CN101554596A - Method for preparing solid base catalyst with high specific surface by hybrid composite precursors - Google Patents
Method for preparing solid base catalyst with high specific surface by hybrid composite precursors Download PDFInfo
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- CN101554596A CN101554596A CNA200910084375XA CN200910084375A CN101554596A CN 101554596 A CN101554596 A CN 101554596A CN A200910084375X A CNA200910084375X A CN A200910084375XA CN 200910084375 A CN200910084375 A CN 200910084375A CN 101554596 A CN101554596 A CN 101554596A
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Abstract
The invention relates to a method for preparing solid base catalyst with high specific surface by hybrid composite precursors, belonging to the technical field of preparation of composite metal oxide. The method comprises the following steps of: according to the characteristics of designability in structure and adjustability in laminate composition of laminated composite metal hydroxide, introducing a certain amount of Mg<2+> and Al<3+>, or Ca<2+>, Cu<2+>, Co<2+>, In<3+> and Ga<3+> on the laminate, preparing laminated compound, obtaining hybrid composite precursors by hybridization with carbon, then conducting high-temperature roasting on the precursors and obtaining the solid base catalyst of composite metal oxide with high specific surface and mesoporous structure. Due to introduction of the carbon into the precursors, the composite metal oxide obtained by the method has the characteristics of narrow pore size distribution and large specific surface area and the like, and the application of the catalyst in Knoevenagel condensation reaction of benzaldehyde and ethyl cyanoacetate shows good base catalytic activity.
Description
Technical field
The invention belongs to the composite metal oxide preparing technical field, particularly provide a kind of and prepared the method for solid base catalyst with high specific surface by hybrid composite precursors, the hybrid composite precursors preparation has meso-hole structure.
Technical background
The homogeneous phase base catalysis is industrial important catalytic process, and its status can't shake so far, but the shortcoming of homogeneous phase base catalysis also is tangible.At first, participate in reaction owing to be the homogeneous phase mode, have etching apparatus, drawbacks such as contaminated environment with reactant liquor as base catalysts such as NaOH, KOH.Secondly, catalyst and reactant are in same liquid phase, and the separation of catalyst is extremely bothered, and are not easy to realize continuous production, and production scale also is not easy to enlarge, and production cost is higher.The 3rd, the base catalyst that remains in the reactant generally also needs pickling and washing, discharges a large amount of sewage, and environmental pollution is serious.At this problem, the catalysis workers launch than systematic research the base catalyst that participates in reaction with solid form, find to substitute homogeneous phase solution alkali with solid base, can overcome above-mentioned shortcoming, catalyst is easy to separate with reactant simultaneously, is convenient to regeneration, also is convenient to continuous production.In addition, solid base can catalytic fluid alkali can not catalysis chemical reaction, and utilize the space behavior of solid base and duct to select the shape effect and also can improve the selectivity of reaction.
Alkaline earth oxides such as MgO, CaO, BaO are through all being very activated base catalyst after the suitable activation processing, and their basic sites is mainly derived from hydroxyl and the electronegative Lattice Oxygen that produces after the surperficial adsorbed water.At present, the alkaline earth oxide catalyst mainly is that the method by burning carbon hydrochlorate, hydroxide or acetate precursor prepares, but since during high-temperature calcination product reunite easily, whole homogeneity is poor, specific area is very little, has seriously influenced their application.In order to overcome the defective of traditional preparation process method, (Jose Salmones such as Jose Salmones, Beatriz Zeifert, Miguel Hesiquio Garduno, Jose Contreras-Larios, Synthesis and characterization ofhydrotalcites by mechanical milling and conventional method, Catalysis Today 133-135 (2008) 886-890) prepares magnalium carbonate type hydrotalcite precursor with coprecipitation, obtained alkaline Al-Mg composite metal oxide by mechanical ball milling then, but preparation process complexity, the alkaline composite metal oxide material specific area that obtains is little, and particle size is bigger; (V.V.Brei such as V.V.Brei, O.V.Melezhyk, G.M.Starukh, E.I.Oranskaya, P.A.Mutovkin, Organic precursor synthesis of Al-Mg mixed oxides andhydrotalcites, Microporous and Mesoporous Materials 113 (2008) 411-417) magnalium carbonate hydrotalcite precursor and then the roasting that organises by preparation prepares the composite metal oxide with nanostructured, but owing to need a large amount of organic solvents such as formic acid in the preparation, environmental pollution is serious.Given this, the present invention proposes the layered double hydroxide (LDHs) that will contain catalytic active component and form hybrid composite precursors, and further obtain having the high-ratio surface compound metal oxide solid base catalyst of meso-hole structure by firing precursor with the carbon assembling.
