CN103537316A - Catalyst for wet oxidation technique and preparation method thereof - Google Patents
Catalyst for wet oxidation technique and preparation method thereof Download PDFInfo
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- CN103537316A CN103537316A CN201210258918.7A CN201210258918A CN103537316A CN 103537316 A CN103537316 A CN 103537316A CN 201210258918 A CN201210258918 A CN 201210258918A CN 103537316 A CN103537316 A CN 103537316A
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Abstract
The invention relates to a catalyst for an organic garbage treatment wet oxidation technique and a preparation method thereof, belonging to the technical field of environmental protection. In the catalyst, a ZSM-5 molecular sieve is used as a supporter, transition metals Fe and Mn and a rare-earth element Ce are used as active components, and the loading capacities of the metal phases for the supporter are respectively 4-8 wt%. The preparation method comprises the following steps: cleaning the catalyst using ZSM-5 as the supporter, and drying to constant weight; and impregnating the obtained ZSM-5 supporter in a solution of metal salts of the rare-earth element Ce and transition elements Fe and Mn, drying, roasting the dried mixture in air to obtain the catalyst for an organic garbage treatment wet oxidation technique, wherein the loading capacities of the metal phases for the supporter are respectively 4-8 wt%. The catalyst does not use any expensive noble metal material, and has the advantages of low cost, high catalytic activity and high stability.
Description
Technical field
The present invention relates to the Catalysts and its preparation method in a kind of technology of garbage disposal and environment functional material field, specifically a kind of Catalysts and its preparation method for garbage disposal wet-type oxidation technology.
Background technology
Industry develop the rapid growth that has promoted Chinese national economy rapidly, but produced simultaneously environmental pollution has also restricted expanding economy, high concentration, poisonous, harmful, difficult organic industrial sewage of carrying out a biological disposal upon are one of main sources of environmental pollution.Wet air oxidation (WAO) be under high temperature (120～380 ℃), high pressure (0.5～20MPa) and liquid-phase condition with a kind of high-level oxidation technology of solubilised state in oxidant (air or oxygen) oxidize water or suspended state organic matter and reduction-state inorganic matter, there is applied widely, pollutant complete decomposition, the time of staying is short, secondary pollution is few.But it also has some limitations, be mainly that reaction temperature is high, reaction pressure is large, equipment and materials requirement is high, low to the removal efficiency of some organic matter (as Polychlorinated biphenyls etc.).CWO (CWAO) method, on WAO basis, by adding suitable catalysis catalyst to improve organic oxidation rate, reduces reaction temperature and pressure, thereby can reduce operating cost and equipment investment.
Homogeneous catalyst has the advantages such as activity is high, reaction speed is fast, but because catalyst is water-soluble, for fear of catalyst loss, need to carry out subsequent treatment.Heterogeneous catalysis has advantages of easily separated recovery, and the extensive use that stable, efficient, the cheap heterogeneous catalysis of research preparation is oxidized catalysis humidifying is significant.Heterogeneous noble metal catalyst series has higher catalytic activity and stability, but catalyst cost is higher; The serial oxide heterogeneous catalysis such as transition metal copper, iron, manganese, zinc, cobalt, nickel, although there is good catalytic activity, but in reaction, there is more serious catalyst activity component stripping phenomenon, make catalyst activity reduction, and can cause secondary pollution problem.Another kind of more outstanding Catalysts Deactivation Problems is catalyst surface carbon deposit, in CWO course of reaction, generate the few polymer of the many hydrogen of a class carbon, this class material can be adsorbed on catalyst surface securely, covered the activated centre of catalytic reaction, also may be blocked in the micro channel of catalyst simultaneously, make reactant be difficult to be diffused on the activated centre of micropore inside, thereby cause the activity decreased of catalyst.These extensive uses for Wet Oxidation Process have formed obstacle.
Al
2o
3, SiO
2, clay is poor in high temperature, high pressure, strong hydrothermal, acid (or alkali) property Water Under heat endurance and antiacid caustic corrosion, long-term operation cannot guarantee the intensity of catalyst, by cause catalyst loss of active component, break, efflorescence, and then stop up reaction tube; And active carbon and relevant new carbon long term exposure can be oxidized gradually under oxidation atmosphere, catalytic efficiency is not high.
