CN102909022A - Porous cobalt oxide catalyst preparation method - Google Patents
Porous cobalt oxide catalyst preparation method Download PDFInfo
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- CN102909022A CN102909022A CN2012104109201A CN201210410920A CN102909022A CN 102909022 A CN102909022 A CN 102909022A CN 2012104109201 A CN2012104109201 A CN 2012104109201A CN 201210410920 A CN201210410920 A CN 201210410920A CN 102909022 A CN102909022 A CN 102909022A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000003054 catalyst Substances 0.000 title abstract description 27
- 229910000428 cobalt oxide Inorganic materials 0.000 title abstract description 12
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 title abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000007787 solid Substances 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 8
- 239000011734 sodium Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 22
- 230000003647 oxidation Effects 0.000 claims description 18
- 238000007254 oxidation reaction Methods 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 14
- 239000003426 co-catalyst Substances 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000012423 maintenance Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000002351 wastewater Substances 0.000 abstract description 5
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract 2
- 230000001376 precipitating effect Effects 0.000 abstract 2
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 238000001556 precipitation Methods 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 5
- 238000002242 deionisation method Methods 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 4
- 229960001545 hydrotalcite Drugs 0.000 description 4
- 229910001701 hydrotalcite Inorganic materials 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 241000446313 Lamella Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003933 environmental pollution control Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- -1 unsaturated fatty acid ester Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a porous cobalt oxide catalyst preparation method in the field of catalytic degradation of waste water or waste pollutants. The porous cobalt oxide catalyst preparation method includes respectively dissolving CoCl2 and AlCl3 into water to prepare two kinds of solutions with concentration ranging from 1-2mol/L, mixing the two kinds of solutions, keeping mole ratio of Co and Al ranging from 2 to 4, dripping NaOH into water bath at the constant temperature of 70-80 DEG C, keeping the pH (potential of hydrogen) within 12-13, reacting for 2-3 hours, ageing for 12-24 hours, precipitating and separating, washing 2-3 times by deionized water; adding obtained solids into sodium cobaltinitrite solution with concentration of 2-4mol/L according to solid to liquid ratio 1:1.0-1:50, stirring for 4-5 hours, precipitating and separating to obtain products, washing the products twice or three times by deionized water, and roasting the washed products at the temperature of 400-500 DEG C to obtain porous cobalt oxide catalyst which has good porous structure and larger specific surface area and is beneficial to adsorption and catalyzing and capable of playing nano effect.
Description
Technical field
The present invention relates to the exploitation of environmental pollution control new material, relate in particular to the preparation method of the porous oxidation Co catalysts of a kind of catalytic degradation waste water or waste pollutant.
Background technology
Cobalt oxide catalyst is used wider, for example ethene and water-gas are under the Co catalysts effect, can obtain aldehyde and alcohol, novel co-based fischer-tropsch catalyst can be used for synthetic long chain hydrocarbon and clear energy sources (Chem. Rev. 2007,107,1692-1744), two key peroxidating (Xiamen University's journal (natural science edition) in the unsaturated fatty acid ester that supported cobalt catalysts promotes, 2010,49 volumes, 03 phase, 373-380), cobalt oxide catalyst take Al (OH) x as carrier carries out cyclohexane and toluene selective oxidation under the condition of not using a large amount of solvents, obtained good result (catalysis journal, 2004,25 volumes, 11 phases, 887～891).Aspect the pollutant of some difficult degradations of catalytic oxidation, preferably application prospect is arranged also in addition, such as: at room temperature the organic matter such as catalyze oxidation of formaldehyde, catalytic oxidation of cyclohexane (Catal. Commun. 2005,6,211-214).But in the situation that does not have suitable carrier, the efficient of cobalt oxide is low; Have and study with CNT or mesopore silicon oxide (petroleum journal (PETROLEUM PROCESSING); 01 phase in 2011, chemical journal; 16 phases in 2008); but these material prices are relatively costly; and in the situation that carrier is arranged, thickness and the area of load have a great impact catalytic effect, and catalyst often can occur can be blocked up in the inhomogeneous some areas of carrier surface load; or some place situation that can not load to, cause the waste of catalyst or carrier.In addition, the active force between catalyst and the carrier how, also can have influence on catalytic effect, then can occur catalyst a little less than crossing and come off or be adsorbed in the carrier cavity.
