CN103203232B - High dispersion supported nano noble metal catalyst and preparation method and application thereof - Google Patents
High dispersion supported nano noble metal catalyst and preparation method and application thereof Download PDFInfo
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- CN103203232B CN103203232B CN201310131856.8A CN201310131856A CN103203232B CN 103203232 B CN103203232 B CN 103203232B CN 201310131856 A CN201310131856 A CN 201310131856A CN 103203232 B CN103203232 B CN 103203232B
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Abstract
The invention relates to a high dispersion supported nano noble metal catalyst and a preparation method and application thereof. The preparation method comprises the following steps of: simultaneously compositing and reducing in one step under solvothermal condition based on an MgAl laminated double metal hydroxide of metal coordination ionic intercalation with palladium and platinum to obtain high dispersion amorphous carbon and laminated double metal hydroxide supported high dispersion noble metal Pd or Pt nano catalyst; applying to citral selective hydration to reaction for preparing citronellal or citronellol; and displaying excellent activity and high selectivity to products citronellal and citronellol. The catalyst is novel and unique in structure, green and energy-saving in process and strong in stability, and has wide application prospect.
Description
Technical field
The present invention relates to catalyst preparation technical field, particularly relate to a kind of loaded nano noble metal catalyst and preparation method thereof.This catalyst is for the selective hydrogenation of citral.
Technical background
Citral is the most challenging α, one of beta-unsaturated aldehyde ketone, and it has comprised three unsaturated bonds: two two keys of C=C and the two keys of C=O.Because citronellal (CAL) or citronellol (COL) are to prepare requisite raw material in spices, improve the main purpose that its productive rate is selective hydrogenation citral.Precious metals pd and Pt, because of its good catalytic activity, are conventional citral hydrogenation catalysts.Conventionally first loaded noble metal catalyst is that precious metal salt is immersed on carrier, then after deposition, dry, roasting, reduces and obtains ([Ruixia Liu, et al.J Catal with additional reducing agent (hydrogen and boron hydride etc.), 2010,269,191] [Ran Ma, et al.J Phys.Chem.C, 2010,114,15417] [Betiana C.Campo, et al.Ind.Eng.Chem.Res., 2009,48,10234]).But this preparation method's process is loaded down with trivial details, when consumption energy consumption, and in the catalyst obtaining active component particle size large, with the combination of carrier weak and dispersiveness and poor stability, the therefore low and easy inactivation of catalytic activity in catalytic reaction.Therefore the noble metal nano metallic catalyst of developing a kind of support type high dispersive newly, easy and high stable remains has a challenging target.
Layered double hydroxide, has another name called hydrotalcite, is called for short LDHs, is the compound being formed by interlayer anion and positively charged laminate ordered fabrication.LDHs chemical constitution formula is [M
2+ 1-xm
3+ x(OH)
2] (A
n- x/n) mH
2o, wherein M
2+and M
3+represent respectively divalence and trivalent metal cation, be positioned on main body laminate; A
n-for interlayer anion.The layer structure of LDHs makes it have peculiar property, as laminate forms adjustable sex change, interlayer anion interchangeability and acidity and basic character etc.Due to the flexibility of its structure, LDHs has become the important materials of the various catalyst of preparation, catalyst precarsor, catalyst carrier in recent years.
The present invention has set up a kind of easy method of preparing loaded nano noble metal catalyst.With MgAl-LDHs and glucose compound and reduction by a step while under solvent heat condition of noble metal coordination ion intercalation, obtain the amorphous carbon of high dispersive and the high dispersive noble metal nano catalyst of LDH load, and it is effectively applied to citral selective hydrogenation prepares in the reaction of citronellal or citronellol, catalyst structure is novel unique, technique green energy conservation, and catalyst stability is strong, thereby be with a wide range of applications.
Summary of the invention
The object of the invention is to provide a kind of easy new method of preparing high-dispersion loading type nano-noble metal catalyst, and uses it for selective hydrogenation citral.
In the present invention, the preparation scheme of catalyst is as follows: the hydrotalcite LDHs that first prepares noble metal coordination ion (chlorine palladium acid group or chloroplatinic acid root) intercalation by intercalation package technique, again by with glucose in next step the simultaneously compound and reduction of solvent heat condition, utilize the reduction characteristic of glucose itself, obtain the nano-noble metal catalyst with amorphous carbon and LDH load.Wherein the average grain diameter of nano-noble metal (Pd or Pt) particle is 3～10nm; In catalyst, the quality percentage composition of noble metal is 2.0～4.5%; In carrier, the mass percent of Mg, Al and C is respectively 5～25%, and 5～20% and 35～75%.
