CN102101053A - Catalyst for treating organic wastewater and preparation method thereof - Google Patents
Catalyst for treating organic wastewater and preparation method thereof Download PDFInfo
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- CN102101053A CN102101053A CN2009101177544A CN200910117754A CN102101053A CN 102101053 A CN102101053 A CN 102101053A CN 2009101177544 A CN2009101177544 A CN 2009101177544A CN 200910117754 A CN200910117754 A CN 200910117754A CN 102101053 A CN102101053 A CN 102101053A
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Abstract
The invention discloses a catalyst for treating organic wastewater and a preparation method thereof. The catalyst is a metal carbonyl loaded catalyst, a precursor of the catalyst is one or a combination of ruthenium carbonyl and cobalt carbonyl, a second component Ce or Fe is added at the same time, and a carrier of the catalyst is selected from one or a compound oxide of active carbon, gamma-Al2O3 and TiO2. The catalyst can be used for oxidizing and degrading different organic matters with various concentrations in water under a milder condition so as to greatly reduce COD (Chemical Oxygen Demand) in wastewater and improve the removal efficiency of the COD in the wastewater.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method that is used to handle organic wastewater, is to handle organic wastewater with supported catalyst under comparatively gentle condition specifically, belongs to water technology and environment functional material field.
Background technology
Along with the fast development of industry, the water environment pollution problem also is on the rise.Especially the development of industries such as medicine, chemical industry, dyestuff makes high concentration hard-degraded organic waste water more and more, is a big difficult point of wastewater treatment.In recent years, developed country all attached great importance to the substitute technology of exploitation innovation in the world, to scheme to improve treatment effeciency and reduction disposal cost.Occur with new vitality so CWO is very fast, it can reduce the needed pressure and temperature of reaction, accelerates reaction rate, thereby carries out extensive and deep research and development in states such as the U.S., Japan, the European Community.
General heterogeneous catalysis mainly is divided into noble metal series and base metal series in the catalytic wet air oxidation.Though non-precious metal catalyst also has certain catalytic activity, the stripping of its catalyst and coking are still unresolved so far.A large amount of noble metal catalyst series that studies show that is handled in the waste water at catalytic wet air oxidation very high activity and stability (Janez Levec, Albin Pintar, Catalysis Today 124 (2007) 172-184).
The wet oxidizing catalyst that is used for wastewater treatment at present is mostly with TiO
2, ZrO
2, CeO
2Deng oxide or composite oxides is carrier, Nippon Shokubai Co., Ltd (CN101045204A) as Japan disclosed " be used for the catalyst of wastewater treatment and use as described in the method for wastewater treatment of catalyst " and CN1498861A disclosed " a kind of CWO is handled the method for high phenol wastewater ", and patent such as US4699720 all is at TiO
2Or ZrO
2And carried noble metal on the composite oxides.A lot of patents and document all are devoted to the preparation of carrier when research supported precious metal catalyst CWO is handled waste water, and noble metal precursor all is chloride and the nitrate of Pt, Pd, Ru, Ir, Rh etc., bullion content is generally higher, the complicated process of preparation of carrier.Because noble metal costs an arm and a leg, the noble metal catalyst of high capacity amount will certainly influence its cost, and the high capacity amount of metal can produce stripping and coking to a certain extent and influence its catalytic activity and life-span.
Metal carbonyl is because it decomposes the noble metal good dispersion that the back produces, and interact with carrier to a certain extent, thereby embody distinguished catalytic activity, it is catalyst precarsor that the metal carbonyl of employing is for example all arranged in synthetic ammonia (CN1193825C), CO methanation researchs such as (US004510267, US004508846).There are a lot of people to study the decomposition mechanism of load metal carbonyl in early days, studied Al as people such as A.Beck, Xueying Zhao, Xu Huizhen
2O
3, ZrO
2, TiO
2Decomposition situation etc. carrier loaded ruthenium.The application study of metal carbonyl aspect catalytic oxidation is not a lot, especially almost do not report aspect sewage disposal.
In the heterogeneous catalytic oxidation process study, find to have synergy mutually between the active component and between active component and the carrier, help improving activity of such catalysts, increase stability.Though load metal carbonyl complex compound catalyst also has very high activity separately, in order further to reduce conditions such as its reaction temperature, pressure, increase the catalytic activity and the stability of catalyst, consider to add second component, make that the load capacity of noble metal is lower.
Summary of the invention
The object of the present invention is to provide a kind of Catalysts and its preparation method that is used to handle high concentrated organic wastewater.
The present invention is catalyst precarsor with the metal carbonyl, a certain amount of rare earth element or transition metal mix, prepare the catalyst of low load capacity, high activity, high stability with simple catalyst preparation process, the CWO that is used for waste water can make the COD in the high concentrated organic wastewater reduce significantly under the condition of gentleness.
