CN104069883A - Cobalt-based catalyst for generating ester by alcohol oxidation, and preparation method and application of cobalt-based catalyst - Google Patents
Cobalt-based catalyst for generating ester by alcohol oxidation, and preparation method and application of cobalt-based catalyst Download PDFInfo
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Abstract
The invention belongs to the technical field of liquid phase oxidation, and discloses a cobalt-based catalyst for generating ester by alcohol oxidation, and a preparation method and application of the cobalt-based catalyst. The cobalt-based catalyst mainly comprises the following elements in percentage by weight: 27.0-50.0 percent of cobalt, 45.0-60.0 percent of carbon and 0.5-20.0 percent of nitrogen, wherein the particle diameter of cobalt nano particles in the cobalt-based catalyst is 5-40 nm. The cobalt-based catalyst is prepared in a pyrolysis mode in an inert atmosphere with ZIF-67 as a precursor. In the presence of the cobalt-based catalyst, alkaline aids are not added in the normal-temperature and normal-pressure atmospheric environment, and two alcohols react to prepare ester compounds. The cobalt-based catalyst is easy to synthesize in quantity, and is magnetic and recyclable. A method for catalyzing alcohol oxidation to generate ester in the presence of the cobalt-based catalyst has the advantages of low cost, simplicity in operation, environment friendliness, mild reaction condition, easiness in product separation and the like.
Description
Technical field
The invention belongs to liquid phase oxidation technical field, relate to a kind of cobalt-base catalyst, be specifically related to a kind of cobalt-base catalyst that generates ester for alcohol oxidation and preparation method thereof and application.
Background technology
Ester group, as one of most important functional group of organic chemistry filed, is extensively present in various fine chemicals, natural chemicals, polymer, can be used as food additives or cosmetic additive agent, and some ester class can be used for medicine and other fields.Such as methyl ester, be widely used as flavor enhancement, solvent, diluent and extractant etc., there is very high commercial value.Aromatic ester, because it has multifunctionality through being commonly used for organic synthesis intermediate, is widely used as micro-liquid crystal polymer, cosmetics, pharmaceuticals etc.
At present, researcher is mainly by four approach synthesizing ester compounds.The sour derivative of main employing of last century Mo synthesizes as acyl chlorides or acid anhydrides etc. reacts with alcohol, but this reaction path can generate some unwanted accessory substances, and cause the wasting of resources and environmental pollution (Larock R C, " Comprehensive organic transformations:a guide to functional group preparations ", New York:Wiley-VCH.1999).About 2005, it is found that more direct synthesis path is to react with alcohol and generate ester type compound with transition-metal catalyst catalysis halogenated aryl hydrocarbon, but this wherein will relate to halogenated aryl hydrocarbon carbonylation, reaction condition comparatively harshness all requires high temperature and at CO atmosphere and high pressure, not environmental protection of reaction system (halogenated aryl hydrocarbon contaminated environment).Researcher finds to be reacted with alcohol by aldehyde generation ester subsequently, but in reaction system, will add the slaine of equivalent or metal oxide (as potassium acid sulfate or manganese dioxide) as oxidant.In addition, aldehyde in reactant also need to be generated by alcohol oxidation, relatively take time and effort (Xu B, Liu X, Haubrich J, " Vapour-phase gold-surface-mediated coupling of aldehydes with methanol ", Nature Chemistry, 2010,2,61).The synthesis path of above three kinds of esters all easy not and reaction in there is more accessory substance, raw material availability is not high.As can be from a large amount of one of the most basic chemicals that obtain of nature, directly by alcohol, generate the route of synthesis that ester is the simplest, economy, environmental protection.
A large amount of catalyst is developed and is applied to take alcohol as monoreactant oxidation generates ester reaction at present, comprises homogeneous catalysis and heterogeneous catalysis two individual system.
Homogeneous catalysis system aspect, be mainly Lei in 2011 etc. to take the two acetonitrile palladium bichlorides of noble metal be catalyst, the sodium tert-butoxide of two equivalents is alkali, fluorine boronation silver is additive, under oxygen atmosphere, efficient catalytic alcohol generates ester (Liu C, Wang J, Meng L, " Palladium ?Catalyzed Aerobic Oxidative Direct Esterification of Alcohols ", Angew.Chem.Int.Ed., 2011,123,5250).
