CN113461065A - Preparation method of lithium manganate catalyst for formaldehyde degradation - Google Patents
Preparation method of lithium manganate catalyst for formaldehyde degradation Download PDFInfo
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 128
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000003054 catalyst Substances 0.000 title claims abstract description 30
- 230000015556 catabolic process Effects 0.000 title claims abstract description 23
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 42
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 33
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims abstract description 32
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims abstract description 32
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 19
- 230000035484 reaction time Effects 0.000 claims abstract description 13
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 239000012153 distilled water Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000000967 suction filtration Methods 0.000 claims abstract description 7
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 5
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 5
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- 206010028980 Neoplasm Diseases 0.000 description 2
- 239000012494 Quartz wool Substances 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 231100000357 carcinogen Toxicity 0.000 description 2
- 239000003183 carcinogenic agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
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- 238000007664 blowing Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000003908 liver function Effects 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- WURFKUQACINBSI-UHFFFAOYSA-M ozonide Chemical compound [O]O[O-] WURFKUQACINBSI-UHFFFAOYSA-M 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1235—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]2-, e.g. Li2Mn2O4, Li2[MxMn2-x]O4
-
- 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
- B01J23/16—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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
Abstract
The invention discloses a method for preparing lithium manganate by using lithium hydroxide monohydrate, potassium permanganate and a reducing agent as raw materials by a hydrothermal method. The method comprises the following steps: respectively dissolving potassium permanganate and lithium hydroxide monohydrate in deionized water with the same volume, and then pouring the lithium hydroxide monohydrate solution into the potassium permanganate solution to be uniformly mixed; secondly, adding solid powder of a reducing agent, and stirring at room temperature for 5-10 minutes at the stirring speed of 200-300r/min to obtain a mixed solution; thirdly, transferring the mixed solution into a reaction kettle, wherein the reaction temperature is 150 ℃ and 250 ℃, and the reaction time is 1-5 hours; and (IV) carrying out suction filtration on the solution, washing with distilled water, then putting the obtained powder into a vacuum box, and drying to obtain a product, namely the lithium manganate powder. The method has simple steps and easy operation, and the prepared formaldehyde degradation catalyst has higher formaldehyde degradation efficiency and good stability.
Description
Technical Field
The invention relates to a preparation technology for synthesizing a lithium manganate catalyst for formaldehyde degradation by using potassium permanganate, lithium hydroxide monohydrate and a reducing agent, belonging to the preparation range of inorganic materials.
Background
Formaldehyde is the most prominent volatile Organic compound, VOCs (volatile Organic Compounds), and is higher in the priority control list of Chinese toxic chemicals at position 2. Formaldehyde is one of the most main indoor air pollutants, affects the upper respiratory tract and the lung of a human body, causes the abnormality of liver function, immune function and nervous system, and causes the loss of partial functions of the central nervous system; and exposure to high quality formaldehyde concentrations for extended periods of time can lead to the development of a variety of cancers. In 6 months 2004, formaldehyde rose from two carcinogens to one carcinogen by the international agency for research on cancer. The release process of the indoor formaldehyde is as long as 3-15 years, China clearly stipulates in indoor air quality standard implemented in 3/1/2003, and the maximum allowable average mass concentration of the formaldehyde in the indoor air within 1h is 0.1mg/m3But currently most cases are much higher than this standard. Since the formaldehyde release process is a slow process, it is relatively difficult to eliminate formaldehyde from the air. Although the technologies for treating formaldehyde are numerous, the technologies have more or less defects: the ozone anion technology method has slow reaction rate and may generate secondary pollutants; the adsorption method has the advantages that the adsorption rate is low, and part of the adsorption method is easy to desorb; the low temperature plasma technology has the disadvantages of expensive equipment, high energy consumption, and secondary pollutants such as carbon monoxide andozone and the like; the photocatalytic oxidation method is one of the more researches at present, but needs ultraviolet light energy, and the proportion of ultraviolet light in sunlight is very small. The metal oxide catalysis method is carried out under the room temperature and no light condition, the reaction condition is mild, the operation is simple and convenient, the adsorption effect is good, and the development prospect is good. The manganese dioxide is a catalyst for deep oxidation, wherein the reaction activity of oxygen is high, acid is not generated by reaction with aldehyde, and the manganese dioxide plays a role in catalytic oxidation in the process of removing formaldehyde. Research finds that Li+Can improve the catalytic activity of manganese dioxide, Li+Embedded in MnO2The crystal structure of manganese dioxide is changed in crystal lattices to form a crystal similar to lithium manganate, so that the surface area is increased, and more reaction sites can be provided. The lithium manganate as a widely used battery anode material has the advantages of rich resources, low cost, no pollution, good safety and the like, wherein Li+Can be inserted and extracted by charging and discharging, and does not cause the collapse of the structure, thereby having higher stability. Therefore, the lithium manganate can be used for carrying out catalytic degradation on formaldehyde.
