CN102451720B - Ruthenium-base calcium-substituting cerous phosphate catalyst, and preparation and application thereof - Google Patents
Ruthenium-base calcium-substituting cerous phosphate catalyst, and preparation and application thereof Download PDFInfo
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- CN102451720B CN102451720B CN201010526804.7A CN201010526804A CN102451720B CN 102451720 B CN102451720 B CN 102451720B CN 201010526804 A CN201010526804 A CN 201010526804A CN 102451720 B CN102451720 B CN 102451720B
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Abstract
The invention relates to a catalyst for selectively oxidizing alcohol into aldehyde ketone, particularly a novel ruthenium-base calcium-substituting cerous phosphate catalyst prepared by a chemical precipitation method and an ion-exchange method. The active component of the catalyst is Ru of which the mass content is 1-10%, the different contents of calcium substitution can implement the regulation and control on the catalyst activity, and the mass content of the calcium is 0.1-10%. The catalyst prepared by the method can react in a liquid phase system at 60-100 DEG C by using molecular oxygen as an oxygen source, thereby converting the alcohol into the corresponding aldehyde ketone in a high selectivity way, and the optimum reaction temperature is 80 DEG C. The catalyst provided by the invention has the characteristics of mild reaction conditions and high selectivity, and is recyclable and environment-friendly.
Description
Technical field
The present invention relates to the catalyst of pure selective oxidation aldehydes or ketones, specifically a kind of novel ruthenium base calcium replaces cerous phosphate catalyst and preparation and application.
Background technology
Aldehyde, ketonic compound are the important intermediate during fine chemistry industry is produced, and pure oxidation is the main path of this compounds of preparation.And traditional inorganic oxidizer such as permanganate, bichromate and hypochlorite etc. are all toxic, and can produce a large amount of discarded objects, cause serious environmental pollution.Therefore, development of new, economy and environment close friend's pure catalyst for selective oxidation receives people's concern gradually.The selective oxidation of realizing alcohol take air or oxygen as catalyst is undoubtedly the simplest, direct, cheapness effective method.
At present, the active component of the pure catalyst for selective oxidation take air or oxygen as oxygen source mainly contains Pt, Pd, Au, Ru etc. mainly take noble metal as main.Compare with other noble metal, the activity of Ru is lower, but has the characteristics of cheap and high selectivity, is adapted to industrialized production.At present from invention disclosed patent and bibliographical information, ruthenium catalyst generally needs higher noble metal loading, some in addition reach 17wt%, improved the cost of catalyst.And the deficiency of catalyst activity is so that they are difficult to reach the alcohol conversion of hope, and this is mainly reflected on the extremely low reaction transformation frequency (TOF value), as: the RuHAp(2 h of 17wt%
-1), Ru/Al
2O
3(40 h
-1), RuO
2XH
2O(1.4 h
-1) and RuO
2/ FAU zeolite (8.7 h
-1) etc.These have greatly restricted the process of industrialization of ruthenium catalyst in pure selective oxidation reaction.In recent years, people have developed the ruthenium catalyst of greater activity, such as Ru/Ni (OH)
2Composite, Ru (OH)
x/ TiO
2(160 h
-1) and the magnetic RuHAp-γ-Fe of tool
2O
3Composite (196 h
-1) etc.Yet the catalyst that exploitation has low precious metal content, high activity and high selectivity still seems particularly urgent.
Summary of the invention
The object of the present invention is to provide the ruthenium base calcium that a kind of cost is low, catalytic activity is good to replace cerous phosphate catalyst and preparation and application; When catalyst of the present invention was used for the selective oxidation of alcohol, reaction condition was gentle, and is selective high, renewable circulation and environmental friendliness.
For achieving the above object, the technical solution used in the present invention is:
A kind of ruthenium base calcium replaces the cerous phosphate catalyst, and described catalyst activity component is Ru, and its mass content in catalyst is 0.5 ~ 18%, and the replacement by different content calcium realizes the regulation and control to catalyst activity, and the mass content of calcium is 0.1 ~ 10% in the cerous phosphate calcium.
