CN103028409A - Supported copper-based metal catalyst with high dispersion as well as preparation method and application thereof - Google Patents
Supported copper-based metal catalyst with high dispersion as well as preparation method and application thereof Download PDFInfo
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- CN103028409A CN103028409A CN2011102982542A CN201110298254A CN103028409A CN 103028409 A CN103028409 A CN 103028409A CN 2011102982542 A CN2011102982542 A CN 2011102982542A CN 201110298254 A CN201110298254 A CN 201110298254A CN 103028409 A CN103028409 A CN 103028409A
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Abstract
The invention provides a supported copper-based metal catalyst with high dispersion as well as a preparation method and application thereof. The catalyst is obtained by loading Cu (Copper) nanoparticles and MO (Molybdenum) on a surface of gamma-Al2O3 (Aluminum Oxide), and a chemical formula of the catalyst is Cu/MO/gamma-Al2O3. The preparation method of the supported copper-based metal catalyst comprises the following steps of: placing a gamma-Al2O3 carrier into a mixed salt solution containing divalent metal ions of copper ions, crystallizing the mixed solution to obtain a supported copper-based lamellar bimetal hydroxide precursor at 100 to 140 DEG C, and then roasting, decomposing and reducing the supported copper-based lamellar bimetal hydroxide precursor to obtain the supported copper-based metal catalyst. The Cu content in the catalyst is 0.5% to 10% by mass. The catalyst is mainly used for the selective catalytic hydrogenation of cinnamyl aldehyde; and furthermore, when the Cu content in the catalyst is 3% to 6% by mass, the percent conversion and the selectivity can reach up to 92% to 99% and 88% to 97%, respectively. In addition, the supported copper-based metal catalyst with high dispersion has the characteristics of high efficiency, cheapness and easiness in separation and recycling as well.
Description
Technical field
The invention belongs to catalyst preparation technical field, particularly relate to a kind of preparation method of high-dispersion loading type copper base metal catalyst and this catalyst is used for the selective catalytic hydrogenation course of reaction of cinnamic acid.
Technical background
Cinnamyl alcohol is typical α, and beta unsaturated alcohol is one of important intermediate in fine chemistry industry is synthetic, is widely used in preparation and the synthetic field of medicine of essence, spices.At present, cinnamyl alcohol makes by the cinnamic acid selective hydrogenation mostly, because the bond energy (715kJ/mol) of C=O key is greater than the bond energy (615kJ/mol) of C=C key, there are simultaneously again conjugation C=C key and C=O key, keep the two keys of C=C and difficult if think to make selectively C=O key hydrogenation.Studies show that, in order to improve the selective hydrogenation to cinnamic acid, many noble metals and precious metal alloys catalyst are used to that selective hydrogenation changes into cinnamyl alcohol to cinnamic acid.For example, Milone etc. [Milone C, et al.Appl.Catal.A:Gen, 2008,163,167] research is found noble metal Au is loaded on TiO
2On to make cinnamic acid be 93% at conversion ratio, cinnamyl alcohol selectively be 47%; [the Koo-amornpattana W such as Koo-amornpattana, et al.Catal.Today, 2001,277,287] utilize the Pt-Co alloy of optimal proportion under the alkaline solution condition, cinnamic acid to be carried out selective hydrogenation, its conversion ratio be 98% time cinnamyl alcohol selectively be 93%.But because the cost compare of noble metal is high, this has just strengthened and has been applied to the large-scale industrial production difficulty.Therefore, the research of the cheap and high activity of preparation, dispersed catalysts has important theory significance and prospects for commercial application.
Ball-type γ-Al
2O
3Have when using as carrier that specific surface is large, intensity is high and the advantage such as pore structure is good, greatly improved mass transfer and catalytic effect.Metallic catalyst is loaded on ball-type γ-Al
2O
3On, can improve to a great extent the dispersiveness of active component, make prepared catalyst have higher strength and stability, and in commercial Application, be easy to separate and recycling.
