CN1672786A - RE CeO2 supporting wet oxidizing catalyst and its prepn - Google Patents
RE CeO2 supporting wet oxidizing catalyst and its prepn Download PDFInfo
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- CN1672786A CN1672786A CN 200510011119 CN200510011119A CN1672786A CN 1672786 A CN1672786 A CN 1672786A CN 200510011119 CN200510011119 CN 200510011119 CN 200510011119 A CN200510011119 A CN 200510011119A CN 1672786 A CN1672786 A CN 1672786A
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- ceo
- ceo2
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- catalyzer
- noble metal
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- 239000003054 catalyst Substances 0.000 title claims abstract description 26
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 12
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 title abstract description 11
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 title abstract description 11
- 238000009279 wet oxidation reaction Methods 0.000 claims abstract description 17
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 9
- 238000000975 co-precipitation Methods 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 3
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 3
- 239000012266 salt solution Substances 0.000 claims abstract description 3
- 239000010970 precious metal Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011363 dried mixture Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 150000000703 Cerium Chemical class 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 238000005516 engineering process Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000005416 organic matter Substances 0.000 abstract 2
- 239000003513 alkali Substances 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 description 15
- 238000006731 degradation reaction Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 230000003647 oxidation Effects 0.000 description 13
- 238000007254 oxidation reaction Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- -1 Small molecules carboxylic acid Chemical class 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 239000003295 industrial effluent Substances 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The present invention belongs to the field of water processing technology and environment protecting functional material. The RE CeO2 supported wet oxidizing catalyst has RE CeO2 as carrier and noble metal M or noble metal oxide MOx as the active component, with the loaded noble metal amount being 1-3 wt%. The preparation process includes the following steps: preparing CeO2 carrier with Ce salt and alkali matter as material and through co-precipitation; soaking the CeO2 carrier is noble metal salt solution to load noble metal in 1-3 wt%; and drying and roasting to reduce to obtain the wet oxidizing MOx/CeO2 or M/CeO2 catalyst. The MOx/CeO2 or M/CeO2 catalyst has reduced operation condition of wet oxidation to degrade high concentration hard-to-degrade organic matter, can raise the organic matter deeply oxidizing effect and is favorable to catalytic wet oxidation.
Description
Technical field
The present invention relates to the rare earth oxide cerium dioxide is carrier, it with the precious metal loaded catalyst of activeconstituents and preparation method thereof, can be used for Catalytic Wet Oxidation and handle high density, indegradable industrial effluent, belong to water technology and environment functional material field.
Background technology
The Catalytic Wet Oxidation technology is the efficient oxidation technology that generally acknowledge at present a kind of handles high density, poisonous, harmful, organic wastewater with difficult degradation thereby, advantages such as, reaction times little with its equipment volume is short, secondary pollution is few and be subjected to paying close attention to widely have a good application prospect.The catalyzer of high reactivity, stability is one of Catalytic Wet Oxidation The Application of Technology gordian technique.Homogeneous catalyst has advantages such as activity is high, speed of response is fast, but because catalyzer is water-soluble, for fear of catalyst loss, need carry out subsequent disposal.Heterogeneous catalyst has advantages such as activity is high, easily separated, good stability, has been subjected to common attention, becomes the research focus of wet oxidizing catalyst.Wherein the precious metal catalyst series has advantages of high catalytic activity and stability, but the catalyzer cost is higher; Though catalytic activity is preferably arranged, there is more serious catalyst activity component stripping phenomenon in serial oxide catalysts such as metallic copper, iron, manganese, cobalt in reaction, make catalyst activity reduction, and can cause the secondary pollution problem.
Summary of the invention
The objective of the invention is to propose a kind of Catalytic Wet Oxidation reaction that is used for, has organic active high and stable Catalysts and its preparation methods such as handling the difficult degradation organic acid, to reduce the operational condition of wet oxidation reaction, and improve organic rate of oxidation, thereby promote the Catalytic Wet Oxidation broad application.
The invention provides a kind of RE CeO 2 supporting wet oxidizing catalyst, it is characterized in that: this catalyzer is with Rare-Earth Ce O
2Be carrier, precious metal M or metal oxide containing precious metals MOx are activeconstituents, and the noble metal support amount is 1-3wt%.