Viewpoint based on sustainable development, research heterogeneous catalysis system has attracted more researcher's sight.The heterogeneous reaction catalyst system and catalyzing of the ester of article catalytic oxidation alcohol generation in recent years below, what mainly use is all noble metal catalyst, as Au, Pd etc.It is Au catalyst that heterogeneous catalysis alcohol oxidation in recent years generates ester catalyst the most widely used, and researcher is nearly all dispersed in gold on carrier and reduces golden size to improve golden dispersiveness, and this is because more short grained golden catalytic activity is higher.With Au this noble metal do under the condition of catalyst, most of document all also needs to add alkali and promotes alcohol dehydrogenase process, and nearly all requires to carry out under oxygen atmosphere, reaction temperature is also relatively high.Kobayashi in 2010 etc. are by synthetic Au/Pt bimetallic catalyst, at the potash of three equivalents, be alkali, have realized the reaction that alcohol oxidation generates ester under oxygen atmosphere.Alcohol is oxidized to after aldehyde, aldehyde is preferentially through aquation, to generate glycol, or the preferential hemiacetal that forms, and author thinks that its Au/Pt bimetallic catalyst exists coordinating effect to promote aldehyde to generate hemiacetal, thereby promoted this reaction to carry out (Kaizuka K, Miyamura H, Kobayashi S, " Remarkable Effect of Bimetallic Nanocluster Catalysts for Aerobic Oxidation of Alcohols:Combining Metals Changes the Activities and the Reaction Pathways to Aldehydes/Carboxylic Acids or Esters ", Journal of the American Chemical Society, 2010, 132, 15096).
In addition, Stahl in 2013 etc. utilize Pd/charcoal (5wt%) catalyst, at Bi (NO
3)
3, Te metal coordinative role under, in heterogeneous reaction, take first palladium as catalyst alcohol oxidation reaction.Bi and Te can accelerate the productive rate of reaction rate, selective and target product, this catalyst system and catalyzing substrate applicability is good, the esterification of the fatty alcohol of the energy most of aromatic alcohols of catalysis and more difficult reaction, but this reaction also needs to add the potassium methoxide of monovalent and needs pure oxygen atmosphere (Powell A B, Stahl S S, " Aerobic Oxidation of Diverse Primary Alcohols to Methyl Esters with a Readily Accessible Heterogeneous Pd/Bi/Te Catalyst ", Organic Letters, 2013,15,5072).
Although increasing bibliographical information confirms that by the directly synthetic ester of alcohol oxidation be a up-and-coming direction, but still need to improve the catalytic efficiency of catalyst and Practical Performance further.Homogeneous catalysis alcohol oxidative esterification reaction often needs to add inorganic base or inorganic acid, under noble metal or visible ray, could catalytic alcohol generate ester, and the activity of reaction system need to promote, and has reacted comparatively complexity of rear separation.Heterogeneous catalysis alcohol oxidative esterification reaction mostly needs precious metal to make catalyst, need to add alkali and promote alcohol dehydrogenase process, and mostly require to carry out under pure oxygen atmosphere, and requisite oxygen atmospheric pressure is sometimes even up to 1MPa, and reaction temperature is also relatively high.Due to finiteness and the expensive price thereof of Precious Metals Resources, the cheap catalyst of finding economic environmental protection is to promote alcohol direct oxidation to generate the key of ester commercial Application.For reaction substrate, aromatic alcohol is owing to having the existence of this active group of phenyl ring therefore activity is higher, and fatty alcohol and heterocyclic alcohol reaction response activity are undesirable, mostly need than aromatic alcohol more exacting terms reaction just can carry out.
Summary of the invention
In order to overcome the shortcoming and deficiency of prior art, preparation has highly active cheap metal catalyst, and being applied to the direct ester that generates of alcohol oxidation under mild reaction conditions, primary and foremost purpose of the present invention is to provide a kind of cobalt-base catalyst that generates ester for alcohol oxidation;
Another object of the present invention is to provide the preparation method of above-mentioned cobalt-base catalyst;
A further object of the present invention is to provide the application of cobalt-base catalyst.
