CN114275819B - Efficient recovery method of active manganese dioxide - Google Patents
Efficient recovery method of active manganese dioxide Download PDFInfo
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 294
- 238000000034 method Methods 0.000 title claims abstract description 66
- 238000011084 recovery Methods 0.000 title claims abstract description 53
- 238000005273 aeration Methods 0.000 claims abstract description 64
- 230000008569 process Effects 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 239000012670 alkaline solution Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- RUMOYJJNUMEFDD-UHFFFAOYSA-N perillyl aldehyde Chemical compound CC(=C)C1CCC(C=O)=CC1 RUMOYJJNUMEFDD-UHFFFAOYSA-N 0.000 abstract description 43
- 238000007254 oxidation reaction Methods 0.000 abstract description 24
- 230000003647 oxidation Effects 0.000 abstract description 21
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 19
- 239000013078 crystal Substances 0.000 abstract description 7
- 238000004064 recycling Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 230000010718 Oxidation Activity Effects 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 4
- NDTYTMIUWGWIMO-UHFFFAOYSA-N perillyl alcohol Chemical compound CC(=C)C1CCC(CO)=CC1 NDTYTMIUWGWIMO-UHFFFAOYSA-N 0.000 description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 33
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- 229930007631 (-)-perillyl alcohol Natural products 0.000 description 16
- 238000001816 cooling Methods 0.000 description 16
- 235000005693 perillyl alcohol Nutrition 0.000 description 16
- 238000007789 sealing Methods 0.000 description 16
- 230000001590 oxidative effect Effects 0.000 description 14
- 239000007800 oxidant agent Substances 0.000 description 13
- GOPYZMJAIPBUGX-UHFFFAOYSA-N [O-2].[O-2].[Mn+4] Chemical class [O-2].[O-2].[Mn+4] GOPYZMJAIPBUGX-UHFFFAOYSA-N 0.000 description 9
- 230000003213 activating effect Effects 0.000 description 9
- 238000001994 activation Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 230000001105 regulatory effect Effects 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000007689 inspection Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000004321 preservation Methods 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 238000005070 sampling Methods 0.000 description 8
- 238000003892 spreading Methods 0.000 description 8
- 230000007480 spreading Effects 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 3
- 238000006053 organic reaction Methods 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- -1 firstly Chemical compound 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- RUMOYJJNUMEFDD-SNVBAGLBSA-N (R)-(+)-Perillaldehyde Natural products CC(=C)[C@H]1CCC(C=O)=CC1 RUMOYJJNUMEFDD-SNVBAGLBSA-N 0.000 description 1
- HVCXHPPDIVVWOJ-UHFFFAOYSA-N [K].[Mn] Chemical compound [K].[Mn] HVCXHPPDIVVWOJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 125000001743 benzylic group Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 238000005360 mashing Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229940045997 vitamin a Drugs 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a high-efficiency recovery method of active manganese dioxide, which comprises the following steps: and mixing the manganese dioxide to be recovered with an alkaline solution for aeration treatment and heat treatment to complete the recovery of the active manganese dioxide. According to the invention, exposure of a high-activity crystal face of manganese dioxide can be promoted by carrying out aeration and heat treatment on the manganese dioxide to be recovered, so that the manganese dioxide has more excellent oxidation activity, the oxidation reaction time of perillaldehyde can be shortened from more than 8 hours to 4 hours, the yield of perillaldehyde is maintained to be more than 70% after more than 50 times of recycling, and the oxidation effect is kept stable. The efficient recovery method of the active manganese dioxide has the advantages of simple process, convenient operation, low recovery cost, mild reaction condition, safety, controllability, high recovery efficiency, high product yield, stable performance, environmental protection and the like, is a novel technology capable of efficiently recovering the active manganese dioxide and realizing the recycling of the active manganese dioxide, and has high use value and good application prospect.
Description
Technical Field
The invention relates to a high-efficiency recovery method of active manganese dioxide.