The preparation method of the high dispersive noble metal nano catalyst of above-mentioned amorphous carbon and LDH load is as follows:
A. prepare the mixed solution of magnesium nitrate, aluminum nitrate and precious metal salt by deionized water, and to make the wherein concentration of magnesium nitrate be 0.05～0.20mol/L, the concentration of aluminum nitrate is 0.05～0.20mol/L, and the concentration of precious metal salt is 1.0～5.0mmol/L.Wherein, the molar concentration rate of magnesium nitrate and aluminum nitrate is 1～3:1, and the molar concentration rate of magnesium nitrate and precious metal salt is 25～30:1.Described precious metal salt is the one in the acid of chlorine palladium or chloroplatinic acid.
B. the mixed solution of steps A preparation is poured in reaction vessel, it is 7～9 that the LiOH aqueous slkali that is 0.1～0.3mol/L by concentration is adjusted the pH value of solution; Pass into nitrogen crystallization 6～10h at 20～40 DEG C of temperature; Be cooled to room temperature, filter, to neutral, obtain the hydrotalcite of noble metal coordination ion intercalation with deionized water washing.
C. glucose is dissolved in the mixed solvent of alcohol and water, compound concentration is the glucose solution of 0.1～0.5mol/L, the hydrotalcite that step B is obtained and glucose solution add in crystallization device, and the mol ratio that makes glucose and hydrotalcite la m metal ion is [C
6h
12o
6]/[Mg
2++ Al
3+]=1～5:1, is heated to 100～180 DEG C after sealing, reaction 5～10h; Naturally cool to room temperature, take out mixture centrifugal, with ethanol washing 2～4 times, dry at 50～80 DEG C of temperature, obtain loaded catalyst.
In the mixed solvent of described alcohol and water, the volume ratio of alcohol and water is 1:1～3, and described alcohol is methyl alcohol, the one in ethanol or isopropyl alcohol;
The carried noble metal nanocatalyst obtaining is carried out to structural characterization test, the results are shown in Fig. 1-2.Fig. 1 is the XRD spectra of embodiment 1 catalyst.As can be seen from Figure, the MgAl-LDH of chlorine palladium acid group intercalation has typical hydrotalcite (003), (006), (012), (110) and (113) characteristic diffraction peak.Also there are (111) of Pd metal simultaneously, (200) and (220) characteristic peak, this illustrates carrying out in assembling process with glucose, PdCl
4 2-ion is generated Pd simple substance by in-situ reducing.Fig. 2 is transmission electron microscope (TEM) photo of catalyst described in embodiment 1.Can find out that nano metal is evenly dispersed on carrier surface, and size homogeneous, particle size average out to 5.5nm.Demonstrate carrier is made up of LDHs and the amorphous carbon of stratiform simultaneously.
The catalyst preparing is applied to liquid phase citral selective hydrogenation.Citral is dissolved in 100ml isopropanol solvent, and being configured to concentration is the citral solution of 58.4mmol/L, joins in autoclave with the 0.073g loaded with nano metallic catalyst obtaining in embodiment 1 simultaneously, passes into the H of 1.0MPa
2, temperature rises to 100 DEG C of reactions, makes the conversion ratio of citral hydrogenation reaction and citronellal or citronellol are selectively respectively to 95～100% and 85.0～95.0%.Fig. 3 is the citral conversion ratio that records of the metallic catalyst of the load that obtains of embodiment 1 and the selective time dependent curve of citronellal or citronellol.
The present invention has following remarkable result: (1) is compound by layered double hydroxide and the glucose of noble metal coordination ion intercalation, and utilize the reduction characteristic of glucose itself, without high-temperature roasting and additional reducing agent, a step obtains taking layered double hydroxide and amorphous carbon as carrier loaded noble metal nano metallic catalyst; (2) in solvent heat process, the hydridization product of glucose has not only served as good C carrier, and itself has gentle reproducibility, precious metal ion that can in-situ reducing intercalation; (3) carrier of high-ratio surface is conducive to disperse noble metal nano particles, and strong interaction between carrier and nano particle can improve the structural stability of catalyst; (4) the alkalescence effect of high activity, polymolecularity and the carrier based on loaded nano particle self, this catalyst has embodied excellent catalytic performance in the hydrogenation reaction of citral, be 95～100% to citral conversion ratio, to citronellal or citronellol be selectively 85.0～95.0%, there is potential actual application value.