The mass content of described Ru in catalyst is preferably 1 ~ 10%; The best in quality content of calcium is 3 ~ 5% in the cerous phosphate calcium (representing with CCP, lower same).
The preparation of described catalyst: calcium is replaced cerous phosphate place 1.41 * 10 as predecessor
-3In the soluble-salt solution of-0.0141 mM trivalent ruthenium, predecessor is 1g:50-150ml with the ratio of solution, stirs 10-24h under the room temperature, obtains ruthenium base calcium by ion-exchange and replaces the cerous phosphate catalyst, and drying obtains required product, and baking temperature is 60 ~ 80 ℃.
Replace in the manufacture method of cerous phosphate at calcium of the present invention, use soluble calcium salt and the cerium salt such as halide, acetate or nitrate of calcium and cerium, wherein the preferably nitrate compound; The used presoma of active component trivalent Ru is solution and the solubility oxysalts such as nitric acid ruthenium, ruthenium sulfate such as ruthenic chloride, ruthenium bromide.
The application of described catalyst, described catalyst can be take molecular oxygen as oxygen source, and under liquid-phase system (under solvent existence or solvent-free condition), but highly selective is converted into corresponding aldehydes or ketones with alcohol, its reaction temperature is 60-100 ℃, reaction time 0.25-2h.Its optimal reaction temperature is 80 ℃.
When carrying out conversion reaction, when the consumption of substrate alcohol is 1-100mmol, described catalyst amount is 0.05-0.2g, and preferred scope is 0.05-0.1g; Described oxygen source is air or oxygen, and in the course of reaction, the molecular oxygen flow-control is at 10-30 ml/min, preferred 20-30ml/min.
Described liquid-phase system can be made of jointly solvent and alcohol (also can only self be made of substrate alcohol, namely can carry out) under solvent-free state, solvent is toluene, water or benzotrifluoride, and when the consumption of substrate alcohol is 1-100mmol, solvent load is 10-20 ml.
In the recycling of catalyst, use centrifugal or isolated by filtration, and washing, dry catalyst.
The present invention has the following advantages:
1. the present invention adopts chemical precipitation method and ion-exchange to prepare required catalyst.The advantages such as operating process is simple, mild condition, good reproducibility (see implementation for details and prepare example);
2. the catalyst of the inventive method preparation has active controlled characteristics, and the adding of different content calcium can be regulated and control the reactivity of catalyst, plays the effect of activation Ru, has reduced the content of noble metal Ru, and the catalyst cost is reduced greatly;
3. the catalyst that the present invention relates to can become aldehyde and ketone with pure selective oxidation efficiently under temperate condition;
4. the catalyst that the present invention relates to has eco-friendly characteristics, and still keeps high activity and selectivity after 5 regeneration cycle are used.
More than these advantages overcome the high and active low deficiency of traditional ruthenium catalyst bullion content, have economy and environment close friend's characteristics, a kind of catalyst that prospects for commercial application is arranged is provided.This catalyst also may be applied to the selective oxidation of amine, the racemization of alcohol, other reactions such as chloroform decomposition.
The specific embodiment
The below illustrates the present invention with embodiment, but the present invention is not subjected to the restriction of these embodiment.