It is a kind of typical anionic type laminated material that the layered bi-metal complex hydroxide is called again hydrotalcite (Layered Double Hydroxides is abbreviated as LDHs), and its general structure is: [M
1-x 2+M
x 3+(OH)
2]
X+(A
N-)
X/nMH
2O, wherein M
2+, M
3+Expression is positioned at bivalent cation and the Tricationic on the laminate, A respectively
N-Tradable charge compensation ion between presentation layer.Because the structure of hydrotalcite uniqueness makes it have the characteristics such as laminate metal species, charge density and particle size are adjustable, interlayer anion is interchangeable.Metal ion on the hydrotalcite laminate is to distribute uniformly by certain way, has formed specific chemical composition and structure.But hydrotalcite easily caves in through laminate after the high-temperature roasting and sintering is assembled, and the metal oxide particle size that obtains is large and dispersed relatively poor.If the hydrotalcite original position is loaded on ball-type γ-Al
2O
3On, can prevent that not only sintering is assembled after hydrotalcite is because of high-temperature roasting, but also can improve the dispersiveness of specific surface and particle, make the metallic catalyst for preparing for precursor thus have high activity, high dispersive, high strength and stable preferably, have very large using value at aspects such as Industrial Catalysis.
Summary of the invention
The object of the invention provides a kind of high-dispersion loading type copper base metal Catalysts and its preparation method, and is applied to the reaction of cinnamic acid selective catalytic hydrogenation.
Technical scheme of the present invention is to provide alkaline environment take urea as precipitating reagent, ball-type γ-Al
2O
3Under alkali condition, decomposite Al (OH)
4 -, constantly there is Cu in activated surface Al source owing in the solution
2+, other bivalent metal ions and anion, can be at ball-type γ-Al
2O
3Surface in situ synthesizes copper-based hydrotalcite, passes through pyrolytic and reduction again, obtains high-dispersion loading type copper base metal catalyst.
Described high-dispersion loading type copper base metal catalyst is at γ-Al
2O
3Area load Cu and MO, its chemical formula are Cu/MO/ γ-Al
2O
3, wherein M is a kind of among Zn, Mg, Co, the Ni, and the quality percentage composition of Cu is 0.5～10% in the catalyst, and better quality percentage composition is 3～6%, and the particle diameter of copper nano-particle is distributed as 3～9nm.
High-dispersion loading type copper base metal catalyst preparation step of the present invention is as follows:
A. original position is synthesized carried copper based hydrotalcite LDHs/ γ-Al
2O
3
Mixing salt solution with deionized water preparation copper nitrate and other divalent metal nitrate, wherein the concentration of copper nitrate is 1.50～0.50mol/L, the concentration of other divalent metal nitrate is 0.50～1.50mol/L, and the mol ratio of copper nitrate and other divalent metal nitrate is 0.3～3: 1; And then to add concentration to it be 4～10mol/L urea, wherein take 6～8mol/L as best;
With spherical gamma-Al
2O
3Carrier joins in the above-mentioned mixing salt solution in the ratio of 0.3-0.6g/mL, behind dipping 1～6h, transfer to the autoclave of packing in the polytetrafluoroethylliner liner, in 100～140 ℃ of reaction 6～24h, reaction naturally cools to room temperature after finishing, take out the bead washing by soaking repeatedly to neutral, put into the dry 10～24h of 40～80 ℃ of baking ovens, obtain original position carried copper based hydrotalcite LDHs/ γ-Al
2O
3
Described other divalent metal nitrate are Zn (NO
3)
2, Mg (NO
3)
2, Co (NO
3)
2Or Ni (NO
3)
2In a kind of.
B. the preparation of high-dispersion loading type copper base metal catalyst
Get LDHs/ γ-Al that steps A obtains
2O
3Place Muffle furnace, roasting under air atmosphere is warming up to 500～800 ℃ and be incubated 5～8h with the heating rate of 5～10 ℃/min, obtains corresponding original position support type composite metal oxide after naturally cooling to room temperature;
Again the original position support type composite metal oxide that obtains is placed tube-type atmosphere furnace, under hydrogen atmosphere, be warming up to 200～600 ℃ and be incubated 3～5h with the heating rate of 5～10 ℃/min, room temperature to be naturally cooled to obtains corresponding high-dispersion loading type copper base metal catalyst.