Summary of the invention
Layered double hydroxide (LDHs) is the novel nano inorganic functional material that a class has layer structure, and its chemical composition can be expressed as [M
Z+ 1-XM
3+ X(OH)
2]
X+(A
N-)
X/nMH
2O, wherein M
2+Be Mg
2+, Ni
2+, Co
2+, Zn
2+, Cu
2+Deng divalent metal; M
3+Be Al
3+, Cr
3+, Ga
3+, In
3+, Fe
3+, Sc
3+Deng trivalent metal cation; A
N-Be anion, as CO
3 2-, NO
3 -, Cl
-, OH
-, SO
4 2-, PO
4 3-, C
6H
4(COO)
2 2-Etc. inorganic, organic ion and complex ion, the X value is between 0.17～0.33.In the LDHs crystal structure, owing to be subjected to the influence of minimum effect of lattice energy and lattice orientation effect thereof, make metal ion on laminate, evenly distribute in a certain way, promptly on laminate in each small construction unit, its chemical composition and structure are constant; And be positioned at the anion of interlayer owing to be subjected to the coordination, electronics transfer effect or the like of restriction, interlayer ion and laminate group in attraction, the repulsion between interlayer ion, the layer space of laminate electric charge and influence, it is also very even to distribute.Because this chemical composition and Modulatory character on the microstructure and the whole uniformity of LDHs itself are again the two-dimensional nano materials, so the material of this special construction and composition is synthetic good precursor with multicomponent reactive component height composite metal oxide.
The object of the present invention is to provide a kind of preparation method with solid base catalyst with high specific surface of meso-hole structure.Specific characteristic according to LDHs laminate The Nomenclature Composition and Structure of Complexes uniformity and adjustable sex change on microcosmic thereof, the component that will contain catalytic activity is introduced the LDHs laminate, and in the LDHs crystallization process, introduce carbohydrate molecule as carbon source, crystallization and the glycan molecule carbonization of LDHs are taken place simultaneously, assembling forms whole homogeneous, but the LDHs/C type hybrid composite precursors of The Nomenclature Composition and Structure of Complexes modulation, remove the carbon in the hybrid composite precursors and LDHs is decomposed by high-temperature roasting then, finally obtain forming, but structure and performance modulation has a meso-hole structure, the compound metal oxide solid base catalyst of high-ratio surface.LDHs's consists of [Mg in the hybrid composite precursors
1-x-yM
2+YAl
3+ X-zM
3+ z(OH)
2]
X+(A
N-)
X/n(0.17≤x≤0.33; 0≤y≤(1-x)/2; 0≤z≤x/2), wherein bivalent metal ion M
2+Be Ca
2+, Cu
2+, Co
2+In one or more, trivalent metal ion M
3+Be In
3+, Ga
3+In one or both; The specific area of compound metal oxide solid base catalyst is 120～280m
2/ g, the most probable aperture is 6～18nm's.Because it has the active component high degree of dispersion, the narrow characteristics of the big and mesoporous pore-size distribution of specific area, this compound metal oxide solid base catalyst has shown higher activity and selectivity in the Knoevenagel of catalysis cyan-acetic ester and benzaldehyde condensation reaction, the conversion ratio of cyan-acetic ester is 80～95%, and the selectivity of product alpha-cyano ethyl cinnamate is 100%.