Object of the present invention is achieved through the following technical solutions:
For alcohol oxidation, generate a cobalt-base catalyst for ester, described cobalt-base catalyst is mainly comprised of transition metals cobalt and carbon, nitrogen element, and wherein each element wt ratio is: cobalt 27.0～50.0wt%, carbon 45.0～60.0wt%, nitrogen 0.5～20.0wt%; In described cobalt-base catalyst, the particle diameter of cobalt nano-particle is 5～40nm.
A preparation method according to the above-mentioned cobalt-base catalyst for alcohol oxidation generation ester, comprises the steps:
(1) preparation of metallic organic framework structural material ZIF-67 and activation: take respectively cabaltous nitrate hexahydrate, glyoxal ethyline (is write a Chinese character in simplified form: Im) be added in water, stirring at room, obtains mixed solution; By described mixed solution centrifugation, filtration is precipitated, and water washes away unreacted part in precipitation, then rinses described precipitation with methanol solution; Finally described precipitation is vacuumized to processing, obtain metallic organic framework structural material ZIF-67;
(2) preparation of catalyst: step (1) the gained metallic organic framework structural material ZIF-67 of take is precursor, in inert atmosphere, be heated to target temperature, isothermal pyrolysis, then be cooled to room temperature, obtain powdery product, be the described cobalt-base catalyst for alcohol oxidation generation ester.
Preferably, the molar ratio of cabaltous nitrate hexahydrate, glyoxal ethyline and the water described in step (1) is Co
2+: Im:H
2o=1:58:1100.
Preferably, the time of the described stirring at room of step (1) is 6～8 hours.
Preferably, the described application of vacuum of step (1) vacuumizes 12～36h for being deposited in 80～200 ℃ described in general.
Preferably, the described target temperature of step (2) is 400～1200 ℃.
Preferably, the time of the described isothermal pyrolysis of step (2) is 0.5～12h.
The above-mentioned cobalt-base catalyst that generates ester for alcohol oxidation does not add the oxidation of alkali air atmosphere catalytic alcohol at normal temperature and pressure and generates the application in ester.
The preferred version of above-mentioned application comprises the steps: described cobalt-base catalyst and alcohol to put into reactor, carries out at normal temperatures and pressures stirring reaction, can produce corresponding ester.
Preferably, described alcohol is fragrant primary alconol, fatty alcohol or glycol; The controlled condition of carrying out stirring reaction under described normal temperature and pressure is 15～35 ℃ of reaction temperatures, and reaction pressure is normal pressure, and the stirring reaction time is 3～5 days; The mol ratio of described alcohol and cobalt-base catalyst (cobalt of take calculates) is 1～10;
Preferably, described cobalt-base catalyst after 300～450 ℃ of hydrogen reducing 0.5～4h, recycling capable of circulation.
Principle of the present invention:
Cobalt-base catalyst provided by the present invention is to take metallic organic framework structure as precursor, adopts a step pyrolysismethod to be prepared from.The advantage that the selected catalyst precarsor ZIF-67 of the present invention possesses is: one, and synthetic ZIF-67 size is less, and after pyrolysis, material granule is little has a larger active surface; Its two, the phosphorus content of ZIF-67 is high, can effectively hinder the reunion of cobalt nano-particle in pyrolytic process; And the nitrogen content of ZIF-67 is high, the nitrogen element being entrained in after pyrolysis in catalyst can promote the carrying out reacting.
The present invention has following advantage and effect with respect to prior art:
(1) cobalt-base catalyst of the present invention is easy to a large amount of synthesizing, and has magnetic, utilizes Magnetic Isolation catalyst and reaction mixture after reaction, and operation is very simple.
(2) cobalt-base catalyst provided by the present invention, adopt heterogeneous catalysis system, under normal temperature and pressure conditions, do not add alkaline assistant, can realize efficiently alcohol oxidation and generate ester, solve under temperate condition the low and alcohol oxidation of catalyst activity and generated the problem that ester needs alkaline assistant, avoid using the reaction condition (as higher temperature and pressure) of traditional noble metal (gold, palladium etc.), harshness, there is the advantages such as cost is low, simple to operate, environmental protection, reaction condition is gentle, product separation is simple.