Brief description of the drawings
Fig. 1. the XRD spectra of the catalyst of preparing for embodiment 1.
Fig. 2. the TEM spectrogram of the carried noble metal metallic catalyst of preparing for embodiment 1.
Fig. 3. be embodiment 1 citral hydrogenation conversion and the selective time history plot to citronellal.
Detailed description of the invention
Embodiment 1
A. by the Mg (NO of 1.5384g
3)
26H
2al (the NO of O and 1.1254g
3)
39H
2o is mixed with 50ml mixing salt solution; Get the H of 0.04mol/L with pipette
2pdCl
4solution 5ml is added in above-mentioned mixed solution;
B. the mixing salt solution of steps A is added in reaction vessel, ultrasonic dispersion 20min, mixes it; The LiOH solution that dropping concentration is 0.18mol/L, in above-mentioned mixed salt solution, is adjusted the pH=8.0 of solution; At N
2atmosphere, crystallization 8h under 40 DEG C of reaction temperatures; Be cooled to room temperature, to neutral, be precipitated thing with deionized water centrifuge washing.
C. take 4.4588g glucose and dissolve in (V in 50ml ethanol water
c2H5OH/ V
h2O=1:3), sediment obtained above is slowly poured in the glucitol aqueous solution into ultrasonic dispersion 20min; Mixed solution is poured in reactor, and sealing, puts into 150 DEG C of baking ovens, hydridization 10h; Be cooled to room temperature and take out product, centrifuge washing, to neutral, dry, obtains Pd/C-LDH catalyst.Wherein the average grain diameter of Pd particle is 5.5nm; In catalyst, the quality percentage composition of Pd element is 2.5%; Mg in carrier, the mass percent of Al and C is respectively 10.5%, 9.7% and 67.8%.
Citral hydrogenation catalyst reaction, first toward the reactant citral, the catalyst obtaining in 0.073g embodiment 1 and the 100ml isopropanol solvent that add 58.4mmol/L in autoclave simultaneously.Reaction unit is installed, tightened, pass into nitrogen and be put into preheating 2h in 100 DEG C of oil bath pans.Finally emit N
2gas, passes into H
2gas, to 1.0MPa, stirs and starts reaction.When hydrogenation reaction proceeds to 60min, the conversion ratio of citral has reached 97.0%, and to citronellal is selectively 94.4%.
Embodiment 2
By the Mg (NO of 2.3076g
3)
26H
2al (the NO of O and 1.1254g
3)
39H
2o is mixed with 50ml mixed solution; Get the H of 0.04mol/L with pipette
2pdCl
4solution 5ml is added in above-mentioned mixed solution; The LiOH solid that takes 0.648g is dissolved in 150ml deionized water preparation alkaline solution, and wherein the concentration of LiOH aqueous slkali is 0.18mol/L.
The mixed salt solution configuring is added in reaction vessel, and ultrasonic dispersion 20min, mixes it; Alkaline solution is added drop-wise in above-mentioned mixed salt solution with buret, adjusts the pH=7.0 of solution; At N
2atmosphere, crystallization 8h under 40 DEG C of reaction temperatures; Be cooled to room temperature, to neutral, be precipitated thing with deionized water centrifuge washing.
Take 2.6753g glucose and dissolve in (V in 50ml methanol aqueous solution
cH3OH/ V
h2O=1:1), sediment obtained above is slowly poured in the glucitol aqueous solution; Mixed solution is poured in reactor, tightened and put into 150 DEG C of baking ovens, hydridization 8h; Be cooled to room temperature and take out product, centrifuge washing, dry, obtains Pd catalyst.Wherein the average grain diameter of Pd particle is 6.6nm; In catalyst, the quality percentage composition of Pd element is 3.6%; Mg in carrier, the mass percent of Al and C is respectively 23.8%, 14.6% and 47.5%.
Be that 58.4mmol/L citral, 0.050g Supported Pd-Catalyst are dissolved in 100ml isopropanol solvent jointly by concentration, then join in autoclave.Add after reaction substrate, catalysts and solvents, reaction unit is installed, tightened, pass into nitrogen and be put into preheating 2h in 100 DEG C of oil bath pans.Finally pass into H
2gas, to 1.0MPa, starts reaction.When hydrogenation reaction proceeds to 45min, the conversion ratio of citral has reached 100%, and to citronellal is selectively 86.2%.
Embodiment 3
By the Mg (NO of 1.9230g
3)
26H
2al (the NO of O and 1.1254g
3)
39H
2o is mixed with 50ml mixed solution; Get the H of 0.04mol/L with pipette
2ptCl
4solution 5ml is added in above-mentioned mixed solution; The LiOH solid that takes 0.648g is dissolved in 150ml deionized water preparation alkaline solution, and wherein the concentration of LiOH is 0.18mol/L.
The mixed salt solution configuring is added in reaction vessel, and ultrasonic dispersion 20min, mixes it; Alkaline solution is slowly added drop-wise in above-mentioned mixed salt solution, adjusts the pH=6.5 of solution; At N
2atmosphere, crystallization 8h under 30 DEG C of reaction temperatures; Be cooled to room temperature, to neutral, be precipitated thing with deionized water centrifuge washing.
Take 1.7835g glucose and dissolve in (V in 60ml ethanol water
c2H5OH/ V
h2O=1:2), sediment obtained above is slowly poured in the glucitol aqueous solution into ultrasonic dispersion 20min; Mixed solution is poured in reactor into hydridization 9h at 150 DEG C of temperature; Be cooled to room temperature and take out product, centrifuge washing, to neutral, dry, obtains catalyst.Wherein the average grain diameter of Pt particle is 5.0nm; In catalyst, the quality percentage composition of Pt element is 2.0%; Mg in carrier, the mass percent of Al and C is respectively 9.7%, 6.9% and 72.3%.
Be that 58.4mmol/L citral, 0.150g supported Pt catalysts, 100ml isopropanol solvent join in autoclave simultaneously by concentration.Then reaction unit is installed, tightened, pass into nitrogen and be put into preheating 1h in 100 DEG C of oil bath pans.Finally pass into H
2gas starts to react to 1.0MPa.When hydrogenation reaction proceeds to 40min, the conversion ratio of citral has reached 100%, and to citronellol is selectively 93.2%.
Embodiment 4
By the Mg (NO of 1.5384g
3)
26H
2al (the NO of O and 1.1254g
3)
39H
2o is mixed with 50ml mixed solution; Get the H of 0.04mol/L with pipette
2ptCl
4solution 5ml is added in above-mentioned mixed solution; The LiOH solid of 0.648g is dissolved in 150ml deionized water preparation alkaline solution, and wherein the concentration of LiOH is 0.18mol/L.
The mixed salt solution configuring is added in reaction vessel, and ultrasonic dispersion 20min, mixes it; Drip alkaline solution in above-mentioned mixed salt solution, adjust the pH=7.0 of solution; At N
2atmosphere, crystallization 8h under 35 DEG C of reaction temperatures; Be cooled to room temperature, to neutral, be precipitated thing with deionized water centrifuge washing.
Take 0.8918g glucose and dissolve in (V in 65ml isopropanol water solution
c3H7OH/ V
h2O=1:1.5), sediment obtained above is slowly poured in the glucitol aqueous solution; Mixed solution is poured in reactor into hydridization 8h under 150 DEG C of reaction temperatures; Be cooled to room temperature and take out product, centrifuge washing, to neutral, dry, obtains catalyst.Wherein the average grain diameter of Pt particle is 7.5nm; In catalyst, the quality percentage composition of Pt element is 5.0%; Mg in carrier, the mass percent of Al and C is respectively 24.4%, 20.6% and 39.2%.
Be that 58.4mmol/L citral, 0.032g supported Pt catalysts are jointly dissolved in 100ml isopropanol solvent, and join in autoclave by concentration.Add after reaction substrate, catalysts and solvents, reaction unit is installed, pass into nitrogen and be put into preheating 2h in 100 DEG C of oil bath pans.Finally emit N
2gas, passes into H
2gas is to 1.0MPa, and magnetic agitation starts reaction.When hydrogenation reaction proceeds to 60min, the conversion ratio of citral has reached 100%, and to citronellol is selectively 90.3%.
