxethyl ethyl alcohol |
| CN111097426B (en) * | 2019-12-30 | 2022-08-30 | 天津市长芦化工新材料有限公司 | Copper-based gas phase catalyst and preparation method and application thereof |
| CN115611659A (en) * | 2022-09-05 | 2023-01-17 | 湖南师范大学 | Method for preparing aluminum oxide and copper-nickel-aluminum-oxygen composite film on surface of aluminum nitride substrate |
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