CN104399486B - A kind of manganese dioxide composite catalyst and its preparation method and application - Google Patents
A kind of manganese dioxide composite catalyst and its preparation method and application Download PDFInfo
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Abstract
The invention discloses the synthetic method of the preparation method of a kind of manganese dioxide composite catalyst and 2-pyridine carboxaldehyde, belong to organic synthesis field. The present invention first by potassium permanganate load on the modified attapulgite of acid, obtain MnO4 --attapulgite, then again by coprecipitation by Fe3O4Load is at MnO4 -On-attapulgite, after roasting, obtain the MnO of a kind of high catalytic activity2Composite catalyst, the present invention is successfully by the catalysis advantage of manganese dioxide and attapulgite-Fe3O4The sharp separation advantage of magnetic material combines so that catalyst manganese dioxide can reclaim and repeatable utilization. By MnO2Composite catalyst is used for preparing 2-pyridine carboxaldehyde, and reaction yield is high, mild condition, and reaction terminates rear catalyst and can be separated from reactant liquor by magnetic sedimentation and be recycled. The present invention has the advantages such as environmental pollution is little, reaction cost is low, is suitable to industrial applications.
Description
Technical field
The invention belongs to organic synthesis field, specifically, the preparation method relating to a kind of medicine intermediate, more particularly, it relates to the synthetic method of the preparation method of a kind of manganese dioxide composite catalyst and 2-pyridine carboxaldehyde.
Background technology
2-pyridine carboxaldehyde is the intermediate of caccagogue bisacodyl (bisacody1), is also widely used as the raw material of Minute Organic Synthesis. The 2-pyridine carboxaldehyde synthetic route of bibliographical information has a variety of, but it is summed up the route mainly with two kinds of different initiation materials, one is with 2-Pyridinecarboxylic Acid for initiation material, through esterification, hydrazinolysis, reoxidize to obtain 2-pyridine carboxaldehyde (Huang Shengtang, Huang Wenlong, the improvement [J] of Zhang Huibin .2-pyridine carboxaldehyde synthesis technique. chemical reagent, 2005,27 (1): 58); Two is be raw material with 2-picoline, preparation 2-pyridine carboxaldehyde (Dan Shiming is reoxidized after N-oxidation, rearrangement, hydrolysis, Yu Shuqin, Liao Hong, waits the synthesis [J] of .2-pyridine carboxaldehyde. Chinese Journal of Pharmaceuticals, and 1997,28 (8): 377-378), but oxidant selenium dioxide used or lead tetraacetate toxicity are big, easily cause environmental pollution, and yield is not high. Being synthesized aldehyde by alcohol is the very important reaction of class in organic synthesis, aldehyde can be obtained by the oxidation of primary alconol, but owing to aldehyde is the intermediate oxidation state material that a class is in alcohol and carboxylic acid, course of reaction is easy to hyperoxidation and generates carboxylic acid, therefore, suitable oxidant must be selected, under suitable reaction condition, oxidation of primary alcohols is become aldehyde.
Through retrieval, Chinese patent application publication number CN101906068A, the applying date is the preparation method that the patent application document on June 4th, 2009 discloses a kind of 2-pyridine carboxaldehyde, the steps include: that (1) is with 2-picoline for raw material, halogenated hydrocarbons is solvent, Benzoylamide be catalyst, three chlorine isocyanates is chlorinating agent, and temperature rising reflux is obtained by reacting 2-chloromethylpyridine; (2) 2-chloromethylpyridine is hydrolyzed in the basic conditions, and temperature reaction prepares 2-piconol;(3) 2-piconol is with halogenated hydrocarbons for solvent, 2,2,6,6-tetramethyl piperidine nitrogen oxides and potassium bromide are catalyst, it is cooled to-10～0 DEG C, the oxidant of dropping 10wt.% be liquor natrii hypochloritis, droplet finishes and to obtain 2-pyridine carboxaldehyde 10～25 DEG C of insulations, this invention with oxidisability more weak 2,2,6,6-tetramethyl piperidine nitrogen oxides and potassium bromide are that 2-piconol is oxidized to 2-pyridine carboxaldehyde by catalyst, and reaction terminates rear catalyst and cannot recycle, not only waste also contaminated environment so that reaction cost increases. Chinese patent application publication number CN102241624A, the applying date is the preparation method that the patent application document on July 15th, 2011 discloses a kind of pyridine-2-formaldehyde, the method includes: preparation is with titanium dioxide for carrier, molybdenum bismuth oxide is main body, transition metal oxide is the loaded catalyst containing acidity regulator of auxiliary, with 2-picoline, oxygen, water is as raw material, fixed bed catalytic reactor reacts, carry out gas phase oxidation in 250-350 DEG C and generate the thick product of pyridine-2-formaldehyde, thick product is after dichloromethane extraction, extract decompression is distilled off dichloromethane, then rectification obtains content more than 98% sterling, this invention needs to pass into oxygen during pyridine synthesis-2-formaldehyde, reaction has certain danger, and containing contents of many kinds of heavy metal ion in catalyst, these heavy metal ion in the reaction can slow release in reactant liquor, make content of beary metal in product higher, not easily remove, affect the subsequent applications of pyridine-2-formaldehyde.
