CN100395021C - Rare earth composite oxide catalyst in catalytic wet oxidation process and preparing method thereof - Google Patents
Rare earth composite oxide catalyst in catalytic wet oxidation process and preparing method thereof Download PDFInfo
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- CN100395021C CN100395021C CNB2005100111768A CN200510011176A CN100395021C CN 100395021 C CN100395021 C CN 100395021C CN B2005100111768 A CNB2005100111768 A CN B2005100111768A CN 200510011176 A CN200510011176 A CN 200510011176A CN 100395021 C CN100395021 C CN 100395021C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 229910052761 rare earth metal Inorganic materials 0.000 title claims description 17
- 150000002910 rare earth metals Chemical class 0.000 title claims description 17
- 238000000034 method Methods 0.000 title abstract description 14
- 238000009279 wet oxidation reaction Methods 0.000 title abstract description 14
- 230000003197 catalytic effect Effects 0.000 title abstract description 5
- 238000005516 engineering process Methods 0.000 claims abstract description 23
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012670 alkaline solution Substances 0.000 claims abstract description 10
- 150000000703 Cerium Chemical class 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 239000013049 sediment Substances 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 4
- 230000003647 oxidation Effects 0.000 claims description 19
- 238000007254 oxidation reaction Methods 0.000 claims description 19
- 238000006555 catalytic reaction Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 229910052684 Cerium Inorganic materials 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000000975 co-precipitation Methods 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000036632 reaction speed Effects 0.000 abstract description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 2
- 230000004913 activation Effects 0.000 abstract 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000008204 material by function Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- -1 small-molecule organic acid Chemical class 0.000 abstract 1
- 150000003754 zirconium Chemical class 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 17
- 150000007524 organic acids Chemical class 0.000 description 12
- 230000015556 catabolic process Effects 0.000 description 9
- 238000006731 degradation reaction Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000009938 salting Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
The present invention relates to an RE composite oxide catalyst in a catalytic wet oxidation process and a preparation method thereof, which belongs to water treatment technologies and the field of environment functional materials. The present invention discloses an RE composite oxide catalyst for reducing the temperature and the pressure of a wet oxidation reaction and increasing the total wet oxidation reaction speed of organic matters. The present invention is solid powdery and comprises a composite oxide of ZrO2 and CeO2 in the molar ratio of 1: 1 to 1: 11. The present invention also discloses a preparation method of the catalyst. The method comprises the following steps: a mixed solution of zirconium salt and cerium salt is prepared and is added to an acutely stirred alkaline solution in drops to obtain a gel sediment which is filtered; again, the gel sediment is dispersed in deionized water of which the pH value is regulated to be alkaline so that the gel sediment can flow back in the hot alkaline solution; then, the alkaline solution is dried and roasted to obtain the catalyst. The catalyst of the present invention has favorable activation and comparatively high stability to wastewater containing hardly dissolvable small-molecule organic acid with high concentration, and the production cost is low.
Description
Technical field
The present invention is used for catalysis wet-type oxidation technology and handles the waste water that contains the high-concentration hardly-degradable small molecular organic acid, belongs to water technology and environment functional material field.
Background technology
The wet oxidation technology is a kind of very effective senior chemical oxidize water treatment technology, is specially adapted to the processing of poisonous and harmful and high concentrated organic wastewater.The wet oxidation technology with its treatment effeciency height, secondary pollution is low, oxidation rate is fast, equipment volume is little and advantage such as recoverable energy and be subjected to paying close attention to widely, have a good application prospect.But the wet oxidation Technology Need is operated under higher temperature and pressure, and the scientific worker utilizes catalysis wet-type oxidation technology to overcome these shortcomings by adding catalyst to reaction system.Thereby efficient, stable, cheap and easily and moisture from the exploitation of heterogeneous catalysis become one of key technology of CWO technology.In addition, it is relatively poor that small molecular organic acid (especially acetate) effect is handled in wet oxidation, and small molecular organic acid is the important intermediate that most organic matter decomposes, and their oxidation Decomposition speed has often determined the general speed that the organic matter wet oxidation is decomposed.Therefore, efficiently to handle the catalyst of the small molecular organic acid in the waste water be one of focus of current domestic and international CWO research in development.
The heterogeneous catalysis of research mainly contains noble metal catalyst series, metallic copper (comprising iron, manganese, cobalt etc.) catalyst series, rare earth metal catalyst at present in catalytic wet technology.
