CN112246238B - Hongshi manganese lithium nano-spar catalytic material and preparation method thereof - Google Patents
Hongshi manganese lithium nano-spar catalytic material and preparation method thereof Download PDFInfo
- Publication number
- CN112246238B CN112246238B CN202011130494.7A CN202011130494A CN112246238B CN 112246238 B CN112246238 B CN 112246238B CN 202011130494 A CN202011130494 A CN 202011130494A CN 112246238 B CN112246238 B CN 112246238B
- Authority
- CN
- China
- Prior art keywords
- manganese
- catalytic material
- nano
- lithium
- spar
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 66
- 239000000463 material Substances 0.000 title claims abstract description 64
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 235000011157 hong shi Nutrition 0.000 title description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 105
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000002245 particle Substances 0.000 claims abstract description 64
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 31
- 239000011029 spinel Substances 0.000 claims abstract description 31
- 239000004575 stone Substances 0.000 claims abstract description 21
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 150000002696 manganese Chemical class 0.000 claims abstract description 8
- 239000011148 porous material Substances 0.000 claims abstract description 8
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 7
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract 2
- 239000002994 raw material Substances 0.000 claims abstract 2
- 230000002194 synthesizing effect Effects 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 52
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 32
- 238000000746 purification Methods 0.000 claims description 16
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 16
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 13
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910001868 water Inorganic materials 0.000 claims description 11
- 229940099596 manganese sulfate Drugs 0.000 claims description 9
- 235000007079 manganese sulphate Nutrition 0.000 claims description 9
- 239000011702 manganese sulphate Substances 0.000 claims description 9
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 9
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- 239000011656 manganese carbonate Substances 0.000 claims description 2
- 229940093474 manganese carbonate Drugs 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- 239000010979 ruby Substances 0.000 abstract description 15
- 229910001750 ruby Inorganic materials 0.000 abstract description 15
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 abstract 1
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 12
- 239000000843 powder Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 6
- 230000002349 favourable effect Effects 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000003421 catalytic decomposition reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical group O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/40—
-
- B01J35/617—
-
- B01J35/647—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/704—Solvents not covered by groups B01D2257/702 - B01D2257/7027
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/45—Gas separation or purification devices adapted for specific applications
- B01D2259/4508—Gas separation or purification devices adapted for specific applications for cleaning air in buildings
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
Abstract
The application relates to a ruby manganese lithium nano-spinel catalytic material and a preparation method thereof, wherein the preparation method comprises the following steps: in the whole process of synthesizing manganese oxide by taking potassium permanganate and manganese salt as raw materials, adding powdery lithium salt and sodium bicarbonate, adopting a closed environment with the atmospheric pressure being 2-3 times, rapidly releasing pressure after reacting for 10-15 min to enable reaction liquid to be sprayed out from a liquid outlet so as to prepare the red stone manganese lithium nano-spar, and then heating the prepared red stone manganese lithium catalytic material to more than 120 ℃ to prepare the much Kong Gongdan manganese lithium nano-spar; average grain diameter is less than or equal to 30nm, specific surface area is more than or equal to 500g/m 2 The porosity is more than or equal to 50 percent, and the porous pore diameter is less than or equal to 5nm. According to the rubble manganese lithium nano-spar catalytic material and the preparation method thereof, the rubble manganese lithium nano-spar particles with porous structures can be obtained, and the size and the specific surface area of the rubble manganese lithium nano-spar particles can be effectively controlled; the red Dan Mengli nanocrystalline stone catalytic material prepared by the method has better formaldehyde catalytic performance.
Description
Technical Field
The application belongs to the technical field of catalytic materials, and relates to a rubble manganese lithium nano-spinel catalytic material and a preparation method thereof.
Background
Formaldehyde is used as a toxic gas to deeply influence the physical health of people, and formaldehyde pollution caused by home decoration is more so that people are not worth mentioning. Most of the existing formaldehyde removing technologies are in an activated carbon adsorption mode, the adsorption capacity of activated carbon to large molecular weight gas is strong, but the adsorption capacity of activated carbon to formaldehyde with small molecular weight is limited, and the problem of secondary pollution caused by formaldehyde desorption exists.