(3) cobalt-base catalyst of the present invention recycle functional.By the cobalt-base catalyst reclaiming, at 300～450 ℃ of hydrogen reducing 0.5～4h, the cobalt-base catalyst after reduction is reused repeatedly rear catalytic activity and is not selectively all changed.
(4) utilize cobalt-base catalyst catalytic alcohol of the present invention to produce the catalyst system and catalyzing of ester, gentle, efficient, the selective height of reaction condition and good stability, and accessory substance is few, does not need alkaline assistant, environmental protection is the catalyst system and catalyzing that eco-friendly catalytic alcohol oxidation generates ester.
(5) cobalt-base catalyst of the present invention has good substrate applicability, can the various alcohol reactions of efficient catalytic generate corresponding ester, and the yield of ester reaches as high as more than 99%.
Accompanying drawing explanation
Fig. 1 is the high power transmission electron microscope picture of cobalt-base catalyst of the present invention.
The specific embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Metallic organic framework structural material ZIF-67 used in the present invention, can prepare according to following embodiment 1 or 2:
Embodiment 1
Take respectively cabaltous nitrate hexahydrate, glyoxal ethyline is added in deionized water, molar ratio is Co
2+: Im:H
2o=1:58:1100, stirring at room 6 hours, obtains being the mixed solution of purple; To be the mixed solution centrifugation of purple, filter the precipitation that obtains purple, by a large amount of deionized waters, wash away unreacted part, then rinse purple precipitation 3 times with methanol solution; Finally the purple of collection is deposited in to 80 ℃ and vacuumizes 24h, obtain metallic organic framework structural material ZIF-67.
Embodiment 2
Take respectively cabaltous nitrate hexahydrate, glyoxal ethyline is added in deionized water, molar ratio is Co
2+: Im:H
2o=1:58:1100, stirring at room 6 hours, obtains being the mixed solution of purple; To be the mixed solution centrifugation of purple, filter the precipitation that obtains purple, by a large amount of deionized waters, wash away unreacted part, then rinse purple precipitation 3 times with methanol solution; Finally the purple of collection is deposited in to 200 ℃ and vacuumizes 24h, obtain metallic organic framework structural material ZIF-67.
Cobalt-base catalyst for alcohol oxidation generation ester of the present invention can be prepared by the method described in embodiment 3～10 any one:
Embodiment 3
Take ZIF-67 as precursor, in inert atmosphere, be heated to after 400 ℃ of target temperatures, isothermal pyrolysis 0.5h, then be cooled to room temperature; The black powder of collecting is the described cobalt-base catalyst that generates ester for alcohol oxidation.
Embodiment 4
Take ZIF-67 as precursor, in inert atmosphere, be heated to after 400 ℃ of target temperatures, isothermal pyrolysis 12h, then be cooled to room temperature; The black powder of collecting is the described cobalt-base catalyst that generates ester for alcohol oxidation.
Embodiment 5
Take ZIF-67 as precursor, in inert atmosphere, be heated to after 1200 ℃ of target temperatures, isothermal pyrolysis 0.5h, then be cooled to room temperature; The black powder of collecting is the described cobalt-base catalyst that generates ester for alcohol oxidation.
Embodiment 6
Take ZIF-67 as precursor, in inert atmosphere, be heated to after 1200 ℃ of target temperatures, isothermal pyrolysis 12h, then be cooled to room temperature; The black powder of collecting is the described cobalt-base catalyst that generates ester for alcohol oxidation.
Embodiment 7
Take ZIF-67 as precursor, in inert atmosphere, be heated to after 600 ℃ of target temperatures, isothermal pyrolysis 8h, then be cooled to room temperature; The black powder of collecting is the described cobalt-base catalyst that generates ester for alcohol oxidation.
Embodiment 8
Take ZIF-67 as precursor, in inert atmosphere, be heated to after 700 ℃ of target temperatures, isothermal pyrolysis 8h, then be cooled to room temperature; The black powder of collecting is the described cobalt-base catalyst that generates ester for alcohol oxidation.