The preparation method of this solid base catalyst is:
A. use soluble M g
2+And Al
3+, or other divalent metal M
2+With trivalent metal M
3+Nitrate preparation mixing salt solution, wherein the molar concentration of each metal ion species is respectively Mg
2+: 0.1～0.4mol/L, M
2+: 0～0.2mol/L, Al
3+: 0.025～0.3mol/L; M
3+: 0～0.15mol/L; Described M
2+Can be Co
2+, Cu
2+Or Ca
2+In one or more, described M
3+Can be In
3+Or Ga
3+In one or both; NaOH and sodium carbonate are dissolved in preparation mixed-alkali solution in the deionized water, and wherein the NaOH molar concentration is 0.5～2.5mol/L, and the sodium carbonate molar concentration is 0.2～1.0mol/L;
B. the mixing salt solution and the mixed ammonium/alkali solutions that configure are at room temperature poured in the colloid mill of rotation (3000～6000 rev/mins) at a high speed fast with the speed of 20～30ml/s, vigorous stirring 2-5 minute, then that the suspension that obtains is centrifugal, washing 3～5 times promptly obtains houghite precursor nucleus to neutral.
C. compound concentration is the aqueous solution of the sugar of 0.05～0.2g/ml, and sugar can be any one in glucose, sucrose or the fructose; The houghite precursor nucleus that step b is obtained adds in the sugar aqueous solution, and wherein the mol ratio of metal ion and sugar is 0.25～1 in the precursor nucleus; The syrup mixed solution that adds houghite precursor nucleus is transferred in the autoclave of polytetrafluoroethylliner liner, be heated to 150～180 ℃ after the sealing, be incubated 12～48 hours; Naturally cool to room temperature afterwards, filter, wash, obtain hybrid composite precursors.
D. the hybrid composite precursors that step c is prepared places Muffle furnace, speed with 5～15 ℃/min is warming up to 400～700 ℃, insulation 2～5h naturally cools to room temperature then, obtains having meso-hole structure, the compound metal oxide solid base catalyst of high-ratio surface.
Remarkable result of the present invention: 1,, realized the regulation and control of pore structure, specific area and catalytic activity to solid base catalyst by the ratio of modulation houghite precursor layer plate element, carbon source and metal ion; 2, the catalytic active component in the hybrid composite precursors by roasting after alkaline active sites high degree of dispersion in composite metal oxide, having shown pore-size distribution, narrow (the most probable aperture is 6～18nm), the big (120～280m of specific area
2/ g), active component combines with carrier by force, catalytic activity is high, catalyst does not run off characteristic; 3, technical process of the present invention does not have corrosiveness to production equipment, and non-environmental-pollution is fit to suitability for industrialized production.
The specific embodiment:
Embodiment 1
Take by weighing Mg (NO
3)
26H
2O and Al (NO
3)
39H
2O is dissolved in the 30ml deionized water and prepares mixing salt solution, wherein Mg
2+Molar concentration be 0.3mol/L, Al
3+Molar concentration is 0.1mol/L; With NaOH and sodium carbonate preparation NaOH molar concentration is 0.64mol/L, and concentration of sodium carbonate is 30 milliliters of the mixed ammonium/alkali solutions of 0.2mol/L.The mixing salt solution and the mixed ammonium/alkali solutions that configure are at room temperature poured into rapidly in the colloid mill of rotation (6000 rev/mins) at a high speed, and 5 fens kinds are stirred in violent rotation, and the suspension centrifugation with obtaining is washed to PH=7 again, obtains sediment.0.54g glucose is dissolved in obtain solution in the 30ml deionized water, and add the sediment that obtains, wherein the mol ratio of metal ion and sugar is 0.25 in the sediment; Above-mentioned mixed solution is transferred in the autoclave of polytetrafluoroethylliner liner, be heated to 150 ℃ after the sealing, be incubated 12 hours; Naturally cool to room temperature afterwards, filter, wash, obtain hybrid composite precursors.Hybrid composite precursors is placed in the Muffle furnace, and 10 ℃/min of heating rate rises to 500 ℃, is incubated 2 hours, promptly obtains the compound metal oxide solid base catalyst.Low temperature N
2The absorption representation specific area is 150m
2/ g, the most probable aperture is 15.0nm.