The present invention also provides the preparation method of above-mentioned RE CeO 2 supporting wet oxidizing catalyst, comprises the steps:
1) is raw material with cerium salt and alkaline matter, adopts coprecipitation method to prepare CeO
2The carrier precursor; With described carrier precursor drying, at the muffle furnace roasting 2-7h of air atmosphere, 350-600 ℃, obtain CeO then
2Carrier;
2) with CeO
2Carrier impregnation is in precious metal salt solution, and the noble metal support amount is 1-3wt%, and dipping time is 10-20h, and is dry afterwards;
3) dried mixture roasting 2-7h in air atmosphere, in the muffle furnace of 300-600 ℃ obtains being used for the MOx/CeO of wet oxidation
2Catalyzer; Or, obtain being used for the M/CeO of wet oxidation with dried mixture roasting 2-7h in hydrogen atmosphere, in the muffle furnace of 300-500 ℃
2Catalyzer.
In the present invention, described precious metal is one or more among Ru, Pt, Pd, Rh or the Au.
MOx/CeO of the present invention
2Or M/CeO
2Catalyzer (M represents precious metal) has good performance for the organic acid of degrading high concentration, difficult degradation.Utilize the 1L autoclave, catalyzer of the present invention has been carried out the experiment of wet-type oxidation degradation organic acid.Small molecules carboxylic acid with high density, difficult degradation---acetate and butyric acid is target compound, is 230 ℃ in temperature of reaction, and total pressure is 5MPa, react about 30min after, the chemical oxygen demand (COD) of wet-type oxidation degradation carboxylic acid (being abbreviated as COD) place to go rate can reach more than 90%.In addition, containing the larger molecular organics of phenyl ring class with complexity---phenol has been carried out the experiment of wet-type oxidation degradation high concentration phenol solution as the target compound of wet oxidation, in temperature of reaction is 150 ℃, total pressure is 4MPa, and behind the reaction 2h, the place to go rate of phenol is also higher.Show that catalyzer of the present invention has good catalytic activity.In addition, utilize ICP-MS that catalyzer M and Ce ionic stripping situation in wet-type oxidation degradation organism process are measured, the stripping quantity of metal ion illustrates that all less than 0.6mg/L catalyzer of the present invention has satisfactory stability.Simultaneously, utilize the X-ray powder diffraction that catalyzer of the present invention is analyzed, obtain grain-size in the catalyzer in 15nm, show that the cerium oxide loaded catalyst has good dispersiveness.In addition, in catalyzer of the present invention, the consumption of precious metal is less, thereby has reduced the cost of catalyzer.Therefore, adopt above catalyst preparation process can obtain the low MOx/CeO of high reactivity, stability and price
2Or M/CeO
2Catalyzer, this helps applying of wet oxidation technology.
Based on the above results, rare earth cerium oxide loading type MOx/CeO of the present invention
2Or M/CeO
2Catalyzer has the following advantages:
(1) catalyzer is for high density, activity that the difficult degradation organic carboxyl acid is very high;
(2) catalyzer has good catalytic activity for the waste water of high density;
(2) catalyzer has satisfactory stability in wet-type oxidation degradation organism process;
(3) catalyst size is a nano level, and on the surface good dispersiveness is arranged;
(4) catalyst production cost is lower.
Embodiment
MOx/CeO of the present invention
2Or M/CeO
2Catalyzer can reduce the operational condition of wet-type oxidation degradation high density, hardly degraded organic substance, improves organic deep oxidation effect, helps the popularization of Catalytic Wet Oxidation technology.
Describe the present invention in detail below in conjunction with embodiment and accompanying drawing.
Embodiment 1:
With Ce (NO
3)
36H
2O and NaOH are raw material, adopt coprecipitation method, with Ce (NO
3)
3Drips of solution is added among the NaOH, the carrier precursor that obtains, and dry about 24h places muffle furnace afterwards in the baking oven in air atmosphere in about 100 ℃, and 350 ℃ of roasting 7h obtain CeO in air atmosphere
2Carrier; With 5gCeO
2Impregnated in and contain 0.3073gRuCl
3The aqueous solution in, at room temperature flood 10h, dry about 12h in 110 ℃ of left and right sides baking ovens in air atmosphere afterwards, then in air, in muffle furnace 300 ℃ of roasting 7h, prepare RuO
2/ CeO
2Catalyzer.