The noble metal catalyst series has advantages of high catalytic activity and stability, and especially the small molecular organic acid for difficult degradation has activity preferably, but the high price of noble metal self has caused the catalyst cost higher.
Though the metallic copper catalyst series has catalytic activity preferably, in reaction, there is more serious catalyst activity component stripping phenomenon, make catalyst activity reduction, and can cause the secondary pollution problem.
Main metal zirconium and the cerium of using in the rare earth metal catalyst, their prices are lower, have certain activity and well stable in wet oxidation, but rare earth metal are lower for the clearance of small molecular organic acid.
Summary of the invention
The objective of the invention is to propose a kind of being applied in the catalysis wet-type oxidation technology, have and handle low rare earth catalyst of the active height of difficult degradation small molecular organic acid, good stability and production cost and preparation method thereof, to reduce the temperature and pressure of wet oxidation reaction, improve total organic matter wet oxidation reaction speed.
Technical scheme of the present invention is as follows:
The application of a kind of rare-earth composite oxide catalyst in catalysis wet-type oxidation technology is characterized in that: described rare-earth composite oxide catalyst is a solid powdery, and component is ZrO
2And CeO
2Composite oxides, the mol ratio of Zr and Ce is 1: 1～1: 11.
As preferably, at the ZrO of described rare-earth composite oxide catalyst
2And CeO
2In the component, the mol ratio of Zr and Ce is 1: 9.
Wherein, the preparation method of described rare-earth composite oxide catalyst is as follows: the mixed solution of at first preparing zirconates and cerium salt, the molar concentration rate of zirconates and cerium salt is 1: 1～1: 11, adopt coprecipitation, slowly be added drop-wise to mixed solution in the alkaline solution, the volume ratio of mixed solution and alkaline solution is 1: 4～1: 20, and the vigorous stirring while dripping is filtered the gel precipitate that obtains; Then described sediment is dispersed in the deionized water again, behind adjusting pH value to 9～11, in heat alkali liquid, refluxed 24～36 hours; In air atmosphere in baking oven dry 24 hours, place muffle furnace afterwards then, 300～600 ℃ of roasting 3～8h obtain ZrO in air atmosphere
2-CeO
2Composite oxide catalysts.
As preferably, when the mixed solution of preparation zirconates and cerium salt, the molar concentration rate of zirconates and cerium salt is 1: 9.
In the 1L autoclave, with the little carboxylic acids of high concentration, difficult degradation---acetate and butyric acid are object, are 230 ℃ in reaction temperature, and gross pressure is 5MPa, uses ZrO of the present invention
2-CeO
2Catalyst has carried out the research of wet-type oxidation degradation organic acid.And utilize ICP-MS that catalyst stripping situation of Zr and Ce ion in catalysis wet-type oxidation degradation organic acid process is measured, result of study shows that catalyst of the present invention has the following advantages:
(1) catalyst of the present invention is used for catalysis wet-type oxidation technology, for the small molecular organic acid waste water that contains high-concentration hardly-degradable good activity is arranged.Can effectively reduce the operating temperature and the pressure of wet-type oxidation technology, accelerate the oxidation rate of the small molecular organic acid of difficult degradation in the waste water.
(2) utilize ICP-MS that catalyst stripping situation of Zr and Ce ion in catalysis wet-type oxidation degradation organic acid process is measured, find that the stripping quantity of metal ion is all very little, this illustrates that this catalyst has good stable.
(3) catalyst of the present invention adopts relatively inexpensive Zr and Ce as the activity of such catalysts composition, and production technology is simple and easy to do, so catalyst production cost is lower.
The above-mentioned advantage of catalyst of the present invention can promote the promotion and application of wet oxidation technology.
Description of drawings
Fig. 1 contains acetate COD removal variation diagram for CWO.
Fig. 2 contains n-butyric acie COD removal variation diagram for CWO.