At present, the conventional solid phase method is adopted in industry to prepare spinel lithium manganate, the method of directly carrying out ball milling and calcining treatment on raw materials cannot ensure the uniform distribution of lithium salt and manganese salt, the energy consumption of high-temperature treatment is high, and the prepared lithium manganate has the disadvantages of non-uniform particle size, irregular shape, poor high-temperature cycle performance and poor storage performance. Hydrothermal method is generally considered to be a very ideal method for preparing nano materials due to its unique phase transition mechanism. The lithium manganate prepared by the method has the advantages of high purity, good uniformity and the like. However, most of hydrothermal reactions for preparing nano lithium manganate require a very long reaction time, or lithium manganate prepared by a hydrothermal method needs to be subjected to a roasting treatment to show excellent performance, and these disadvantages offset the advantages of the hydrothermal reactions to some extent. Based on the analysis, the development of a preparation method of lithium manganate, which has the advantages of easily controlled reaction process, simple equipment and low cost, is the focus of the current research. The invention provides a method for preparing lithium manganate by using lithium hydroxide monohydrate, potassium permanganate and a reducing agent as raw materials through a hydrothermal method.
Disclosure of Invention
The invention aims to overcome the defects of difficult control of process conditions, complex preparation, low purity, difficult control of reaction, poor uniformity and the like of a liquid phase method in the conventional lithium manganate preparation method; in particular to the problems of long reaction time, high roasting treatment temperature, high energy consumption and the like of a hydrothermal method, the invention provides a method for preparing a lithium manganate catalyst for formaldehyde degradation by using lithium hydroxide monohydrate, potassium permanganate and a reducing agent as raw materials by using the hydrothermal method.
The specific technical scheme is as follows:
the preparation method of the lithium manganate catalyst for formaldehyde degradation comprises the following steps:
respectively dissolving potassium permanganate and lithium hydroxide monohydrate in deionized water with the same volume, and then pouring the lithium hydroxide monohydrate solution into the potassium permanganate solution to be uniformly mixed to obtain a mixed solution a, wherein the concentration of potassium permanganate in the mixed solution is 0.05-0.3mol/L, and the concentration ratio of the lithium hydroxide monohydrate to the potassium permanganate is 0.5/1-2/1;
secondly, adding solid powder of a reducing agent into the mixed solution a obtained in the step one according to the mass concentration of 1-5g/L, and stirring at the room temperature for 5-30 minutes at the stirring speed of 100-300r/min to obtain mixed solution b;
thirdly, transferring the mixed solution b obtained in the step (II) to a reaction kettle, wherein the reaction temperature is 100 ℃ and 250 ℃, and the reaction time is 1-8 hours;
and (IV) carrying out suction filtration on the solution obtained after the reaction in the step (III), washing with distilled water, then putting the obtained powder into a vacuum box, and drying to obtain a product, namely the lithium manganate powder.
In the step (two) of the present invention, the reducing agent is preferably one of sodium thiosulfate and glucose.
The concentration of the potassium permanganate in the step (one) of the invention is preferably 0.05-0.2mol/L
The molar ratio of the potassium permanganate to the lithium hydroxide monohydrate in step (one) of the present invention is preferably from 0.5/1 to 1/1.
The mass concentration of the solid powder of the reducing agent in the step (two) of the present invention is preferably 1 to 3 g/L.
The stirring time in the step (two) of the present invention is preferably 5 to 10 minutes.
The stirring speed in step (two) of the present invention is preferably 200-300 rpm.
The reaction temperature in step (III) of the present invention is preferably 150 ℃ to 250 ℃.
The reaction time in step (three) of the present invention is preferably 1 to 5 hours.
The invention has the beneficial effects that:
(1) the lithium manganate prepared by the method has the advantages of high purity and good uniformity.
(2) The method has the advantages of wide raw material source, simple preparation method, easy control of reaction process and low cost.
(3) The lithium manganate prepared by the method has high stability and can keep the formaldehyde catalytic activity for a long time.
Drawings
FIG. 1 is an XRD pattern of lithium manganate obtained in example V.