Summary of the invention
1. the problem solved
For prior art exists catalyst can not recycle, contaminated environment and the easy problem such as peroxidating, the present invention provides the preparation method of a kind of manganese dioxide composite catalyst and the synthetic method of 2-pyridine carboxaldehyde, to be fixed on the MnO on attapulgite2For catalyst, the oxidation of 2-piconol obtaining 2-pyridine carboxaldehyde, reaction yield is high, and reaction terminates rear catalyst and can recycle by magnetic sedimentation, free from environmental pollution and saving cost, is suitable to industrial applications.
2. technical scheme
In order to solve the problems referred to above, the technical solution adopted in the present invention is as follows:
The preparation method of a kind of manganese dioxide composite catalyst, the steps include:
(1) attapulgite breeze is mixed with deionized water 1:4 in mass ratio, stir 40min, then stand 2h, discard the supernatant and lower floor's sandy soil, obtain the suspension of attapulgite, the attapulgite obtained is placed in baking oven under 80 DEG C of conditions dry after suspension centrifugation, standby;
(2) attapulgite obtained in above-mentioned steps is mixed with 2.5mol/L sulfuric acid solution 1:3 in mass ratio, 1h is stirred under 80 DEG C of conditions, it is subsequently cooled to room temperature, with deionized water rinsing to neutral, dry under 80 DEG C of conditions in baking oven and grind, cross 200 mesh sieves, obtain the attapulgite that acid is modified;
(3) attapulgite modified for the acid obtained in above-mentioned steps is added in the potassium permanganate solution of 0.15-0.30mol/L, 30min is stirred under 40 DEG C of conditions, attapulgite is made to fully absorb potassium permanganate, it is then centrifuged for separating, it is washed with distilled water to neutrality, subsequently with absolute ethanol washing 3-4 time, then product is placed in and is dried to constant weight under 40-50 DEG C of condition and obtains MnO4 --attapulgite;
(4) MnO that will obtain in above-mentioned steps4 --attapulgite adds containing Fe2+And Fe3+Saturated mixed solution in, under 40 DEG C of condition, stir 15-20min with the speed of 250-300rpm, make the saturated absorption ferrum Fe of attapulgite2+And Fe3+, then dripping the ammonia spirit of 0.5-0.6mol/L, ammonia continues ageing 20min after dropwising, and obtains MnO4 --attapulgite-Fe3O4Composite, wherein, Fe2+With Fe3+Molar concentration rate be 1:(2-3);
(5) after in above-mentioned steps, ageing terminates, with magnetic separation method by MnO4 --attapulgite-Fe3O4Composite is separated from suspension, and is washed with distilled water to neutrality, uses absolute ethanol washing 3-4 time subsequently, is then placed in the drying baker of 40-50 DEG C by product and is dried to constant weight;
(6) by the MnO in above-mentioned steps4 --attapulgite-Fe3O4Composite is placed in reacting furnace, and under inert gas shielding, temperature programming is to 250-300 DEG C of roasting 3-4h, then naturally cools to room temperature, obtains MnO2Composite catalyst;
(7) MnO that will obtain in above-mentioned steps2Composite catalyst grinds, and crosses 200 mesh sieves, obtains MnO2Composite catalyst powder body.
Preferably, in described step (3), the mass ratio of potassium permanganate solution and attapulgite is (2-3): 1.
Preferably, MnO in described step (4)4 --attapulgite, ferric ion solutions, ammonia mass ratio be (3-5): 1:(2-3).
Preferably, described step (6) Program programming rate is 4 DEG C/min.
The synthetic method of a kind of 2-pyridine carboxaldehyde, the steps include:
A 2-piconol is dissolved in dichloromethane and stirs by (), wherein the concentration of 2-piconol is 0.3-0.5g/mL;
B () is by above-mentioned MnO2Composite catalyst powder body adds mix homogeneously in the solution in step (a), back flow reaction 3-4h under 38-45 DEG C of condition;
C reactant liquor is cooled to room temperature after terminating by () back flow reaction, then with magnetic separation method by MnO2Composite catalyst powder body is separated from reactant liquor, obtains dichloromethane reactant liquor;
D dichloromethane reactant liquor Distillation recovery dichloromethane at ambient pressure that () will obtain in step (c), then distills under fine vacuum reduced pressure, collects the fraction of 63～65 DEG C/1.73KPa, obtains 2-pyridine carboxaldehyde.
Preferably, MnO in described step (b)2The concentration of composite catalyst powder body is 0.05-0.1g/mL.
Preferably, in described step (b) under 40 DEG C of conditions back flow reaction 3.5h.
A kind of MnO2Composite catalyst, adopts and prepares with the aforedescribed process.
MnO2Composite catalyst application in preparing 2-pyridine carboxaldehyde.
3. beneficial effect
Compared to prior art, the invention have the benefit that
(1) with the modified method activation attapulgite of acid in the present invention so that it is specific surface area enlarges markedly, and is then absorbed and fixed on attapulgite by potassium permanganate, obtains MnO4 --attapulgite, by MnO4 -The follow-up MnO obtained of-attapulgite roasting 3-4h under inert gas shielding2-attapulgite has catalysis activity, so that catalyst is easy to separate from reactant liquor, by coprecipitation by Fe in the present invention3O4Load is at MnO4 --attapulgite, then carries out roasting and obtains highly active MnO2Composite catalyst powder body;
(2) preparation method of a kind of manganese dioxide composite catalyst in the present invention, under appropriate conditions by catalyst manganese dioxide load at attapulgite-Fe3O4On magnetic material, successfully by the catalysis advantage of manganese dioxide and attapulgite-Fe3O4The sharp separation advantage of magnetic material combines, catalyst manganese dioxide can be reclaimed and repeatable utilization, manganese dioxide after load still keeps significantly high catalysis activity, compared with prior art, greatly reduce environmental pollution, and make the later separation purification of product simpler, highly purified 2-pyridine carboxaldehyde can be obtained through decompression distillation;
(3) synthetic method of the 2-pyridine carboxaldehyde of the present invention is with the activated manganese dioxide of load for catalyst, back flow reaction obtains 2-pyridine carboxaldehyde under appropriate conditions, reaction yield is high, catalyst can be recycled by magnetic sedimentation, dichloromethane can recycle and reuse, and the product purity that decompression distillation obtains is high, does not have catalyst to remain in product, reaction cost is low, and income is high;
(4) the manganese dioxide load method of the present invention and 2-pyridine carboxaldehyde preparation method technique are simple, and mild condition easily operates, free from environmental pollution and save cost, are suitable to industrial applications.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of preparation method of the present invention;
Fig. 2 is the structural representation of 2-pyridine carboxaldehyde in the present invention.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further described below.
Embodiment 1
As depicted in figs. 1 and 2,
The preparation method of a kind of manganese dioxide composite catalyst, the steps include:
(1) attapulgite breeze is mixed with deionized water 1:4 in mass ratio, stir 40min, then stand 2h, discard the supernatant and lower floor's sandy soil, obtain the suspension of attapulgite, the attapulgite obtained is placed in baking oven under 80 DEG C of conditions dry after suspension centrifugation, standby;
(2) attapulgite obtained in above-mentioned steps is mixed with 2.5mol/L sulfuric acid solution 1:3 in mass ratio, 1h is stirred under 80 DEG C of conditions, it is subsequently cooled to room temperature, with deionized water rinsing to neutral, dry under 80 DEG C of conditions in baking oven and grind, cross 200 mesh sieves, obtain the attapulgite that acid is modified;
(3) attapulgite modified for the acid obtained in above-mentioned steps is added in the potassium permanganate solution of 0.15mol/L, the mass ratio of potassium permanganate solution and attapulgite is 3:1,30min is stirred under 40 DEG C of conditions, attapulgite is made to fully absorb potassium permanganate, it is then centrifuged for separating, it is washed with distilled water to neutrality, subsequently with absolute ethanol washing 3 times, then product is placed in and is dried to constant weight under 40 DEG C of conditions and obtains MnO4 --attapulgite;
(4) MnO that will obtain in above-mentioned steps4 --attapulgite adds containing Fe2+And Fe3+Saturated mixed solution in, under 40 DEG C of condition, stir 20min with the speed of 250rpm, make the saturated absorption ferrum Fe of attapulgite2+And Fe3+, then dripping the ammonia spirit of 0.5mol/L, ammonia continues ageing 20min after dropwising, and obtains MnO4 --attapulgite-Fe3O4Composite, wherein, Fe2+With Fe3+Molar concentration rate be 1:2, MnO4 --attapulgite, ferric ion solutions, ammonia mass ratio be 3:1:2;
(5) after in above-mentioned steps, ageing terminates, with magnetic separation method by MnO4 --attapulgite-Fe3O4Composite is separated from suspension, and is washed with distilled water to neutrality, uses absolute ethanol washing 3 times subsequently, is then placed in the drying baker of 40 DEG C by product and is dried to constant weight;
(6) by the MnO in above-mentioned steps4 --attapulgite-Fe3O4Composite is placed in reacting furnace, is warming up to 250 DEG C of roasting 4h with 4 DEG C/min speed program, then naturally cools to room temperature, obtain MnO under inert gas shielding2Composite catalyst;
(7) MnO that will obtain in above-mentioned steps2Composite catalyst grinds, and crosses 200 mesh sieves, obtains MnO2Composite catalyst powder body.
The synthetic method of a kind of 2-pyridine carboxaldehyde, the steps include:
A 2-piconol is dissolved in dichloromethane and stirs by (), wherein the concentration of 2-piconol is 0.3g/mL;
B () is by above-mentioned MnO2Composite catalyst powder body adds mix homogeneously in the solution in step (a), back flow reaction 4h under 38 DEG C of conditions, wherein MnO2The concentration of composite catalyst powder body is 0.05g/mL;
C reactant liquor is cooled to room temperature after terminating by () back flow reaction, then with magnetic separation method by MnO2Composite catalyst powder body is separated from reactant liquor, obtains dichloromethane reactant liquor;
D dichloromethane reactant liquor Distillation recovery dichloromethane at ambient pressure that () will obtain in step (c), then distills under fine vacuum reduced pressure, collects the fraction of 63～65 DEG C/1.73KPa, obtains 2-pyridine carboxaldehyde.
The productivity preparing 2-pyridine carboxaldehyde in the present embodiment is 92%, analyzes its purity through chromatography of gases and reaches 99.5%, the MnO obtained after Magneto separate2Composite catalyst powder body stable in catalytic performance, it is possible to continue on for preparation 2-pyridine carboxaldehyde.
Embodiment 2
The preparation method of a kind of manganese dioxide composite catalyst, the steps include:
(1) attapulgite breeze is mixed with deionized water 1:4 in mass ratio, stir 40min, then stand 2h, discard the supernatant and lower floor's sandy soil, obtain the suspension of attapulgite, the attapulgite obtained is placed in baking oven under 80 DEG C of conditions dry after suspension centrifugation, standby;
(2) attapulgite obtained in above-mentioned steps is mixed with 2.5mol/L sulfuric acid solution 1:3 in mass ratio, 1h is stirred under 80 DEG C of conditions, it is subsequently cooled to room temperature, with deionized water rinsing to neutral, dry under 80 DEG C of conditions in baking oven and grind, cross 200 mesh sieves, obtain the attapulgite that acid is modified;
(3) attapulgite modified for the acid obtained in above-mentioned steps is added in the potassium permanganate solution of 0.25mol/L, the mass ratio of potassium permanganate solution and attapulgite is 2.5:1,30min is stirred under 40 DEG C of conditions, attapulgite is made to fully absorb potassium permanganate, it is then centrifuged for separating, it is washed with distilled water to neutrality, subsequently with absolute ethanol washing 4 times, then product is placed in and is dried to constant weight under 45 DEG C of conditions and obtains MnO4 --attapulgite;
(4) MnO that will obtain in above-mentioned steps4 --attapulgite adds containing Fe2+And Fe3+Saturated mixed solution in, under 40 DEG C of condition, stir 18min with the speed of 280rpm, make the saturated absorption ferrum Fe of attapulgite2+And Fe3+, then dripping the ammonia spirit of 0.6mol/L, ammonia continues ageing 20min after dropwising, and obtains MnO4 --attapulgite-Fe3O4Composite, wherein, Fe2+With Fe3+Molar concentration rate be 1:2.5, MnO4 --attapulgite, ferric ion solutions, ammonia mass ratio be 4:1:2.5;
(5) after in above-mentioned steps, ageing terminates, with magnetic separation method by MnO4 --attapulgite-Fe3O4Composite is separated from suspension, and is washed with distilled water to neutrality, uses absolute ethanol washing 4 times subsequently, is then placed in the drying baker of 45 DEG C by product and is dried to constant weight;
(6) by the MnO in above-mentioned steps4 --attapulgite-Fe3O4Composite is placed in reacting furnace, is warming up to 270 DEG C of roasting 3.5h with 4 DEG C/min speed program, then naturally cools to room temperature, obtain MnO under inert gas shielding2Composite catalyst;
(7) MnO that will obtain in above-mentioned steps2Composite catalyst grinds, and crosses 200 mesh sieves, obtains MnO2Composite catalyst powder body.
The synthetic method of a kind of 2-pyridine carboxaldehyde, the steps include:
A 2-piconol is dissolved in dichloromethane and stirs by (), wherein the concentration of 2-piconol is 0.4g/mL;
B () is by above-mentioned MnO2Mix homogeneously in solution in composite catalyst powder body addition step (a), back flow reaction 3.5h under 40 DEG C of conditions, wherein, MnO2The concentration of composite catalyst powder body is 0.08g/mL;
C reactant liquor is cooled to room temperature after terminating by () back flow reaction, then with magnetic separation method by MnO2Composite catalyst powder body is separated from reactant liquor, obtains dichloromethane reactant liquor;
D dichloromethane reactant liquor Distillation recovery dichloromethane at ambient pressure that () will obtain in step (c), then distills under fine vacuum reduced pressure, collects the fraction of 63～65 DEG C/1.73KPa, obtains 2-pyridine carboxaldehyde.
The productivity preparing 2-pyridine carboxaldehyde in the present embodiment is 94%, analyzes its purity through chromatography of gases and reaches 99.3%, the MnO obtained after Magneto separate2Composite catalyst powder body stable in catalytic performance, it is possible to continue on for preparation 2-pyridine carboxaldehyde.
Embodiment 3
The preparation method of a kind of manganese dioxide composite catalyst, the steps include:
(1) attapulgite breeze is mixed with deionized water 1:4 in mass ratio, stir 40min, then stand 2h, discard the supernatant and lower floor's sandy soil, obtain the suspension of attapulgite, the attapulgite obtained is placed in baking oven under 80 DEG C of conditions dry after suspension centrifugation, standby;
(2) attapulgite obtained in above-mentioned steps is mixed with 2.5mol/L sulfuric acid solution 1:3 in mass ratio, 1h is stirred under 80 DEG C of conditions, it is subsequently cooled to room temperature, with deionized water rinsing to neutral, dry under 80 DEG C of conditions in baking oven and grind, cross 200 mesh sieves, obtain the attapulgite that acid is modified;
(3) attapulgite modified for the acid obtained in above-mentioned steps is added in the potassium permanganate solution of 0.30mol/L, the mass ratio of potassium permanganate solution and attapulgite is 2:1,30min is stirred under 40 DEG C of conditions, attapulgite is made to fully absorb potassium permanganate, it is then centrifuged for separating, it is washed with distilled water to neutrality, subsequently with absolute ethanol washing 4 times, then product is placed in and is dried to constant weight under 50 DEG C of conditions and obtains MnO4 --attapulgite;
(4) MnO that will obtain in above-mentioned steps4 --attapulgite adds containing Fe2+And Fe3+Saturated mixed solution in, under 40 DEG C of condition, stir 15min with the speed of 300rpm, make the saturated absorption ferrum Fe of attapulgite2+And Fe3+, then dripping the ammonia spirit of 0.6mol/L, ammonia continues ageing 20min after dropwising, and obtains MnO4 --attapulgite-Fe3O4Composite, wherein, Fe2+With Fe3+Molar concentration rate be 1:3, MnO4 --attapulgite, ferric ion solutions, ammonia mass ratio be 5:1:3;
(5) after in above-mentioned steps, ageing terminates, with magnetic separation method by MnO4 --attapulgite-Fe3O4Composite is separated from suspension, and is washed with distilled water to neutrality, uses absolute ethanol washing 4 times subsequently, is then placed in the drying baker of 50 DEG C by product and is dried to constant weight;
(6) by the MnO in above-mentioned steps4 --attapulgite-Fe3O4Composite is placed in reacting furnace, is warming up to 300 DEG C of roasting 3h with 4 DEG C/min speed program, then naturally cools to room temperature, obtain MnO under inert gas shielding2Composite catalyst;
(7) MnO that will obtain in above-mentioned steps2Composite catalyst grinds, and crosses 200 mesh sieves, obtains MnO2Composite catalyst powder body.
The synthetic method of a kind of 2-pyridine carboxaldehyde, the steps include:
A 2-piconol is dissolved in dichloromethane and stirs by (), wherein the concentration of 2-piconol is 0.5g/mL;
B () is by above-mentioned MnO2Mix homogeneously in solution in composite catalyst powder body addition step (a), back flow reaction 3h under 45 DEG C of conditions, wherein, MnO2The concentration of composite catalyst powder body is 0.1g/mL;
C reactant liquor is cooled to room temperature after terminating by () back flow reaction, then with magnetic separation method by MnO2Composite catalyst powder body is separated from reactant liquor, obtains dichloromethane reactant liquor;
D dichloromethane reactant liquor Distillation recovery dichloromethane at ambient pressure that () will obtain in step (c), then distills under fine vacuum reduced pressure, collects the fraction of 63～65 DEG C/1.73KPa, obtains 2-pyridine carboxaldehyde.
The productivity preparing 2-pyridine carboxaldehyde in the present embodiment is 93%, analyzes its purity through chromatography of gases and reaches 99.6%, the MnO obtained after Magneto separate2Composite catalyst powder body stable in catalytic performance, it is possible to continue on for preparation 2-pyridine carboxaldehyde.
Claims (6)
1. a preparation method for manganese dioxide composite catalyst, the steps include:
(1) attapulgite breeze is mixed with deionized water 1:4 in mass ratio, stir 40min, then stand 2h, discard the supernatant and lower floor's sandy soil, obtain the suspension of attapulgite, the attapulgite obtained is placed in baking oven under 80 DEG C of conditions dry after suspension centrifugation, standby;
(2) attapulgite obtained in above-mentioned steps is mixed with 2.5mol/L sulfuric acid solution 1:3 in mass ratio, 1h is stirred under 80 DEG C of conditions, it is subsequently cooled to room temperature, with deionized water rinsing to neutral, dry under 80 DEG C of conditions in baking oven and grind, cross 200 mesh sieves, obtain the attapulgite that acid is modified;
(3) attapulgite modified for the acid obtained in above-mentioned steps is added in the potassium permanganate solution of 0.15-0.30mol/L, 30min is stirred under 40 DEG C of conditions, attapulgite is made to fully absorb potassium permanganate, it is then centrifuged for separating, it is washed with distilled water to neutrality, subsequently with absolute ethanol washing 3-4 time, then product is placed in and is dried to constant weight under 40-50 DEG C of condition and obtains MnO4 --attapulgite;
(4) MnO that will obtain in above-mentioned steps4 --attapulgite adds containing Fe2+And Fe3+Saturated mixed solution in, under 40 DEG C of condition, stir 15-20min with the speed of 250-300rpm, make the saturated absorption ferrum Fe of attapulgite2+And Fe3+, then dripping the ammonia spirit of 0.5-0.6mol/L, ammonia continues ageing 20min after dropwising, and obtains MnO4 --attapulgite-Fe3O4Composite, wherein, Fe2+With Fe3+Molar concentration rate be 1:(2-3);
(5) after in above-mentioned steps, ageing terminates, with magnetic separation method by MnO4 --attapulgite-Fe3O4Composite is separated from suspension, and is washed with distilled water to neutrality, uses absolute ethanol washing 3-4 time subsequently, is then placed in the drying baker of 40-50 DEG C by product and is dried to constant weight;
(6) by the MnO in above-mentioned steps4 --attapulgite-Fe3O4Composite is placed in reacting furnace, and under inert gas shielding, temperature programming is to 250-300 DEG C of roasting 3-4h, then naturally cools to room temperature, obtains MnO2Composite catalyst;
(7) MnO that will obtain in above-mentioned steps2Composite catalyst grinds, and crosses 200 mesh sieves, obtains MnO2Composite catalyst powder body.
2. the preparation method of a kind of manganese dioxide composite catalyst according to claim 1, it is characterised in that: in described step (3), potassium permanganate solution is (2-3) with the mass ratio of attapulgite: 1.
3. the preparation method of a kind of manganese dioxide composite catalyst according to claim 1, it is characterised in that: MnO in described step (4)4 --attapulgite, ferric ion solutions, ammonia mass ratio be (3-5): 1:(2-3).
4. the preparation method of a kind of manganese dioxide composite catalyst according to claim 1, it is characterised in that: described step (6) Program programming rate is 4 DEG C/min.
5. a MnO2Composite catalyst, it is characterised in that: adopt the method in claim 1 to prepare.
6. the MnO described in claim 52Composite catalyst application in preparing 2-pyridine carboxaldehyde.
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| CN112191264B (en) * | 2020-10-28 | 2022-02-18 | 安徽大学 | Manganese dioxide composite material and preparation method and application thereof |
| CN114015450B (en) * | 2021-11-01 | 2022-11-04 | 白银丰宝农化科技有限公司 | Attapulgite-based saline-alkali soil conditioner and preparation method thereof |
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| US20030166466A1 (en) * | 1995-01-20 | 2003-09-04 | Hoke Jeffrey B. | Catalyst and adsorption compositions having improved adhesion characteristics |
| CN100411984C (en) * | 2006-04-30 | 2008-08-20 | 合肥工业大学 | Method for preparing magnetic granule-attapulgite nano composite material |
| CN101148400A (en) * | 2006-09-22 | 2008-03-26 | 中国科学院大连化学物理研究所 | Method for preparing aldehydes and ketones by using oxygen gas to oxidize alcohols |
| CN101906068B (en) * | 2009-06-04 | 2013-01-02 | 浙江医药股份有限公司新昌制药厂 | Preparation method of 2-pyridine carboxaldehyde |
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| CN102241624B (en) * | 2011-07-15 | 2012-12-12 | 浙江大学 | Preparation method of pyridine-2-formaldehyde |
| CN102847543A (en) * | 2012-09-25 | 2013-01-02 | 中国石油化工股份有限公司 | Coal ash-attapulgite iron manganese base low-temperature denitration catalyst, and preparation method thereof |
| CN102847531A (en) * | 2012-10-12 | 2013-01-02 | 南京师范大学 | Preparation method for attapulgite and manganese dioxide nanocomposite |
| CN103230796A (en) * | 2013-04-25 | 2013-08-07 | 六安科瑞达新型材料有限公司 | Preparation method of attapulgite supported ferroferric oxide |
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