Get 2.5gRuO
2/ CeO
2Catalyzer wet oxidation small molecules acid---acetate, COD is 5600mg/L, and temperature of reaction is 230 ℃, and the reaction total pressure is 5MPa, and the reaction times is 2h, the results are shown in Figure 1.Find out that by Fig. 1 when not using catalyzer, in the wet-type oxidation degradation acetate, behind the reaction 2h, acetate is degraded hardly; When in reaction process, adding CeO
2Behind the carrier, behind the wet-type oxidation degradation acetic acidreaction 2h, its COD clearance is about 15%; But add RuO of the present invention
2/ CeO
2Catalyzer, behind the reaction 30min, the COD clearance has reached 96%.
Embodiment 2:
With CeCl
3And NH
3H
2O is a raw material, adopts coprecipitation method, with NH
3H
2O is added drop-wise to CeCl
3In the solution, generate the carrier precursor, in air atmosphere, dry about 24h in 110 ℃ of left and right sides baking ovens, in muffle furnace, 500 ℃ of roasting 3h obtain CeO in air atmosphere afterwards
2Carrier; 3gCeO
2Carrier impregnation is in containing 0.3796gRu
3(CO)
12The aqueous solution in, at room temperature flood 15h, dry about 24h in 100 ℃ of left and right sides baking ovens in air afterwards, then in air, in muffle furnace 400 ℃ of roasting 3h, prepare RuO
2/ CeO
2Catalyzer.
Get 2.5gRuO
2/ CeO
2-TiO
2Catalyzer wet-type oxidation degradation small molecular organic acid---butanic acid, COD are 8700mg/L, and temperature of reaction is 230 ℃, and the reaction total pressure is 5MPa, and the reaction times is 2h, and the result as shown in Figure 2.As seen from the figure, add RuO
2/ CeO
2During catalyzer, behind the reaction 45min, the COD clearance reaches 100%, far above the degradation effect of catalyst-free.
Embodiment 3:
With CeCl
3With urea be raw material, adopt coprecipitation method, CeCl
3Drips of solution is added in the urea, and heating obtains the carrier precursor, and dry about 36h places afterwards in 700 ℃ of roasting 2h of muffle furnace in the baking oven in air atmosphere about 85 ℃, obtains CeO
2Carrier; 2gCeO
2Impregnated in and contain 0.0409gRuCl
3The aqueous solution in, at room temperature flood 20h, afterwards in air atmosphere, dry about 10h in 120 ℃ of left and right sides baking ovens, then in air, 600 ℃ of roasting 2h, prepare RuO
2/ CeO
2Catalyzer.
Get the prepared catalyzer wet-type oxidation degradation phenol solution of 2g, solution C OD is 11000mg/L, is 150 ℃ in temperature of reaction, and the reaction total pressure is 4MPa, reacts for behind the 2h, and the COD of phenol is more than 70.5%, shows good catalytic activity.
Embodiment 4:
With Ce (NO
3)
36H
2O and NH
3H
2O is a raw material, adopts coprecipitation method, with Ce (NO
3)
3Drips of solution is added to NH
3H
2Among the O, the carrier precursor that obtains, dry about 12h places muffle furnace afterwards in the baking oven in air atmosphere in about 110 ℃, and 400 ℃ of roasting 3h obtain CeO in air atmosphere
2Carrier; With 4gCeO
2Impregnated in and contain 0.2523gH
2PtCl
6The aqueous solution in, at room temperature flood 12h, dry about 12h in 110 ℃ of left and right sides baking ovens in air atmosphere afterwards, then in hydrogen 300 ℃ reduce 3h, prepare Pt/CeO
2Catalyzer.