Background
Manganese has various valence states as a transition metal element, and exists in the natural world in various mineral forms such as pyrolusite, ramsdellite, and potassium manganese ore. The rich valence state of the manganese element ensures that the manganese element shows unique physical and chemical properties in various fields such as oxidation, catalysis, electrochemistry and the like. Among these, manganese dioxide is a typical manganese oxide, and is widely present in nature in the form of pyrolusite or the like, and is generally a powder or crystal of color or black brown. As the manganese dioxide has the double performances of oxidation and reduction in the intermediate valence state of manganese element, compared with high valence state manganese compounds such as potassium permanganate, the manganese dioxide has milder oxidizing property, so the manganese dioxide is very suitable for being used as a selective oxidant for some organic reactions. The manganese dioxide has various crystal forms such as alpha, beta, gamma, delta, epsilon and the like, the crystallization degree, specific surface area and other properties of the manganese dioxide with different crystal forms are different, and the oxidation performance is different, so that the physicochemical properties of the manganese dioxide can be effectively regulated by acid treatment, heat treatment and other methods, the manganese dioxide is activated, and the oxidation efficiency is improved.
The use of activated manganese dioxide in organic reactions is quite extensive, most typically the selective oxidation of unsaturated alcohols without affecting other functional groups, and as early as forty of the twentieth century, ball et al successfully oxidized vitamin a to retinoids using manganese dioxide as the oxidant. Manganese dioxide is used as an oxidant, ethyl acetate is used as a solvent, the perilla alcohol can be oxidized into the perilla aldehyde, the conversion rate can reach 99.7%, and the yield exceeds 70%; in addition, the application of the active manganese dioxide in the oxidation of C-H bonds is also wider, such as the dehydrogenation and the aromatization of heterocycle, or the selective oxidation of C-H bonds at allylic and benzylic positions in the presence of acid to generate oxygen-containing derivatives such as alcohols, aldehydes, carboxylic acids, and the like; in addition to being used as an oxidant, active manganese dioxide can also be used as a catalyst for air oxidation of certain alcohols, and tends to show better catalytic performance and selectivity.
The research on the application of the active manganese dioxide in the organic reaction is common, so that if the green recovery of the active manganese dioxide can be realized and the active manganese dioxide can be recycled, the demand of the active manganese dioxide in large-scale production can be effectively reduced, the storage and transportation pressure can be reduced, and the cost can be reduced. However, there are few related studies and patents for exploring the recycling problem of active manganese dioxide after reaction, and meanwhile, the existing active manganese dioxide recovery process mainly recovers active manganese dioxide through the combination of chlorate oxidation and permanganate activation, and the recovery process still has the following defects: (a) the process is complex, the recovery period is long, and the efficiency is low; (b) The used medicaments are more and the dosage is large, so that the recovery cost is higher, and the solid oxidant used in the recovery process is easy to introduce impurities, thereby reducing the activity of manganese dioxide; (c) The recovery temperature is high, the reaction condition is strictly required, and the strong heat release phenomenon exists, so that the safety accident is easy to cause. Therefore, how to obtain the efficient recovery method of the active manganese dioxide, which has the advantages of simple process, convenient operation, low recovery cost, mild reaction condition, safety and controllability, high recovery efficiency, high product yield, stable performance and environmental protection, has great significance for realizing the efficient recycling of the active manganese dioxide and effectively reducing the use cost of the active manganese dioxide.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the efficient recovery method of the active manganese dioxide, which has the advantages of simple process, convenient operation, low recovery cost, mild reaction condition, safety, controllability, high recovery efficiency, high product yield, stable performance and environmental protection.
In order to solve the technical problems, the invention adopts the following technical scheme:
an efficient recovery method of active manganese dioxide, comprising the following steps:
s1, mixing manganese dioxide to be recovered with an alkaline solution for aeration treatment;
s2, carrying out heat treatment on the manganese dioxide subjected to the aeration treatment in the step S1, and completing recovery of the active manganese dioxide.
In the above-mentioned high-efficiency recovery method, further improved, in step S1, the pH value of the alkaline solution is 10 to 12.
In the above-mentioned efficient recovery method, further improved, in step S1, the alkaline solution is a sodium hydroxide solution and/or a potassium hydroxide solution.
In the above-mentioned high-efficiency recovery method, further improved, in step S1, the gas used in the aeration treatment is air.
In the above-mentioned efficient recovery method, further improved, in step S1, the aeration rate in the aeration treatment process is 6.0L min -1 kg -1 ～8.0L min -1 kg -1 Based on the mass of manganese dioxide to be recovered.
In the above-mentioned high-efficiency recovery method, further improved, in step S1, the aeration treatment is performed at a temperature of 50 ℃ to 80 ℃.
In the above-mentioned high-efficiency recovery method, further improved, in step S1, the aeration treatment time is 2h to 4h.
In a further improved step S2, the heat treatment is performed at a temperature of 200-350 ℃.
In the above-mentioned high-efficiency recovery method, further improved, in step S2, the time of the heat treatment is 3h to 5h.
Compared with the prior art, the invention has the advantages that:
(1) The invention provides a high-efficiency recovery method of active manganese dioxide, firstly, manganese dioxide to be recovered is mixed with alkaline solution for aeration treatment, and aeration is carried out in an alkaline environment, so that the method has the stirring effect, can promote the sufficient contact of oxygen and manganese oxide, and simultaneously aeration is carried out in the alkaline environment, hydroxide ions can play a role in assisting oxidation in the aeration process, promote the generation of basic manganese oxide, and dehydrate to generate manganese dioxide in the subsequent heat treatment process; and then the manganese dioxide after aeration treatment is subjected to heat treatment, and the manganese dioxide is activated by heat treatment under the high-temperature condition, so that the activity of the manganese dioxide is further improved, and the efficient recovery of the active manganese dioxide is realized. According to the invention, exposure of a high-activity crystal face of manganese dioxide can be promoted by carrying out aeration and heat treatment on the manganese dioxide to be recovered, so that the manganese dioxide has more excellent oxidation activity, the reaction time required by the process of recovering the higher than 70% of the perillaldehyde can be shortened to 4 hours from 8 hours or more, and meanwhile, after the process of recovering and using for more than 50 times, the higher than 70% of the perillaldehyde is still maintained, so that the oxidation effect of the perillaldehyde is still stable. The efficient recovery method of the active manganese dioxide has the advantages of simple process, convenient operation, low recovery cost, mild reaction condition, safety, controllability, high recovery efficiency, high product yield, stable performance, environmental protection and the like, is a novel technology capable of efficiently recovering the active manganese dioxide and realizing the recycling of the active manganese dioxide, and has high use value and good application prospect.
(2) In the invention, air is adopted for aeration, so that the full contact of water and air can be promoted, the concentration of dissolved oxygen is effectively improved, the oxidation reaction is promoted, meanwhile, the aeration can play a role in stirring, the full contact of multiple phases is promoted, and the solid sinking is avoided. Furthermore, by properly increasing the aeration treatment temperature, on one hand, the concentration of dissolved oxygen is effectively increased, and on the other hand, the intrinsic rate of oxidation reaction is promoted, so that the recovery efficiency is greatly improved. In the invention, the advantages of the aeration technology are fully utilized, the efficient mixing reaction of manganese dioxide and oxygen is realized through aeration, the stirring effect is achieved, the additional addition of stirring equipment is avoided, the process flow is simplified, and the industrial production is facilitated.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
FIG. 1 is a schematic view of an aeration apparatus in example 1 of the present invention.
FIG. 2 is an XRD pattern of a manganese dioxide raw product, manganese dioxide to be recovered and active manganese dioxide in example 1 of the present invention.
Detailed Description
The invention is further described below in connection with the drawings and the specific preferred embodiments, but the scope of protection of the invention is not limited thereby.
The materials and instruments used in the examples below are all commercially available; the equipment and the preparation process adopted are conventional equipment and conventional process unless otherwise specified.
Example 1
An efficient recovery method of active manganese dioxide, comprising the following steps:
and (3) an aeration process: aeration is performed using an aeration apparatus as shown in fig. 1. 1000g of clear water was weighed, an appropriate amount of sodium hydroxide solution was added dropwise, the pH of the system was adjusted to=10, and then the solution was added to a 2L jacketed aeration tank. Starting an aeration device, adding 1000g of manganese dioxide (A) to be recovered into an aeration tank, and regulating the gas flow to 6.0L min -1 And (3) introducing hot circulating water into the jacket, controlling the temperature of the system to be 60 ℃, aerating for 3 hours, stopping heat preservation, and washing with clear water for several times after suction filtration to obtain the recycled manganese dioxide.
And (3) an activation process: and (3) uniformly spreading the recovered manganese dioxide in a metal tray, placing in a muffle furnace, preserving heat for 4 hours at 300 ℃, taking out the manganese dioxide when the manganese dioxide is hot, and placing in a dryer for cooling to prevent the manganese dioxide from absorbing water. After cooling to room temperature, gently mashing the caking generated in the high-temperature drying and activating process by using a spoon, and then sealing and collecting by using a self-sealing bag to obtain the recovered and activated manganese dioxide powder, namely the active manganese dioxide.
And (3) effect inspection: the recovered active manganese dioxide is used as an oxidant for preparing perillyl aldehyde by selective oxidation of perillyl alcohol, and the reaction formula is as follows:
specifically, ethyl acetate is used as a solvent, m (perillyl alcohol): m (MnO) 2 ) =1: 4, reflux reaction is carried out for 4 hours, sampling analysis is carried out, and the yield of perillaldehyde is 72.6%. In contrast, when the raw active manganese dioxide is reacted under the same conditions, the time required for the perillaldehyde yield to reach about 71.5% exceeds 8 hours. Thus, the active manganese dioxide recovered by the method can shorten the reaction time from more than 8 hours to 4 hours when the yield of the perillaldehyde reaches more than 70%, which proves that the method for recovering and activating the manganese dioxide can effectively recover the manganese dioxide and can further improve the reaction activity.
FIG. 2 is an XRD pattern of a manganese dioxide raw product, manganese dioxide to be recovered and active manganese dioxide in example 1 of the present invention. As shown in FIG. 2, by comparing XRD diffraction peak intensities of the manganese dioxide raw material, the manganese dioxide to be recovered and the active manganese dioxide, certain high-activity crystal faces of the manganese dioxide are exposed after aeration and heat treatment in the method of the invention, so that the oxidation activity and selectivity of the manganese dioxide are improved.
Example 2
An efficient recovery method of active manganese dioxide, comprising the following steps:
and (3) an aeration process: 1000g of clear water was weighed, an appropriate amount of sodium hydroxide solution was added dropwise, the pH of the system was adjusted to=10, and then the solution was added to a 2L jacketed aeration tank. Starting an aeration device, adding 1000g of manganese dioxide to be recovered into an aeration tank, and regulating the gas flow to 6.0L min -1 And (3) introducing hot circulating water into the jacket, controlling the temperature of the system to be 50 ℃, aerating for 4 hours, stopping heat preservation, and washing with clear water for several times after suction filtration to obtain the recycled manganese dioxide.
And (3) an activation process: and (3) uniformly spreading the recovered manganese dioxide in a metal tray, placing in a muffle furnace, preserving heat for 4 hours at 300 ℃, taking out the manganese dioxide when the manganese dioxide is hot, and placing in a dryer for cooling to prevent the manganese dioxide from absorbing water. After cooling to room temperature, the caking generated in the high-temperature drying and activating process is gently smashed by a spoon, and then the self-sealing bag is used for sealing and collecting, thus obtaining the recovered and activated manganese dioxide powder.
And (3) effect inspection: the recovered active manganese dioxide is used as an oxidant for preparing the perillyl aldehyde by the selective oxidation of the perillyl alcohol, ethyl acetate is used as a solvent, and m (perillyl alcohol): m (MnO) 2 ) =1: 4, reflux reaction is carried out for 4 hours, sampling analysis is carried out, and the yield of perillaldehyde is 72.4%.
Example 3
An efficient recovery method of active manganese dioxide, comprising the following steps:
and (3) an aeration process: 1000g of clear water was weighed, an appropriate amount of sodium hydroxide solution was added dropwise, the pH of the bulk system was adjusted to=10, and then the solution was added to a 2L jacketed aeration tank. Starting an aeration device, adding 1000g of manganese dioxide to be recovered into an aeration tank, and regulating the gas flow to 6.0L min -1 And (3) introducing hot circulating water into the jacket, controlling the temperature of the system to be 80 ℃, aerating for 2 hours, stopping heat preservation, and washing with clear water for several times after suction filtration to obtain the recycled manganese dioxide.
And (3) an activation process: and (3) uniformly spreading the recovered manganese dioxide in a metal tray, placing in a muffle furnace, preserving heat for 4 hours at 300 ℃, taking out the manganese dioxide when the manganese dioxide is hot, and placing in a dryer for cooling to prevent the manganese dioxide from absorbing water. After cooling to room temperature, the caking generated in the high-temperature drying and activating process is gently smashed by a spoon, and then the self-sealing bag is used for sealing and collecting, thus obtaining the recovered and activated manganese dioxide powder.
And (3) effect inspection: the recovered active manganese dioxide is used as an oxidant for preparing the perillyl aldehyde by the selective oxidation of the perillyl alcohol, ethyl acetate is used as a solvent, and m (perillyl alcohol): m (MnO) 2 ) =1: 4, reflux reaction is carried out for 4 hours, sampling analysis is carried out, and the yield of perillaldehyde is 72.9%.
Example 4
An efficient recovery method of active manganese dioxide, comprising the following steps:
and (3) an aeration process: 1000g of clear water was weighed, an appropriate amount of sodium hydroxide solution was added dropwise, the pH of the system was adjusted to=10, and then the solution was added to a 2L jacketed aeration tank. Starting an aeration device, adding 1000g of manganese dioxide to be recovered into an aeration tank, and regulating the gas flow to 6.0L min -1 Introducing heat circulating water into the jacket, and controlling the temperature of the system to beAerating at 60 ℃ for 3h, stopping heat preservation, and washing with clear water for several times after suction filtration to obtain the recovered manganese dioxide.
And (3) an activation process: and (3) uniformly spreading the recovered manganese dioxide in a metal tray, placing in a muffle furnace, preserving heat for 3 hours at 350 ℃, taking out the manganese dioxide while the manganese dioxide is hot, and placing in a dryer for cooling to prevent the manganese dioxide from absorbing water. After cooling to room temperature, the caking generated in the high-temperature drying and activating process is gently smashed by a spoon, and then the self-sealing bag is used for sealing and collecting, thus obtaining the recovered and activated manganese dioxide powder.
And (3) effect inspection: the recovered active manganese dioxide is used as an oxidant for preparing the perillyl aldehyde by the selective oxidation of the perillyl alcohol, ethyl acetate is used as a solvent, and m (perillyl alcohol): m (MnO) 2 ) =1: 4, reflux reaction is carried out for 4 hours, sampling analysis is carried out, and the yield of perillaldehyde is 72.5%.
Example 5
An efficient recovery method of active manganese dioxide, comprising the following steps:
and (3) an aeration process: 1000g of clear water was weighed, an appropriate amount of sodium hydroxide solution was added dropwise, the pH of the system was adjusted to=10, and then the solution was added to a 2L jacketed aeration tank. Starting an aeration device, adding 1000g of manganese dioxide to be recovered into an aeration tank, and regulating the gas flow to 6.0L min -1 And (3) introducing hot circulating water into the jacket, controlling the temperature of the system to be 60 ℃, aerating for 3 hours, stopping heat preservation, and washing with clear water for several times after suction filtration to obtain the recycled manganese dioxide.
And (3) an activation process: and (3) uniformly spreading the recovered manganese dioxide in a metal tray, placing in a muffle furnace, preserving heat at 200 ℃ for 6 hours, taking out the manganese dioxide while the manganese dioxide is hot, and placing in a dryer for cooling to prevent the manganese dioxide from absorbing water. After cooling to room temperature, the caking generated in the high-temperature drying and activating process is gently smashed by a spoon, and then the self-sealing bag is used for sealing and collecting, thus obtaining the recovered and activated manganese dioxide powder.
And (3) effect inspection: the recovered active manganese dioxide is used as an oxidant for preparing the perillyl aldehyde by the selective oxidation of the perillyl alcohol, ethyl acetate is used as a solvent, and m (perillyl alcohol): m (MnO) 2 ) =1: 4, reflux reaction is carried out for 4 hours, sampling analysis is carried out, and the yield of perillaldehyde is 72.6%.
Example 6
An efficient recovery method of active manganese dioxide, comprising the following steps:
and (3) an aeration process: 1000g of clear water was weighed, an appropriate amount of sodium hydroxide solution was added dropwise, the pH of the system was adjusted to=10, and then the solution was added to a 2L jacketed aeration tank. Starting an aeration device, adding 1000g of manganese dioxide to be recovered into an aeration tank, and regulating the gas flow to 8.0L min -1 And (3) introducing hot circulating water into the jacket, controlling the temperature of the system to be 60 ℃, aerating for 3 hours, stopping heat preservation, and washing with clear water for several times after suction filtration to obtain the recycled manganese dioxide.
And (3) an activation process: and (3) uniformly spreading the recovered manganese dioxide in a metal tray, placing in a muffle furnace, preserving heat for 4 hours at 300 ℃, taking out the manganese dioxide when the manganese dioxide is hot, and placing in a dryer for cooling to prevent the manganese dioxide from absorbing water. After cooling to room temperature, the caking generated in the high-temperature drying and activating process is gently smashed by a spoon, and then the self-sealing bag is used for sealing and collecting, thus obtaining the recovered and activated manganese dioxide powder.
And (3) effect inspection: the recovered active manganese dioxide is used as an oxidant for preparing the perillyl aldehyde by the selective oxidation of the perillyl alcohol, ethyl acetate is used as a solvent, and m (perillyl alcohol): m (MnO) 2 ) =1: 4, reflux reaction is carried out for 4 hours, sampling analysis is carried out, and the yield of perillaldehyde is 72.7%.
Example 7
An efficient recovery method of active manganese dioxide, comprising the following steps:
and (3) an aeration process: 1000g of clear water was weighed, an appropriate amount of sodium hydroxide solution was added dropwise, the system ph=12 was adjusted, and then the solution was added to a 2L jacketed aeration tank. Starting an aeration device, adding 1000g of manganese dioxide to be recovered into an aeration tank, and regulating the gas flow to 6.0L min -1 And (3) introducing hot circulating water into the jacket, controlling the temperature of the system to be 60 ℃, aerating for 3 hours, stopping heat preservation, and washing with clear water for several times after suction filtration to obtain the recycled manganese dioxide.
And (3) an activation process: and (3) uniformly spreading the recovered manganese dioxide in a metal tray, placing in a muffle furnace, preserving heat for 4 hours at 300 ℃, taking out the manganese dioxide when the manganese dioxide is hot, and placing in a dryer for cooling to prevent the manganese dioxide from absorbing water. After cooling to room temperature, the caking generated in the high-temperature drying and activating process is gently smashed by a spoon, and then the self-sealing bag is used for sealing and collecting, thus obtaining the recovered and activated manganese dioxide powder.