A kind of catalyst that is used to handle organic wastewater, it is characterized in that this catalyst is a load metal carbonyl catalyst, catalyst precarsor is a kind of of ruthenium and carbonyl cobalt or their combination, adds second component Ce or the Fe simultaneously, and the carrier of catalyst is selected from active carbon, γ-Al
2O
3, TiO
2In a kind of or their composite oxides; The metallic element weight percentage of catalyst is 0.1～5%, and wherein the weight percentage of noble metal Ru is 0.01～0.3%, and the weight percentage of Ce or Fe is 0.1～5%.
Ruthenium comparative optimization of the present invention be ten dicarbapentaborane, three rutheniums.
Carbonyl cobalt comparative optimization of the present invention be cobalt octacarbonyl.
Preparation of catalysts method of the present invention adopts secondary dipping process, specifically is that first soluble compound with metal Ce or Fe is carried on the carrier 50～120 ℃ of dryings, 200～800 ℃ of roastings; The metal carbonyl complex compound be impregnated on the carrier of Ce or Fe, 50～100 ℃ of dryings are again with 5 ℃/min rising temperature, at N again
2, H
2Or CO
2200～800 ℃ of roastings under the atmosphere.
Adopt catalyst of the present invention that waste water middle and high concentration organic matter is carried out CWO and handle, its operating condition is as follows: catalyst concn is 2.5～50g/L, 90～240 ℃ of reaction temperatures, and reaction pressure 1.0～6.0MPa reacted 1～3 hour.
Catalyst of the present invention can be used for the oxidative degradation of most of organic matters in the waste water or nitrogen-containing compound, wherein is specially isopropyl alcohol, phenol, acetate, N, dinethylformamide (DMF), and the COD concentration range in the waste water is 10
2～10
5Mg/L.
The invention has the advantages that (1) is catalyst with the load metal carbonyl of high dispersive; (2) the Preparation of catalysts method is simple to operation; (3) bullion content is very low in the catalyst, and has high activity, long-life, environment such as high temperature resistant, high pressure; (4) catalyst is applicable to the processing of various different high concentrated organic wastewaters; (5) to handle in the various high concentrated organic wastewaters reaction condition in the catalytic wet oxidation method gentle for catalyst of the present invention, COD clearance height.
The specific embodiment
The invention provides a kind of CWO and handle the catalyst and the preparation method of high concentrated organic wastewater.Adopt this catalyst can be under comparatively gentle condition to water in the different organic matters (for example compounds such as alcohol, phenol, aromatic hydrocarbons, carboxylic acid and itrogenous organic substance) of various high concentrations carry out oxidative degradation, reduce the COD in the waste water significantly, improve the removal efficient of COD in the waste water.
Because the metal carbonyl complex compound decomposition back that is carried on the carrier is dispersed fine, makes it have higher activity.Preparation of catalysts among the present invention is to be precursor with ruthenium and carbonyl cobalt, by the roasting of different atmosphere, can make its complete decomposition, improves the dispersiveness of its metal, further improves its catalytic activity.
In addition, though load metal carbonyl complex compound catalyst also has very high activity separately,, increase the catalytic activity and the stability of catalyst in order further to reduce conditions such as its reaction temperature, pressure, consider to add second component Ce or the Fe, make that the load capacity of noble metal is lower.
The catalytic activity of catalyst of the present invention can be tested with catalytic wet oxidation and be estimated, and contains phenol, isopropyl alcohol, N in the simulated wastewater, typical organic compound such as dinethylformamide (DMF), acetate, and the concentration of preparation is by measuring its COD value control.
Below by embodiment the present invention is described further.
Embodiment 1
Adopt double-steeping to prepare 0.3%Ru/0.6%Ce/C: the 10g active carbon is immersed in the cerous nitrate solution, the room temperature dipping, 110 ℃ of dry 3h, 600 ℃ of roasting 6h make 0.6%Ce/C.And then with the Ru of 0.063g
3(CO)
12Be dissolved in an amount of n-hexane, flood above-mentioned 0.6%Ce/C, 100 ℃ of dry 3h feed N
2Heating rate with 5 ℃/min rises to 500 ℃ of roasting 5h, makes the 0.3%Ru/0.6%Ce/C catalyst.
Above-mentioned catalyst is used to handle isopropyl alcohol simulated wastewater (COD 8g/L), and catalyst concn is 25g/L, aerating oxygen, and stagnation pressure 4.0MPa, reaction temperature is 200 ℃, reaction time 2h.The clearance of COD is 88.3%.