Embodiment 5:
With CeCl
3And NH
3H
2O is a raw material, adopts coprecipitation method, with CeCl
3Drips of solution is added to NH
3H
2Among the O, the carrier precursor that obtains, dry about 15h places muffle furnace afterwards in the baking oven in air atmosphere in about 100 ℃, and 350 ℃ of roasting 3.5h obtain CeO in air atmosphere
2Carrier; With 5gCeO
2Impregnated in and contain 0.2409gRuCl
3And 0.0410gH
2In the aqueous solution of PtCl, at room temperature flood 20h, dry about 24h in 110 ℃ of left and right sides baking ovens in air atmosphere afterwards, then in hydrogen 350 ℃ reduce 3h, prepare Ru-Pt/CeO
2Catalyzer.
In like manner, utilize precious metals pd, Rh or Au salts solution to carry out load, can prepare RE CeO 2 supporting wet oxidizing catalyst equally, realize the present invention.
Characteristics of the present invention are to have utilized the profuse rare earth resources starting material of China, have invented with rare earth oxide CeO
2Loaded catalyst for carrier, can reduce the consumption of the precious metal material that costs an arm and a leg, therefore can solve the stripping problem of transition metal oxides such as copper, iron, manganese series again, cerium dioxide of the present invention high activity loading type wet oxidizing catalyst of being carrier and preparation method thereof has great importance for the wet oxidation broad application.
Claims (4)
1. RE CeO 2 supporting wet oxidizing catalyst, it is characterized in that: this catalyzer is with Rare-Earth Ce O
2Be carrier, precious metal M or metal oxide containing precious metals MOx are activeconstituents, and the noble metal support amount is 1-3wt%.
2. loaded catalyst according to claim 1 is characterized in that: described precious metal is one or more among Ru, Pt, Pd, Rh or the Au.
3. the preparation method of RE CeO 2 supporting wet oxidizing catalyst is characterized in that, described method comprises the steps:
1) is raw material with cerium salt and alkaline matter, adopts coprecipitation method to prepare CeO
2The carrier precursor; With described carrier precursor drying, at the muffle furnace roasting 2-7h of air atmosphere, 350-600 ℃, obtain CeO then
2Carrier;
2) with CeO
2Carrier impregnation is in precious metal salt solution, and the noble metal support amount is 1-3wt%, and dipping time is 10-20h, and is dry afterwards;
3) dried mixture roasting 2-7h in air atmosphere, in the muffle furnace of 300-600 ℃ obtains being used for the MOx/CeO of wet oxidation
2Catalyzer; Or, obtain being used for the M/CeO of wet oxidation with dried mixture roasting 2-7h in hydrogen atmosphere, in the muffle furnace of 300-500 ℃
2Catalyzer.
4. loaded catalyst according to claim 3 is characterized in that: described precious metal is one or more among Ru, Pt, Pd, Rh or the Au.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510011119XA CN1317070C (en) | 2005-01-07 | 2005-01-07 | RE CeO2 supporting wet oxidizing catalyst and its prepn |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510011119XA CN1317070C (en) | 2005-01-07 | 2005-01-07 | RE CeO2 supporting wet oxidizing catalyst and its prepn |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1672786A true CN1672786A (en) | 2005-09-28 |
| CN1317070C CN1317070C (en) | 2007-05-23 |
Family
ID=35045717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200510011119XA Expired - Fee Related CN1317070C (en) | 2005-01-07 | 2005-01-07 | RE CeO2 supporting wet oxidizing catalyst and its prepn |
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|---|---|
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100409940C (en) * | 2006-07-17 | 2008-08-13 | 大连理工大学 | Catalyst for simultaneously removing nitrogen oxide and CO in automobile exhaust |
| CN101948195A (en) * | 2010-09-08 | 2011-01-19 | 淄博包钢灵芝稀土高科技股份有限公司 | Method for performing water treatment by using tetravalent cerium |