And (3) effect inspection: the recovered active manganese dioxide is used as an oxidant for preparing the perillyl aldehyde by the selective oxidation of the perillyl alcohol, ethyl acetate is used as a solvent, and m (perillyl alcohol): m (MnO) 2 ) =1: 4, reflux reaction is carried out for 4 hours, sampling analysis is carried out, and the yield of perillaldehyde is 72.2%.
Example 8
An efficient recovery method of active manganese dioxide, comprising the following steps:
and (3) an aeration process: 1000g of clear water was weighed, an appropriate amount of potassium hydroxide solution was added dropwise, the pH of the system was adjusted to=10, and then the solution was added to a 2L jacketed aeration tank. Starting an aeration device, adding 1000g of manganese dioxide to be recovered into an aeration tank, and regulating the gas flow to 6.0L min -1 And (3) introducing hot circulating water into the jacket, controlling the temperature of the system to be 60 ℃, aerating for 3 hours, stopping heat preservation, and washing with clear water for several times after suction filtration to obtain the recycled manganese dioxide.
And (3) an activation process: and (3) uniformly spreading the recovered manganese dioxide in a metal tray, placing in a muffle furnace, preserving heat for 4 hours at 300 ℃, taking out the manganese dioxide when the manganese dioxide is hot, and placing in a dryer for cooling to prevent the manganese dioxide from absorbing water. After cooling to room temperature, the caking generated in the high-temperature drying and activating process is gently smashed by a spoon, and then the self-sealing bag is used for sealing and collecting, thus obtaining the recovered and activated manganese dioxide powder.
And (3) effect inspection: the recovered active manganese dioxide is used as an oxidant for preparing the perillyl aldehyde by the selective oxidation of the perillyl alcohol, ethyl acetate is used as a solvent, and m (perillyl alcohol): m (MnO) 2 ) =1: 4, reflux reaction is carried out for 4 hours, sampling analysis is carried out, and the yield of perillaldehyde is 72.5%.
From the above data, it is clear that in the present invention, exposure of the manganese dioxide highly active crystal face can be promoted by aeration and heat treatment of manganese dioxide to be recovered, so that the manganese dioxide has more excellent oxidation activity, the reaction time required for the production of perillaldehyde to be 70% or more can be shortened from 8 hours or more to 4 hours, and at the same time, the production of perillaldehyde is still maintained to be 70% or more after more than 50 times of recovery use, and the oxidation effect is still stable. The efficient recovery method of the active manganese dioxide has the advantages of simple process, convenient operation, low recovery cost, mild reaction condition, safety, controllability, high recovery efficiency, high product yield, stable performance, environmental protection and the like, is a novel technology capable of efficiently recovering the active manganese dioxide and realizing the recycling of the active manganese dioxide, and has high use value and good application prospect.
The above examples are only preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the concept of the invention belong to the protection scope of the invention. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be within the scope of the present invention.
Claims (5)
1. The efficient recovery method of the active manganese dioxide is characterized by comprising the following steps of:
s1, mixing manganese dioxide to be recovered with an alkaline solution for aeration treatment; the pH value of the alkaline solution is 10-12; the aeration rate in the aeration treatment process is 6.0L min -1 kg -1 ～8.0L min -1 kg -1 Taking the mass of manganese dioxide to be recovered as a weight; the aeration treatment is carried out at the temperature of 50-80 ℃; the aeration treatment time is 2-4 hours;
s2, carrying out heat treatment on the manganese dioxide subjected to the aeration treatment in the step S1, and completing recovery of the active manganese dioxide.
2. The efficient recovery method according to claim 1, wherein in step S1, the alkaline solution is a sodium hydroxide solution and/or a potassium hydroxide solution.
3. A high efficiency recovery method according to claim 2, wherein in step S1, the gas used for the aeration treatment is air.
4. A high efficiency recovery method according to any one of claims 1 to 3, wherein in step S2, the heat treatment is performed at a temperature of 200 ℃ to 350 ℃.
5. The method according to claim 4, wherein the heat treatment is performed for 3 to 5 hours in step S2.
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