The manganese oxide has wide application prospect in the field of formaldehyde purification as a high-efficiency catalytic material. The particle size, porous structure and doping structure of the manganese oxide powder greatly influence the catalytic activity of the manganese oxide powder. The existing manganese oxide preparation technology is mainly prepared by a chemical synthesis method through a synthesis reaction of potassium permanganate and manganese sulfate, the particle size of the prepared manganese oxide is generally 30-1000 nm, all particles with the particle size are solid structures, and the specific surface area is small (20-70 g/m 2 ) The manganese oxide with the particle size has certain catalytic performance, but has a large lifting space from the rapid catalytic decomposition of formaldehyde, so that the threat of formaldehyde on the health of people can be greatly reduced by realizing the rapid catalytic decomposition of formaldehyde. Patent CN107537473a discloses a nano manganese catalyst for catalyzing and oxidizing formaldehyde at room temperature and a preparation method thereof, which improves the catalytic efficiency by loading manganese dioxide on an oxide carrier, but the actual catalytic formaldehyde efficiency is only 82% because the manganese dioxide is prepared as well as common manganese dioxide.
Therefore, the research of the nano manganese oxide catalytic material capable of rapidly and efficiently catalyzing and decomposing formaldehyde has very important significance.
Disclosure of Invention
The application aims to solve the problem that materials capable of rapidly and efficiently catalyzing and decomposing formaldehyde are not available in the prior art, and provides a nano manganese oxide catalytic material capable of rapidly and efficiently catalyzing and decomposing formaldehyde and a preparation method thereof.
In order to achieve the above purpose, the application adopts the following scheme:
the quick pressure release after 10-15 min reaction is selected because the early pressure release easily causes incomplete reaction and the later pressure release, the manganese oxide particles are larger, and the quick pressure release cannot play a role; the mode of high reaction pressure and then release to normal pressure is selected because the flash evaporation of water during rapid pressure release can lead to smaller prepared ruby manganese lithium.
Compared with the preparation method in the prior art, the rubble manganese lithium nano-spinel catalytic material and the preparation method thereof are mainly different from each other as follows:
1) The lithium doping and sodium bicarbonate pore-forming agent is added, and the lithium doping and sodium bicarbonate pore-forming agent is not added in the existing reaction process for preparing the manganese oxide, the lithium doping manganese oxide can enhance the catalytic activity of the manganese oxide, and the addition of the sodium bicarbonate pore-forming agent is beneficial to improving the specific surface area of the manganese oxide nano particles and increasing the reaction sites of the manganese oxide nano particles and gas, so that the catalytic performance of the product is greatly improved;
2) The technology that the pressure is quickly released to normal pressure after the reaction is finished in a short time is adopted, the existing reaction is carried out under normal pressure, the quick pressure release after the short time reaction is favorable for quickly stopping the reaction, and the generated manganese oxide particles are prevented from further growing, because the manganese oxide powder gradually grows along with the progress of the reaction in the reaction process, the instant pressure release can lead the moisture flash evaporation to disappear so as to inhibit the progress of the reaction, the further growth of the powder is prevented, and the strong pressure difference formed by the pressure release is favorable for forming the manganese oxide particles with smaller particle sizes. After the pressure is released rapidly, a large amount of calcium carbonate molecules remain in the formed manganese oxide powder, and the manganese oxide powder is heated to be more than 120 ℃ to form a porous structure, so that the specific surface area of the manganese oxide is improved.
As a preferred scheme:
the preparation method of the rubble manganese lithium nano-spinel catalytic material comprises the steps of preparing a reaction system from potassium permanganate, manganese salt, lithium salt, sodium bicarbonate and water before the reaction starts.
According to the rubble manganese lithium nano-spinel catalytic material and the preparation method thereof, the molar ratio of potassium permanganate, manganese salt, lithium salt, sodium bicarbonate and water in a reaction system is 1:2-3 before the reaction starts: 2-3:1-2: a molar ratio of 4 to 5, which is optimum, is too large and too small, which results in insufficient reaction.
The manganese salt is one or more of manganese sulfate, manganese chloride, manganese oxalate, manganese carbonate and manganese acetate.