ZSM-5 is a kind of micro porous molecular sieve, with 10 yuan of oxygen rings, form pore canal system, there is medium sized aperture and cage is walked upwards not have in ， duct, aperture, in catalytic process, be difficult for carbon deposit, and there is good hydrothermal stability, suitable acidity, good resistance to acids and bases and hydrophobicity.Because high selectivity, high activity, the anti-carbon deposit of ZSM-5 zeolite is difficult for the features such as inactivation, be therefore a kind of desirable wet oxidizing catalyst carrier.
The Preparing and characterization anoptimal supported ceria catalyst for the catalytic wet air oxidation of phenol (Preparation and characterization of load ceria in CWO phenol) one that is entitled as that Chen I.P etc. deliver at Appl.Catal.B:Environ. (applied catalysis B prints environment) 50 volume 49-58 pages in 2004 the article pointed out: load capacity 20%CeO
2catalyst degradation of phenol is had to optimum efficiency, (180 ℃ of temperature, oxygen partial pressure 1.5Mpa, reaction time 2h) can degrade 100% phenol and COD (COD) of 80% under operating condition.This weak point is: cerium content (CeO
2) 20% load capacity is higher.
" the CeO that Yang Shaoxia etc. deliver on the 246th phase 222-228 page at < < Surface Science application > > for 2005
2interpolation to RuO
2/ γ-Al
2o
3catalyst structure and active modified effect ", in this article, propose to adopt infusion process to prepare RuO
2/ γ-Al
2o
3, RuO
2-CeO
2/ γ-Al
2o
3.Its weak point is to have used noble metal Ru as active component.
" the Fe processing for waste water from dyestuff CWPO that Liu Yan etc. deliver at < < Journal of Chemical Industry and Engineering > > the 57th volume 2303-2308 page in 2006
2o
3-CeO
2/ γ-Al
2o
3the preparation of catalyst and activity " adopt layering infusion process to prepare Fe
2o
3-CeO
2/ γ-Al
2o
3catalyst.Its weak point is Al
2o
3hydrothermal stability and antiacid caustic corrosion are poor, and long-term operation will cause loss of active component, breaks, efflorescence, and then stop up reaction tube.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, provide a kind of new Catalysts and its preparation method for wet-type oxidation technology, i.e. the supporting wet oxidizing catalyst of ZSM-5 molecular sieve supported rare earth metal oxide and transition elements.This catalyst only need be used rare earth element and transition metal, does not use noble metal, take ZSM-5 molecular sieve as carrier, adopts infusion process to be prepared from.Compare with traditional catalyst, both reduced catalyst cost, improved again the activity of catalyst, make the reaction condition milder of wet oxidation.
The present invention is achieved by the following technical solutions:
Catalyst for wet-type oxidation technology involved in the present invention, comprise the active component on carrier and carrier, described carrier is ZSM-5 molecular sieve, described active component is transition-metal Fe, Mn or their oxide, rare earth element ce or its oxide, each Metal Phase is 4wt%-8wt% for the load capacity of ZSM-5 molecular sieve carrier.
The preparation method of the catalyst for wet-type oxidation technology involved in the present invention, comprises the following steps:
The first step, take ZSM-5 molecular sieve as carrier, cleans, and dries to constant weight;
Described bake out temperature is 110 ℃.
Second step, the ZSM-5 molecular sieve carrier impregnation that the first step is obtained is in rare earth element ce and transition-metal Fe, Mn metal salt solution, and each Metal Phase is 4wt%-8wt% to the load capacity of carrier, and dipping is then dry;
Described dip time is 15h-30h.
The 3rd step, by the roasting in air ambient of dried mixture, obtains for wet oxidation Fe
2o
3--MnO
2-CeO
2/ ZSM-5 catalyst.
Described roasting is roasting in Muffle furnace.
Described roasting, its temperature is 300-600 ℃, the time is 4h-8h.
Fe of the present invention
2o
3-MnO
2---CeO
2/ ZSM-5 catalyst has the following advantages: 1) catalyst has good catalytic activity to the wet oxidation Catalytic processes of rubbish; 2) utilize rare earth element ce can improve the feature of catalyst activity and stability, adding rare earth element can reduce costs simultaneously; 3) take transition-metal Fe, Mn is active component, has higher catalytic activity, and wide material sources, cheap; 4) carrier ZSM-5 molecular sieve has good hydrothermal stability, suitable acidity, large, the Stability Analysis of Structures of resistance to acids and bases, specific area, anti-carbon, load active component are difficult for running off preferably.