The compound metal oxide solid base catalyst is used for the Knoevenagel condensation reaction, concrete course of reaction is: add cyan-acetic ester 5.6555g (50mmol) in the 50ml there-necked flask, benzaldehyde 5.068g (50mmol), adding mass fraction is the catalyst of 1% (0.1096g), N
2Atmosphere protection, the cyan-acetic ester conversion ratio is 86% behind 60 ℃ of following reaction 12h, the selectivity of alpha-cyano ethyl cinnamate is 100%.
Embodiment 2
Take by weighing Mg (NO
3)
26H
2O, Ca (NO
3)
24H
2O and Al (NO
3)
39H
2O is dissolved in the 30ml deionized water and prepares mixing salt solution, wherein Mg
2+Molar concentration be 0.3mol/L, Ca
2+Molar concentration be 0.1mol/L, Al
3+Molar concentration is 0.2mol/L; With NaOH and sodium carbonate preparation NaOH molar concentration is 1.0mol/L, and concentration of sodium carbonate is 30 milliliters of the mixed ammonium/alkali solutions of 0.5mol/L.The mixing salt solution and the mixed ammonium/alkali solutions that configure are at room temperature poured into rapidly in the colloid mill of rotation (5000 rev/mins) at a high speed, and 2 fens kinds are stirred in violent rotation, and the suspension centrifugation with obtaining is washed to PH=7 again, obtains sediment.3.24g sucrose is dissolved in obtain solution in the 30ml deionized water, and add the sediment that obtains, wherein the mol ratio of metal ion and sugar is 1.0 in the sediment; Above-mentioned mixed solution is transferred in the autoclave of polytetrafluoroethylliner liner, be heated to 160 ℃ after the sealing, be incubated 36 hours; Naturally cool to room temperature afterwards, filter, wash, obtain hybrid composite precursors.Hybrid composite precursors is placed in the Muffle furnace, and 5 ℃/min of heating rate rises to 400 ℃, is incubated 5 hours, promptly obtains the compound metal oxide solid base catalyst.Low temperature N
2The absorption representation specific area is 220m
2/ g, the most probable aperture is 10.5nm.
Catalyst is used for catalysis Knoevenagel condensation reaction, and concrete course of reaction is: add cyan-acetic ester 5.6555g (50mmol) in the 50ml there-necked flask, and benzaldehyde 5.068g (50mmol), adding mass fraction is the catalyst of 1% (0.1096g), N
2Atmosphere protection, the cyan-acetic ester conversion ratio is 93% behind 60 ℃ of following reaction 12h, the selectivity of alpha-cyano ethyl cinnamate is 100%.
Embodiment 3
Take by weighing Mg (NO
3)
26H
2O, Co (NO
3)
26H
2O, Cu (NO
3)
26H
2O and Al (NO
3)
39H
2O is dissolved in the 30ml deionized water and prepares mixing salt solution, wherein Mg
2+Molar concentration be 0.4mol/L, Cu
2+Molar concentration be 0.1mol/L, Co
2+Molar concentration be 0.05mol/L, Al
3+Molar concentration is 0.3mol/L; With NaOH and sodium carbonate preparation NaOH molar concentration is 2.5mol/L, and concentration of sodium carbonate is 30 milliliters of the mixed ammonium/alkali solutions of 1.0mol/L.The mixing salt solution and the mixed ammonium/alkali solutions that configure are at room temperature poured into rapidly in the colloid mill of rotation (4000 rev/mins) at a high speed, and 3 fens kinds are stirred in violent rotation, and the suspension centrifugation with obtaining is washed to PH=7 again, obtains sediment.3.4g fructose is dissolved in obtain solution in the 30ml deionized water, and add the sediment that obtains, wherein the mol ratio of metal ion and sugar is 0.75 in the sediment; Above-mentioned mixed solution is transferred in the autoclave of polytetrafluoroethylliner liner, be heated to 180 ℃ after the sealing, be incubated 48 hours; Naturally cool to room temperature afterwards, filter, wash, obtain hybrid composite precursors.Hybrid composite precursors is placed in the Muffle furnace, and 5 ℃/min of heating rate rises to 700 ℃, is incubated 5 hours, promptly obtains the compound metal oxide solid base catalyst.Low temperature N
2The absorption representation specific area is 120m
2/ g, the most probable aperture is 18nm.