Hydrotalcite-based compound (LDHs) is to pile up the compound that forms by interlayer anion and positively charged laminate.The hydrotalcite chemical structure of general formula is: [M
2+ 1-xM
3+X (OH)
2]
X+[(A
N-)
X/nMH
2O], M wherein
2+And M
3+Be respectively the divalence and the trivalent metal cation that are positioned on the main body laminate, such as Mg
2+, Ni
2+, Zn
2+, Mn
2+, Cu
2+, Co
2+, Pd
2+, Fe
2+Deng bivalent cation and Al
3+, Cr
3+, Co
3+, Fe
3+All can form hydrotalcite Deng Tricationic; A
N –Be interlayer anion, can comprise inorganic anion, organic anion, complex anion, same many and heteropolyanion; X is M
3+/ (M
2++ M
3+) molar ratio, approximately be that 4:1 is to 2:1; M is the number of intermediary water molecule.Its structure is similar to shepardite Mg (OH)
2, share seamed edge and form the main body laminate by octahedron.Be positioned at the divalent metal M on the laminate
2+Can be by the close trivalent metal cation M of ion half price in certain proportion
3+The isomorphous replaces so that laminate is positively charged, interlayer exist can exchange anion and the positive charge balance on the laminate so that the overall structure of LDHs is electroneutral.The anion of interlayer can be exchanged, and through a series of modifications, hydrotalcite material can obtain the many kinds of materials that performance is different.
Summary of the invention
The objective of the invention is provides a kind of preparation method of porous oxidation Co catalysts for overcoming the deficiency that the carrier price is high in the prior art, load process is complicated.
The technical solution used in the present invention is in turn include the following steps:
1) with CoCl
2And AlCl
3Be dissolved into respectively in the water, be configured to two kinds of solution that concentration is 1 ~ 2 mol/L, two kinds of solution are mixed, Co in the maintenance mixed solution and the mol ratio of Al are 2 ~ 4, splash into NaOH in 70 ~ 80 ℃ of water-baths of constant temperature, and keeping the pH value is 12 ~ 13, reaction 2 ~ 3 h, aging 12 ~ 24 h, precipitate and separate is washed 2 ~ 3 times with deionized water;
2) solid that obtains is joined in the cobaltinitrite sodium solution that concentration is 2 ~ 4 mol/L, solid-to-liquid ratio is 1:10 ~ 1:50, stirs 4 ~ 5 h, precipitate and separate, the product that obtains at 400 ~ 500 ℃ temperature lower calcination, obtains the porous oxidation Co catalysts after washing 2 ~ 3 times with deionized water.
Advantage of the present invention is:
(1) passes through coprecipitation reaction, cobalt is being mingled with a small amount of aluminium and is forming the larger lamellar structure of specific area, exchange into natrium cobaltinitrosum at the sheet interlayer again, forming cobalt oxide by high-temperature calcination again supports, make and separate between lamella and the lamella and fixing, can not separate or closed and form regular nano aperture, make this material have good pore structure and larger specific area, be conducive to absorption and catalysis.
(2) catalyst distribution is even, the situation that some surface does not have catalyst can not occur, and interlamellar spacing is supported for the nanometer grade cobalt oxide particle, and the corresponding nano effect of the performance of utilization is arranged.
(3) in whole catalyst, do not have carrier, only have a small amount of aluminium to support as the lamella skeleton, do not have the weak problem of active force between carrier and the catalyst.
The specific embodiment
With CoCl
2And AlCl
3Be dissolved into respectively in the water, be configured to two kinds of solution that concentration is 1 ~ 2 mol/L, two kinds of solution are mixed, and keeping the mol ratio of Co and Al is 2 ~ 4, splashes into a certain amount of NaOH in 70 ~ 80 ℃ of water-baths of constant temperature, keeping the pH value is 12 ~ 13, reaction 2 ~ 3 h, aging 12 ~ 24 h form the precipitation with layer structure in this process, precipitate and separate, deionization washing 2 ~ 3 times.The solid that precipitation is obtained joins in the cobaltinitrite sodium solution that concentration is 2 ~ 4 mol/L, solid-to-liquid ratio is 1:10 ~ 1:50, stir 4 ~ 5 h, precipitate and separate, the solid that obtains is after with deionized water washing 2 ~ 3 times, at 400 ~ 500 ℃ temperature lower calcination, can obtain the porous oxidation Co catalysts.