The preparation method of the ruby manganese lithium nano-spinel catalytic material comprises the following specific steps: the specific process is as follows: firstly heating the reaction system to 80-100 ℃ for reaction for 10-15 min under a closed environment with 2-3 times of atmospheric pressure, wherein the temperature and time range are the optimal reaction conditions, the particle size of the manganese oxide particles prepared under the conditions is moderate, the powder which is excessively high or excessively long and continuously reacts continuously can grow above the generated particles, then rapidly releasing the pressure to normal atmospheric pressure, and enabling the reaction solution to be atomized and separated from a liquid outlet to prepare the red stone manganese lithium nano-spar.
The application also provides a ruby manganese lithium nano-spinel catalytic material prepared by adopting any one of the above materials and a preparation method thereof, which is characterized in that: is porous particles; the porous particles are made of lithium doped manganese oxide, the average particle diameter is less than or equal to 30nm, and the specific surface area is more than or equal to 500g/m 2 The porosity is more than or equal to 50 percent, and the porous pore diameter is less than or equal to 5nm. The nanometer manganese oxide catalytic material prepared by the prior art is solid particles, the particle size range is 30-1000 nm, and the specific surface area is 20-70 g/m 2 As can be seen by comparison, the catalytic material provided by the application has smaller particle size, larger specific surface area and more pores, is favorable for fully absorbing formaldehyde, increases the contact probability of formaldehyde molecules and the catalytic material, and further can play a better role in catalyzing formaldehyde decomposition.
As a preferred scheme:
the red stone manganese lithium nano-spar catalytic material is characterized in that the average particle diameter of the porous particles is 10-30 nm, and the specific surface area is 500-900 g/m 2 The porosity is 50-80%, and the porous pore diameter is 2-5 nm.
The red stone manganese lithium nano-spinel catalytic material is characterized in that the purification efficiency of the red stone manganese lithium nano-spinel catalytic material after decomposing formaldehyde for 20min is 98-99.99%, the purification efficiency of the manganese oxide catalytic material in the prior art for 20min is about 80%, the purification efficiency refers to the rate of purifying formaldehyde by the material in a certain time, and the calculation formula is as follows: (initial formaldehyde concentration-final formaldehyde concentration)/initial formaldehyde concentration is 100%.
The beneficial effects are that:
(1) According to the ruby manganese lithium nano-spinel catalytic material and the preparation method thereof, ruby manganese lithium particles with porous structures can be obtained, and the size and specific surface area of the ruby manganese lithium particles can be effectively controlled;
(2) The red stone manganese lithium nano-spinel catalytic material prepared by the red stone manganese lithium nano-spinel catalytic material and the preparation method thereof have smaller particle size, porous structure and larger specific surface area, and can rapidly and efficiently catalyze formaldehyde decomposition.
Detailed Description
The application is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present application, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
Example 1
The preparation process of nanometer manganese oxide catalyst material includes the following steps:
(1) Heating a reaction system of potassium permanganate, manganese sulfate, lithium chloride, sodium bicarbonate and water in a molar ratio of 1:2:2:1:4 to 80 ℃ for reaction for 15min, and carrying out 2 times of atmospheric pressure;
(2) After the reaction was completed, the pressure was rapidly released to normal atmospheric pressure, and the collected particles were placed in an oven at 130℃for 4 hours.
The finally prepared red stone manganese lithium nano-spinel catalytic material is porous lithium doped manganese oxide particles, the average particle size is 22nm, and the specific surface area is 556g/m 2 The porosity is 68%, the porous aperture is 3-5 nm, and the purification efficiency after formaldehyde is decomposed for 20min by adopting the nano manganese oxide catalytic material is 97.9%.
Comparative example 1
A ruby manganese lithium nano-spinel catalytic material and a preparation method thereof have the same basic steps as those of the example 1, and are different in that the steps (1) and (2) do not adopt a sodium bicarbonate material treatment reaction system, and finally the prepared nano-manganese oxide catalytic material is solid manganese oxide particles, the average particle size is 90nm, and the specific surface area is 20g/m 2 The porosity is 18%, the particle surface has no redundant pores, and the purification efficiency after formaldehyde is decomposed for 20min by adopting the nano manganese oxide catalytic material is 50%.
Comparing example 1 with comparative example 1 shows that the nano manganese oxide particles prepared in example 1 have smaller particle size, higher specific surface area and better purification efficiency, because the sodium bicarbonate material is adopted to treat the reaction system in the whole reaction process in example 1, the surface of the nano manganese oxide particles has a large amount of pore structures, which is beneficial to improving the specific surface area of the red stone lithium nano particles and increasing the reaction sites of the red stone lithium nano particles and gas, thereby greatly improving the catalytic performance.