The specific embodiment
The invention provides a kind of rare-earth composite oxide catalyst that is used for catalysis wet-type oxidation technology, it is a solid powdery, and component is ZrO
2And CeO
2Composite oxides, the mol ratio of Zr and Ce is 1: 1～1: 11.Its preparation method comprises the steps: at first to prepare the mixed solution of zirconates and cerium salt, the molar concentration rate of zirconates and cerium salt is 1: 1～1: 11, adopt coprecipitation, slowly be added drop-wise to mixed solution in the alkaline solution, the volume ratio of mixed solution and alkaline solution is 1: 4～1: 20, the vigorous stirring while dripping is filtered the gel precipitate that obtains; Then described sediment is dispersed in the deionized water again, behind adjusting pH value to 9～11, in heat alkali liquid, refluxed 24～36 hours; In air atmosphere in baking oven dry 24 hours, place muffle furnace afterwards then, 300～600 ℃ of roasting 3～8h obtain ZrO in air atmosphere
2-CeO
2Composite oxide catalysts.
Describe the present invention in detail below in conjunction with embodiment and accompanying drawing.
Embodiment one
The ZrOCl of preparation 0.1mol/L
28H
2Ce (the NO of O and 0.9mol/L
3)
36H
2O mixed solution 50ml and 0.5mol/L ammoniacal liquor 1000ml, salting liquid is slowly dripped in the ammoniacal liquor of vigorous stirring, the gel precipitate that obtains is filtered, and is dispersed in again in the deionized water of 400ml, the pH value is transferred to 10 after, 24h refluxes in heat alkali liquid, dry in baking oven then, baking temperature is 100 ℃, places muffle furnace afterwards, 400 ℃ of roasting 6h obtain ZrO in air atmosphere
2-CeO
2Composite oxide catalysts.
Utilize the catalyst of method for preparing to come CWO to contain high-concentration acetic acid waste water then:
Preparation COD concentration is about the acetic acid solution of 5000mg/L, adds ZrO
2-CeO
2Catalyst 2.7g stops heating after placing reactor to be heated to 230 ℃, and aerating oxygen to gross pressure is 5MPa, treats that temperature reduces to 230 ℃ and continue heating and holding temperature at 230 ± 3 ℃, and the reaction time is 2h, the results are shown in Figure 1.Find out by Fig. 1, when not using catalyst, wet-type oxidation degradation acetate, behind the reaction 2h, acetate is degraded hardly; When in course of reaction, adding ZrO
2-CeO
2Behind the catalyst, wet-type oxidation degradation acetate, behind the reaction 2h, its COD clearance reaches 76%.
Embodiment two:
The ZrOCl of preparation 0.1mol/L
28H
2Ce (the NO of O and 0.9mol/L
3)
36H
2O mixed solution 50ml and 0.5mol/L ammoniacal liquor 1000ml, salting liquid is slowly dripped in the ammoniacal liquor of vigorous stirring, the gel precipitate that obtains is filtered, and is dispersed in again in the 400ml deionized water, the pH value is transferred to 10 after, 24h refluxes in heat alkali liquid, dry in baking oven then, baking temperature is 100 ℃, places muffle furnace afterwards, 400 ℃ of roasting 6h obtain ZrO in air atmosphere
2-CeO
2Composite oxide catalysts.
Catalyst wet oxidation with method for preparing contains high concentration n-butyric acie waste water then:
Preparation COD concentration is about the n-butyric acie solution of 9000mg/L, adds ZrO
2-CeO
2Catalyst 2.0g stops heating after placing reactor to be heated to 230 ℃, and aerating oxygen to gross pressure is 5MPa, treats that temperature reduces to 230 ℃ and continue heating and holding temperature at 230 ± 3 ℃, and the reaction time is 2h, and the result as shown in Figure 2.As seen from the figure, add ZrO
2-CeO
2During catalyst, behind the reaction 2h, the COD clearance reaches 87%, far above the degradation effect of catalyst-free.
Embodiment three:
The ZrOCl of preparation 0.1mol/L
28H
2Ce (the NO of O and 1.1mol/L
3)
36H
2O mixed solution 50ml and 0.5mol/L ammoniacal liquor 1000ml, salting liquid is slowly dripped in the ammoniacal liquor of vigorous stirring, the gel precipitate that obtains is filtered, and is dispersed in again in the 400ml deionized water, the pH value is transferred to 11 after, 36h refluxes in heat alkali liquid, dry in baking oven then, baking temperature is 80 ℃, places muffle furnace afterwards, 600 ℃ of roasting 8h obtain ZrO in air atmosphere
2-CeO
2Composite oxide catalysts.
