CN101367041A - Preparation of solid base catalyst, uses of the same in hydroxide aldehyde condensation reaction - Google Patents
Preparation of solid base catalyst, uses of the same in hydroxide aldehyde condensation reaction Download PDFInfo
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- CN101367041A CN101367041A CNA2008102005076A CN200810200507A CN101367041A CN 101367041 A CN101367041 A CN 101367041A CN A2008102005076 A CNA2008102005076 A CN A2008102005076A CN 200810200507 A CN200810200507 A CN 200810200507A CN 101367041 A CN101367041 A CN 101367041A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a preparation method for a solid base catalyst and the application thereof. The catalyst comprises CoII (CoIII2-xAlIIIx)O4, wherein x is more than or equal to 0.6 and less than 2, the catalyst has a crystalline phase similar to Co(CoAl)O4, the grain size is 20-100 nanometers, the specific surface area is 70-300m2/g, the pore volume is 0.15-0.83cm3/g, and the catalyst has mesoporous nanometer structures. The solid base catalyst has the advantages of high specific surface, good thermal stability, high activity, simple preparation, low cost, easy regeneration, and the like. In addition, the catalyst can be used for catalyzing a plurality of aldol condensation reactions. For example, in the condensation reaction of furfural and acetone, after the catalyst is used and the reaction is carried out at 145 DEG C for 10 hours, the furfural conversion rate reaches 98 percent, the fural acetone selectivity reaches 85 percent, and the yield reaches 83.3 percent. Furthermore, the catalyst can be regenerated for at least 5 times, the fural acetone selectivity basically remains unchanged, and the yield is still kept as about 60 percent.
Description
Technical field
This patent relates to a kind of preparation method of mesoporous nano cobalt aluminate type solid base catalyst and the application in aldol reaction thereof.
Background technology
Aldol reaction is to form one of most important reaction of C-C key in the organic chemistry, also is commercial synthetic a series of approach commonly used with chemicals of ad hoc structure and performance.Industrial general employing liquid base such as NaOH, potassium hydroxide aqueous solution homogeneous catalysts such as (or adding other solvents), adopt liquid base to add methyl alcohol catalysis acetone as Chinese patent (CN85100473) and produce DAA from condensation, but there is its follow-up separation costs height, catalyst is difficult for reclaiming, etching apparatus, shortcoming such as adopt that batch reactor can not be produced continuously.
Current people are more and more stricter to environmental protection requirement, and the idea of Green Chemistry is rooted in the hearts of the people, and novel, eco-friendly solid base catalyst has caused people's extensive concern.With respect to liquid alkali catalyst, solid base catalyst has tangible advantage: separate easily, and can be recycling, can regenerate, equipment is not had corrosion, environmental friendliness, the temperature operation scope is wide even can react in gas phase, can also make the technical process serialization, improves production capacity.But since the solid base catalyst complicated process of preparation, the cost height, and base strength is lower, and very easily by airborne CO
2And H
2Therefore O etc. pollute inactivation, and specific area is smaller, really can be at the solid base catalyst of industrial use seldom.
The solid base catalyst that is used for aldol reaction at present is mainly houghite, composite oxides, alkali metal or alkaline earth metal hydroxide or oxide carried loaded catalyst on carrier, utilize alkaline species hydrotalcite synthesizing chalcone (Journal ofCatalysis 221 (2004) 474-482) as people such as A.Corma, though it is active high, very easily with airborne CO
2Contact and inactivation need be prerequisite with the nitrogen protection usually when causing it to participate in reaction as catalyst has improved the cost of reaction, and its activation and regenerative process are loaded down with trivial details, and heat endurance is not high.Its activity of composite oxides as a comparison is far below the alkaline species hydrotalcite, and composite oxides generally are unformed, and poor stability actively descends soon, and the effect of regeneration is bad.Chinese patent (CN 1429194) adopt alkali metal or alkaline earth metal hydroxide or oxide carried on carrier as the catalyst of aldol condensation, its preparation process complexity, and the active component of its load can irreversiblely run off gradually.