Comparative Examples 1
(the list of references: Yanjie Zhang, Jinjun Lu of chemical precipitation method routinely; Crystal Growth ﹠amp; Design, 2008,8 (7): 2101-2107) numeral of preparation catalyst series 1%Ru-HAp, 5%Ru-HAp and 10%Ru-HAp(Ru front is the mass percent of Ru, and is lower same):
Take by weighing respectively 7.08g and 2.38g Ca (NO
3)
24H
2O and (NH
4)
2HPO
4In two 250ml beakers, add separately 150ml and 100ml deionized water dissolving, after raw material dissolves fully, with rare nitric acid two pHs are adjusted to separately ~ 2, two solution are mixed to get the precursor solution of clarification, then under agitation regulate the pH value to ~ 8 with ammoniacal liquor, after the turbid solution that will contain white presoma places 60 ℃ of water-baths reaction 24h, centrifugation, deionized water are washed to cleaning solution and are neutral, and 60 ℃ of dryings obtain presoma hydroxyapatite (HAp).Respectively at 70ml 1.41 * 10
-3MM, 7.05 * 10
-3The ruthenic chloride of mM and 0.0141 mM (
) in the aqueous solution, add the HAp powder after 1.0g grinds, stir 24h under the room temperature, centrifugation, drying obtains catalyst series 1%Ru-HAp, 5%Ru-HAp and 10%Ru-HAp.
Embodiment 1
The cerous phosphate method routinely that calcium replaces is synthetic.
The catalyst series 1%Ru-CePO of preparation different calcium content
4, 1%Ru-C
0.25The numeral of CP and 1%Ru-CCP(Ru front is the mass percent of Ru, and is lower same):
Take by weighing respectively 7.08g(or 0g, or 0.25g) and the Ca (NO of 2.38g
3)
24H
2O and (NH
4)
2HPO
4In two 250ml beakers, add separately 150ml and 100ml deionized water dissolving wiring solution-forming A and solution B, after raw material dissolves fully, with rare nitric acid two pHs are adjusted to separately ~ 2, with 7.56g Ce (NO
3)
37H
2O adds in the solution A, under agitation solution B is added in the solution A, then regulating the pH value to ~ 10 with ammoniacal liquor, after the turbid solution that will contain white presoma places 60 ℃ of water-baths reaction 24h, centrifugation, deionized water is washed to cleaning solution and is neutral, obtains presoma cerous phosphate calcium (or CePO behind drying and 400 ℃ of calcining 2h
4, or C
0.25CP).At 70ml 1.41 * 10
-3The ruthenic chloride of mM (
) in the aqueous solution, add the precursor powder after 1.0g grinds, stir 24h under the room temperature, centrifugation, drying obtains the catalyst series 1%Ru-CePO of different calcium content
4, 1%Ru-C
0.25CP and 1%Ru-CCP.
Embodiment 2
Preparing calcareous amount content is 4% catalyst series 1%Ru-CCP, 5%Ru-CCP and 10%Ru-CCP:
Preparation method and preparation condition are with embodiment 1.Take by weighing respectively the Ca (NO of 7.08g and 2.38g
3)
24H
2O and (NH
4)
2HPO
4In two 250ml beakers, add separately 150ml and 100ml deionized water dissolving wiring solution-forming A and solution B, after raw material dissolves fully, with rare nitric acid two pHs are adjusted to separately ~ 2, with 7.56g Ce (NO
3)
37H
2O adds in the solution A, under agitation solution B is added in the solution A, then regulating the pH value to ~ 10 with ammoniacal liquor, after the turbid solution that will contain white presoma places 60 ℃ of water-baths reaction 24h, centrifugation, deionized water is washed to cleaning solution and is neutral, obtains presoma cerous phosphate calcium (CCP) behind drying and 400 ℃ of calcining 2h.Respectively at 70ml 1.41 * 10
-3MM, 7.05 * 10
-3The ruthenic chloride of mM and 0.0141 mM (
) in the aqueous solution, add the cerous phosphate calcium powder after 1.0g grinds, stir 24h under the room temperature, centrifugation, drying obtains catalyst series 1%Ru-CCP, 5%Ru-CCP and 10%Ru-CCP.
