CN104162432A - A homo-dispersed efficient biomass reforming catalyst and a preparing method thereof - Google Patents
A homo-dispersed efficient biomass reforming catalyst and a preparing method thereof Download PDFInfo
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- CN104162432A CN104162432A CN201410289091.5A CN201410289091A CN104162432A CN 104162432 A CN104162432 A CN 104162432A CN 201410289091 A CN201410289091 A CN 201410289091A CN 104162432 A CN104162432 A CN 104162432A
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Abstract
The invention relates to a homo-dispersed efficient biomass reforming catalyst and a preparing method thereof and belongs to the technical field of catalysts. The catalyst comprises homo-dispersed nanometer particles with metal active centers, hydrotalcite calcinated oxide and spinel. The metal active centers are at least one of Cu, Ni, Co and Fe. The homo-dispersed catalyst is prepared by reduction of a hydrotalcite precursor. The catalyst is homo-dispersed and is used for catalyzing HMF to prepare DMF, the HMF can be fully converted in a reaction at 130 DEG C under 0.7 MPa for about 6 h, the yield is 75.8%, and the yield is far more than 48% of non-noble metal Cu catalysts reported in literature and reaches the catalytic yield 71% of noble metal RuCu/C (higher than 220 DEG C).
Description
Technical field
The invention belongs to catalyst technical field, efficient living beings reforming catalyst of a kind of Monodispersed and preparation method thereof is particularly provided
Background technology
Reproducible biomass-making has great importance to solving fossil energy crisis for furyl bio-fuel.Furyl bio-fuel DMF, is considered to desirable transportable liquid fuel, has high-energy-density with respect to industrial alcohol, low volatility (boiling point is higher), and high-octane rating, does not dissolve each other with water, dissolves each other with gasoline.As: DMF (31.5MJ/L), the advantages such as low volatility (94 DEG C of bp92 –).
It is mainly noble metal catalyst that current biomass derivatives 5 hydroxymethyl furfural (HMF) is prepared bio-fuel DMF catalyst.Conventional noble metal has Ru, Pd.Mandan Chidambaram in 2010 and Alexis T.Bell have reported noble metal Ru/C, Pd/C, and Pt/C, Rh/C transforms HMF, 120 DEG C, 62bar H
2under condition, react 1h, HMF conversion ratio <25% and DMF be very low <15% (Green Chem., 2010,12,1253 – 1262) selectively.HMF reacts 3h under 1-propanol solution Pd/C, 60 DEG C of conditions, conversion ratio 100%, DMF productive rate 36% (Luijkx G C, Heterocycles., 2009,77 (2): 1037-1044).Within 2012, Pd/C catalyst reacts 1.5h under 260 DEG C of conditions, catalytic mixtures 5-HMF: furfural is 1:1, and conversion ratio is 99.8%, productive rate DMF60.3%, MF61.9% (Energy.Fuels., 26 (7): 4560-4567.).For precious metal catalyst low-yield problems, forefathers propose two solutions: the first, and noble metal is worked in coordination with chemical stoichiometric acid reagent, and collaborative fracture HMF prepares DMF.Todsapon Thananatthanachon in 2010 and Thomas B.Rauchfuss precious metals pd/C-HCOOH reaction system of having reported for work, reacts 15h, catalysis HMF under the condition that THF solution refluxes.HCOOH is by forming formate ester fracture C-O key with hydroxyl, HMF conversion ratio 100%, and DMF productive rate has reached 95% (Angew.Chem.Int.Ed., 2010,49 (37): 6616-6618).But this system has been used the HCOOH of 10 times of HMF stoichiometric chemistries, and environment is unfriendly.The second, transition metal is modified noble metal and is prepared bimetallic catalyst, increases and modifies noble metal electronics and the geometry free degree.RuCu/C catalysis HMF is converted into DMF and reacts 10h in 220 DEG C, 2-butanol solution, and HMF conversion ratio 100%, selectively brings up to 71% (Yuriy Roma ' n-Leshkov, Nature., 2007,447 (7147): 982-985).In document with report in 2013, mention, RuSn/C catalysis HMF hydrogenation fracture C-O key, 473K reacts 3h, obtains DMF productive rate 46% (Green Chem., 2013,15 (1): 85-90).Ru/Co in 2014