Comparative example 2
The basic steps of the preparation method of the ruby manganese lithium nano-spinel catalytic material are the same as those of the embodiment 1, except that the steps (1) and (2) do not have the processes of high-pressure treatment and rapid pressure release, and the finally prepared nano-manganese oxide catalytic material is solid manganese oxide particles, has the average particle size of 50nm and the specific surface area of 20g/m 2 The porosity is 34%, and the purification efficiency after formaldehyde is decomposed for 20min by adopting the nano manganese oxide catalytic material is 75%.
As can be seen from comparing example 1 with comparative example 2, the manganese oxide particles produced in example 1 are smaller in particle size, higher in purification efficiency, and higher in porosity, because the instantaneous pressure release can make the moisture flash off to suppress the progress of the reaction, prevent further growth of the powder, and the strong pressure difference formed by the pressure release is favorable for the formation of manganese oxide particles smaller in particle size.
Comparative example 3
The basic steps of the preparation method of the ruby manganese lithium nano-spinel catalytic material are the same as those of the embodiment 1, except that no lithium salt is doped in the step 1, and the finally prepared nano-manganese oxide catalytic material is pure manganese oxide particles, the average particle size is 78nm, and the specific surface area is 14g/m 2 The porosity is 13%, and the purification efficiency after formaldehyde is decomposed for 20min by adopting the nano manganese oxide catalytic material is 50%.
As can be seen by comparing example 1 with comparative example 3, the manganese oxide particles produced in example 1 are more catalytically active because the presence of lithium ions is advantageous in promoting electron transfer within the manganese element.
Example 2
The preparation method of the ruby manganese lithium nano-spinel catalytic material comprises the following basic steps:
(1) Heating a reaction system of potassium permanganate, manganese sulfate, lithium chloride, sodium bicarbonate and water in a molar ratio of 1:3:2:1:4 to 86 ℃ for reaction for 10min, and carrying out 2 times of atmospheric pressure;
(2) After the reaction was completed, the pressure was rapidly released to normal atmospheric pressure, and the collected particles were placed in an oven at 130℃for 4 hours.
The finally prepared red stone manganese lithium nano-spinel catalytic material is porous lithium doped manganese oxide particles, the average particle diameter is 20nm, and the specific surface area is 529g/m 2 The porosity is 62%, the porous aperture is 3-5 nm, and the purification efficiency after formaldehyde is decomposed for 20min by adopting the nano manganese oxide catalytic material is 98.2%.
Example 3
The preparation method of the ruby manganese lithium nano-spinel catalytic material comprises the following basic steps:
(1) Heating a reaction system of potassium permanganate, manganese sulfate, lithium chloride, sodium bicarbonate and water in a molar ratio of 1:2:2:2:4 to 88 ℃ for reaction for 13min, and carrying out 3 times of atmospheric pressure;
(2) After the reaction was completed, the pressure was rapidly released to normal atmospheric pressure, and the collected particles were placed in an oven at 150℃for 2 hours.
The finally prepared red stone manganese lithium nano-spinel catalytic material is porous lithium doped manganese oxide particles and flatAverage particle diameter of 14nm and specific surface area of 548g/m 2 The porosity is 65%, the porous aperture is 3-5 nm, and the purification efficiency after formaldehyde is decomposed for 20min by adopting the nano manganese oxide catalytic material is 99.1%.
Example 4
The preparation method of the ruby manganese lithium nano-spinel catalytic material comprises the following basic steps:
(1) Heating a reaction system of potassium permanganate, manganese sulfate, lithium chloride, sodium bicarbonate and water in a molar ratio of 1:2:2:1:5 to 93 ℃ for reaction for 11min, and carrying out 3 times of atmospheric pressure;
(2) After the reaction was completed, the pressure was rapidly released to normal atmospheric pressure, and the collected particles were placed in an oven at 140℃for 3 hours. .
The finally prepared red stone manganese lithium nano-spinel catalytic material is porous lithium doped manganese oxide particles, the average particle size is 12nm, and the specific surface area is 565g/m 2 The porosity is 67%, the porous aperture is 3-5 nm, and the purification efficiency after formaldehyde is decomposed for 20min by adopting the nano manganese oxide catalytic material is 99.5%.