Use the catalyst of method for preparing then, remove the test of acetate effect according to the method for testing among the embodiment one, the result shows can obtain removal effect preferably, and the test according to the method for testing among the embodiment two is removed the n-butyric acie effect also can obtain removal effect preferably.
Embodiment four:
The ZrOCl of preparation 0.2mol/L
28H
2Ce (the NO of O and 0.2mol/L
3)
36H
2O mixed solution 250ml and 0.5mol/L ammoniacal liquor 1000ml, salting liquid is slowly dripped in the ammoniacal liquor of vigorous stirring, the gel precipitate that obtains is filtered, and is dispersed in again in the 400ml deionized water, the pH value is transferred to 9 after, 24h refluxes in heat alkali liquid, dry in baking oven then, baking temperature is 120 ℃, places muffle furnace afterwards, 600 ℃ of roasting 3h obtain ZrO in air atmosphere
2-CeO
2Composite oxide catalysts.
Use the catalyst of method for preparing then, remove the test of acetate effect according to the method for testing among the embodiment one, the result shows can obtain removal effect preferably, and the test according to the method for testing among the embodiment two is removed the n-butyric acie effect also can obtain removal effect preferably.
In like manner, when taking Zr (NO
3)
45H
2O, Ce (NO
3)
36H
2Salting liquids such as O, and alkaline solutions such as NaOH solution or KOH solution are during as raw material, the catalyst of taking top preparation method to obtain all can be obtained treatment effect preferably through test.
Claims (3)
1. the application of rare-earth composite oxide catalyst in catalysis wet-type oxidation technology, it is characterized in that: described rare-earth composite oxide catalyst is a solid powdery, component is ZrO
2And CeO
2Composite oxides, the mol ratio of Zr and Ce is 1: 1～1: 11.
2. the application of rare-earth composite oxide catalyst according to claim 1 in catalysis wet-type oxidation technology is characterized in that: at the ZrO of described rare-earth composite oxide catalyst
2And CeO
2In the component, the mol ratio of Zr and Ce is 1: 9.
3. the application of rare-earth composite oxide catalyst according to claim 1 in catalysis wet-type oxidation technology, it is characterized in that, the preparation method of described rare-earth composite oxide catalyst is as follows: the mixed solution of at first preparing zirconates and cerium salt, the molar concentration rate of zirconates and cerium salt is 1: 1～1: 11, adopt coprecipitation, slowly be added drop-wise to mixed solution in the alkaline solution, the volume ratio of mixed solution and alkaline solution is 1: 4～1: 20, the vigorous stirring while dripping is filtered the gel precipitate that obtains; Then described sediment is dispersed in the deionized water again, behind adjusting pH value to 9～11, in heat alkali liquid, refluxed 24～36 hours; In air atmosphere in baking oven dry 24 hours, place muffle furnace afterwards then, 300～600 ℃ of roasting 3～8h obtain ZrO in air atmosphere
2-CeO
2Composite oxide catalysts.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100371071C (en) * | 2005-11-11 | 2008-02-27 | 清华大学 | Granular Ru/Zr Ce O catalyst and its prepn |
| CN101485987B (en) * | 2009-02-25 | 2011-08-10 | 北京林业大学 | Catalyst for normal temperature and pressure catalysis wet-type oxidation technology and preparation method |
| 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 |
| CN102218309A (en) * | 2011-04-15 | 2011-10-19 | 清华大学 | Method for preparing rare-earth cerium oxide composite oxide catalyst for catalyzing ozonation |
| CN102513093B (en) * | 2011-12-01 | 2013-06-12 | 连云港阳方催化科技有限公司 | High-concentration salt-containing wastewater liquid phase oxidation catalyst, preparation method thereof and treatment method |
| CN114425319B (en) * | 2020-10-15 | 2023-08-04 | 中国石油化工股份有限公司 | Wet oxidation catalyst and preparation method thereof |
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Non-Patent Citations (6)
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| CeO2/ZrO2复合氧化物对金属蜂窝整体催化剂性能的影响. 李淑莲等.催化学报，第23卷第4期. 2002 |
| CeO2/ZrO2复合氧化物对金属蜂窝整体催化剂性能的影响. 李淑莲等.催化学报，第23卷第4期. 2002 * |
| 碱液回流老化设备高表面积二氧化锆. 尹双凤等.催化学报，第23卷第3期. 2002 |
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