Catalyst is used for catalysis Knoevenagel condensation reaction, and concrete course of reaction is: add cyan-acetic ester 5.6555g (50mmol) in the 50ml there-necked flask, and benzaldehyde 5.068g (50mmol), adding mass fraction is the catalyst of 1% (0.1096g), N
2Atmosphere protection, the cyan-acetic ester conversion ratio is 80% behind 60 ℃ of following reaction 12h, the selectivity of alpha-cyano ethyl cinnamate is 100%.
Embodiment 4
Take by weighing Mg (NO
3)
26H
2O, In (NO
3)
3And Al (NO
3)
39H
2O is dissolved in the 30ml deionized water and prepares mixing salt solution, wherein Mg
2+Molar concentration be 0.35mol/L, In
3+Molar concentration be 0.05mol/L, Al
3+Molar concentration be 0.15mol/L; With NaOH and sodium carbonate preparation NaOH molar concentration is 2.0mol/L, and concentration of sodium carbonate is 30 milliliters of the mixed ammonium/alkali solutions of 0.5mol/L.The mixing salt solution and the mixed ammonium/alkali solutions that configure are at room temperature poured into rapidly in the colloid mill of rotation (3000 rev/mins) at a high speed, and 5 fens kinds are stirred in violent rotation, and the suspension centrifugation with obtaining is washed to PH=7 again, obtains sediment.1.5g glucose is dissolved in obtain solution in the 30ml deionized water, and add the sediment that obtains, wherein the mol ratio of metal ion and sugar is 0.5 in the sediment; Above-mentioned mixed solution is transferred in the autoclave of polytetrafluoroethylliner liner, be heated to 150 ℃ after the sealing, be incubated 12 hours; Naturally cool to room temperature afterwards, filter, wash, obtain hybrid composite precursors.Hybrid composite precursors is placed in the Muffle furnace, and 10 ℃/min of heating rate rises to 500 ℃, is incubated 2 hours, promptly obtains the compound metal oxide solid base catalyst.Low temperature N
2The absorption representation specific area is 280m
2/ g, the most probable aperture is 6.0nm.
Catalyst is used for catalysis Knoevenagel condensation reaction, and concrete course of reaction is: add cyan-acetic ester 5.6555g (50mmol) in the 50ml there-necked flask, and benzaldehyde 5.068g (50mmol), adding mass fraction is the catalyst of 1% (0.1096g), N
2Atmosphere protection, the cyan-acetic ester conversion ratio is 95% behind 60 ℃ of following reaction 12h, the selectivity of alpha-cyano ethyl cinnamate is 100%.
Claims (4)
1. one kind prepares the method for solid base catalyst with high specific surface by hybrid composite precursors, it is characterized in that preparation process is:
A. use soluble M g
2+And Al
3+, or other divalent metal M
2+With trivalent metal M
3+Nitrate preparation mixing salt solution; NaOH and sodium carbonate are dissolved in preparation mixed-alkali solution in the deionized water, and wherein the NaOH molar concentration is 0.5～2.5mol/L, and the sodium carbonate molar concentration is 0.2～1.0mol/L;
B. at room temperature pouring the mixing salt solution that configures and mixed ammonium/alkali solutions into the rotation revolution fast with the speed of 20～30ml/s is in 3000～6000 rev/mins the colloid mill, stirred 2-5 minute, then that the suspension that obtains is centrifugal, washing 3～5 times obtains houghite precursor nucleus to neutral;
C. compound concentration is the aqueous solution of the sugar of 0.05～0.2g/ml, and the houghite precursor nucleus that step B is obtained adds sugar aqueous solution, and wherein the mol ratio of metal ion and sugar is 0.25～1 in the precursor nucleus; The syrup mixed solution that adds houghite precursor nucleus is transferred in the autoclave of polytetrafluoroethylliner liner, be heated to 150～180 ℃ after the sealing, be incubated 12～48 hours; Naturally cool to room temperature afterwards, filter, wash, obtain hybrid composite precursors;
D. the hybrid composite precursors that step C is prepared places Muffle furnace, speed with 5～15 ℃/min is warming up to 400～700 ℃, insulation 2～5h naturally cools to room temperature then, obtains having meso-hole structure, the compound metal oxide solid base catalyst of high-ratio surface.