Summary of the invention
The object of the present invention is to provide a kind of mesoporous nano cobalt aluminate type solid base catalyst and preparation method that can be used for aldol reaction, it is characterized in that having the specific area height, pore-size distribution is narrow, uniform particle diameter, Heat stability is good is active high, applied widely, preparation is simple, and is with low cost, easily the characteristics of regeneration.
Mesoporous nano catalyst of the present invention consist of Co
II(Co
III 2-xAl
III x) O
4, wherein 0.6≤x＜2 is characterized in that having similar spinelle Co (CoAl) O
4Crystalline phase, be the hexagonal flake loose structure, about 20～100 nanometers of particle size, specific area is at 70～300m
2/ g, pore volume are 0.15～0.83cm
3/ g, and have the mesoporous nano structure.
Concrete technical scheme of the present invention is as follows:
Mesoporous nano Preparation of catalysts method of the present invention, its feature may further comprise the steps: the mixed solution (I) of preparing the soluble-salt of certain density cobaltous soluble-salt and trivalent aluminium; Prepare the mixed ammonium/alkali solutions (II) of certain density alkali and solubility inorganic potassium (or sodium) salt; Adopt urea water solution or stable state and flow titration to be prepared, and control certain pH value, move into after the vigorous stirring in the band teflon-lined stainless steel cauldron, at a certain temperature crystallization a period of time; Through centrifugation, the solid that obtains obtains the layered double hydroxide presoma after spending deionised water, oven dry, grinding then, makes mesoporous cobalt aluminate nano solid base catalyst through roasting at last.
Mixed solution for described soluble-salt is characterised in that: the soluble-salt of cobaltous soluble-salt and trivalent aluminium is 1～2 kind in nitrate, sulfate, acetate or the chloride.Described cobaltous soluble-salt is preferably Co (NO
3)
2, the concentration of its aqueous solution is 0.01～1 mol.The soluble-salt of described trivalent aluminium is preferably Al (NO
3)
3, the concentration of its aqueous solution is 0.01～1 mol.
Be characterised in that for described mixed ammonium/alkali solutions: described alkali is potassium hydroxide or NaOH, is preferably NaOH, and the concentration of its aqueous solution is 0.06～6 mol.Described solubility inorganic potassium (or sodium) salt is a kind of in potash, potassium sulfate, potassium chloride, sodium carbonate, sodium sulphate, the sodium chloride, is preferably Na
2CO
3, the concentration of its aqueous solution is 0.03～3 mol.
When preparing catalyst with urea method, it is characterized in that: after the urea liquid of the mixed solution (I) of soluble-salt and 0.1～5 mol is under agitation mixed, move in the band teflon-lined stainless steel cauldron, 80～150 ℃ of crystallization 12～96 hours.
Decide legal system when being equipped with catalyst with stable state and drip, it is characterized in that: solution (I) and solution (II) are added in the beaker that contains deionized water at 5～70 ℃ and drip, and the pH value is regulated and control 8～12.Move into then in the band teflon-lined stainless steel cauldron, 40～150 ℃ of crystallization 12～96 hours.
The baking temperature of the solid that obtains is 50～120 ℃; Sintering temperature is 300～800 ℃, and heating rate is 1～15 ℃/minute, and roasting time is 2～18 hours.
Catalyst of the present invention can be applicable to the aldol reaction of aldehyde or ketone, and chemical equation can be expressed as:
Described aldehyde or ketone (I) and structure (II) is characterized by R
1, R
2And R
4Can be hydrogen, C
1-6Alkyl, halogen or the C that replaces of hydroxyl
1-6Alkyl, unsaturated C
1-6Alkyl, C
1-6Alkoxyl and the aromatic ring or the hetero-aromatic ring that replace arbitrarily; R
3Can be C
1-6Alkyl, halogen or the C that replaces of hydroxyl
1-6Alkyl, unsaturated C
1-6Alkyl, C
1-6Alkoxyl and the aromatic ring or the hetero-aromatic ring that replace arbitrarily.