Example 5
The preparation method of the ruby manganese lithium nano-spinel catalytic material comprises the following basic steps:
(1) Heating a reaction system of potassium permanganate, manganese sulfate, lithium chloride, sodium bicarbonate and water in a molar ratio of 1:3:3:2:4 to 95 ℃ for reaction for 10min, and carrying out 2 times of atmospheric pressure;
(2) After the reaction was completed, the pressure was rapidly released to normal atmospheric pressure, and the collected particles were placed in an oven at 128℃for 5 hours.
The finally prepared red stone manganese lithium nano-spinel catalytic material is porous lithium doped manganese oxide particles, the average particle diameter is 10nm, and the specific surface area is 600g/m 2 The porosity is 70%, the porous aperture is 3-5 nm, and the purification efficiency after formaldehyde is decomposed for 20min by adopting the nano manganese oxide catalytic material is 99.9%.
Example 6
The preparation method of the ruby manganese lithium nano-spinel catalytic material comprises the following basic steps:
(1) Heating a reaction system of potassium permanganate, manganese sulfate, lithium chloride, sodium bicarbonate and water in a molar ratio of 1:2:4:1:4 to 95 ℃ for reaction for 13min, and carrying out 3 times of atmospheric pressure;
(2) After the reaction was completed, the pressure was rapidly released to normal atmospheric pressure, and the collected particles were placed in an oven at 128℃for 5 hours. .
The finally prepared red stone manganese lithium nano-spinel catalytic material is porous lithium doped manganese oxide particles, the average particle size is 30nm, and the specific surface area is 300g/m 2 The porosity is 40%, the porous aperture is 3-5 nm, and the purification efficiency after formaldehyde is decomposed for 20min by adopting the nano manganese oxide catalytic material is 95.0%.
Claims (6)
1. The preparation method of the rubble manganese lithium nano-spinel catalytic material is characterized in that in the whole process of synthesizing manganese oxide by taking potassium permanganate and manganese salt as raw materials, powdery lithium salt and sodium bicarbonate are added, the reaction is carried out for 10-15 min under a closed environment of 2-3 times of atmospheric pressure, the pressure is quickly released, so that a reaction solution is sprayed out from a liquid outlet to prepare the rubble manganese lithium nano-spinel, and then the prepared rubble manganese lithium catalytic material is heated to more than 120 ℃ to prepare the Kong Gongdan manganese lithium nano-spinel; before the reaction starts, the reaction system consists of potassium permanganate, manganese salt, lithium salt, sodium bicarbonate and water; before the reaction starts, the mol ratio of potassium permanganate, manganese salt, lithium salt, sodium bicarbonate and water in the reaction system is 1:2-3:2-3:1-2:4-5.
2. The method according to claim 1, wherein the manganese salt is one or more of manganese sulfate, manganese chloride, manganese oxalate, manganese carbonate and manganese acetate.
3. The preparation method of the manganese lithium nano-spinel is characterized by comprising the specific steps of heating a reaction system to 80-100 ℃ for reaction for 10-15 min under a closed environment of 2-3 times of atmospheric pressure, and rapidly releasing pressure to normal atmospheric pressure to enable a reaction liquid to be atomized and separated from a liquid outlet to prepare the manganese lithium nano-spinel.
4. The red stone manganese lithium nano-spar catalytic material prepared by the preparation method according to any one of claims 1 to 3, which is characterized by being porous particles; the porous particles are made of lithium doped manganese oxide, the average particle size is less than or equal to 30nm, the specific surface area is more than or equal to 500g/m < 2 >, the porosity is more than or equal to 50%, and the porous pore diameter is less than or equal to 5nm.
5. The red stone manganese lithium nano-spar catalytic material according to claim 4, wherein the average particle size of the porous particles is 10-30 nm, the specific surface area is 500-900 g/m2, the porosity is 50-80%, and the pore diameter of the porous particles is 2-5 nm.