FIG. 2 is a graph showing the catalytic activity of lithium manganate obtained in example V with respect to formaldehyde.
Detailed Description
Example one
The preparation method of the lithium manganate catalyst for formaldehyde degradation comprises the following steps:
respectively dissolving potassium permanganate and lithium hydroxide monohydrate in deionized water with the same volume, and then pouring the lithium hydroxide monohydrate solution into the potassium permanganate solution to be uniformly mixed to obtain a mixed solution a, wherein the concentration of potassium permanganate in the mixed solution is 0.05mol/L, and the concentration ratio of the lithium hydroxide monohydrate to the potassium permanganate is 0.5/1;
adding glucose solid powder into the mixed solution a obtained in the step (I) according to the mass concentration of 3g/L, and stirring at room temperature for 5 minutes at the stirring speed of 100r/min to obtain mixed solution b;
thirdly, transferring the mixed solution b obtained in the step (II) to a reaction kettle, wherein the reaction temperature is 100 ℃, and the reaction time is 1 hour;
and (IV) carrying out suction filtration on the solution obtained after the reaction in the step (III), washing with distilled water, repeating for three times, then putting the obtained powder into a vacuum box at 80 ℃, and drying for 24 hours to obtain a product, namely lithium manganate powder, which is marked as A. The content of solid A obtained in the above examples was analyzed by ICP, and the results are shown in Table I.
Fifthly, wrapping 0.5g of catalyst on two sides of quartz wool, placing the quartz wool in a sealed glass tube in a constant-temperature oven, and setting the temperature of the oven to be 25 ℃; then, opening a nitrogen and oxygen steel cylinder, introducing a mixed gas of nitrogen (the flow rate is 140sccm) and oxygen (the flow rate is 60sccm) into a gas flowmeter, leading the mixed gas to pass through 0.1% formaldehyde solution in a water bath at 0 ℃, and blowing out formaldehyde gas (the concentration is 3-4ppm) in the formaldehyde solution by a bubbling method; the formaldehyde gas reacts with the catalyst through a glass tube in a constant-temperature oven, and during testing, the formaldehyde concentration C at the front end of the reactor is measured at an air valve at the inlet of the glass tube by a formaldehyde concentration tester1And measuring the concentration C of formaldehyde at the rear end of the reactor at an outlet gas valve at the rear end of the glass tube2And (3) calculating the catalytic efficiency of the catalyst to formaldehyde at the moment according to the formula (1), wherein the efficiency is recorded in a table II. Finally, the undegraded formaldehyde gas is recovered in a beaker filled with 500ml of water at the rear end of the device.
Example two
The preparation method of the lithium manganate catalyst for formaldehyde degradation comprises the following steps:
respectively dissolving potassium permanganate and lithium hydroxide monohydrate in deionized water with the same volume, and then pouring the lithium hydroxide monohydrate solution into the potassium permanganate solution to be uniformly mixed to obtain a mixed solution a, wherein the concentration of potassium permanganate in the mixed solution is 0.2mol/L, and the concentration ratio of the lithium hydroxide monohydrate to the potassium permanganate is 1/1;
adding glucose solid powder into the mixed solution a obtained in the step (I) according to the mass concentration of 1g/L, and stirring at room temperature for 10 minutes at the stirring speed of 200r/min to obtain mixed solution b;
thirdly, transferring the mixed solution b obtained in the step (II) to a reaction kettle, wherein the reaction temperature is 150 ℃, and the reaction time is 5 hours;
and (IV) carrying out suction filtration on the solution obtained after the reaction in the step (III), washing with distilled water, repeating for three times, then putting the obtained powder into a vacuum box at 80 ℃, and drying for 24 hours to obtain a product, namely lithium manganate powder, which is marked as B. The solids obtained in the above examples were analyzed for content by ICP, and the results are shown in Table I. The activity of the catalyst was tested as described in example one (five) and summarized in table two.
EXAMPLE III
Respectively dissolving potassium permanganate and lithium hydroxide monohydrate in deionized water with the same volume, and then pouring the lithium hydroxide monohydrate solution into the potassium permanganate solution to be uniformly mixed to obtain a mixed solution a, wherein the concentration of potassium permanganate in the mixed solution is 0.3mol/L, and the concentration ratio of the lithium hydroxide monohydrate to the potassium permanganate is 2/1;
adding sodium thiosulfate solid powder into the mixed solution a obtained in the step (I) according to the mass concentration of 5g/L, and stirring at room temperature for 30 minutes at the stirring speed of 300r/min to obtain mixed solution b;
thirdly, transferring the mixed solution b obtained in the step (II) to a reaction kettle, wherein the reaction temperature is 250 ℃, and the reaction time is 8 hours;
and (IV) carrying out suction filtration on the solution obtained after the reaction in the step (III), washing with distilled water, repeating for three times, then putting the obtained powder into a vacuum box at 80 ℃, and drying for 24 hours to obtain a product, namely lithium manganate powder, which is marked as C. The solids obtained in the above examples were analyzed for content by ICP, and the results are shown in Table I. The activity of the catalyst was tested as described in example one (five) and summarized in table two.
