CN109806873A - A method of preparing the meso-porous carbon material of load Ni using solid-state synthetic method - Google Patents
A method of preparing the meso-porous carbon material of load Ni using solid-state synthetic method Download PDFInfo
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- CN109806873A CN109806873A CN201910076468.1A CN201910076468A CN109806873A CN 109806873 A CN109806873 A CN 109806873A CN 201910076468 A CN201910076468 A CN 201910076468A CN 109806873 A CN109806873 A CN 109806873A
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Abstract
The invention discloses a kind of methods of meso-porous carbon material that load Ni is prepared using solid-state synthetic method.It is carbon source that this method, which is using the tannin of biomass resource and the lignin of several types, three block compound F127 is template, it is prepared for a series of meso-porous carbon material of Ni loads by solid-state synthetic method, and is applied and shows excellent performance on the catalytic hydrogenation of biomass.In atmosphere of hydrogen, by the Eucalyptus powder of 2g, the catalyst of 0.2g and the ethyl alcohol of 50ml will enter in autoclave, 280 DEG C of reaction 6h.Catalyst has biggish aperture and lesser Ni nano particle in the present invention, and the yield of single phenol is up to 31.07% after hydrogenolysis wood powder.
Description
Technical field
The invention belongs to the preparation fields of carbon material, and in particular to a kind of to prepare the mesoporous of Ni load using solid-state synthetic method
The method of carbon material.
Background technique
In recent decades, limited fossil resource consumption increases sharply in world wide, has aggravated greenhouse effects and drop
Low air quality.Therefore, to find fossil feedstock substitute, biomass resource is converted into the energy as the main purpose and chemical industry is former
The research of material causes the concern of many countries in the world.Biomass energy is considered as the cleaning energy for 21 century having development potentiality
Source, with from a wealth of sources, cheap and reproducible feature.Lignocellulosic is the most abundant renewable biomass resources
(annual 170000000000 tons of the whole world), mainly by lignin (10-35%), hemicellulose (20-30%) and cellulose (40-50%)
Composition.Wherein lignin is biomass material uniquely with special aromatic skeleton.Therefore lignocellulosic is in production fuel, life
There are huge potentiality in terms of substance sill and the phenolic compound of fossil sources.Lignin is made full use of to can be improved wooden
The utilization rate and alleviation oil crisis of cellulose.
Most of catalyst currently used for lignin depolymerization is based on noble metal (Pd, Pt, Ru, Rh, Au) and your non-gold
Belong to (Ni, Fe, Co, Mo, Cu), and carrier is mostly carbon-based and zeolites.Noble metal has high catalytic activity and recycling rate of waterused,
But the reserves in its whole world are lower, and it is at high price, it is at high cost, however base metal has the characteristics that reserves height and cheap,
So that there are very big potentiality to substitute noble metal for it.The performance of carrier plays the role of vital in catalyst, different
Carrier have different catalytic performances.Klamrassamee et al. (Bioresource Technology, 2015,180:222-
229) MCM-41 and SBA-15 catalyst is prepared for using soft template method, living with excellent catalysis in lignin depolymerization
Property.Either most of carbon material or zeolitic materials are prepared by two methods of soft template method and hard template method at present
It forms, these mesoporous catalysts are usually to synthesize under the conditions of acid (HCl) or alkaline (NaOH), so that the technique is more multiple
It is miscellaneous, time-consuming and unfriendly to environment, however the preparation process of traditional mesoporous carbon (MC) material is then more complicated and expensive, because
Hard template route or soft template strategy must be used, and passes through HF, NH4HF2Or NaOH goes removing template that could prepare mesoporous carbon materials
Material, technique is more time-consuming and pollutes environment.