Application examples 1
The application 1%Ru-HAp of catalyst
Catalyst adopts the catalyst that obtains in the Comparative Examples 1, in the 30ml there-necked flask, add the catalyst that 0.20g makes, the 1mmol phenmethylol is matrix, 10ml toluene is solvent, oxygen gas flow rate is 20ml/min, 80 ℃ of reaction 2h under refluxing, the conversion ratio of phenmethylol〉99%, benzaldehyde selective〉99%.Reaction transformation frequency (TOF) is 25.3h
-1
Application examples 2
The application 1%Ru-CePO of catalyst
4
Catalyst adopts the catalyst that obtains among the embodiment 1, in the 30ml there-necked flask, add respectively the catalyst that 0.10g makes, the 1mmol phenmethylol is matrix, 10ml toluene is solvent, oxygen gas flow rate is 20ml/min, 80 ℃ of reaction 0.67h under refluxing, the conversion ratio of phenmethylol is respectively〉99%, benzaldehyde selectively greater than 99%.Reaction transformation frequency (TOF) is respectively 148 h
-1
Application examples 3
The application 1%Ru-C of catalyst
0.25CP (calcareous amount content is 1%)
Catalyst adopts the catalyst that obtains among the embodiment 1, in the 30ml there-necked flask, add respectively the catalyst that 0.10g makes, the 1mmol phenmethylol is matrix, 10ml toluene is solvent, oxygen gas flow rate is 20ml/min, 80 ℃ of reaction 0.67h under refluxing, the conversion ratio of phenmethylol〉99%, benzaldehyde selective〉99%.Reaction transformation frequency (TOF) is 148 h
-1
Application examples 4
The application 1%Ru-CCP of catalyst (calcareous amount content is 4%)
Catalyst adopts the catalyst that obtains among the embodiment 1, in the 30ml there-necked flask, add respectively the catalyst that 0.1g makes, the 1mmol phenmethylol is matrix, 10ml toluene is solvent, oxygen gas flow rate is 20ml/min, 80 ℃ of reaction 0.25h under refluxing, the conversion ratio of phenmethylol〉99%, benzaldehyde selective〉99%.Reaction transformation frequency (TOF) is 408 h
-1
Application examples 5
The application 1%Ru-CCP of catalyst (calcareous amount content is 4%)
Catalyst adopts the catalyst that obtains among the embodiment 1, in the 30ml there-necked flask, add respectively the catalyst that 0.05g makes, the 1mmol phenmethylol is matrix, 10ml toluene is solvent, oxygen gas flow rate is 20ml/min, 80 ℃ of reaction 0.5h under refluxing, the conversion ratio of phenmethylol is 92.7%, benzaldehyde selective〉99%.
Application examples 6
The application 1%Ru-CCP of catalyst (calcareous amount content is 4%)
Catalyst adopts the catalyst that obtains among the embodiment 1, in the 30ml there-necked flask, add respectively the catalyst that 0.1g makes, 1mmol 1-benzyl carbinol is matrix, 10ml toluene is solvent, oxygen gas flow rate is 20ml/min, 80 ℃ of reaction 1.5h under refluxing, the conversion ratio of phenmethylol is 96%, benzaldehyde selective〉99%.
Application examples 7
The application 1%Ru-CCP of catalyst (calcareous amount content is 4%)
Catalyst adopts the catalyst that obtains among the embodiment 1, in the 30ml there-necked flask, add respectively the catalyst that 0.1g makes, the 1mmol cinnamyl alcohol is matrix, 10ml toluene is solvent, oxygen gas flow rate is 20ml/min, 80 ℃ of reaction 2h under refluxing, the conversion ratio of phenmethylol is 98%, benzaldehyde selective〉99%.
By gas-chromatography reactant mixture is analyzed, the conversion ratio of matrix, the selective and reaction transformation frequency (TOF) of various products is calculated by following formula respectively.