4 embodiment of the present invention below further are provided:
Embodiment 1
With CoCl
2And AlCl
3Be dissolved into respectively in the water, be configured to the solution that concentration is 2 mol/L, two kinds of solution are mixed, and keeping the mol ratio of Co and Al is 4, splashes into a certain amount of NaOH in 80 ℃ of water-baths of constant temperature, keeping the pH value is 13, react 3 h, aging 24 h form the precipitation with layer structure in this process, precipitate and separate, deionization washing 3 times; The solid that precipitation is obtained joins in the cobaltinitrite sodium solution that concentration is 4 mol/L, and solid-to-liquid ratio is 1:10, stirs 5 h, precipitate and separate, the solid that obtains at 500 ℃ temperature lower calcination, can obtain the porous oxidation Co catalysts after with deionized water washing 3 times.
Adopt U-shaped pipe (internal diameter 4 mm) continuous-flow reaction evaluating device, in the synthetic cobalt oxide catalyst disposed tubes that obtains of weighing 100 mg, the flow velocity of regulating air is 40 mL/min, Air Flow drives formaldehyde gas and enters in the U-shaped pipe reactor, and the gas volume (being air speed) that per hour flows through every liter of catalyst is 55000 h
-1Under 25 ℃ of conditions, it is that the formaldehyde gas complete oxidation of 100 ppm is carbon dioxide and water that this catalyst can make 73% concentration.
Embodiment 2
With CoCl
2And AlCl
3Be dissolved into respectively in the water, be configured to the solution that concentration is 1mol/L, two kinds of solution are mixed, and keeping the mol ratio of Co and Al is 2, splashes into a certain amount of NaOH in 70 ℃ of water-baths of constant temperature, keeping the pH value is 12, react 2 h, aging 12 h form the precipitation with layer structure in this process, precipitate and separate, deionization washing 2 times; The solid that precipitation is obtained joins in the cobaltinitrite sodium solution that concentration is 2 mol/L, and solid-to-liquid ratio is 1:50, stirs 4 h, precipitate and separate, the solid that obtains at 400 ℃ temperature lower calcination, can obtain the porous oxidation Co catalysts after with deionized water washing 2 times.
Adopt U-shaped pipe (internal diameter 4 mm) continuous-flow reaction evaluating device, in the synthetic cobalt oxide catalyst disposed tubes that obtains of weighing 100 mg, the flow velocity of regulating air is 40 mL/min, Air Flow drives methanol gas and enters in the U-shaped pipe reactor, and the gas volume (being air speed) that per hour flows through every liter of catalyst is 55000 h
-1Under 25 ℃ of conditions, it is that the formaldehyde gas complete oxidation of 100 ppm is carbon dioxide and water that this catalyst can make 91% concentration.
Embodiment 3
With CoCl
2And AlCl
3Be dissolved into respectively in the water, be configured to the solution that concentration is 2 mol/L, two kinds of solution are mixed, and keeping the mol ratio of Co and Al is 3, splashes into a certain amount of NaOH in 75 ℃ of water-baths of constant temperature, keeping the pH value is 12, react 3 h, aging 16 h form the precipitation with layer structure in this process, precipitate and separate, deionization washing 3 times; The solid that precipitation is obtained joins in the cobaltinitrite sodium solution that concentration is 4 mol/L, and solid-to-liquid ratio is 1:30, stirs 5 h, precipitate and separate, the solid that obtains at 450 ℃ temperature lower calcination, can obtain the porous oxidation Co catalysts after with deionized water washing 3 times.
Adopt U-shaped pipe (internal diameter 4 mm) continuous-flow reaction evaluating device, in the synthetic cobalt oxide catalyst disposed tubes that obtains of weighing 100 mg, the flow velocity of regulating air is 40 mL/min, Air Flow drives toluene gas and enters in the U-shaped pipe reactor, and the gas volume (being air speed) that per hour flows through every liter of catalyst is 55000 h
-1Under 25 ℃ of conditions, it is that the formaldehyde gas complete oxidation of 100 ppm is carbon dioxide and water that this catalyst can make 62% concentration.