Example four
The preparation method of the lithium manganate catalyst for formaldehyde degradation comprises the following steps:
respectively dissolving potassium permanganate and lithium hydroxide monohydrate in deionized water with the same volume, and then pouring the lithium hydroxide monohydrate solution into the potassium permanganate solution to be uniformly mixed to obtain a mixed solution a, wherein the concentration of potassium permanganate in the mixed solution is 0.15mol/L, and the concentration ratio of the lithium hydroxide monohydrate to the potassium permanganate is 1/1;
adding sodium thiosulfate solid powder into the mixed solution a obtained in the step (I) according to the mass concentration of 3g/L, and stirring at room temperature for 10 minutes at the stirring speed of 300r/min to obtain mixed solution b;
thirdly, transferring the mixed solution b obtained in the step (II) to a reaction kettle, wherein the reaction temperature is 180 ℃, and the reaction time is 5 hours;
and fourthly, carrying out suction filtration on the solution obtained after the reaction in the third step, washing with distilled water, repeating the washing for three times, then putting the obtained powder into a vacuum box at 80 ℃, and drying for 24 hours to obtain a product, namely lithium manganate powder, which is marked as D. The solids obtained in the above examples were analyzed for content by ICP, and the results are shown in Table I. The activity of the catalyst was tested as described in example one (five) and summarized in table two.
EXAMPLE five
The preparation method of the lithium manganate catalyst for formaldehyde degradation comprises the following steps:
respectively dissolving potassium permanganate and lithium hydroxide monohydrate in deionized water with the same volume, and then pouring the lithium hydroxide monohydrate solution into the potassium permanganate solution to be uniformly mixed to obtain a mixed solution a, wherein the concentration of potassium permanganate in the mixed solution is 0.1mol/L, and the concentration ratio of the lithium hydroxide monohydrate to the potassium permanganate is 0.77/1;
adding sodium thiosulfate solid powder into the mixed solution a obtained in the step (I) according to the mass concentration of 2.5g/L, and stirring at room temperature for 5 minutes at the stirring speed of 300r/min to obtain mixed solution b;
thirdly, transferring the mixed solution b obtained in the step (II) to a reaction kettle, wherein the reaction temperature is 230 ℃, and the reaction time is 4 hours;
and fourthly, filtering the solution obtained after the reaction in the third step, washing with distilled water, repeating the process for three times, then putting the obtained powder into a vacuum box at 80 ℃, and drying for 24 hours to obtain a product, namely lithium manganate powder, and marking as E. The solids obtained in the above examples were analyzed for content by ICP, and the results are shown in Table I. The activity of the catalyst was tested as described in example one (five) and summarized in table two.
Comparative example 1
Respectively dissolving potassium permanganate and lithium hydroxide monohydrate in deionized water with the same volume, and then pouring the lithium hydroxide monohydrate solution into the potassium permanganate solution to be uniformly mixed to obtain a mixed solution a, wherein the concentration of potassium permanganate in the mixed solution is 0.2mol/L, and the concentration ratio of the lithium hydroxide monohydrate to the potassium permanganate is 1/1.
And (II) adding ascorbic acid solid powder into the mixed solution A obtained in the step (I) according to the mass concentration of 1.5g/L, and stirring at room temperature for 10 minutes at the stirring speed of 200r/min to obtain a mixed solution b.
And (III) transferring the mixed solution B obtained in the step (II) to a reaction kettle, wherein the reaction temperature is 130 ℃, and the reaction time is 2 hours.
And (IV) filtering the solution obtained after the reaction in the step (III), washing with distilled water, repeating the process for three times, putting the obtained powder into a vacuum box at the temperature of 80 ℃, and drying for 24 hours to obtain a black solid, which is marked as F.
The solid obtained using ascorbic acid as reducing agent is Li1.27Mn1.73O4The XRD result showed that it was not lithium manganate and had poor crystallinity.