Embodiment 2
Adopt repeatedly dipping preparation 0.2%Ru/3%Co/0.6%Ce/Al-Ti: 10g12～35 purpose Al-Ti carriers (Ti content is 20wt%) are immersed in the cerous nitrate solution, the room temperature dipping, 110 ℃ of dry 3h, 600 ℃ of roasting 6h make 0.6%Ce/Al-Ti.Then with 0.870g Co
2(CO)
8Be dissolved in the n-hexane, flood above-mentioned 0.6%Ce/Al-Ti, 100 ℃ of dry 3h, 300 ℃ of roasting 6h make 3%Co/0.6%Ce/Al-Ti.At last again with 0.042g Ru
3(CO)
12Be dissolved in the n-hexane, flood above-mentioned 3%Co/0.6%Ce/Al-Ti, at 100 ℃ of dry 3h, logical H
2Gas is warming up to 300 ℃ of roasting 5h with 5 ℃/min, makes 0.2%Ru/3%Co/0.6%Ce/Al-Ti.
Above-mentioned catalyst is used to handle isopropyl alcohol simulated wastewater (COD 10g/L), and catalyst concn is 25g/L, aerating oxygen, and stagnation pressure 3.0MPa, reaction temperature is 200 ℃, reaction time 2h.The clearance of COD is 99.3%.
Embodiment 3
Adopt double-steeping to prepare 3%Co/2%Ce/ γ-Al
2O
3: with 10g12～35 purpose γ-Al
2O
3Immerse in the cerous nitrate solution, the room temperature dipping, 110 ℃ of dry 3h, 600 ℃ of roasting 6h make 2%Ce/ γ-Al
2O
3And then with 0.870gCo
2(CO)
8Be dissolved in the n-hexane, flood above-mentioned 2%Ce/ γ-Al
2O
3, the room temperature dipping, at 100 ℃ of dry 3h, logical H
2Gas is warming up to 300 ℃ of roasting 5h with 5 ℃/min, makes 3%Co/2%Ce/ γ-Al
2O
3
Above-mentioned catalyst is used to handle isopropyl alcohol simulated wastewater (COD 8g/L), and catalyst concn is 25g/L, aerating oxygen, and stagnation pressure 5.0MPa, reaction temperature is 220 ℃, reaction time 2h.The clearance of COD is 70.8%.
Embodiment 4
Adopt double-steeping to prepare 0.3%Ru/3%Fe/ γ-Al
2O
3: with 10g12～35 purpose γ-Al
2O
3Immerse in the iron nitrate solution, the room temperature dipping, 110 ℃ of dry 3h, 600 ℃ of roasting 6h make 3%Fe/ γ-Al
2O
3And then with 0.063g Ru
3(CO)
12Be dissolved in the n-hexane, flood above-mentioned 3%Fe/ γ-Al
2O
3, the room temperature dipping, at 100 ℃ of dry 3h, logical CO
2Gas is warming up to 300 ℃ of roasting 5h with 5 ℃/min, makes 0.3%Ru/3%Fe/ γ-Al
2O
3
Above-mentioned catalyst is used to handle isopropyl alcohol simulated wastewater (COD 40g/L), and catalyst concn is 25g/L, aerating oxygen, and stagnation pressure 6.0MPa, reaction temperature is 230 ℃, reaction time 2h.The clearance of COD is 98.8%.
Embodiment 5 to 8
Adopt double-steeping to prepare 0.3%Ru/0.3%Ce/ γ-Al
2O
3: with 10g 12～35 purpose γ-Al
2O
3Immerse in the cerous nitrate solution, the room temperature dipping, 110 ℃ of dry 3h, 600 ℃ of roasting 6h make 0.3%Ce/ γ-Al
2O
3And then ten dicarbapentaborane, three rutheniums of 0.063g are dissolved in the n-hexane, flood above-mentioned 0.3%Ce/ γ-Al
2O
3, 100 ℃ of dry 3h feed H
2Heating rate with 5 ℃/min rises to 500 ℃ of roasting 5h, makes 0.3%Ru/0.3%Ce/ γ-Al
2O
3Catalyst.
Above-mentioned catalyst is used for processing contains different organic simulated wastewaters (COD 10g/L), catalyst concn is 25g/L, aerating oxygen, stagnation pressure 5.0MPa, reaction time 2h.The clearance of COD sees Table 1.
Table 1
| Organic matter in the water | Reaction temperature (℃) | COD clearance (%) | |
| Embodiment 5 | Phenol | 110 | 99.6 |
| Embodiment 6 | Isopropyl alcohol | 200 | 99.2 |
| Embodiment 7 | DMF | 230 | 85.1 |
| Embodiment 8 | Acetate | 200 | 98.5 |
Claims (4)
1. catalyst that is used to handle organic wastewater, it is characterized in that this catalyst is a load metal carbonyl catalyst, catalyst precarsor is a kind of of ruthenium and carbonyl cobalt or their combination, adds second component Ce or the Fe simultaneously, and the carrier of catalyst is selected from active carbon, γ-Al
2O
3, TiO
2In a kind of or their composite oxides; The metallic element weight percentage of catalyst is 0.1～5%, and wherein the weight percentage of noble metal Ru is 0.01～0.3%, and the weight percentage of Ce or Fe is 0.1～5%.