2. method according to claim 1 is characterized in that the molar concentration of each metal ion species is respectively Mg in the mixing salt solution of steps A
2+: 0.1～0.4mol/L, M
2+: 0～0.2mol/L, Al
3+: 0.025～0.3mol/L; M
3+: 0～0.15mol/L; Described M
2+For being Co
2+, Cu
2+Or Ca
2+In one or more, described M
3+Be In
3+Or Ga
3+In one or both.
3, method according to claim 1 is characterized in that, described sugar is any one in glucose, sucrose or the fructose.
4, method according to claim 1 is characterized in that, the revolution of described high speed rotation is 3000～6000 rev/mins.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102259021A (en) * | 2011-05-27 | 2011-11-30 | 广州有色金属研究院 | Molecular sieve type solid alkali catalyst and preparation method thereof |
| CN102976373A (en) * | 2012-12-04 | 2013-03-20 | 北京化工大学 | Method for synthesizing monodisperse stable LDHs (layered double hydroxides) colloid nanocrystalline |
| CN103223345A (en) * | 2013-05-17 | 2013-07-31 | 北京化工大学 | Loaded nickel-indium (Ni-In) intermetallic compound catalyst and preparation method thereof |
| CN104016973A (en) * | 2014-05-28 | 2014-09-03 | 台州学院 | New method for preparing double-(hetero)aromatic-ring substituted alkene |
| CN104262416A (en) * | 2014-08-26 | 2015-01-07 | 厦门大学 | Chemical method for catalyzing glucose into fructose through isomerization |
| CN108726901A (en) * | 2018-05-29 | 2018-11-02 | 丁嘉鹏 | A kind of preparation method of eggshell base porous solid alkali |
| CN109718785A (en) * | 2019-02-13 | 2019-05-07 | 成都理工大学 | The derivative cobalt-base catalyst of hydrocalumite for acetic acid self-heating reforming hydrogen manufacturing |
| CN109999820A (en) * | 2019-05-09 | 2019-07-12 | 福州大学 | A kind of nickel-base catalyst and the preparation method and application thereof for hydrogenated petroleum resin preparation |
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2009
- 2009-05-22 CN CNA200910084375XA patent/CN101554596A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102259021A (en) * | 2011-05-27 | 2011-11-30 | 广州有色金属研究院 | Molecular sieve type solid alkali catalyst and preparation method thereof |
| CN102259021B (en) * | 2011-05-27 | 2013-05-01 | 广州有色金属研究院 | Molecular sieve type solid alkali catalyst and preparation method thereof |
| CN102976373A (en) * | 2012-12-04 | 2013-03-20 | 北京化工大学 | Method for synthesizing monodisperse stable LDHs (layered double hydroxides) colloid nanocrystalline |
| CN103223345A (en) * | 2013-05-17 | 2013-07-31 | 北京化工大学 | Loaded nickel-indium (Ni-In) intermetallic compound catalyst and preparation method thereof |
| CN104016973A (en) * | 2014-05-28 | 2014-09-03 | 台州学院 | New method for preparing double-(hetero)aromatic-ring substituted alkene |
| CN104262416A (en) * | 2014-08-26 | 2015-01-07 | 厦门大学 | Chemical method for catalyzing glucose into fructose through isomerization |
| CN108726901A (en) * | 2018-05-29 | 2018-11-02 | 丁嘉鹏 | A kind of preparation method of eggshell base porous solid alkali |
| CN109718785A (en) * | 2019-02-13 | 2019-05-07 | 成都理工大学 | The derivative cobalt-base catalyst of hydrocalumite for acetic acid self-heating reforming hydrogen manufacturing |
| CN109999820A (en) * | 2019-05-09 | 2019-07-12 | 福州大学 | A kind of nickel-base catalyst and the preparation method and application thereof for hydrogenated petroleum resin preparation |
| CN109999820B (en) * | 2019-05-09 | 2022-01-18 | 福州大学 | Nickel-based catalyst for preparing hydrogenated petroleum resin and preparation method and application thereof |
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