ICP is adopted to analyze the content of the solid F obtained in the specific embodiment, and the result is shown in the table I; the activity of the catalyst was tested as described in example one (five) and summarized in table two.
TABLE-lithium manganese content in various examples and comparative examples
| Sample numbering | Manganese oxide species | Content (%) |
| A | Lithium manganate | 92.26 |
| B | Lithium manganate | 92.88 |
| C | Lithium manganate | 92.66 |
| D | Lithium manganate | 95.46 |
| E | Lithium manganate | 99.50 |
| F | Li1.27Mn1.73O4 | - |
TABLE II summary of formaldehyde degradation rate of each catalyst
The foregoing detailed description is exemplary only, and is not intended to limit the scope of the patent, as defined by the appended claims; any equivalent alterations or modifications made according to the spirit of the disclosure of this patent are intended to be included in the scope of this patent.
Claims (9)
1. A preparation method of a lithium manganate catalyst for formaldehyde degradation is characterized by comprising the following steps:
respectively dissolving potassium permanganate and lithium hydroxide monohydrate in deionized water, pouring the lithium hydroxide monohydrate solution into the potassium permanganate solution, and uniformly mixing to obtain a mixed solution a, wherein the concentration of potassium permanganate in the mixed solution is 0.05-0.3mol/L, and the concentration ratio of the lithium hydroxide monohydrate to the potassium permanganate is 0.5/1-2/1;
secondly, adding solid powder of a reducing agent into the mixed solution a obtained in the step one according to the mass concentration of 1-5g/L, and stirring at the room temperature for 5-30 minutes at the stirring speed of 100-300r/min to obtain mixed solution b;
thirdly, transferring the mixed solution b obtained in the step (II) to a reaction kettle, wherein the reaction temperature is 100 ℃ and 250 ℃, and the reaction time is 1-8 hours;
and (IV) carrying out suction filtration on the solution obtained after the reaction in the step (III), washing with distilled water, then putting the obtained powder into a vacuum box, and drying to obtain the product, namely the lithium manganate catalyst powder for formaldehyde degradation.
2. The method for preparing a lithium manganate catalyst for formaldehyde degradation according to claim 1, wherein said reducing agent in said step (two) is one of sodium thiosulfate and glucose.
3. The method for preparing a lithium manganate catalyst for formaldehyde degradation according to claim 1 or 2, characterized in that the concentration of potassium permanganate in said step (i) is 0.05-0.2 mol/L.
4. The method for preparing a lithium manganate catalyst for formaldehyde degradation according to claim 1 or 2, wherein said molar ratio of potassium permanganate to lithium hydroxide monohydrate in said step (a) is 0.5/1 to 1/1.
5. The method for preparing a lithium manganate catalyst for formaldehyde degradation according to claim 1 or 2, characterized in that the mass concentration of solid powder of reducing agent in said step (two) is 1-3 g/L.
6. The method for preparing a lithium manganate catalyst for formaldehyde degradation according to claim 1 or 2, characterized in that the stirring time in said step (two) is 5 to 10 minutes.
7. The method for preparing a lithium manganate catalyst for formaldehyde degradation as set forth in claim 1 or 2, wherein the stirring speed in the step (II) is 200-300 rpm.
8. The method for preparing a lithium manganate catalyst for formaldehyde degradation as set forth in claim 1 or 2, wherein the reaction temperature in said step (three) is 150-250 ℃.
9. The method for preparing a lithium manganate catalyst for formaldehyde degradation according to claim 1 or 2, characterized in that the reaction time in said step (three) is 1-5 hours.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102280617A (en) * | 2011-07-06 | 2011-12-14 | 中国科学院过程工程研究所 | Carbon material modified composite lithium manganese oxide cathode material applied to lithium ion battery and preparation method thereof |
| CN102275996A (en) * | 2010-06-09 | 2011-12-14 | 遵义师范学院 | Preparation method for nano spinel lithium manganate of lithium ion battery anode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102275996A (en) * | 2010-06-09 | 2011-12-14 | 遵义师范学院 | Preparation method for nano spinel lithium manganate of lithium ion battery anode material |
| CN102280617A (en) * | 2011-07-06 | 2011-12-14 | 中国科学院过程工程研究所 | Carbon material modified composite lithium manganese oxide cathode material applied to lithium ion battery and preparation method thereof |
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| YAN-YU LIANG ET AL.: ""One-Step, Low-Temperature Route for the Preparation of Spinel LiMn2O4 as a Cathode Material for Rechargeable", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》 * |
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