3o
4at 130 DEG C of reaction 24h, conversion ratio reaches 100%, selective 93.4% (Appl.Catal.B:Environ., 2014,146:244-248).Within 2014, report that in hollow carbon balls, the PtCo nanoparticle catalyst of burden reacts 2h Efficient Conversion HMF at 180 DEG C, obtained the DMF (Guang-Hui Wang, Nat Mater., 2014,13 (3): 293-300.) of 98% high yield.Precious metal catalyst has reached extraordinary catalytic effect (>90%DMF), but noble metal is rare metal, and storage is limited, and noble metal is expensive, is not suitable for suitability for industrialized production.So developing nonmetal alternative noble metal is research tendency.2012 report Cu-MPO using methyl alcohol as hydrogen source, 260 DEG C, 3h, conversion ratio 100%, DMF productive rate 48% (Green Chem., 2012,14 (9): 2457-2461.).Severe reaction conditions (temperature is high), DMF productive rate is not high.It is productive rate not high (<50%) that base metal substitutes noble metal present Research, and reaction temperature very high (>200 DEG C), severe reaction conditions.So develop efficient catalyst especially non-precious metal catalyst transform efficiently HMF to prepare 2,5-dimethyl furan be a great challenge.
Summary of the invention
The object of the present invention is to provide the efficient non-precious metal catalyst of a kind of Monodispersed, can gentle efficient catalytic biomass derivatives prepare bio-fuel 2,5-dimethyl furan Catalysts and its preparation method.
Catalyst of the present invention is formed by oxide and the spinelle of the calcining of the metal active center nano particle by Monodispersed and hydrotalcite, metal active center is at least one in Cu, Ni, Co, Fe, if metal active center is Co, Cu, Ni, Fe, CoNi, CoCu or CoFe; Or above-mentioned just bivalent metal reactive center replaces the bivalent metal oxide of hydrotalcite calcining.The content at preferred catalyst metal active center is 5～70wt%.Active metal medium particle diameter is distributed in 10～70nm.
This catalyst is called again hydrotalcite (Layered Double Hydroxides, is abbreviated as LDHs) for precursor makes with LDHs, and hydrotalcite laminate bivalent cation is selected Zn
2+or Mg
2+, Tricationic is selected Al
3+, the metal active central ion entering between laminate is Cu
2+, Ni
2+, Co
2+, Fe
3+in at least one, Zn
2+or Mg
2+with Ni
2+, Co
2+, Cu
2+mol ratio is (0～10): 1.The all divalent metal M of hydrotalcite laminate
2+the all trivalent metal cation M of/hydrotalcite laminate
3+mol ratio=(2～5): 1, by hydrotalcite precursor at H
2/ N
2in=5/95 gaseous mixture, reduce, reduction temperature is controlled at 400 DEG C～850 DEG C, and the recovery time is controlled at 5min～6h, can obtain catalyst M-(ZnO-ZnAl
2o
4), M-(MgO-MgAl
2o
4) or M--Al
2o
3, wherein M is metal active center, as Co, Cu, Ni, Fe, CoNi, CoCu or CoFe etc.
The above-mentioned catalyst of the present invention is prepared the method for DMF for catalysis HMF: the mass fraction that adds substrate HMF is 1～10wt%, catalyst addition is 0.5:1～6:1 with the mass ratio of add HMF, reaction temperature is 130～160 DEG C, reaction pressure is 0.5～2.0MPa, reaction time is 6～24h, reaction dissolvent oxolane.
Tool of the present invention has the following advantages:
1. utilize the feature of hydrotalcite laminate metal ion ratio and composition Modulatory character, preparation load capacity and the adjustable Monodispersed load type metal catalyst of composition, catalysis HMF prepares DMF, productive rate reaches 75.8%, far exceed the non-precious metal catalyst Cu-MPO48% productive rate (260 DEG C) of bibliographical information, reached noble metal RuCu/C catalysis productive rate 71% (>220 DEG C).