| CN106622227A (en) * | 2016-12-29 | 2017-05-10 | 天津大学 | Preparation method of monoatomic catalyst for indoor air purification |
| CN106732582A (en) * | 2016-12-08 | 2017-05-31 | 中国科学院兰州化学物理研究所 | Meso-porous nano CeO2Hollow ball supported catalyst and its preparation method and application |
| CN107537515A (en) * | 2017-09-11 | 2018-01-05 | 中国科学技术大学 | A kind of application of carried copper Mn catalyst and preparation method thereof and CO catalytic oxidation under low temperature |
| CN108499518A (en) * | 2018-04-17 | 2018-09-07 | 广西大学 | The preparation and its application of the modified porous silicon substrate microsphere adsorbing agent of cerium oxide |
| CN108855071A (en) * | 2018-07-12 | 2018-11-23 | 杭州晟睿新材料有限公司 | A kind of preparation method and applications of cerium oxide support type high-dispersion nano catalyst |
| CN110075856A (en) * | 2019-05-21 | 2019-08-02 | 南京工业大学 | Catalyst for catalyzing wet oxidation of nitrochlorobenzene wastewater and preparation method thereof |
| CN114471552A (en) * | 2022-01-26 | 2022-05-13 | 合肥综合性国家科学中心能源研究院(安徽省能源实验室) | Preparation of synthetic ammonia catalyst and synthetic ammonia system and method |
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|---|---|---|---|---|
| US6699815B2 (en) * | 2000-06-21 | 2004-03-02 | Min-Hon Rei | Boron nitride supported noble metal catalyst |
| CN1224579C (en) * | 2002-11-06 | 2005-10-26 | 中国科学院大连化学物理研究所 | Method for treating wastewater with high hydroxybenzene contained through catalyzing wet oxidation |
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2005
- 2005-01-07 CN CNB200510011119XA patent/CN1317070C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100409940C (en) * | 2006-07-17 | 2008-08-13 | 大连理工大学 | Catalyst for simultaneously removing nitrogen oxide and CO in automobile exhaust |
| CN101948195A (en) * | 2010-09-08 | 2011-01-19 | 淄博包钢灵芝稀土高科技股份有限公司 | Method for performing water treatment by using tetravalent cerium |
| CN101948195B (en) * | 2010-09-08 | 2012-07-11 | 淄博包钢灵芝稀土高科技股份有限公司 | Method for performing water treatment by using tetravalent cerium |
| CN106732582A (en) * | 2016-12-08 | 2017-05-31 | 中国科学院兰州化学物理研究所 | Meso-porous nano CeO2Hollow ball supported catalyst and its preparation method and application |
| CN106622227B (en) * | 2016-12-29 | 2019-03-08 | 天津大学 | A kind of preparation method of the monatomic catalyst of indoor air purification |
| CN106622227A (en) * | 2016-12-29 | 2017-05-10 | 天津大学 | Preparation method of monoatomic catalyst for indoor air purification |
| CN107537515A (en) * | 2017-09-11 | 2018-01-05 | 中国科学技术大学 | A kind of application of carried copper Mn catalyst and preparation method thereof and CO catalytic oxidation under low temperature |
| CN107537515B (en) * | 2017-09-11 | 2020-04-17 | 中国科学技术大学 | Supported copper-manganese catalyst, preparation method thereof and application of supported copper-manganese catalyst in low-temperature catalytic oxidation of CO |
| CN108499518A (en) * | 2018-04-17 | 2018-09-07 | 广西大学 | The preparation and its application of the modified porous silicon substrate microsphere adsorbing agent of cerium oxide |
| CN108855071A (en) * | 2018-07-12 | 2018-11-23 | 杭州晟睿新材料有限公司 | A kind of preparation method and applications of cerium oxide support type high-dispersion nano catalyst |
| CN110075856A (en) * | 2019-05-21 | 2019-08-02 | 南京工业大学 | Catalyst for catalyzing wet oxidation of nitrochlorobenzene wastewater and preparation method thereof |
| CN114471552A (en) * | 2022-01-26 | 2022-05-13 | 合肥综合性国家科学中心能源研究院(安徽省能源实验室) | Preparation of synthetic ammonia catalyst and synthetic ammonia system and method |
| CN114471552B (en) * | 2022-01-26 | 2023-11-17 | 合肥综合性国家科学中心能源研究院(安徽省能源实验室) | Preparation of synthetic ammonia catalyst, synthetic ammonia system and synthetic ammonia method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1317070C (en) | 2007-05-23 |
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