Claims (3)
1. a preparation method for high-dispersion loading type nano-noble metal catalyst, concrete steps are as follows:
A. prepare the mixed solution of magnesium nitrate, aluminum nitrate and precious metal salt by deionized water, and to make the wherein concentration of magnesium nitrate be 0.05 ~ 0.20 mol/L, the concentration of aluminum nitrate is 0.05 ~ 0.20 mol/L, and the concentration of precious metal salt is 1.0 ~ 5.0 mmol/L; Wherein, the molar concentration rate of magnesium nitrate and aluminum nitrate is 1 ~ 3:1, and the molar concentration rate of magnesium nitrate and precious metal salt is 25 ~ 30:1; Described precious metal salt is the one in the acid of chlorine palladium or chloroplatinic acid;
B. the mixed solution of steps A preparation is poured in reaction vessel, adjusting the pH value of solution with the LiOH aqueous slkali that concentration is 0.1 ~ 0.3 mol/L is 7 ~ 9; Pass into nitrogen crystallization 6 ~ 10 h at 20 ~ 40 DEG C of temperature; Be cooled to room temperature, filter, to neutral, obtain the hydrotalcite of noble metal coordination ion intercalation with deionized water washing;
C. glucose is dissolved in the mixed solvent of alcohol and water, compound concentration is the glucose solution of 0.1 ~ 0.5 mol/L, the hydrotalcite that step B is obtained and glucose solution add in crystallization device, and the mol ratio that makes glucose and hydrotalcite la m metal ion is [C
6h
12o
6]/[Mg
2++ Al
3+]=1 ~ 5:1, is heated to 100 ~ 180 DEG C after sealing, reaction 5 ~ 10 h; Naturally cool to room temperature, take out mixture centrifugal, with ethanol washing 2 ~ 4 times, dry at 50 ~ 80 DEG C of temperature, obtain loaded catalyst;
In the mixed solvent of described alcohol and water, the volume ratio of alcohol and water is 1:1 ~ 3, and described alcohol is methyl alcohol, the one in ethanol or isopropyl alcohol.
2. the high-dispersion loading type nano-noble metal catalyst that prepared by method according to claim 1, wherein the average grain diameter of nano-noble metal particle is 3 ~ 10 nm; In catalyst, the quality percentage composition of noble metal is 2.0 ~ 4.5 %; In carrier, the mass percent of Mg, Al and C is respectively 5 ~ 25 %, 5 ~ 20 % and 35 ~ 75 %.
3. an application for high-dispersion loading type nano-noble metal catalyst claimed in claim 2, this catalyst is for the selective hydrogenation of citral.
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| CN104148059B (en) * | 2014-06-19 | 2017-02-22 | 北京化工大学 | Reforming catalyst with high dispersion stability and preparation method thereof |
| CN106001598B (en) * | 2016-05-11 | 2018-06-26 | 北京化工大学 | A kind of method of hydrotalcite layers synthesizing flaky gold nanoparticle |
| CN106025293B (en) * | 2016-07-08 | 2019-08-13 | 青岛大学 | A kind of preparation of platinum/carbon ball@zinc-iron layered double hydroxide composite material |
| CN107308933A (en) * | 2017-08-15 | 2017-11-03 | 浙江大学 | A kind of application of high dispersive noble metal catalyst in electrochemistry evolving hydrogen reaction |
| CN107670663B (en) * | 2017-08-30 | 2020-07-03 | 江南大学 | Composite AuAgPd catalyst for alkynol hydrolysis and oxidation reaction and preparation method thereof |
| CN108311158B (en) * | 2018-01-31 | 2020-11-13 | 中南民族大学 | Catalyst, preparation method thereof and application thereof in reduction of vanillin |
| CN109569599B (en) * | 2018-12-22 | 2021-11-30 | 江西师范大学 | Catalyst for preparing 1, 3-dihydroxyacetone and preparation method thereof |
| CN112121793B (en) * | 2020-09-17 | 2022-08-05 | 万华化学集团股份有限公司 | Catalyst for preparing citronellal by citral hydrogenation, preparation method of catalyst, and method for preparing citronellal by citral hydrogenation |
| CN116116442B (en) * | 2023-02-20 | 2023-12-22 | 常州大学 | Preparation method and application of low-load sub-nanometer noble metal catalyst |
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| CN102059113A (en) * | 2010-11-30 | 2011-05-18 | 北京化工大学 | Stratiform bimetal hydroxide for growing carbon nano-fibers and preparation method thereof |
| CN102872872A (en) * | 2011-07-12 | 2013-01-16 | 北京化工大学 | Loading nano Ni-B type catalyst by using Al2O3 and C as carrier, and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102059113A (en) * | 2010-11-30 | 2011-05-18 | 北京化工大学 | Stratiform bimetal hydroxide for growing carbon nano-fibers and preparation method thereof |
| CN102872872A (en) * | 2011-07-12 | 2013-01-16 | 北京化工大学 | Loading nano Ni-B type catalyst by using Al2O3 and C as carrier, and preparation method thereof |
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