6. The red stone manganese lithium nano-spar catalytic material according to claim 4 or 5, wherein the purification efficiency after formaldehyde is decomposed for 20min by adopting the red stone manganese lithium nano-spar catalytic material is 98-99.99%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011130494.7A CN112246238B (en) | 2020-10-21 | 2020-10-21 | Hongshi manganese lithium nano-spar catalytic material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011130494.7A CN112246238B (en) | 2020-10-21 | 2020-10-21 | Hongshi manganese lithium nano-spar catalytic material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112246238A CN112246238A (en) | 2021-01-22 |
| CN112246238B true CN112246238B (en) | 2023-11-03 |
Family
ID=74264340
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011130494.7A Active CN112246238B (en) | 2020-10-21 | 2020-10-21 | Hongshi manganese lithium nano-spar catalytic material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112246238B (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8968669B2 (en) * | 2013-05-06 | 2015-03-03 | Llang-Yuh Chen | Multi-stage system for producing a material of a battery cell |
| CN106238065B (en) * | 2016-07-08 | 2018-10-16 | 宁波钛安新材料科技有限公司 | A kind of composite catalyst and preparation method thereof of catalysis Formaldehyde decomposition |
| CN110639507A (en) * | 2019-09-27 | 2020-01-03 | 华南理工大学 | Li-Mn bimetallic oxide composite denitration catalyst and preparation method and application thereof |
| CN110563047B (en) * | 2019-09-27 | 2022-04-08 | 岭南师范学院 | Manganese dioxide composite material and preparation method thereof |
-
2020
- 2020-10-21 CN CN202011130494.7A patent/CN112246238B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112246238A (en) | 2021-01-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2021506583A (en) | Catalysts for catalyzing formaldehyde oxidation and their preparation and use | |
| CN102794168A (en) | Method of preparing vanadium/tungsten/titania-based catalyst | |
| CN112958061B (en) | Oxygen vacancy promoted direct Z mechanism mesoporous Cu2O/TiO2Photocatalyst and preparation method thereof | |
| CN111530471A (en) | Ferromanganese composite oxide based monolithic denitration catalyst and preparation method thereof | |
| CN108083347B (en) | Preparation of cobalt ion induced flower-like cobalt manganese oxide and product and application thereof | |
| CN110813303B (en) | Preparation of flower-like iron-doped cerium dioxide with porous structure and desulfurization application of flower-like iron-doped cerium dioxide | |
| CN113943030A (en) | Biomass carbon-coated nano zero-valent iron composite material for treating chlorobenzene-polluted water body by activating peroxymonosulfate and preparation and application thereof | |
| CN113318759A (en) | Dopamine-mediated bismuth oxychloride photocatalyst and preparation method and application thereof | |
| CN112536057A (en) | Carbon material and preparation method and application thereof | |
| CN110368930A (en) | A kind of nano manganese oxide catalysis material and preparation method thereof | |
| CN110394052A (en) | A kind of purifying formaldehyde function nano material and preparation method thereof | |
| CN112246238B (en) | Hongshi manganese lithium nano-spar catalytic material and preparation method thereof | |
| CN115212869A (en) | CeO preparation based on Ce-MOF precursor 2 /TiO 2 Preparation method of composite thermal catalytic material | |
| CN110950421A (en) | MgO micro-sphere with high specific surface area and preparation method and application thereof | |
| CN110252375B (en) | Iron, nitrogen and cobalt co-doped titanium dioxide/activated carbon compound, preparation method and application as photocatalyst | |
| CN112246268A (en) | Novel efficient ozone catalytic material and preparation method thereof | |
| CN109482171B (en) | Bi/beta-Bi2O3Nanometer flower ball shaped photocatalyst and preparation method thereof | |
| CN115487823A (en) | Preparation method and application of high-humidity-resistance ozonolysis catalyst | |
| CN113967476B (en) | Perovskite supported cobalt high-efficiency catalyst, preparation method and method for preparing methanol by partial oxidation of methane | |
| CN110975879A (en) | Metal-doped ceramsite catalyst and preparation method and application thereof | |
| CN115025796A (en) | Biomass-loaded MOFs-derived composite catalyst and preparation method and application thereof | |
| CN107096560A (en) | A kind of ruthenium-based ammonia synthetic catalyst and preparation method thereof | |
| KR100803325B1 (en) | Titanium dioxide added alkali-carbonate regenerable sorbent for carbon dioxide removal | |
| CN111185178A (en) | Preparation method of carbon quantum dot modified denitration catalyst | |
| CN110368929A (en) | A kind of toilet ammonia decontamination nano catalytic material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |