CN101927178B - Solid super basic catalyst and preparation method and application thereof - Google Patents
Solid super basic catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a novel compound metallic oxide base solid super basic catalyst, comprising 60-93 wt% of Mg-La binary composite oxide and 7-40 wt% of modified component, wherein Mg-La binary composite oxide comprises 11-33 wt% of magnesium oxide and 67-89 wt% of lanthanum oxide, and the modified component is potassium hydroxide, potassium nitrate, potassium fluoride or sodium hydroxide. The invention also provides a preparation method and the catalysis application thereof of the novel solid super basic catalyst. The solid super basic catalyst provided by the invention has simple component, high catalytic activity and simple and easy preparation; when applied to catalytic cyanogen ethylation reaction, the solid super basic catalyst has small catalyst dosage, does not corrode a reactor, has moderate reaction condition and belongs to an environmentally-friendly catalyst. After the reaction ends, the catalyst can be reused for several times by centrifugal separation.
Description
[technical field]
The present invention relates to catalysis and organic chemical synthesis technical field, relate in particular to a kind of preparation and application of novel solid super-strong base catalyst.
[background technology]
Solid base refer to can the chemisorbed acidic materials solid maybe can make the solid of acid indicator variable color.Solid super base refers to the alkaline matter of base strength (breathing out several H-that do not write) greater than 26, can think that also strength ratio neutral substance (H_=7) exceeds the alkaline matter of 19 units.The currently reported solid super basic catalyst of finding H_＞37.Solid super base shows excellent performance as catalyst in multiple reaction: (1) catalytic activity is high, the reaction condition gentleness; (2) selectively high, the product purity height easily separates with product, and technology is simple; (3) catalyst is reusable, also can use continuously; (4) little to consersion unit corrosivity, post processing is simple.In addition, solid super basic catalyst in various organic reactions unlike solid strong acid catalyst because of the easy inactivation of coking.
Alkali solid catalyst commonly used mainly contains alkaline earth oxide and hydroxide, alkali metal oxide, loading type alkali metal and alkali metal oxide etc.Though they have high activity, its active component is met water and is easily run off and inactivation, and this is that this class catalyst is difficult to the one of the main reasons in industrial large-scale application.Rare earth oxide is water insoluble, and has and the similar alkalescence of alkaline earth oxide, and the composite oxides of rare earth and other element composition might become the super basic catalyst of function admirable especially.Therefore, employing composite oxides solid base catalyst can not only greatly enrich the kind of solid base, and the achievement in research of alkali division center and formation mechanism has scientific value and realistic meaning for designing and developing novel solid body base catalyst.
(reaction equation is the compound that is generated by alcohol and acrylonitrile generation addition reaction: CH
2=CHCN+ROH → ROCH (R) CH
2CN) has purposes widely in fields such as agricultural chemicals, dyestuff, medicine, pigment.Therefore, cyanoethylation is the very important organic reaction of a class.Cyanoethylation reaction generally needs higher temperature and the condition of base catalysis.Up to now, employed catalyst is mainly homogeneous catalysts such as alkali metal hydroxide, alkali metal alcoholates, quaternary ammonium salt.But these catalyst are difficult to separate with product, and catalyst is non-renewable; And reaction back generation waste water, unfriendly to environment.In order to overcome these shortcomings, chemist is just making great efforts to develop highly active solid base.For example Hajime Kabashima and the Hideshi Hattori aluminium oxide of having reported alkaline earth oxide and load hydrogen potassium oxide or potassium fluoride has certain catalytic activity (Applied Catalysis A:General 161 (1997) L33-L35) (Catalysis Today 44 (1998) 277-283) to the cyanoethylation of methyl alcohol and acrylonitrile.Also have many pieces of bibliographical informations in addition the Mg-Al hydrotalcite to cyanoethylation reaction also have catalytic activity (O.D.Pavel et al.Catalysis Communications 9 (2008) 1974-1978) (Emilian Angelescu et al.Catalysis Communications 5 (2004) 647-651) (Pramod S.Kumbhar et al.Chem.Commun.1998,1091-1092).Although these catalyst have certain catalytic activity to this reaction, needed reaction temperature height, the reaction time is long.
At the deficiency in existing solid base catalyst and the cyanoethylation reaction, industry attempts to develop some novel solid super-strong base catalysts always, and is applied to this catalytic reaction.
[summary of the invention]
The purpose of this invention is to provide a kind of novel solid super-strong base catalyst and preparation method thereof and application.This catalyst is major constituent with the composite metal oxide, and its preparation is simple and easy to do, and catalyst has higher activity, selective and stable, and consumption is little, can reuse, and belongs to environmentally friendly catalyst.
The concrete scheme that realizes the object of the invention provides a kind of solid super basic catalyst, comprise the major constituent of 60wt%-93wt% and the modification component of 7wt%-40wt%, described major constituent is magnesium lanthanum binary composite oxides, and described modification component is to be selected from least a in potassium hydroxide, potassium nitrate, potassium fluoride or the NaOH.
In the above-mentioned solid super basic catalyst, contain the magnesia of 11wt%-33wt% and the lanthana of 67wt%-89wt% in the described magnesium lanthanum binary composite oxides.
Another object of the present invention is to provide the preparation method of above-mentioned solid super basic catalyst, comprise following steps:
S1 prepares major constituent magnesium lanthanum binary composite oxides;
S2 takes by weighing the major constituent of 60wt%-93wt% and the modification component of 7wt%-40wt% respectively, places mortar, adds water and grinds, and oven dry is placed in the roaster at last in N
2Or roasting 3h-12h after being warming up to 450 ℃-900 ℃ under the atmosphere of inert gases, namely; Wherein, described modification component is to be selected from least a in potassium hydroxide, potassium nitrate, potassium fluoride or the NaOH.
Among the preparation method of above-mentioned solid super basic catalyst, the preparation process of described major constituent magnesium lanthanum binary composite oxides is:
A. be that 1: 1～4: 1 ratio takes by weighing magnesium salts soluble in water and lanthanum salt is soluble in water, wiring solution-forming A according to the mol ratio of magnesium, lanthanum element;
B. prepare the inorganic alkali solution B of reacting dose;
C. under agitation solution A is mixed mutually with solution B, make the pH value of reaction system between 10-14, continue to stir 1～6h;
D. above-mentioned mixed liquor is separated, with filter residue and drying, grinds, again in roaster in 650～900 ℃ of following roasting 2～12h, namely.
Among the preparation method of above-mentioned solid super basic catalyst, the separate mode of mixed liquor is direct isolated by filtration mixed liquor or mixed liquor is moved in the crystallizing kettle centrifugation again behind 100～200 ℃ of crystallization 4～16h in the steps d.
Among the preparation method of above-mentioned solid super basic catalyst, the heating rate in the described roaster is 2～12 ℃/minute.
A further object of the present invention is to provide the application of above-mentioned solid super basic catalyst in the catalysis cyanoethylation reaction.
Above-mentioned solid super basic catalyst is when being applied to the catalysis of catalysis cyanoethylation reaction, and this catalyst consumption accounts for the 0.5wt～9wt% of reaction-ure mixture.
Beneficial effect of the present invention is, catalytic activity and selective high, and consumption is little, prepare simple and easy to doly, and catalyst does not have corrosion to reactor, belongs to environment-friendly catalyst, and after the reaction end, catalyst can be realized being repeatedly used by centrifugation.
[specific embodiment]
Embodiment 1
The preparation of magnesium lanthanum binary composite oxide carrier:
A. take by weighing 4.949 gram Mg (NO
3)
26H
2O and 2.096 gram La (NO
3)
3Be dissolved in the 25mL water wiring solution-forming A;
B. take by weighing 2.806 gram KOH and 1.797 gram K respectively
2CO
3Be dissolved in wiring solution-forming B in the 26mL water;
C. stir on the limit, and the limit is added drop-wise to solution A in the solution B by constant pressure funnel, drops to the pH=10-11 of solution, stops to drip, and continues to stir 1h;
D. mixed liquor is moved in the crystallizing kettle, in 100 ℃ of crystallization 16h;
E. with the crystallization product centrifugation, drying in roaster, rises to 650 ℃ by room temperature with 10 ℃/min again, and keeps 3h at 650 ℃.
The preparation of composite metal oxide base novel solid super basic catalyst:
Take by weighing 0.171 gram potassium hydroxide and the above-mentioned magnesium lanthanum binary composite oxide carrier that makes of 0.855 gram respectively, place mortar, add water and grind, oven dry is ground again, is placed at last in the roaster in N
2Be roasting 4h after 5 ℃/min is warming up to 500 ℃ with heating rate under the atmosphere, namely make super basic catalyst.
Take by weighing 0.192 gram methyl alcohol and 0.317 gram acrylonitrile respectively, add in the reaction vessel, the solid super basic catalyst that 0.027 this example of gram is made joins in the reactor; Under stirring condition, room temperature reaction 2 hours filters, catalyst is separated with reactant liquor, and the reactant liquor gas chromatographic analysis, the conversion ratio of acrylonitrile is 99.2%, product selectivity is greater than 99.0%.
Embodiment 2
Take by weighing 0.184 gram potassium fluoride and 0.569 gram respectively by the magnesium lanthanum binary composite oxides that embodiment 1 makes, place mortar, add water and grind, oven dry is ground again, is placed at last in the roaster in N
2Be roasting 4h after 5 ℃/min is warming up to 500 ℃ with heating rate under the atmosphere, namely make solid super basic catalyst.
Take by weighing 0.196 gram methyl alcohol and 0.312 gram acrylonitrile respectively, add in the reaction vessel, the solid super basic catalyst that 0.026 this example of gram is made joins in the reactor; Under stirring condition, room temperature reaction 2 hours filters, catalyst is separated with reactant liquor, and the reactant liquor gas chromatographic analysis, the conversion ratio of acrylonitrile is 98.8%, product selectivity is greater than 99.0%.
Embodiment 3
Take by weighing 0.232 gram potassium nitrate and 1.160 grams respectively by the magnesium lanthanum binary composite oxide carrier that embodiment 1 makes, place mortar, add water and grind, oven dry is ground again, is placed at last in the roaster in N
2Be roasting 4h after 5 ℃/min is warming up to 500 ℃ with heating rate under the atmosphere, namely make catalyst.
Take by weighing 0.192 gram methyl alcohol and 0.314 gram acrylonitrile respectively, add in the reaction vessel, the solid super basic catalyst that 0.026 this example of gram is made joins in the reactor; Under stirring condition, room temperature reaction 2 hours filters, catalyst is separated with reactant liquor, and the reactant liquor gas chromatographic analysis, the conversion ratio of acrylonitrile is 98.5%, product selectivity is greater than 99.0%.
Embodiment 4
Take by weighing 0.192 gram methyl alcohol and 0.318 gram acrylonitrile respectively, add in the reaction vessel, the magnesium lanthanum binary composite oxide carrier that 0.027 gram is made by embodiment 1 joins in the reaction system; Under stirring condition, room temperature reaction 2 hours filters, catalyst is separated with reactant liquor, and the reactant liquor gas chromatographic analysis, the conversion ratio of acrylonitrile is 91.8%, product selectivity is greater than 99.0%.
Embodiment 5
Take by weighing 0.173 gram NaOH and 0.855 gram respectively by the magnesium lanthanum binary composite oxide carrier that embodiment 1 makes, place mortar, add water and grind, oven dry is ground again, is placed at last in the roaster in N
2Be roasting 4h after 5 ℃/min is warming up to 550 ℃ with heating rate under the atmosphere, namely make catalyst.
Take by weighing 0.194 gram methyl alcohol and 0.315 gram acrylonitrile respectively, add in the reaction vessel, the solid super basic catalyst that 0.027 this example of gram is made joins in the reactor; Under stirring condition, room temperature reaction 2 hours filters, catalyst is separated with reactant liquor, and the reactant liquor gas chromatographic analysis, the conversion ratio of acrylonitrile is 99.5%, product selectivity is greater than 99.0%.
Embodiment 6
The preparation of magnesium lanthanum binary composite oxide carrier:
A. take by weighing 1.904 gram MgCl
2Reach 1.767 gram LaCl
36H
2O is dissolved in the 25mL water, wiring solution-forming A;
B. take by weighing 2.806 gram KOH and 1.797 gram K respectively
2CO
3Be dissolved in wiring solution-forming B in the 26mL water;
C. stir on the limit, and the limit is added drop-wise to solution B in the solution A by constant pressure funnel, drops to the pH=12-13 of solution, stops to drip, and continues to stir 6h;
D. sedimentation and filtration is separated, drying in roaster, rises to 700 ℃ by room temperature with 5 ℃/min again,
And at 700 ℃ of maintenance 2h.
Take by weighing 0.145 gram potassium hydroxide and 0.561 gram respectively by the above-mentioned magnesium lanthanum binary composite oxide carrier that makes, place mortar, add water and grind, oven dry is ground again, is placed at last in the roaster in N
2Be roasting 4h after 5 ℃/min is warming up to 500 ℃ with heating rate under the atmosphere, namely make solid super basic catalyst.
Take by weighing 0.193 gram methyl alcohol and 0.318 gram acrylonitrile respectively, add in the reaction vessel, 0.025 this routine prepared solid super basic catalyst of gram is joined in the reaction system; Under stirring condition, room temperature reaction 2 hours filters, catalyst is separated with reactant liquor, and the reactant liquor gas chromatographic analysis, the conversion ratio of acrylonitrile is 98.5%, product selectivity is greater than 99.0%.
Embodiment 7
Reclaim the catalyst among the embodiment 5, add 0.192 gram methyl alcohol and 0.318 gram acrylonitrile respectively; Under stirring condition, room temperature reaction 2 hours filters, catalyst is separated with reactant liquor, and the reactant liquor gas chromatographic analysis, the conversion ratio of acrylonitrile is 97.4%, product selectivity is greater than 99.0%.
Embodiment 8
Take by weighing 0.197 gram potassium fluoride and 0.812 gram respectively by the magnesium lanthanum binary composite oxide carrier that embodiment 5 makes, place mortar, add water and grind, oven dry is ground again, is placed at last in the roaster in N
2Be roasting 4h after 5 ℃/min is warming up to 500 ℃ with heating rate under the atmosphere, namely make super basic catalyst.
Take by weighing 0.194 gram methyl alcohol and 0.318 gram acrylonitrile respectively, add in the reaction vessel, 0.025 this routine prepared solid super basic catalyst of gram is joined in the reaction system; Under stirring condition, room temperature reaction 2 hours filters, catalyst is separated with reactant liquor, and the reactant liquor gas chromatographic analysis, the conversion ratio of acrylonitrile is 99.0%, selectively greater than 99.0%.
Embodiment 9
Take by weighing 0.201 gram potassium nitrate and 0.799 gram respectively by the magnesium lanthanum binary composite oxide carrier that embodiment 1 makes, place mortar, add water and grind, oven dry is ground again, is placed at last in the roaster in N
2Be roasting 4h after 5 ℃/min is warming up to 500 ℃ with heating rate under the atmosphere, namely make super basic catalyst.
Take by weighing 0.194 gram methyl alcohol and 0.316 gram acrylonitrile respectively, add in the reaction vessel, 0.025 this routine prepared solid super basic catalyst of gram is joined in the reaction system; Under stirring condition, room temperature reaction 2 hours filters, catalyst is separated with reactant liquor, and the reactant liquor gas chromatographic analysis, the conversion ratio of acrylonitrile is 98.8%, selectively greater than 99.0%.
Embodiment 10
Take by weighing 0.192 gram methyl alcohol and 0.316 gram acrylonitrile respectively, add in the reaction vessel, the magnesium lanthanum binary composite oxide carrier that 0.025 gram is made by embodiment 5 joins in the reaction system; Under stirring condition, room temperature reaction 2 hours filters, catalyst is separated with reactant liquor, and the reactant liquor gas chromatographic analysis, the conversion ratio of acrylonitrile is 91.4%, selectively greater than 99.0%.
Embodiment 11
The preparation of magnesium lanthanum binary composite oxide carrier:
A. take by weighing 3.302 gram Mg (NO
3)
26H
2O and 4.183 gram La (NO
3)
3Be dissolved in the 25mL water wiring solution-forming A;
B. take by weighing 2.002 gram NaOH and 1.380 gram Na respectively
2CO
3Be dissolved in wiring solution-forming B in the 26mL water;
C. stir on the limit, and the limit is added drop-wise to solution A in the solution B by constant pressure funnel, drops to the pH=12-13 of solution, stops to drip, and continues to stir 2h;
D. sedimentation and filtration is separated, drying in roaster, rises to 650 ℃ by room temperature with 5 ℃/min again, and keeps 3h at 650 ℃.
Take by weighing 0.140 gram potassium hydroxide and the above-mentioned magnesium lanthanum binary composite oxide carrier that makes of 0.691 gram respectively, place mortar, add water and grind, oven dry is ground again, is placed at last in the roaster in N
2Be roasting 4h after 5 ℃/min is warming up to 500 ℃ with heating rate under the atmosphere, namely make super basic catalyst.
Take by weighing 0.192 gram methyl alcohol and 0.317 gram acrylonitrile respectively, add in the reaction vessel, 0.025 this routine prepared solid super basic catalyst of gram is joined in the reaction system; Under stirring condition, room temperature reaction 2 hours filters, catalyst is separated with reactant liquor, and the reactant liquor gas chromatographic analysis, the conversion ratio of acrylonitrile is 99.6%, product selectivity is greater than 99.0%.
Embodiment 12
Take by weighing 0.185 gram potassium fluoride and 0.567 gram respectively by the magnesium lanthanum binary composite oxide carrier that embodiment 10 makes, place mortar, add water and grind, oven dry is ground again, is placed at last in the roaster in N
2Be roasting 4h after 5 ℃/min is warming up to 500 ℃ with heating rate under the atmosphere, namely make super basic catalyst.
Take by weighing 0.192 gram methyl alcohol and 0.317 gram acrylonitrile respectively, add in the reaction vessel, 0.027 this routine prepared solid super basic catalyst of gram is joined in the reactor; Under stirring condition, room temperature reaction 2 hours filters, catalyst is separated with reactant liquor, and the reactant liquor gas chromatographic analysis, the conversion ratio of acrylonitrile is 98.8%, product selectivity is greater than 99.0%.
Embodiment 13
Take by weighing 0.204 gram potassium nitrate and 0.803 gram respectively by the magnesium lanthanum binary composite oxide carrier that embodiment 10 makes, place mortar, add water and grind, oven dry is ground again, is placed at last in the roaster in N
2Roasting 4h after being warming up to 500 ℃ with the heating rate of 5 ℃/min under the atmosphere namely makes super basic catalyst.
Take by weighing 0.192 gram methyl alcohol and 0.317 gram acrylonitrile respectively, add in the reaction vessel, 0.027 this routine prepared solid super basic catalyst of gram is joined in the reactor; Under stirring condition, in room temperature reaction 2 hours, filter, catalyst is separated with reactant liquor, the reactant liquor gas chromatographic analysis, the conversion ratio of acrylonitrile is 98.6%, product selectivity is greater than 99.0%.
Embodiment 14
Take by weighing 0.192 gram methyl alcohol and 0.317 gram acrylonitrile respectively, add in the reaction vessel, the magnesium lanthanum binary composite oxide carrier that 0.027 gram is made by embodiment 10 joins in the reaction system; Under stirring condition, room temperature reaction 2 hours filters, catalyst is separated with reactant liquor, and the reactant liquor gas chromatographic analysis, the conversion ratio of acrylonitrile is 91.4%, selectively greater than 99.0%.
Embodiment 15
Take by weighing 0.295 gram potassium hydroxide and 0.850 gram respectively by the magnesium lanthanum binary composite oxide carrier that embodiment 1 makes, place mortar, add water and grind, oven dry is ground again, is placed at last in the roaster in N
2Be roasting 3h after 5 ℃/min is warming up to 700 ℃ with heating rate under the atmosphere, namely make super basic catalyst.
Take by weighing 0.192 gram methyl alcohol and 0.317 gram acrylonitrile respectively, add in the reaction vessel, the super basic catalyst that 0.025 this example of gram is made joins in the reaction system; Under stirring condition, room temperature reaction 2 hours filters, catalyst is separated with reactant liquor, and the reactant liquor gas chromatographic analysis, the conversion ratio of acrylonitrile is 98.7%, product selectivity is greater than 99.0%.
Embodiment 16
Take by weighing 0.276 gram ethanol and 0.316 gram acrylonitrile respectively, add in the reaction vessel, the super basic catalyst that 0.027 gram embodiment 1 is made joins in the reaction system; Under stirring condition, room temperature reaction 2 hours filters, catalyst is separated with reactant liquor, and the reactant liquor gas chromatographic analysis, the conversion ratio of acrylonitrile is 98.3%, product selectivity is greater than 99.0%.
Embodiment 17
Take by weighing 0.364 gram isopropyl alcohol and 0.316 gram acrylonitrile respectively, add in the reaction vessel, the super basic catalyst that 0.027 gram is made by embodiment 1 joins in the reaction system; Under stirring condition, room temperature reaction 2 hours filters, catalyst is separated with reactant liquor, and the reactant liquor gas chromatographic analysis, the conversion ratio of acrylonitrile is 94.5%, product selectivity is greater than 99.0%.
Embodiment 18
Take by weighing 0.445 gram n-butanol and 0.319 gram acrylonitrile respectively, add in the reaction vessel, the super basic catalyst that 0.025 gram is made by embodiment 1 joins in the reaction system; Under stirring condition, room temperature reaction 2 hours filters, catalyst is separated with reactant liquor, and the reactant liquor gas chromatographic analysis, the conversion ratio of acrylonitrile is 93.2%, product selectivity is greater than 99.0%.
Embodiment 19
Take by weighing 0.358 gram n-propylamine and 0.317 gram acrylonitrile respectively, add in the reaction vessel, the super basic catalyst that 0.025 gram is made by embodiment 1 joins in the reaction system; Under stirring condition, room temperature reaction 2 hours filters, catalyst is separated with reactant liquor, and the reactant liquor gas chromatographic analysis, the conversion ratio of acrylonitrile is 99.5%, product selectivity is greater than 99.0%.
Comparative example 1
Get commercial calcium oxide 1g in roaster, N
2Protection rises to 650 ℃ by room temperature with 10 ℃/min down, and keeps 3h at 650 ℃;
Take by weighing 0.200 gram methyl alcohol and 0.319 gram acrylonitrile respectively, add in the reaction vessel, the calcium oxide catalyst that 0.025 this example of gram is made joins in the reaction system; Under stirring condition, room temperature reaction 2 hours filters, catalyst is separated with reactant liquor, and the reactant liquor gas chromatographic analysis, the conversion ratio of acrylonitrile has only 38.7%, and product selectivity is greater than 99.0%.
Comparative example 2
Get magnesia 1g in roaster, N
2Rise to 650 ℃ by room temperature with 10 ℃/min under the gas shield, and keep 3h at 650 ℃;
Take by weighing 0.194 gram methyl alcohol and 0.316 gram acrylonitrile respectively, add in the reaction vessel, 0.026 gram magnesia catalyst is joined in the reaction system; Under stirring condition, room temperature reaction 2 hours filters, catalyst is separated with reactant liquor, and the reactant liquor gas chromatographic analysis, the conversion ratio of acrylonitrile has only 48.3%, and product selectivity is greater than 99.0%.
Comparative example 3
Get lanthana 1g in roaster, N
2Rise to 650 ℃ by room temperature with 10 ℃/min under the gas shield, and keep 3h at 650 ℃;
Take by weighing 0.196 gram methyl alcohol and 0.316 gram acrylonitrile respectively, add in the reaction vessel, the lanthanum oxide catalyst that 0.025 this example of gram is made joins in the reaction system; Under stirring condition, room temperature reaction 2 hours filters, catalyst is separated with reactant liquor, and the reactant liquor gas chromatographic analysis, the conversion ratio of acrylonitrile has only 45.2%, and product selectivity is greater than 99.0%.
Claims (6)
1. solid super basic catalyst that is used for the catalysis cyanoethylation reaction, comprise the major constituent of 60wt%-93wt% and the modification component of 7wt%-40wt%, it is characterized in that, described major constituent is magnesium lanthanum binary composite oxides, and described modification component is to be selected from least a in potassium hydroxide, potassium nitrate, potassium fluoride or the NaOH; Contain the magnesia of 11wt%-33wt% and the lanthana of 67wt%-89wt% in the described magnesium lanthanum binary composite oxides.
2. the solid super basic catalyst for the catalysis cyanoethylation reaction according to claim 1 is characterized in that, described catalyst consumption accounts for the 0.5wt～9wt% of reaction-ure mixture.
3. the preparation method of the described solid super basic catalyst of claim 1 comprises following steps:
S1 prepares major constituent magnesium lanthanum binary composite oxides;
S2 takes by weighing the major constituent of 60wt%-93wt% and the modification component of 7wt%-40wt% respectively, places mortar, adds water and grinds, and oven dry is placed in the roaster at last in N
2Or roasting 3h-12h after being warming up to 450 ℃-900 ℃ under the atmosphere of inert gases, namely;
Wherein, described modification component is to be selected from least a in potassium hydroxide, potassium nitrate, potassium fluoride or the NaOH.
4. the preparation method of solid super basic catalyst according to claim 3 is characterized in that, the preparation process of described major constituent magnesium lanthanum binary composite oxides is:
A. be that 1: 1～4: 1 ratio takes by weighing magnesium salts soluble in water and lanthanum salt is soluble in water, wiring solution-forming A according to the mol ratio of magnesium, lanthanum element;
B. prepare the inorganic alkali solution B of reacting dose;
C. under agitation solution A is mixed mutually with solution B, make the pH value of reaction system between 10-14, continue to stir 1～6h;
D. above-mentioned mixed liquor is separated, with filter residue and drying, grinds, again in roaster in 650～900 ℃ of following roasting 2～12h, namely.
5. the preparation method of solid super basic catalyst according to claim 4, it is characterized in that, the separate mode of mixed liquor is direct isolated by filtration mixed liquor in the steps d, or mixed liquor is moved in the crystallizing kettle, centrifugation again behind 100～200 ℃ of crystallization 4～16h.
6. the preparation method of solid super basic catalyst according to claim 3 is characterized in that, the heating rate in the described roaster is 2～12 ℃/minute.
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| CN102600827A (en) * | 2011-01-08 | 2012-07-25 | 中国科学院成都有机化学有限公司 | Catalyst for aldol condensation reaction and preparation method thereof |
| CN102247827B (en) * | 2011-05-04 | 2013-01-30 | 湖南大学 | Novel nano solid super-strong alkali catalyst and preparation and application thereof |
| CN102247825B (en) * | 2011-05-04 | 2013-01-02 | 湖南大学 | Cubic composite oxide solid superbase catalyst and preparation method and application thereof |
| CN103736499B (en) * | 2012-10-17 | 2016-06-08 | 中国石油化工股份有限公司 | Fluid bed synthesis gas alkene ferrum-based catalyst processed, preparation method and its usage |
| CN103212398B (en) * | 2013-02-25 | 2016-12-28 | 湖南大学 | A kind of preparation and application of solid super basic catalyst |
| CN103877965B (en) * | 2014-04-04 | 2015-10-28 | 湖南大学 | A kind of preparation and application of tin dioxide solid super basic catalyst |
| CN109368651B (en) * | 2018-10-23 | 2020-07-03 | 浙江大学 | Preparation method of nano solid strong base catalytic material K2[ (OH) F4B3O3] |
| CN111841587A (en) * | 2020-07-06 | 2020-10-30 | 浙江大学衢州研究院 | Solid base catalyst and preparation method thereof |
| CN112142607B (en) * | 2020-11-02 | 2023-10-13 | 安徽绿色谷创客空间股份有限公司 | Method for synthesizing m-diethylaminophenol |
-
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Non-Patent Citations (8)
| Title |
|---|
| Fuels》.2008,第22卷第1966页2.1部分,第1969页3.5.1部分. * |
| Fuels》.2008,第23卷第1787、1789页. * |
| N. Seshu Babu,et al..A heterogeneous strong basic Mg/La mixed oxide catalyst for efficient synthesis of polyfunctionalized pyrans.《Tetrahedron Letters》.2008,第49卷第2731、2732页. * |
| N. Seshu Babu，et al..Room-Temperature Transesterification of Edible and Nonedible Oils Using a Heterogeneous Strong Basic Mg/La Catalyst.《Energy & Fuels》.2008,第22卷第1966页2.1部分，第1969页3.5.1部分. |
| N. Seshu Babu,et al..Room-Temperature Transesterification of Edible and Nonedible Oils Using a Heterogeneous Strong Basic Mg/La Catalyst.《Energy & * |
| Oguzhan Ilgen，et al..Transesterification of Canola Oil to Biodiesel Using MgO Loaded with KOH as a Heterogeneous Catalyst.《Energy & Fuels》.2008,第23卷第1787、1789页. |
| Oguzhan Ilgen,et al..Transesterification of Canola Oil to Biodiesel Using MgO Loaded with KOH as a Heterogeneous Catalyst.《Energy & * |
| Wenlei Xie,et al..Transesterification of soybean oil catalyzed by potassium loaded on alumina as a solid-base catalyst.《Applied Catalysis A: General》.2005,第300卷第68、70-71页. * |
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