Embodiment 9
Take ZIF-67 as precursor, in inert atmosphere, be heated to after 800 ℃ of target temperatures, isothermal pyrolysis 8h, then be cooled to room temperature; The black powder of collecting is the described cobalt-base catalyst that generates ester for alcohol oxidation.As shown in Figure 1, B is the partial enlarged drawing in A square frame to the high power transmission electron microscope picture of the cobalt-base catalyst for alcohol oxidation generation ester of the present embodiment gained.
Embodiment 10
Take ZIF-67 as precursor, in inert atmosphere, be heated to after 900 ℃ of target temperatures, isothermal pyrolysis 8h, then be cooled to room temperature; The black powder of collecting is the described cobalt-base catalyst that generates ester for alcohol oxidation.
The catalytic applications of the cobalt-base catalyst for alcohol oxidation generation ester of the present invention can realize by the scheme of embodiment 11～14:
Embodiment 11
The raw alcohol of the row of reactant shown in table 1, described cobalt-base catalyst, methyl alcohol and n-hexane (solvent) for alcohol oxidation generation ester are joined to test tube and be oxidized the reaction that generates ester, concrete reaction condition is as follows: 25 ℃ of reaction temperatures, reaction pressure is normal pressure (0.1MP), raw alcohol: cobalt-base catalyst (cobalt of take calculates) mol ratio is 6, reaction atmosphere is air atmosphere, and the reaction time is 4 days; Reacted rear naturally cooling, Magnetic Isolation cobalt-base catalyst and reaction mixture, GC-MS detection reaction product, result is as shown in table 1.
Table 1. cobalt-base catalyst catalytic oxidation alcohol and methyl alcohol generate raw material, product and the productive rate of corresponding ester
The cobalt-base catalyst methanol wash reclaiming, reduces 0.5h in 400 ℃ of atmosphere of hydrogen; Cobalt-base catalyst after reduction repeats above-mentioned steps.The productive rate that described cobalt-base catalyst recycles is as shown in table 2, and as can be seen from Table 2, this cobalt-base catalyst reuses 5 secondary response effects not to be reduced yet, and illustrates that this cobalt-base catalyst is very stable, can repeatedly reuse.
Described in table 2., cobalt-base catalyst recycles performance measurement result
Embodiment 12
The raw alcohol of the row of reactant shown in table 1, described cobalt-base catalyst, methyl alcohol and n-hexane (solvent) for alcohol oxidation generation ester are joined to the reaction that is oxidized generation ester in test tube, concrete reaction condition is as follows: 15 ℃ of reaction temperatures, reaction pressure is normal pressure (0.1MP), raw alcohol: cobalt-base catalyst (cobalt of take calculates) mol ratio is 1, reaction atmosphere is air atmosphere, and the reaction time is 3 days.Reaction finishes the product of rear mensuration and the result of productive rate and table 1 is close.
Embodiment 13
The raw alcohol of the row of reactant shown in table 1, described cobalt-base catalyst, methyl alcohol and n-hexane (solvent) for alcohol oxidation generation ester are joined to the reaction that is oxidized generation ester in test tube, concrete reaction condition is as follows: 35 ℃ of reaction temperatures, reaction pressure is normal pressure (0.1MP), raw alcohol: cobalt-base catalyst (cobalt of take calculates) mol ratio is 1, reaction atmosphere is air atmosphere, and the reaction time is 5 days.Reaction finishes the product of rear mensuration and the result of productive rate and table 1 is close.
Embodiment 14
The raw alcohol of the row of reactant shown in table 1, described cobalt-base catalyst, methyl alcohol and n-hexane (solvent) for alcohol oxidation generation ester are joined to the reaction that is oxidized generation ester in test tube, concrete reaction condition is as follows: 35 ℃ of reaction temperatures, reaction pressure is normal pressure (0.1MP), raw alcohol: cobalt-base catalyst (cobalt of take calculates) mol ratio is 10, reaction atmosphere is air atmosphere, and the reaction time is 4 days.Reaction finishes the product of rear mensuration and the result of productive rate and table 1 is close.
The Surface Physical Chemistry property analysis of precursor ZIF-67 and cobalt-base catalyst of the present invention:
Respectively the cobalt-base catalyst of the ZIF-67 of embodiment 1 gained and embodiment 7～10 gained is carried out to Surface Physical Chemistry property analysis.First carrying out specific area and pore volume measures: ZIF-67 and cobalt-base catalyst are after 150 ℃ of vacuum drying 12h, on Micromeritics ASAP2020 analyzer, thereby under 77K condition, carry out specific area and the pore volume that the test of nitrogen adsorption desorption obtains material.Analysis result is as shown in table 3.
The pore structure data of the cobalt-base catalyst that the different carbonization temperatures of table 3. make
From table 3, the specific area of cobalt-base catalyst of the present invention is about 300m
2g
-1, there is relatively concentrated aperture.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under Spirit Essence of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. one kind is oxidized the cobalt-base catalyst that generates ester for alcohol, it is characterized in that: described cobalt-base catalyst is mainly comprised of transition metals cobalt and carbon, nitrogen element, wherein each element wt ratio is: cobalt 27.0～50.0wt%, carbon 45.0～60.0wt%, nitrogen 0.5～20.0wt%; In described cobalt-base catalyst, the particle diameter of cobalt nano-particle is 5～40nm.
2. the preparation method who generates the cobalt-base catalyst of ester for alcohol oxidation according to claim 1, is characterized in that comprising the steps:
(1) preparation of metallic organic framework structural material ZIF-67 and activation: take respectively cabaltous nitrate hexahydrate, glyoxal ethyline (is write a Chinese character in simplified form: Im) be added in water, stirring at room, obtains mixed solution; By described mixed solution centrifugation, filtration is precipitated, and water washes away unreacted part in precipitation, then rinses described precipitation with methanol solution; Finally described precipitation is vacuumized to processing, obtain metallic organic framework structural material ZIF-67;
(2) preparation of catalyst: step (1) the gained metallic organic framework structural material ZIF-67 of take is precursor, in inert atmosphere, be heated to target temperature, isothermal pyrolysis, then be cooled to room temperature, obtain powdery product, be the described cobalt-base catalyst for alcohol oxidation generation ester.
3. preparation method according to claim 2, is characterized in that: the molar ratio of cabaltous nitrate hexahydrate, glyoxal ethyline and water that step (1) is described is Co
2+: Im:H
2o=1:58:1100.
4. preparation method according to claim 2, is characterized in that: the time of the described stirring at room of step (1) is 6～8 hours; The described application of vacuum of step (1) vacuumizes 12～36h for being deposited in 80～200 ℃ described in general.
5. preparation method according to claim 2, is characterized in that: the described target temperature of step (2) is 400～1200 ℃.
6. preparation method according to claim 2, is characterized in that: the time of the described isothermal pyrolysis of step (2) is 0.5～12h.
7. the cobalt-base catalyst that generates ester for alcohol oxidation according to claim 1 does not add the application in alkali air atmosphere catalytic alcohol oxidation generation ester at normal temperature and pressure.
8. application according to claim 8, is characterized in that: comprise the steps: described cobalt-base catalyst and alcohol to put into reactor, carry out at normal temperatures and pressures stirring reaction, can produce corresponding ester.
9. application according to claim 8, is characterized in that: described alcohol is fragrant primary alconol, fatty alcohol or glycol; The controlled condition of carrying out stirring reaction under described normal temperature and pressure is 15～35 ℃ of reaction temperatures, and reaction pressure is normal pressure, and the stirring reaction time is 3～5 days; The mol ratio of described alcohol and cobalt-base catalyst (cobalt of take calculates) is 1～10.
10. application according to claim 8, is characterized in that: described cobalt-base catalyst after 300～450 ℃ of hydrogen reducing 0.5～4h, recycling capable of circulation.
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| CN114904535A (en) * | 2022-04-26 | 2022-08-16 | 天津师范大学 | Preparation method of nano enzyme with activity superior to natural laccase |
| CN114904535B (en) * | 2022-04-26 | 2023-12-22 | 天津师范大学 | Preparation method of nano enzyme with activity superior to that of natural laccase |
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