Other than the mesoporous material that traditional template is prepared in the solution, there are also solid-state synthetic methods to prepare mesoporous carbon
Research.Zhang et al. (Journal of Materials Chemistry A, 2018,6:859-865) utilizes bipyridyl,
CuCl2And SiO2Hydrophilic meso-porous carbon material is prepared for by way of ball milling, calcining for raw material, but its aperture is smaller, it is difficult
To apply in the catalytic degradation of biomass, and its raw material is not environmentally, it is difficult to it is widely applied, and it is wooden about utilizing at present
Element is that carbon source is but rarely reported by the research that solid-state synthesizes hair preparation mesoporous carbon.
Summary of the invention
For overcome the deficiencies in the prior art, the mesoporous of load Ni is prepared using solid-state synthetic method the present invention provides a kind of
The method of carbon material.
A method of preparing the meso-porous carbon material of load Ni using solid-state synthetic method, comprising the following steps:
(1) meso-porous carbon material that ball milling synthesis Ni is loaded in vibration ball milling instrument, and Ni/MC is made in tubular type kiln roasting
Catalyst；
The preparation method of Ni/MC catalyst: by stainless steel ball, carbon source and three block compound are added to vibration ball milling instrument
In stainless steel jar mill, after ball milling 0.5-1h, nickel salt is added, continues ball milling 0.5-1h, it is rear normal three times with ethyl alcohol and water washing
Temperature is dried overnight, and finally 450-800 DEG C of calcining 2-4h of nitrogen protection in tube furnace, obtains Ni/MC catalyst；
(2) in atmosphere of hydrogen, by the Eucalyptus powder of 1-2g, the Ni/MC catalyst of 0.1-0.2g and the ethyl alcohol of 30-50ml will
Enter in autoclave, 260-320 DEG C of reaction 2-8h to get；
The three block compound is polyoxyethylene-poly-oxypropylene polyoxyethylene, polyoxyethylene, polyoxypropylene and poly-
The quantitative proportion of ethylene oxide is 100:65:100.
Further, the stainless steel ball quantity is 6-24.
Further, the carbon source is the tannin or lignin of biomass resource.
Further, the lignin includes alkali lignin, dealkalize lignin and organic solvent lignin.
Further, the carbon source addition is 1-2g.
Further, the additional amount of the three block compound is 0.6-1g.
Further, the nickel salt is nickel acetate tetrahydrate；The additive amount of the nickel salt is 3mmol.
Further, in step (1), the atmosphere of tubular type kiln roasting is N2。
Further, in step (1), calcining time 2-4h.
Further, in step (2), reaction time 2-8h, preferably 6h.
Compared with prior art, the present invention has the advantage that
The present invention is carbon source using tannin and lignin, using the synthesising mesoporous carbon material of solid state process, compares more traditional hard mold
The process of plate method and soft template method preparation mesoporous carbon, the characteristic that meso-porous carbon material obtained has aperture big, and synthesis process
It is solvent-free, succinctly, quickly.Catalyst has biggish aperture and lesser Ni nano particle in the present invention, and after hydrogenolysis wood powder
The yield of single phenol is up to 31.07%.
Detailed description of the invention
Fig. 1 is the adsorption/desorption curve and graph of pore diameter distribution of 1 gained Ni/MC catalyst of embodiment.
Fig. 2 is that the TEM of 1 gained Ni/MC catalyst of embodiment schemes.
Specific embodiment
Specific implementation of the invention is further described below by way of example and attached drawing, but protection scope of the present invention
It is not limited to following embodiment.
Phenolic monomers are by internal standard method for gas chromatography (GC-MS) and gas-chromatography (GC-FID) in the following example
Analysis measures, and the calculation method of GC detection uses internal standard method, and connection hexamethylene is internal standard compound.Catalyst can be transmitted electron microscope
(JEM-2100F) and the full-automatic specific surface area in 2,460 4 station ASAP and Porosimetry characterization (pore-size distribution is by BJH method meter
It obtains).
Embodiment 1-4:
Weigh 1g tannin and 0.8g F127 (polyoxyethylene-poly-oxypropylene polyoxyethylene, Sigma-Aldrich,
P2443), and 6,12,18,24 stainless steel balls are separately added into according to table 1 to be added in ball grinder together, ball milling 0.5h, then claim
The nickel acetate tetrahydrate of 3mmol is taken to be added thereto, after continuing ball milling 0.5h, room temperature after being cleaned three times using deionized water and ethyl alcohol
It is dried overnight, obtained compound N in tube furnace2Atmosphere, 450 DEG C of calcining 2h, obtains Ni/MC, Ni/MC12, Ni/MC18, Ni/
MC24Catalyst.
The Eucalyptus powder of 2g is weighed, the ethyl alcohol of corresponding catalyst and 50ml will enter in autoclave in the table 1 of 0.2g, benefit
With hydrogen substitution gas 4 times repeatedly, 2MPa H is filled with after eliminating air2, 280 DEG C of reaction 6h, after reaction rapidly utilize water
Reaction kettle is dropped to room temperature by bath.Gas is collected, product is separated, obtained phenolic monomers yield is shown in Table lattice 1.
The adsorption/desorption curve and graph of pore diameter distribution of the obtained catalyst of embodiment 1 are as shown in Figure 1, TEM schemes such as Fig. 2 institute
Show.As can be seen from FIG. 1, the aperture of the catalyst belongs to mesoporous, and pore-size distribution is relatively narrow, as shown in Figure 2, the nickel nanoparticle of load
Son distribution is more uniform and particle is smaller, illustrates that the nickel load mesoporous carbon of this method preparation is a kind of catalysis that structural behaviour is excellent
Agent.The preparation of catalyst is a kind of solid-state synthetic method without solvent in the embodiment, is eliminated in traditional mesoporous carbon preparation
Waste water caused by the use of HCl or NaOH, and synthesis process time-consuming is shorter (1-2h), it is more mesoporous than traditional approach preparation
Carbon (8-24h) is succinct, quickly very much.
Influence of the different ball milling condition of table 1 to Eucalyptus powder hydrogenolysis
Embodiment 5,6:
It weighs the tannin of 1g and 0.6g, the F127 of 1g is separately added into according to table 2, and be added to together with 6 stainless steel balls
In ball grinder, ball milling 0.5h, then weigh the nickel acetate tetrahydrate of 3mmol and be added thereto, after continuing ball milling 0.5h, utilize deionization
Water and ethyl alcohol cleaning are several overnight all over rear air drying, obtained compound N in tube furnace2Atmosphere, 450 DEG C of calcining 2h, respectively
Obtain Ni/MC0.6, Ni/MC1Catalyst.The Eucalyptus powder of 2g is weighed, the catalyst of 0.2g and the ethyl alcohol of 50ml will enter reaction under high pressure
In kettle, using hydrogen substitution gas 4 times repeatedly, 2MPa H is filled with after eliminating air2, 280 DEG C of reaction 6h, after reaction rapidly
Reaction kettle is dropped into room temperature using water-bath.Gas is collected, product is separated, obtained phenolic monomers yield is shown in Table lattice 2.
Influence of the raw material proportioning of 2 catalyst of table to Eucalyptus powder hydrogenolysis
Embodiment 7-9:
Weigh the alkali lignin (AL) of 1g, dealkalize lignin (DL) and organic solvent respectively according to carbon source described in table 3
Lignin (OL), and the F127 of 0.8g is weighed, and be added in ball grinder together with 6 stainless steel balls, ball milling 0.5h, then weigh
The nickel acetate tetrahydrate of 3mmol is added thereto, and after continuing ball milling 0.5h, is cleaned using deionized water and ethyl alcohol several dry all over rear room temperature
It is dry overnight, obtained compound N in tube furnace2Atmosphere, 450 DEG C of calcining 2h, respectively obtains Ni/MCAL, Ni/MCDL, Ni/MCOL
Catalyst.The Eucalyptus powder of 2g is weighed, the catalyst of 0.2g and the ethyl alcohol of 50ml will enter in autoclave, and set repeatedly using hydrogen
Ventilation body 4 times, is filled with 2MPa H after eliminating air2, 280 DEG C of reaction 6h are dropped reaction kettle using water-bath rapidly after reaction
To room temperature.Gas is collected, product is separated, obtained phenolic monomers yield is shown in Table lattice 3.
Influence of the different carbon source of table 3 to Eucalyptus powder hydrogenolysis
It must emphasize, above-mentioned described embodiment is intended to be merely illustrative of the present lifted example, without
It is the restriction to implementation method.Those of ordinary skill in the art can also make other differences on the basis of the above description
The variation of form can not provide embodiment without to all embodiments here, but thus amplify out apparent
Variation still in protection scope of the present invention.
Claims (9)
1. a kind of method for the meso-porous carbon material for preparing load Ni using solid-state synthetic method, which comprises the following steps:
(1) meso-porous carbon material that ball milling synthesis Ni is loaded in vibration ball milling instrument, and Ni/MC catalysis is made in tubular type kiln roasting
Agent；
The preparation method of Ni/MC catalyst: by stainless steel ball, carbon source and three block compound are added to the stainless of vibration ball milling instrument
In steel ball grinding jar, after ball milling 0.5-1h, nickel salt is added, continues ball milling 0.5-1h, with air drying mistake after ethyl alcohol and water washing
At night, finally 450-800 DEG C of calcining 2-4h of nitrogen protection in tube furnace, obtains Ni/MC catalyst；
(2) in atmosphere of hydrogen, by the Eucalyptus powder of 1-2g, the Ni/MC catalyst of 0.1-0.2g and the ethyl alcohol of 30-50ml will enter height
Press reaction kettle in, 260-320 DEG C of reaction 2-8h to get；
The three block compound is polyoxyethylene-poly-oxypropylene polyoxyethylene, polyoxyethylene, polyoxypropylene and polyoxy second
The quantitative proportion of alkene is 100:65:100.
2. utilizing the method for the meso-porous carbon material of solid-state synthetic method preparation load Ni according to claim 1, which is characterized in that
The stainless steel ball quantity is 6-24.
3. utilizing the method for the meso-porous carbon material of solid-state synthetic method preparation load Ni according to claim 1, which is characterized in that
The carbon source is tannin or lignin.
4. utilizing the method for the meso-porous carbon material of solid-state synthetic method preparation load Ni according to claim 3, which is characterized in that
The lignin includes alkali lignin, dealkalize lignin, organic solvent lignin or lignosulfonates.
5. utilizing the method for the meso-porous carbon material of solid-state synthetic method preparation load Ni according to claim 1, which is characterized in that
The carbon source addition is 1-2g.
6. utilizing the method for the meso-porous carbon material of solid-state synthetic method preparation load Ni according to claim 1, which is characterized in that
The additional amount of the three block compound is 0.6-1g.
7. utilizing the method for the meso-porous carbon material of solid-state synthetic method preparation load Ni according to claim 1, which is characterized in that
The nickel salt is nickel acetate tetrahydrate；The additive amount of the nickel salt is 1.5-3mmol.
8. utilizing the method for the meso-porous carbon material of solid-state synthetic method preparation load Ni according to claim 1, which is characterized in that
In step (1), calcining time 2-4h.
9. utilizing the method for the meso-porous carbon material of solid-state synthetic method preparation load Ni according to claim 1, which is characterized in that
In step (2), reaction time 2-8h.
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Cited By (1)
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| CN111939891A (en) * | 2020-09-01 | 2020-11-17 | 南开大学 | Tannin-based ordered mesoporous carbon catalyst and preparation method and application thereof |
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| CN104888779A (en) * | 2015-05-05 | 2015-09-09 | 中国矿业大学 | Preparation method of Cu nanoparticle-loaded ordered mesoporous carbon catalyst |
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