2. reaction condition gentleness, energy consumption is low.Reaction 130 DEG C, 5 hydroxymethyl furfural can be transformed completely when the 6h of 0.7MPa left and right.
3. catalytic reaction is easy and simple to handle, in sealed reactor, can occur.
(a) urea method synthetic in Fig. 1 the invention process case 1 and case study on implementation 7 synthesizes CoZnAl-LDH (Co:Zn:Al=0.4:1.6:1); (b) 11.8%Co-(ZnO-ZnAl
2o
4) XRD spectra.Wherein abscissa is 2 θ, unit: degree; Ordinate is intensity
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described, but the present invention is not limited to following examples.
Embodiment 1
Steps A: measure the deionized water of 700mL to there-necked flask, accurately take and add respectively Co (NO
3)
26H
2o, Zn (NO
3)
26H
2o, Al (NO
3)
39H
2o, urea, its corresponding concentration is 2mmolL
-1, 8mmolL
-1, 5mmolL
-1and 35mmolL
-1, in the 700mL deionized water of stirring and dissolving in there-necked flask, adopt magnetic agitation, reflux condensation mode 24h.Reaction finishes rear deionized water filtering and washing 7 times of using, and absolute ethyl alcohol filtering and washing 1 time, puts into baking oven dried overnight.Obtain CoZnAl-CO
3-LDH (Co:Zn:Al=0.4:1.6:1).
Step B:CoZnAl-CO
3-LDH (Co:Zn:Al=0.4:1.6:1) precursor is at H
2/ N
2in=5/95 gaseous mixture, at 800 DEG C of temperature, reduce 4h, obtain catalyst 11.8%Co-(ZnO-ZnAl
2o
4).
Autoclave liner adds HMF126.11mg, 600mg catalyst, and oxolane 5ml, the interior mark decane of certain mass, installation high-voltage still, is filled with H from air inlet
2, the air of displacement in autoclave 10 times, is then filled with the H of 0.7MPa
2, sealing autoclave.Autoclave is heated to preset temperature.130 DEG C, start timing, reaction 6h, HMF transforms completely, and after reaction finishes, cold air is down to room temperature, discharge autoclave gas, the reactant liquor that takes out inside liner is centrifugal.Get supernatant for GC quantitative analysis raw material and product.Record DMF productive rate 74.1%.
Embodiment 2
Steps A: measure 700mL deionized water to there-necked flask, accurately take and add respectively Co (NO
3)
26H
2o, Mg (NO
3)
26H
2o, Al (NO
3)
39H
2o, urea, corresponding concentration 1mmolL
-1, 9mmolL
-1, 5mmolL
-1and 35mmolL
-1, in the 700mL deionized water of stirring and dissolving in there-necked flask, magnetic agitation, reflux condensation mode 24h.Reaction finishes rear deionized water filtering and washing 7 times of using, and absolute ethyl alcohol filtering and washing 1 time, puts into baking oven dried overnight.Obtain CoZnAl-CO
3-LDH (Co:Mg:Al=0.2:1.8:1).
Step B:CoMgAl-CO
3-LDH (Co:Mg:Al=0.2:1.8:1) precursor is at H
2/ N
2in=5/95 gaseous mixture, 800 DEG C of reduction 4h, obtain catalyst 12.1%Co-(MgO-MgAl
2o
4).
Autoclave liner adds HMF126.11mg, 600mg catalyst, and oxolane 5ml, the interior mark decane of certain mass, installation high-voltage still, is filled with H from air inlet
2, the air of displacement in autoclave 10 times, is then filled with the H of 0.7MPa
2, sealing autoclave.Autoclave is heated to preset temperature.130 DEG C, start timing, reaction 24h, after reaction finishes, cold air is down to room temperature, discharge autoclave gas, the reactant liquor that takes out inside liner is centrifugal.Get supernatant for GC quantitative analysis raw material and product.Record DMF productive rate 44.7%.
Embodiment 3
Steps A: measure the deionized water of 700mL to there-necked flask, accurately take and add respectively Zn (NO
3)
26H
2o, Co (NO
3)
26H
2o, Al (NO
3)
39H
2o, urea, its corresponding concentration is 5mmolL
-1, 5mmolL
-1, 5mmolL
-1and 35mmolL
-1, in the 700mL deionized water of stirring and dissolving in there-necked flask, adopt magnetic agitation, reflux condensation mode 24h.Reaction finishes rear deionized water filtering and washing 7 times of using, and absolute ethyl alcohol filtering and washing 1 time, puts into baking oven dried overnight.Obtain CoZnAl-CO
3-LDH (Co:Zn:Al=1:1:1).
Step B:CoZnAl-CO
3-LDH (Co:Zn:Al=1:1:1) precursor is at H
2/ N
2in=5/95 gaseous mixture, at 800 DEG C of temperature, reduce 4h, obtain catalyst 33.8%Co-(ZnO-ZnAl
2o
4).
Autoclave liner adds HMF126.11mg, 600mg catalyst, and oxolane 5ml, the interior mark decane of certain mass, installation high-voltage still, is filled with H from air inlet
2, the air of displacement in autoclave 10 times, is then filled with the H of 0.7MPa
2, sealing autoclave.Autoclave is heated to preset temperature.130 DEG C, start timing, reaction 24h, after reaction finishes, cold air is down to room temperature, discharge autoclave gas, the reactant liquor that takes out inside liner is centrifugal.Get supernatant for GC quantitative analysis raw material and product.Catalyzer with water and ethanol lotion.Record DMF productive rate 70.1%.
Embodiment 4
Steps A: the salting liquid Ni (NO for preparing respectively 300ml
3)
26H
2o, Zn (NO
3)
26H
2o and A1 (NO
3)
39H
2o, corresponding concentration is respectively 0.016molL
-1, 0.64molL
-1, 0.040molL
-1, then prepare respectively aqueous slkali NaOH and the Na of 300ml
2cO
3, wherein OH
-root and CO
3 2-the concentration of root is [OH
-]=1.6 × ([Ni
2+]+[A1
3+]), [CO
3 2-]=2[A1
3+].Aqueous slkali and salting liquid are added drop-wise to the there-necked flask of 1000ml simultaneously, detect constantly the pH value of mixed solution in there-necked flask with pH meter, guarantee that its pH value is 9.0.After titration completes at ambient temperature, be warming up to 65 DEG C, then use magnetic agitation 24h.After reaction, will obtain solid solution suction filtration, with deionized water washing 6 times, and wash 1 time with ethanol lotion.Put into 80 DEG C of oven dryings.After oven dry, take out, grind and weigh.NiZnAl-CO
3-LDH(Ni：Zn：Al＝0.4：1.6：1)。
Step B:NiZnAl-CO
3-LDH (Ni:Zn:Al=0.4:1.6:1) precursor is at H
2/ N
2in=5/95 gaseous mixture, 800 DEG C of reduction 4h, obtain catalyst 12.5%Ni-(ZnO-ZnAl
2o
4).
Autoclave liner adds HMF126.11mg, 600mg catalyst, and oxolane 5ml, the interior mark decane of certain mass, installation high-voltage still, is filled with H from air inlet
2, the air of displacement in autoclave 10 times, is then filled with the H of 0.7MPa
2, sealing autoclave.Autoclave is heated to preset temperature.130 DEG C, start timing, reaction 24h, after reaction finishes, cold air is down to room temperature, discharge autoclave gas, the reactant liquor that takes out inside liner is centrifugal.Get supernatant for GC quantitative analysis raw material and product.Catalyzer with water and ethanol lotion.Record DMF productive rate 27.4%.