In the autoclave of 1L, by solid refuse humidifying, grinding, extrude after, this catalyst is processed to the experiment of solid refuse for wet-type oxidation technology.In reaction temperature, be 150 ℃, gross pressure is 8Mpa, and after reaction 1h, the COD of rubbish (being abbreviated as COD) clearance can reach more than 90%.It is can reusing also very high, shows that catalyst of the present invention has good catalytic activity and durability.X-ray powder diffraction analysis of catalyst crystallite dimension is less, shows that ZSM-5 molecular sieve loaded catalyst has good dispersiveness.In addition, catalyst non precious metal composition of the present invention, production cost is low.Therefore, adopt that above catalyst preparation process can obtain efficiently, the Fe of cheap, good stability
2o
3-MnO
2---CeO
2/ ZSM-5 catalyst.
The specific embodiment
Below case study on implementation of the present invention is elaborated: the implementation case is implemented take technical solution of the present invention under prerequisite, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Fe of the present invention
2o
3-MnO
2-CeO
2/ ZSM-5 catalyst can reduce the process conditions of wet-type oxidation degradation high concentration, hardly degraded organic substance, improves organic deep oxidation effect, is conducive to the popularization of Wet Oxidation Process.
Case study on implementation 1:
Take ZSM-5 molecular sieve as carrier, clean, at 110 ℃, dry to constant weight as catalyst carrier.The nitrate of Ce, Fe, Mn of take is raw material (dipping concentration is 1.0mol/L), adopt step impregnation method, every step dip time is 30h, floods completely all in air ambient, at 120 ℃, to dry 20h, all be placed in afterwards 600 ℃ of roasting 4h of Muffle furnace, finally obtain Fe
2o
3-MnO
2-CeO
2/ ZSM-5 catalyst, the load capacity of metal Ce, Fe, Mn is respectively 6wt%, 5wt%, 5wt%.
Get the solid refuse after the prepared catalyst catalytic wet oxidation degraded humidifying grinding of 5g, rubbish COD is 30000mg/L, 150 ℃ of reaction temperatures, reaction gross pressure is 8Mpa, after reaction 1h, the COD of rubbish (being abbreviated as COD) clearance > 90%, shows good catalytic activity.Reuse this catalyst three times, it,, to the clearance of COD > 90% still, shows good durability.
Case study on implementation 2:
Take ZSM-5 molecular sieve as carrier, clean, at 110 ℃, dry to constant weight as catalyst carrier.The nitrate of Ce, Fe, Mn of take is raw material (dipping concentration is 0.75mol/L), adopt step impregnation method, every step dip time is 20h, floods completely all in air ambient, at 120 ℃, to dry 20h, all be placed in afterwards 500 ℃ of roasting 6h of Muffle furnace, finally obtain Fe
2o
3-MnO
2-CeO
2/ ZSM-5 catalyst, the load capacity of metal Ce, Fe, Mn is 5wt%.
Get the solid refuse after the prepared catalyst catalytic wet oxidation degraded humidifying grinding of 5g, rubbish COD is 30000mg/L, 150 ℃ of reaction temperatures, reaction gross pressure is 8Mpa, after reaction 1h, the COD of rubbish (being abbreviated as COD) clearance > 90%, shows good catalytic activity.Reuse this catalyst three times, it,, to the clearance of COD > 90% still, shows good durability.
Case study on implementation 3:
Take ZSM-5 molecular sieve as carrier, clean, at 110 ℃, dry to constant weight as catalyst carrier.The nitrate of Ce, Fe, Mn of take is raw material (dipping concentration is 0.5mol/L), adopt step impregnation method, every step dip time is 15h, floods completely all in air ambient, to dry 20 hours at 120 ℃, all be placed in afterwards 400 ℃ of roasting 8h of Muffle furnace, finally obtain Fe
2o
3---MnO
2-CeO
2/ ZSM-5 catalyst, the load capacity of metal Ce, Fe, Mn is respectively 5wt%, 4wt%, 4wt%.
Get the solid refuse after the prepared catalyst catalytic wet oxidation degraded humidifying grinding of 5g, rubbish COD is 30000mg/L, 150 ℃ of reaction temperatures, reaction gross pressure is 8Mpa, after reaction 1h, the COD of rubbish (being abbreviated as COD) clearance > 90%, shows good catalytic activity.Reuse this catalyst three times, it,, to the clearance of COD > 90% still, shows good durability.