The metallic catalyst that obtains is characterized, the results are shown in Figure 1-4.Provided the synthetic carried copper based hydrotalcite LDHs/ γ-Al of original position among Fig. 1
2O
3XRD spectra, as can be seen from the figure except having carrier γ-Al
2O
3Characteristic diffraction peak outside, (003) of the architectural feature of LDHs crystal has also appearred, (006), (009) and (110) crystal face characteristic diffraction peak has proved the copper-based hydrotalcite LDHs/ γ-Al of original position load
2O
3Still the structure that has kept original layered double hydroxide.The product that is obtained behind roasting reduction by the copper-based hydrotalcite that can find out the original position load in the XRD spectra of Fig. 2 is the Cu particle, oxide and γ-Al
2O
3Compound.SEM by Fig. 3 can find out that prepared copper base metal catalyst still keeps layer structure, the phenomenon that sintering is assembled do not occur.By finding out among the TEM of Fig. 4 that the Cu uniform particles is dispersed in the laminate surface.
Join in the autoclave with carried copper based metal catalysts and 0.2ml cinnamic acid and take the 50ml isopropyl alcohol as solvent, pass into the H of 1.0MPa
2, temperature rises to 120 ℃, behind the reaction 8h, so that the conversion ratio of cinnamic acid selective hydrogenation and selectively be respectively 92-99% and 88-97%.Fig. 5 is the cinnamic acid selective hydrogenation result that carried copper based metal catalysts that embodiment 1 obtains records, and its conversion ratio is 97%, and to cinnamyl alcohol selectively is 96%.
The invention has the advantages that: the synthetic carried copper based hydrotalcite LDHs/ γ-Al of one step of (1) urea method original position
2O
3, easy to operate simple; (2) catalyst that obtains behind roasting reduction has that specific surface is large, porous and stability preferably, prevents that effectively sintering from assembling, and improves the dispersiveness of active component copper nano particles, exposes more activated centre; (3) based on the high activity of carried copper based metal catalysts, high dispersive, high strength and the speciality of stability preferably, make it have good catalytic performance to cinnamic acid, to cinnamyl alcohol selectively is 88～97%, conversion ratio is 92～99%, has very large potential using value at aspects such as Industrial Catalysis.
Description of drawings
Fig. 1. be the original position supported copper zinc-aluminum hydrotalcite CuZnAl-LDHs/ γ-Al of the embodiment of the invention 1 preparation
2O
3XRD spectra.
Fig. 2. be the high-dispersion loading type copper metallic catalyst Cu/ZnO/ γ-Al of the embodiment of the invention 1 preparation
2O
3XRD spectra.
Fig. 3. be the high-dispersion loading type copper metallic catalyst Cu/ZnO/ γ-Al of the embodiment of the invention 1 preparation
2O
3The SEM spectrogram.
Fig. 4. be the high-dispersion loading type copper metallic catalyst Cu/ZnO/ γ-Al of the embodiment of the invention 1 preparation
2O
3The TEM spectrogram.
Fig. 5. be the embodiment of the invention 1 cinnamic acid conversion ratio and selective time dependent curve.
The specific embodiment
Embodiment 1
Take by weighing the Cu (NO of 0.6444g
3)
26H
2Zn (the NO of O and 1.5866g
3)
26H
2O is dissolved in 4ml deionized water preparation Cu (NO
3)
2And Zn (NO
3)
2Mixing salt solution, and the mol ratio of copper nitrate and zinc nitrate is 0.5: 1; And then to its adding 0.9614g urea.Take by weighing 2g spherical gamma-Al
2O
3Carrier joins in the solution of above-mentioned preparation, behind the dipping 1h, transfer to the autoclave of packing in the 25mL polytetrafluoroethylliner liner, 100 ℃ of reaction 10h, question response naturally cools to room temperature after finishing, and takes out the bead washing by soaking repeatedly to neutral, put into 70 ℃ of dry 12h of baking oven, obtain original position carried copper based hydrotalcite CuZnAl-LDHs/ γ-Al
2O
3With the CuZnAl-LDHs/ γ-Al that obtains
2O
3Place roasting under the Muffle furnace air atmosphere, be warming up to 500 ℃ and be incubated 6h with the heating rate of 5 ℃/min, after naturally cooling to room temperature, obtain corresponding original position support type composite metal oxide.Again the original position support type composite metal oxide that obtains is placed tube-type atmosphere furnace, under hydrogen atmosphere, be warming up to 400 ℃ and be incubated 3h with the heating rate of 10 ℃/min, after naturally cooling to room temperature, obtain corresponding high-dispersion loading type copper base metal Catalysts Cu/ZnO/ γ-Al
2O
3, the quality percentage composition of Cu is 3% in the catalyst, the average grain diameter of Nanometer Copper metal is 4nm.
With 0.5g carried copper based metal catalysts Cu/ZnO/ γ-Al
2O
3Join in the autoclave with the 0.2ml cinnamic acid and take the 50ml isopropyl alcohol as solvent, pass into the H of 1.0MPa
2, temperature is elevated to 120 ℃, and behind the reaction 8h, the conversion ratio of cinnamic acid selective hydrogenation reaches 97%, and cinnamyl alcohol selectively reached 96%.
Embodiment 2
Take by weighing the Cu (NO of 0.9664g
3)
26H
2Mg (the NO of O and 1.0256g
3)
26H
2O is dissolved in 4ml deionized water preparation Cu (NO
3)
2And Mg (NO
3)
2Mixing salt solution, and the mol ratio of copper nitrate and magnesium nitrate is 1: 1; And then to its adding 1.4422g urea.Take by weighing 2g spherical gamma-Al
2O
3Carrier joins in the solution of above-mentioned preparation, behind the dipping 2h, transfer to the autoclave of packing in the 25mL polytetrafluoroethylliner liner, 120 ℃ of reaction 14h, question response naturally cools to room temperature after finishing, and takes out the bead washing by soaking repeatedly to neutral, put into 60 ℃ of oven drying 16h, obtain original position carried copper based hydrotalcite CuMgAl-LDHs/ γ-Al
2O
3With the CuMgAl-LDHs/ γ-Al that obtains
2O
3Place roasting under the Muffle furnace air atmosphere, be warming up to 600 ℃ and be incubated 7h with the heating rate of 10 ℃/min, after naturally cooling to room temperature, obtain corresponding original position support type composite metal oxide.Again the original position support type composite metal oxide that obtains is placed tube-type atmosphere furnace, under hydrogen atmosphere, be warming up to 500 ℃ and be incubated 4h with the heating rate of 5 ℃/min, after naturally cooling to room temperature, obtain corresponding high-dispersion loading type copper base metal Catalysts Cu/MgO/ γ-Al
2O
3, the quality percentage composition of Cu is 8% in the catalyst, the average grain diameter of Nanometer Copper metal is 6nm.
With 0.5g carried copper based metal catalysts Cu/MgO/ γ-Al
2O
3Join in the autoclave with the 0.2ml cinnamic acid and take the 50ml isopropyl alcohol as solvent, pass into the H of 1.0MPa
2, temperature is elevated to 120 ℃, and behind the reaction 8h, the conversion ratio of cinnamic acid selective hydrogenation reaches 93%, and cinnamyl alcohol selectively reached 90%.
Embodiment 3
Take by weighing the Cu (NO of 0.4832g
3)
26H
2Co (the NO of O and 1.7462g
3)
26H
2O is dissolved in 4ml deionized water preparation Cu (NO
3)
2And Co (NO
3)
2Mixing salt solution, and the mol ratio of copper nitrate and zinc nitrate is 0.3: 1; And then to its adding 1.6825g urea.Take by weighing 2g spherical gamma-Al
2O
3Carrier joins in the solution of above-mentioned preparation, behind the dipping 4h, transfer to the autoclave of packing in the 25mL polytetrafluoroethylliner liner, 110 ℃ of reaction 24h, question response naturally cools to room temperature after finishing, and takes out the bead washing by soaking repeatedly to neutral, put into 30 ℃ of oven drying 10h, obtain original position carried copper based hydrotalcite CuCoAl-LDHs/ γ-Al
2O
3With the CuCoAl-LDHs/ γ-Al that obtains
2O
3Place roasting under the Muffle furnace air atmosphere, be warming up to 700 ℃ and be incubated 5h with the heating rate of 5 ℃/min, after naturally cooling to room temperature, obtain corresponding original position support type composite metal oxide.The original position support type composite metal oxide that obtains is placed tube-type atmosphere furnace, under hydrogen atmosphere, be warming up to 200 ℃ and be incubated 5h with the heating rate of 10 ℃/min, after naturally cooling to room temperature, obtain corresponding high-dispersion loading type copper base metal Catalysts Cu/CoO/ γ-Al
2O
3, the quality percentage composition of Cu is 2% in the catalyst, the average grain diameter of Nanometer Copper metal is 7nm.
With 0.5g carried copper based metal catalysts Cu/CoO/ γ-Al
2O
3Join in the autoclave with the 0.2ml cinnamic acid and take the 50ml isopropyl alcohol as solvent, pass into the H of 1.0MPa
2, temperature is elevated to 120 ℃, and behind the reaction 8h, the conversion ratio of cinnamic acid selective hydrogenation reaches 98%, and cinnamyl alcohol selectively reached 93%.
Embodiment 4
Take by weighing the Cu (NO of 1.2885g
3)
26H
2Ni (the NO of O and 0.7755g
3)
26H
2O is dissolved in 4ml deionized water preparation Cu (NO
3)
2And Ni (NO
3)
2Mixing salt solution, and the mol ratio of copper nitrate and zinc nitrate is 2: 1; And then to its adding 0.7211g urea.Take by weighing 2g spherical gamma-Al
2O
3Carrier joins in the solution of above-mentioned preparation, behind the dipping 6h, transfer to the autoclave of packing in the 25mL polytetrafluoroethylliner liner, 140 ℃ of reaction 6h, question response naturally cools to room temperature after finishing, and takes out the bead washing by soaking repeatedly to neutral, put into 80 ℃ of dry 24h of baking oven, obtain original position carried copper based hydrotalcite CuNiAl-LDHs/ γ-Al
2O
3With the CuNiAl-LDHs/ γ-Al that obtains
2O
3Place roasting under the Muffle furnace air atmosphere, be warming up to 650 ℃ and be incubated 5h with the heating rate of 10 ℃/min, after naturally cooling to room temperature, obtain corresponding original position support type composite metal oxide.The original position support type composite metal oxide that obtains is placed tube-type atmosphere furnace, under hydrogen atmosphere, be warming up to 250 ℃ and be incubated 3h with the heating rate of 10 ℃/min, after naturally cooling to room temperature, obtain corresponding high-dispersion loading type copper base metal Catalysts Cu/NiO/ γ-Al
2O
3, the quality percentage composition of Cu is 9% in the catalyst, the average grain diameter of Nanometer Copper metal is 5nm.
With 0.5g carried copper based metal catalysts Cu/NiO/ γ-Al
2O
3Join in the autoclave with the 0.2ml cinnamic acid and take the 50ml isopropyl alcohol as solvent, pass into the H of 1.0MPa
2, temperature is elevated to 120 ℃, and behind the reaction 8h, the conversion ratio of cinnamic acid selective hydrogenation reaches 99%, and cinnamyl alcohol selectively reached 89%.
Claims (6)
1. the preparation method of a high-dispersion loading type copper base metal catalyst, concrete preparation process is as follows:
A. original position is synthesized carried copper based hydrotalcite LDHs/ γ-Al
2O
3
Mixing salt solution with deionized water preparation copper nitrate and other divalent metal nitrate, wherein the concentration of copper nitrate is 1.50～0.50mol/L, the concentration of other divalent metal nitrate is 0.50～1.50mol/L, and the mol ratio of copper nitrate and other divalent metal nitrate is 0.3～3: 1; And then to add concentration to it be 4～10mol/L urea;
With spherical gamma-Al
2O
3Carrier joins in the above-mentioned mixing salt solution in the ratio of 0.3-0.6g/mL, behind dipping 1～6h, transfer to the autoclave of packing in the polytetrafluoroethylliner liner, in 100～140 ℃ of reaction 6～24h, reaction naturally cools to room temperature after finishing, take out the bead washing by soaking repeatedly to neutral, put into the dry 10～24h of 40～80 ℃ of baking ovens, obtain original position carried copper based hydrotalcite LDHs/ γ-Al
2O
3
B. the preparation of high-dispersion loading type copper base metal catalyst
Get LDHs/ γ-Al that steps A obtains
2O
3Place Muffle furnace, roasting under air atmosphere is warming up to 500～800 ℃ and be incubated 5～8h with the heating rate of 5～10 ℃/min, obtains corresponding original position support type composite metal oxide after naturally cooling to room temperature;
Again the original position support type composite metal oxide that obtains is placed tube-type atmosphere furnace, under hydrogen atmosphere, be warming up to 200～600 ℃ and be incubated 3～5h with the heating rate of 5～10 ℃/min, room temperature to be naturally cooled to obtains corresponding high-dispersion loading type copper base metal catalyst.
2. the preparation method of high-dispersion loading type copper base metal catalyst according to claim 1 is characterized in that described other divalent metal nitrate of steps A are Zn (NO
3)
2, Mg (NO
3)
2, Co (NO
3)
2Or Ni (NO
3)
2In a kind of; Described urea concentration is 6～8mol/L.
3. the high-dispersion loading type copper base metal catalyst of a method according to claim 1 preparation, it is at γ-Al
2O
3Area load Cu nano particle and MO, its chemical formula are Cu/MO/ γ-Al
2O
3, wherein M is a kind of among Zn, Mg, Co or the Ni, and the quality percentage composition of Cu is 0.5～10% in the catalyst, and the particle diameter of copper nano-particle is distributed as 3～9nm.
4. high-dispersion loading type copper base metal catalyst according to claim 3, the quality percentage composition that it is characterized in that Cu in the catalyst is 3～6%.
5. the reaction of cinnamic acid selective catalytic hydrogenation is used it in the application of a claim 3 and 4 described high-dispersion loading type copper base metal catalyst.
6. the application of a claim 3 and 4 described high-dispersion loading type copper base metal catalyst, the quality percentage composition that it is characterized in that Cu in the copper-based catalysts is 3～6%, cinnamic acid selective catalytic hydrogenation reaction conversion ratio is 92-99%, selectively is 88-97%.
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Cited By (19)
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1724158A (en) * | 2005-06-24 | 2006-01-25 | 北京化工大学 | Catalyst of high dispersing copper based composite metal oxidate and its preparation process |
| CN101884924A (en) * | 2009-05-15 | 2010-11-17 | 中国石油天然气股份有限公司 | High dispersing nickel catalyst and preparation method and application thereof |
-
2011
- 2011-09-30 CN CN2011102982542A patent/CN103028409A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1724158A (en) * | 2005-06-24 | 2006-01-25 | 北京化工大学 | Catalyst of high dispersing copper based composite metal oxidate and its preparation process |
| CN101884924A (en) * | 2009-05-15 | 2010-11-17 | 中国石油天然气股份有限公司 | High dispersing nickel catalyst and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| VICTORIA S.GUTIÉRREZ，ET AL.: "Cu incorporated MCM-48 for the liquid phase hydrogenation of cinnamaldehyde", 《MICROPOROUS AND MESOPOROUS MATERIALS》, vol. 141, 4 December 2010 (2010-12-04) * |
| 张蕊等: "γ-Al2O3载体孔内原位合成水滑石", 《复旦学报(自然科学版)》, vol. 42, no. 3, 30 June 2003 (2003-06-30) * |
| 李仓: "基于层状双羟基复合金属氧化物构筑结构取向薄膜及其性能研究", 《中国优秀博士学位论文全文数据库 工程科技Ⅰ辑》, no. 11, 15 November 2008 (2008-11-15) * |
| 武文涛等: "肉桂醛选择性加氢合成肉桂醇的研究进展", 《化工中间体》, no. 4, 31 December 2009 (2009-12-31) * |
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