Embodiment 5
Steps A: the salting liquid Ni (NO for preparing respectively 300ml
3)
26H
2o, Co (NO
3)
26H
2o, Zn (NO
3)
26H
2o and A1 (NO
3)
39H
2o, corresponding concentration is respectively 0.008molL
-1, 0.008molL
-1, 0.64molL
-1, 0.040molL
-1, then prepare respectively aqueous slkali NaOH and the Na of 300ml
2cO
3, wherein OH
-root and CO
3 2-the concentration of root is [OH
-]=1.6 × ([Co
2+]+[Cu
2+]+[A1
3+]), [CO
3 2-]=2[A1
3+].Aqueous slkali and salting liquid are added drop-wise to the there-necked flask of 1000ml simultaneously, detect constantly the pH value of mixed solution in there-necked flask with pH meter, guarantee that its pH value is 9.0.After titration completes at ambient temperature, be warming up to 65 DEG C, then use magnetic agitation 24h.After reaction, will obtain solid solution suction filtration, with deionized water washing 6 times, and wash 1 time with ethanol lotion.Put into 80 DEG C of oven dryings.After oven dry, take out, grind and weigh.NiCoZnAl-CO
3-LDH(Ni：Co：Zn：Al＝0.2：0.2：1.6：1)
Step B:NiCoZnAl-CO
3-LDH (Ni:Co:Zn:Al=0.2:0.2:1.6:1) precursor is at H
2/ N
2in=5/95 gaseous mixture, 800 DEG C of reduction 4h, obtain catalyst 11.1%Ni
1co
1-(ZnO-ZnAl
2o
4).
Autoclave liner adds HMF126.11mg, 600mg catalyst, and oxolane 5ml, the interior mark decane of certain mass, installation high-voltage still, is filled with H from air inlet
2, the air of displacement in autoclave 10 times, is then filled with the H of 0.7MPa
2, sealing autoclave.Autoclave is heated to preset temperature.130 DEG C, start timing, reaction 24h, after reaction finishes, cold air is down to room temperature, discharge autoclave gas, the reactant liquor that takes out inside liner is centrifugal.Get supernatant for GC quantitative analysis raw material and product.Record DMF productive rate 51.3%.
Claims (5)
1. the efficient living beings reforming catalyst of Monodispersed, is characterized in that, is made up of the metal active center nano particle of Monodispersed and oxide and the spinelle of hydrotalcite calcining, and metal active center is at least one in Cu, Ni, Co, Fe; Or above-mentioned just bivalent metal reactive center replaces the bivalent metal oxide of hydrotalcite calcining.
2. according to the catalyst of claim 1, it is characterized in that, metal active center is Co, Cu, Ni, Fe, CoNi, CoCu or CoFe.
3. according to the catalyst of claim 1, it is characterized in that, the content in catalyst metals activated centre is 5～70wt%.Active metal medium particle diameter is distributed in 10～70nm.
4. the method for catalyst of preparation claim 1, is characterized in that, catalyst is called again hydrotalcite taking LDHs and makes as precursor in-situ reducing, and hydrotalcite laminate bivalent cation is selected Zn
2+or Mg
2+, Tricationic is selected Al
3+, the metal active central ion entering between laminate is Cu
2+, Ni
2+, Co
2+, Fe
3+in at least one, Zn
2+or Mg
2+with Ni
2+, Co
2+, Cu
2+mol ratio is (0～10): 1; The all divalent metal M of hydrotalcite laminate
2+the all trivalent metal cation M of/hydrotalcite laminate
3+mol ratio=(2～5): 1, by hydrotalcite precursor at H
2/ N
2in=5/95 gaseous mixture, reduce, reduction temperature is controlled at 400 DEG C～850 DEG C, and the recovery time is controlled at 5min～6h, can obtain catalyst M (ZnO-ZnAl
2o
4) or M is (MgO-MgAl
2o
4) or M--Al
2o
3, wherein M is metal active center.
5. arbitrary catalyst of claim 1～3 is prepared bio-fuel 2 for catalysis biomass derivative 5 hydroxymethyl furfural, the method of 5-dimethyl furan, it is characterized in that, the mass fraction that adds substrate HMF is 1～10wt%, catalyst addition is 0.5:1～6:1 with the mass ratio of add 5 hydroxymethyl furfural, and reaction temperature is 130～160 DEG C, and reaction pressure is 0.5～2MPa, reaction time is 6～24h, and reaction dissolvent is oxolane.
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