Claims (7)
1. the catalyst for wet-type oxidation technology, it is characterized in that: comprise the active component on carrier and carrier, described carrier is ZSM-5 molecular sieve, described active component is transition-metal Fe, Mn and rare earth element ce, and each Metal Phase is for the load capacity of ZSM-5 carrier: 4wt%-8wt%
2. a preparation method for the catalyst for wet-type oxidation technology as claimed in claim 1, is characterized in that, comprises the steps:
The first step, take ZSM-5 molecular sieve as carrier, cleans, and dries to constant weight;
Second step, the ZSM-5 molecular sieve carrier impregnation that the first step is obtained is in rare earth element ce and transition-metal Fe, Mn metal salt solution, and each Metal Phase is for the load capacity of carrier: 4wt%-8wt%, dipping, dry afterwards.
The 3rd step, by the roasting in air of dried mixture, obtains the Fe for wet-type oxidation technology
2o
3-MnO
2-CeO
2/ ZSM-5 catalyst.
3. the preparation method of the catalyst for wet-type oxidation technology according to claim 2, is characterized in that, in the first step, and described oven dry, its temperature is 110 ℃.
4. the preparation method of the catalyst for wet-type oxidation technology according to claim 2, is characterized in that, in second step, and described dipping, its time is 15h-30h.
5. the preparation method of the catalyst for wet-type oxidation technology according to claim 2, is characterized in that, in the 3rd step, described roasting, is roasting in Muffle furnace.
6. according to the preparation method of the catalyst for wet-type oxidation technology described in claim 2 or 5, it is characterized in that, in the 3rd step, described roasting, its temperature is 300-600 ℃.
7. according to the preparation method of the catalyst for wet-type oxidation technology described in claim 2 or 5, it is characterized in that, in the 3rd step, described roasting, its time is 4h-8h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108962631A (en) * | 2018-07-06 | 2018-12-07 | 五邑大学 | A kind of preparation method of steam oxidation nickel sulfide energy storage electrode material |
| CN115254176A (en) * | 2022-07-17 | 2022-11-01 | 江苏科技大学 | Nano-zeolite-coated heavy metal cluster catalytic wet oxidation catalyst and preparation method and application thereof |
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|---|---|---|---|---|
| US20070210010A1 (en) * | 2006-03-10 | 2007-09-13 | Nippon Shokubai Co., Ltd. | Catalyst for wastewater treatment and method for wastewater treatment using said catalyst |
| CN101780412A (en) * | 2010-02-12 | 2010-07-21 | 新奥科技发展有限公司 | Catalyst for treating industrial waste water under normal temperature and normal pressure and preparation method thereof |
| CN101898136A (en) * | 2010-04-09 | 2010-12-01 | 上海交通大学 | Titanium-based multi-metal oxide catalyst for removing diesel engine NOx by NH3-SCR in wide temperature window |
| CN102294248A (en) * | 2011-05-30 | 2011-12-28 | 浙江大学 | Fe-Mn composite oxide catalyst for denitration and demercuration at the same time and preparation method thereof |
-
2012
- 2012-07-13 CN CN201210258918.7A patent/CN103537316A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070210010A1 (en) * | 2006-03-10 | 2007-09-13 | Nippon Shokubai Co., Ltd. | Catalyst for wastewater treatment and method for wastewater treatment using said catalyst |
| CN101780412A (en) * | 2010-02-12 | 2010-07-21 | 新奥科技发展有限公司 | Catalyst for treating industrial waste water under normal temperature and normal pressure and preparation method thereof |
| CN101898136A (en) * | 2010-04-09 | 2010-12-01 | 上海交通大学 | Titanium-based multi-metal oxide catalyst for removing diesel engine NOx by NH3-SCR in wide temperature window |
| CN102294248A (en) * | 2011-05-30 | 2011-12-28 | 浙江大学 | Fe-Mn composite oxide catalyst for denitration and demercuration at the same time and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108962631A (en) * | 2018-07-06 | 2018-12-07 | 五邑大学 | A kind of preparation method of steam oxidation nickel sulfide energy storage electrode material |
| CN115254176A (en) * | 2022-07-17 | 2022-11-01 | 江苏科技大学 | Nano-zeolite-coated heavy metal cluster catalytic wet oxidation catalyst and preparation method and application thereof |
| CN115254176B (en) * | 2022-07-17 | 2024-03-15 | 江苏科技大学 | Nano zeolite coated heavy metal cluster catalytic wet oxidation catalyst and preparation method and application thereof |
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Application publication date: 20140129 |