Embodiment 4
With CoCl
2And AlCl
3Be dissolved into respectively in the water, be configured to the solution that concentration is 2 mol/L, two kinds of solution are mixed, and keeping the mol ratio of Co and Al is 3, splashes into a certain amount of NaOH in 80 ℃ of water-baths of constant temperature, keeping the pH value is 13, react 3 h, aging 18 h form the precipitation with layer structure in this process, precipitate and separate, deionization washing 3 times; The solid that precipitation is obtained joins in the cobaltinitrite sodium solution that concentration is 4 mol/L, and solid-to-liquid ratio is 1:20, stirs 5 h, precipitate and separate, the solid that obtains at 500 ℃ temperature lower calcination, can obtain the porous oxidation Co catalysts after with deionized water washing 3 times.
The synthetic catalyst that obtains is joined in the waste water that contains dyestuff gold orange II, dye strength is 30mg/L, the amount that adds catalyst in every liter of waste water is 0.5g, regulating pH is 4, through 2 h, utilize ultraviolet-uisible spectrophotometer to analyze the concentration of Pollutants in Wastewater, after measured, the clearance of dyestuff is 97.5%.
Claims (1)
1. the preparation method of a porous oxidation Co catalysts is characterized in that in turn including the following steps:
1) with CoCl
2And AlCl
3Be dissolved into respectively in the water, be configured to two kinds of solution that concentration is 1 ~ 2 mol/L, two kinds of solution are mixed, Co in the maintenance mixed solution and the mol ratio of Al are 2 ~ 4, splash into NaOH in 70 ~ 80 ℃ of water-baths of constant temperature, and keeping the pH value is 12 ~ 13, reaction 2 ~ 3 h, aging 12 ~ 24 h, precipitate and separate is washed 2 ~ 3 times with deionized water;
2) solid that obtains is joined in the cobaltinitrite sodium solution that concentration is 2 ~ 4 mol/L, solid-to-liquid ratio is 1:10 ~ 1:50, stirs 4 ~ 5 h, precipitate and separate, the product that obtains at 400 ~ 500 ℃ temperature lower calcination, obtains the porous oxidation Co catalysts after washing 2 ~ 3 times with deionized water.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210410920.1A CN102909022B (en) | 2012-10-25 | 2012-10-25 | Porous cobalt oxide catalyst preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210410920.1A CN102909022B (en) | 2012-10-25 | 2012-10-25 | Porous cobalt oxide catalyst preparation method |
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| Publication Number | Publication Date |
|---|---|
| CN102909022A true CN102909022A (en) | 2013-02-06 |
| CN102909022B CN102909022B (en) | 2014-04-09 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106076320A (en) * | 2016-06-12 | 2016-11-09 | 常州大学 | A kind of preparation method of the manganese oxide nanometer sheet for processing waste gas |
| CN111792678A (en) * | 2020-07-24 | 2020-10-20 | 福州大学 | Pure cobalt hydrotalcite-like compound and preparation method thereof |
| CN114436344A (en) * | 2022-01-24 | 2022-05-06 | 广东邦普循环科技有限公司 | Preparation method and application of positive electrode material precursor with large channel |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1688508A (en) * | 2002-08-13 | 2005-10-26 | 英特凯特公司 | Flue gas treatments to reduce NOx and CO emissions |
| CN1806915A (en) * | 2006-02-23 | 2006-07-26 | 上海交通大学 | Composite bismuth vanadium photocatalyst supported by cobalt oxide and preparation method thereof |
-
2012
- 2012-10-25 CN CN201210410920.1A patent/CN102909022B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1688508A (en) * | 2002-08-13 | 2005-10-26 | 英特凯特公司 | Flue gas treatments to reduce NOx and CO emissions |
| CN1806915A (en) * | 2006-02-23 | 2006-07-26 | 上海交通大学 | Composite bismuth vanadium photocatalyst supported by cobalt oxide and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106076320A (en) * | 2016-06-12 | 2016-11-09 | 常州大学 | A kind of preparation method of the manganese oxide nanometer sheet for processing waste gas |
| CN111792678A (en) * | 2020-07-24 | 2020-10-20 | 福州大学 | Pure cobalt hydrotalcite-like compound and preparation method thereof |
| CN114436344A (en) * | 2022-01-24 | 2022-05-06 | 广东邦普循环科技有限公司 | Preparation method and application of positive electrode material precursor with large channel |
| CN114436344B (en) * | 2022-01-24 | 2023-07-07 | 广东邦普循环科技有限公司 | Preparation method and application of positive electrode material precursor with large channel |
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| Publication number | Publication date |
|---|---|
| CN102909022B (en) | 2014-04-09 |
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