Described aromatic ring is:
Wherein R can be amino, nitro, halogen, carboxylic acid and fat thereof, C
1-5Alkyl, undersaturated C
1-5Alkyl, C
1-5The C that alkoxyl, halogen or hydroxyl replace
1-5Alkyl.
Described hetero-aromatic ring is:
Wherein R can be amino, nitro, halogen, carboxylic acid and fat thereof, C
1-5Alkyl, undersaturated C
1-5Alkyl, C
1-5The C that alkoxyl, halogen or hydroxyl replace
1-5Alkyl.
Described aldol reaction is preferably:
The solvent that uses in above-mentioned aldol reaction can be a kind of in carrene, methyl alcohol, the ethanol or not use solvent.
Catalyst of the present invention has the following advantages: this mesoporous nano cobalt aluminate type solid base catalyst specific surface height, uniform particle diameter, heat endurance height.With example technical scheme of the present invention is described below, but protection scope of the present invention is not limited thereto.
The specific embodiment
Embodiment 1
Prepare Co (NO with deionized water
3)
2And Al (NO
3)
3Mixed aqueous solution, Co wherein
2+Concentration is 0.6 mol, Al
3+Concentration is 0.15 mol; Preparation KOH and K
2CO
3Mixed aqueous solution, OH wherein
-Concentration is 2 mol, CO
3 2-Concentration is 0.5 mol.Under continuous stirring, above-mentioned two solution are dropped in the beaker that fills deionized water simultaneously, pH is about 9 in control, waits to dropwise, and slurries is transferred in the stainless steel pressure still of band teflon lined, in 90 ℃ of crystallization 24h.After centrifugation, sediment is spent deionised water to pH=7,, grind, place Muffle furnace again, promptly make required catalyst in 350 ℃ of roastings 10 hours then 100 ℃ of dried overnight.
Get furfural 2.4g, acetone 14.5g, catalyst 0.2g puts into batch reactor, and after 12 hours, gas chromatographic analysis is carried out in sampling 100 ℃ of reactions, and the furfural conversion ratio is 88.7%, and the selectivity of furfural acetone is 82.3%, yield is 73%.
Embodiment 2
Prepare Co (NO with deionized water
3)
2And Al (NO
3)
3Mixed aqueous solution, Co wherein
2+Concentration is 0.13 mol, Al
3+Concentration is 0.13 mol; Preparation KOH and K
2CO
3Mixed aqueous solution, OH wherein
-Concentration is 0.8 mol, CO
3 2-Concentration is 0.6 mol.Under continuous stirring, above-mentioned two solution are dropped in the beaker that fills deionized water simultaneously, pH is about 12 in control, waits to dropwise, and slurries is transferred to 100 ℃ of crystallization 16h in the stainless steel pressure still of being with teflon lined.After centrifugation, sediment is spent deionised water to pH=7,, grind, place Muffle furnace again, promptly make required catalyst in 400 ℃ of roastings 11 hours then 100 ℃ of dried overnight.
Get furfural 2.4g, acetone 14.5g, catalyst 0.2g puts into batch reactor, and after 10 hours, gas chromatographic analysis is carried out in sampling 145 ℃ of reactions, and the furfural conversion ratio is 98%, and furfural acetone selectivity 85%, yield are 83.3%.
Embodiment 3
Prepare Co (NO with deionized water
3)
2, AlCl
3With the mixed solution of urea, wherein Co
2+Concentration is 0.1 mol, Al
3+Concentration is 0.04 mol, and urea concentration is 0.2 mol.After 100 ℃ of vigorous stirring, synthetic liquid is transferred in the stainless steel pressure still of being with teflon lined in 130 ℃ of crystallization 72h.After the centrifugation, with the precipitate with deionized water that obtains wash to the pH value be 7,50 ℃ of dried overnight, grind, place Muffle furnace 800 ℃ of roastings 18 hours again, promptly make required catalyst.
Get 5 hydroxymethyl furfural 3.15g, acetone 14.5g, catalyst 0.2g, put into batch reactor, after 10 hours, gas chromatographic analysis is carried out in sampling 130 ℃ of reactions, the conversion ratio of 5 hydroxymethyl furfural is 92.5%, and 5-methylol furfural acetone selectivity is 87.1%, and yield is 80.6%.
Embodiment 4
Prepare Co (OAc) with deionized water
2And Al (NO
3)
3Mixed solution, wherein Co
2+Concentration is 1 mol, Al
3+Concentration is 1 mol.Preparation KOH and NaCl mixed aqueous solution, wherein OH-concentration is 6 mol, CO
3 2-Concentration is 2 mol.Under continuous stirring, above-mentioned two kinds of solution are dropped in the beaker that fills deionized water simultaneously, pH is between 11.7～12 in control, after dropwising, synthetic liquid is transferred in the stainless steel pressure still of band teflon lined, in 70 ℃ of crystallization 12h.After the centrifugation, the precipitate with deionized water that obtains is washed to pH=7,, grind, place Muffle furnace again 450 ℃ of roastings 8 hours 110 ℃ of dried overnight.
Acetone 15g, catalyst 0.56g puts into batch reactor, after 24 hours, gas chromatographic analysis is carried out in sampling 52 ℃ of reactions, and condensation product is a DAA, do not find other accessory substance, acetone conversion is 4.57%, has reached the thermodynamic limit value of acetone conversion substantially.
Embodiment 5
Prepare CoCl with deionized water
2, AlCl
3With the mixed solution of urea, wherein Co
2+Concentration is 1.5 mol, Al
3+Concentration is 0.25 mol, and urea concentration is 2 mol.After 100 ℃ of vigorous stirring, synthetic liquid is transferred in the stainless steel pressure still of band teflon lined, in 150 ℃ of crystallization 12h.After the centrifugation, it is 7 that the sediment that obtains is spent deionised water to pH value, 120 ℃ of following dried overnight, grinds, and places Muffle furnace 550 ℃ of roastings 5 hours again.
Benzaldehyde 4.2g, acetophenone 9.6g, catalyst 0.5g puts into batch reactor, and 160 ℃ of reactions 10 hours, gas chromatographic analysis was carried out in sampling, and the conversion ratio of benzaldehyde is 80.6%, and the selectivity of chalcone is 95%, the yield of chalcone is 76.6%.
Embodiment 6
1, the regeneration of catalyst
Catalyst is with embodiment 1.
The renovation process of catalyst is: reaction finishes the back centrifugation and goes out catalyst, 100 ℃ of dried overnight, places Muffle furnace 350 ℃ of roastings 10 hours again.
2. the activity test behind the catalyst regeneration
With furfural, condensation of acetone reaction is example, gets furfural 2.4g, acetone 14.5g, and catalyst 0.2g puts into batch reactor, and 100 ℃ of reactions 10 hours, gas chromatographic analysis was carried out in sampling, the results are shown in Table 1.
Table 1 catalyst regeneration result of the test
| Regeneration times | Conversion ratio | Selectivity | Yield |
| 1 | 87.8％ | 83.4％ | 73.2％ |
| 2 | 86.1％ | 82.3％ | 70.9％ |
| 3 | 77.7％ | 87.9％ | 68.3％ |
| 4 | 71.7％ | 80.4％ | 57.6％ |
| 5 | 69％ | 82.6％ | 57％ |
Claims (10)
1. solid base catalyst, it consists of Co
II(Co
III 2-xAl
III x) O
4, wherein 0.6≤x＜2 is characterized by: have similar spinelle Co (CoAl) O
4Crystalline phase, be the hexagonal flake loose structure, particle diameter is 20～100 nanometers, specific area is 70～300m
2/ g, pore volume are 0.15～0.83cm
3/ g, and have the mesoporous nano structure.
2. the preparation method of solid base catalyst according to claim 1, its feature may further comprise the steps: the mixed solution (I) of preparing the soluble-salt of certain density cobaltous soluble-salt and trivalent Al; Prepare the mixed ammonium/alkali solutions (II) of certain density alkali and solubility inorganic potassium (or sodium) salt; Adopt urea water solution or stable state and flow titration to be prepared, and the pH value of control synthesis mother liquid, synthesis mother liquid moves into after vigorous stirring in the band teflon-lined stainless steel cauldron, reacts a period of time at a certain temperature; Then through centrifugation, the sediment that obtains spends deionised water, oven dry, grinding and obtains the layered double hydroxide presoma, makes the cobalt aluminate solid base catalyst through roasting at last.
3. the mixed solution of soluble-salt according to claim 2, it is characterized in that: cobaltous soluble-salt is one or both in nitrate, sulfate, acetate, the chloride, is preferably Co (NO
3)
2, its concentration is 0.01～1 mol; The soluble-salt of trivalent Al is one or both in nitrate, sulfate, acetate, the chloride, is preferably Al (NO
3)
3, its concentration is 0.01～1 mol.
4. mixed ammonium/alkali solutions according to claim 2 is characterized in that described alkali is potassium hydroxide or NaOH, is preferably NaOH, and its concentration is 0.06～6 mol; Solubility inorganic potassium (or sodium) salt is a kind of in potash (or sodium), potassium sulfate (or sodium), the potassium chloride (or sodium), is preferably Na
2CO
3, its concentration is 0.03～3 mol.
5. according to claim 2 when preparing catalyst with urea method, after it is characterized in that urea liquid with the mixed solution (I) of soluble-salt and 0.1～5 mol under agitation mixes, move in the band teflon-lined stainless steel cauldron, 80～100 ℃ of reactions 48～96 hours.
6. according to claim 2ly decide legal system when being equipped with catalyst with stable state and drip, it is characterized in that solution (I) and solution (II) are added in the beaker that contains deionized water at 5～70 ℃ and drip, the regulation and control of pH value are 8～12, move into then in the band teflon-lined stainless steel cauldron, 40～100 ℃ of reactions 48～96 hours.
7. in the method for preparing catalyst according to claim 2, the sediment that it is characterized in that obtaining is after the deionized water washing, 50～120 ℃ of dryings, heat up (heating rate is 1～15 ℃/minute) to 300～800 ℃ of roastings, roasting time is 2～10 hours again.
But 8. the aldol reaction of claim 1 described solid base catalyst catalysis aldehyde or ketone, its chemical equation can be expressed as:
Wherein, R
1, R
2And R
4Can be alkyl, the C1-C6 alkoxyl of the alkyl, halogen of hydrogen, C1-C6 or the alkyl of the C1-C6 that hydroxyl replaces, unsaturated C1-C6 and aromatic ring or the hetero-aromatic ring that replaces arbitrarily; R
3Can be alkyl, the C1-C6 alkoxyl of the alkyl, halogen of C1-C6 or the alkyl of the C1-C6 that hydroxyl replaces, unsaturated C1-C6 and aromatic ring or the hetero-aromatic ring that replaces arbitrarily.
9. at the hetero-aromatic ring described in the claim 8, can be:
Wherein R can be the alkyl of the C1-C5 of the alkyl of amino, nitro, halogen, carboxylic acid and fat thereof, C1-C5, undersaturated C1-C5 alkyl, C1-C5 alkoxyl, halogen or hydroxyl replacement; Described aromatic ring can be:
Wherein R can be the alkyl of the C1-C5 of the alkyl of amino, nitro, halogen, carboxylic acid and fat thereof, C1-C5, undersaturated C1-C5 alkyl, C1-C5 alkoxyl, halogen or hydroxyl replacement.
10. in the described chemical reaction of claim 8, it is characterized in that using a kind of in carrene, methyl alcohol, the ethanol as solvent, perhaps do not use solvent.
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|---|---|---|---|
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|---|---|---|---|
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102847539A (en) * | 2012-09-29 | 2013-01-02 | 上海东升新材料有限公司 | Mixed crystal/solid alkali combined catalyst and preparation method thereof |
| CN102019177B (en) * | 2009-09-18 | 2013-02-13 | 中国石油天然气股份有限公司 | Aldol condensation reaction solid base catalyst and application |
| CN106944028A (en) * | 2017-03-21 | 2017-07-14 | 北京化工大学 | A kind of preparation method of the graphene-based complex solid base catalyst of 3D structures |
| CN109824498A (en) * | 2018-12-22 | 2019-05-31 | 江门谦信化工发展有限公司 | A kind of efficient process units of diacetone alcohol serialization and production technology |
| CN110327929A (en) * | 2019-06-17 | 2019-10-15 | 齐利华(武汉)资源环境科技有限公司 | A kind of cobalt aluminum hydrotalcite Derived Mixed Oxides and the preparation method and application thereof |
| CN110586079A (en) * | 2019-09-23 | 2019-12-20 | 湘潭大学 | Preparation and application of layered CaMnAl hydrotalcite solid base catalyst |
| CN111548330A (en) * | 2020-04-29 | 2020-08-18 | 南京工业大学 | Method for preparing 2, 5-furan dicarbaldehyde by selective oxidation of 5-hydroxymethylfurfural on manganese-based spinel catalyst |
| CN112844387A (en) * | 2020-12-30 | 2021-05-28 | 山西大学 | Difunctional ferronickel hydrotalcite catalyst and preparation method and application thereof |
-
2008
- 2008-09-26 CN CNA2008102005076A patent/CN101367041A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102019177B (en) * | 2009-09-18 | 2013-02-13 | 中国石油天然气股份有限公司 | Aldol condensation reaction solid base catalyst and application |
| CN102847539A (en) * | 2012-09-29 | 2013-01-02 | 上海东升新材料有限公司 | Mixed crystal/solid alkali combined catalyst and preparation method thereof |
| CN102847539B (en) * | 2012-09-29 | 2014-08-06 | 上海东升新材料有限公司 | Mixed crystal/solid alkali combined catalyst and preparation method thereof |
| CN106944028A (en) * | 2017-03-21 | 2017-07-14 | 北京化工大学 | A kind of preparation method of the graphene-based complex solid base catalyst of 3D structures |
| CN109824498A (en) * | 2018-12-22 | 2019-05-31 | 江门谦信化工发展有限公司 | A kind of efficient process units of diacetone alcohol serialization and production technology |
| CN109824498B (en) * | 2018-12-22 | 2021-12-14 | 谦信化工集团有限公司 | Diacetone alcohol continuous production device and production process |
| CN110327929A (en) * | 2019-06-17 | 2019-10-15 | 齐利华(武汉)资源环境科技有限公司 | A kind of cobalt aluminum hydrotalcite Derived Mixed Oxides and the preparation method and application thereof |
| CN110586079A (en) * | 2019-09-23 | 2019-12-20 | 湘潭大学 | Preparation and application of layered CaMnAl hydrotalcite solid base catalyst |
| CN111548330A (en) * | 2020-04-29 | 2020-08-18 | 南京工业大学 | Method for preparing 2, 5-furan dicarbaldehyde by selective oxidation of 5-hydroxymethylfurfural on manganese-based spinel catalyst |
| CN112844387A (en) * | 2020-12-30 | 2021-05-28 | 山西大学 | Difunctional ferronickel hydrotalcite catalyst and preparation method and application thereof |
| CN112844387B (en) * | 2020-12-30 | 2022-07-19 | 山西大学 | Difunctional ferronickel hydrotalcite catalyst and preparation method and application thereof |
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