Conversion ratio (%)=(molal quantity of the matrix of the molal quantity of the matrix of consumption/use) * 100;
Selectively (%)=(molal quantity of the matrix of the molal quantity of various products/consumption) * 100;
Reaction transformation frequency (h
-1Molal quantity/(molal quantity * reaction time of catalyst activity component Ru) of the matrix of)=consume;
Conclusion: application examples 2,3 and 4 and application examples 1 can find out that relatively ruthenium cerous phosphate calcium catalyst is compared with ruthenium hydroxyapatite catalyst, demonstrates very high reactivity, is embodied on the transformation frequency of reaction.The TOF value of catalyst 1%Ru-CCP in the application examples 4 is up to 408 h
-1, be higher than 25.3 h of 1%RuHAp far away
-1, also be higher than application examples 2(1%Ru-CePO
4, TOF=148 h
-1) and application examples 3(1%Ru-C
0.25CP, TOF=148 h
-1) catalytic activity, illustrates and mix calcium catalyst activity improves seldom when less, and catalytic activity significantly improves than high calcium doping content (4 wt%) time, its TOF value almost is 1%Ru-CePO
4Three times.
Analytic explanation: the catalyst ruthenium content that the present invention relates to (1 wt%) has very high reactivity (TOF:408 h simultaneously well below present invention disclosed patent and bibliographical information
-1).In application examples, only use a small amount of catalyst (0.05g) just can reach good catalytic effect, the use cost that these have all greatly reduced this catalyst is conducive to its use in industrialization.
Claims (6)
1. a ruthenium base calcium replaces the cerous phosphate catalyst, it is characterized in that: described catalyst activity component is Ru, its mass content in catalyst is 1 ~ 10%, and the replacement by different content calcium realizes the regulation and control to catalyst activity, and the mass content of calcium is 0.1 ~ 10% in the cerous phosphate calcium.
2. according to catalyst claimed in claim 1, it is characterized in that: the mass content of described Ru in catalyst is 1 ~ 10%; In the cerous phosphate calcium, the mass content of calcium is 3-5%.
3. the application of the described catalyst of claim 1 is characterized in that: described catalyst can be take molecular oxygen as oxygen source, and under liquid-phase system, but highly selective is converted into corresponding aldehydes or ketones with alcohol, and its reaction temperature is 60-100 ℃, reaction time 0.25-2h.
4. according to the application of the described catalyst of claim 3, it is characterized in that: when carrying out conversion reaction, when the consumption of substrate alcohol is 1-100mmol, described catalyst amount is 0.05-0.2g, described oxygen source is air or oxygen, and in the course of reaction, the air or oxygen flow-control is at 10-30ml/min.
5. according to the application of the described catalyst of claim 3, it is characterized in that: described liquid-phase system is made of jointly solvent and alcohol, and solvent is toluene, water or benzotrifluoride, and when the consumption of substrate alcohol is 1-100mmol, solvent load is 10-20ml.
6. according to the application of the described catalyst of claim 3, it is characterized in that: its optimal reaction temperature is 80 ℃.
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| CN201010526804.7A CN102451720B (en) | 2010-11-01 | 2010-11-01 | Ruthenium-base calcium-substituting cerous phosphate catalyst, and preparation and application thereof |
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| CN104888602A (en) * | 2015-05-15 | 2015-09-09 | 浙江大学 | Application of metal oxide modified CePO4 catalyst to collaborative denitration and demercuration |
| CN114405525A (en) * | 2022-01-27 | 2022-04-29 | 河北大学 | Transition metal substituted noble metal hydroxyapatite catalyst and preparation method and application thereof |
Citations (1)
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|---|---|---|---|---|
| CN101745411A (en) * | 2008-12-17 | 2010-06-23 | 中国科学院大连化学物理研究所 | Catalyst using ruthenium based halogen to substitute hydroxyapatite and preparation and application thereof |
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| CN101745411A (en) * | 2008-12-17 | 2010-06-23 | 中国科学院大连化学物理研究所 | Catalyst using ruthenium based halogen to substitute hydroxyapatite and preparation and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Aerobic oxidation of alcohols by organically modified ruthenium hydroxyapatite;Z.Opre et al.;《Journal of Catalysis》;20060609;第241卷;第287-295页 * |
| Z.Opre et al..Aerobic oxidation of alcohols by organically modified ruthenium hydroxyapatite.《Journal of Catalysis》.2006,第241卷第287-295页. |
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