2. catalyst as claimed in claim 1 is characterized in that ruthenium is ten dicarbapentaborane, three rutheniums.
3. catalyst as claimed in claim 1 is characterized in that carbonyl cobalt is a cobalt octacarbonyl.
4. Preparation of catalysts method according to claim 1 is characterized in that earlier the soluble compound of metal Ce or Fe is carried on the carrier 50～120 ℃ of dryings, 200～800 ℃ of roastings; The metal carbonyl complex compound be impregnated on the carrier of Ce or Fe, 50～100 ℃ of dryings are again with 5 ℃/min rising temperature, at N again
2, H
2Or CO
2200～800 ℃ of roastings under the atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101177544A CN102101053A (en) | 2009-12-18 | 2009-12-18 | Catalyst for treating organic wastewater and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101177544A CN102101053A (en) | 2009-12-18 | 2009-12-18 | Catalyst for treating organic wastewater and preparation method thereof |
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| Publication Number | Publication Date |
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Family
ID=44154233
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102372344A (en) * | 2011-10-18 | 2012-03-14 | 中国石油化工集团公司 | Method for carrying out FeCl2/C-Cu catalytic hydrolysis on aniline and nitrobenzene biochemical wastewater |
| CN103848492A (en) * | 2012-12-06 | 2014-06-11 | 中国科学院兰州化学物理研究所 | Method for treating high-concentration mixed organic wastewater via continuous air oxidation method |
| CN104671386A (en) * | 2013-11-29 | 2015-06-03 | 中国科学院兰州化学物理研究所 | Water treatment method for continuously degrading high concentration macromolecular compounds in water |
| CN105964308A (en) * | 2016-05-27 | 2016-09-28 | 东莞市联洲知识产权运营管理有限公司 | Preparation method of carrier material for catalyst for sewage treatment |
| CN105967311A (en) * | 2015-04-09 | 2016-09-28 | 江苏九九久科技股份有限公司 | Simple-process 3,5,6-trichloropyridine-2-sodium alcoholate wastewater processing method |
| CN106582711A (en) * | 2016-11-25 | 2017-04-26 | 南宁市黑晶信息技术有限公司 | Wastewater precipitation and purification method |
| CN106745958A (en) * | 2016-11-25 | 2017-05-31 | 南宁市黑晶信息技术有限公司 | A kind of method for processing organic wastewater |
| CN106975488A (en) * | 2016-01-15 | 2017-07-25 | 上海乐泽环境工程有限公司 | It is a kind of that aluminium-nano-TiO is activated with Ni-2For the efficient elctro-catalyst of active centre |
| CN109701551A (en) * | 2018-12-12 | 2019-05-03 | 佛山科学技术学院 | A kind of loaded catalyst and preparation method thereof, treatment method of printing and dying wastewater |
| CN111420665A (en) * | 2020-04-26 | 2020-07-17 | 万华化学集团股份有限公司 | Modified Fenton-like catalyst, preparation method and application |
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2009
- 2009-12-18 CN CN2009101177544A patent/CN102101053A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102372344A (en) * | 2011-10-18 | 2012-03-14 | 中国石油化工集团公司 | Method for carrying out FeCl2/C-Cu catalytic hydrolysis on aniline and nitrobenzene biochemical wastewater |
| CN102372344B (en) * | 2011-10-18 | 2013-05-01 | 中国石油化工集团公司 | Method for carrying out FeCl2/C-Cu catalytic hydrolysis on aniline and nitrobenzene biochemical wastewater |
| CN103848492A (en) * | 2012-12-06 | 2014-06-11 | 中国科学院兰州化学物理研究所 | Method for treating high-concentration mixed organic wastewater via continuous air oxidation method |
| CN104671386A (en) * | 2013-11-29 | 2015-06-03 | 中国科学院兰州化学物理研究所 | Water treatment method for continuously degrading high concentration macromolecular compounds in water |
| CN105967311B (en) * | 2015-04-09 | 2018-09-11 | 江苏九九久科技有限公司 | The processing method of the simple 3,5,6- trichloropyridines -2- sodium alkoxide waste water of flow |
| CN105967311A (en) * | 2015-04-09 | 2016-09-28 | 江苏九九久科技股份有限公司 | Simple-process 3,5,6-trichloropyridine-2-sodium alcoholate wastewater processing method |
| CN106975488A (en) * | 2016-01-15 | 2017-07-25 | 上海乐泽环境工程有限公司 | It is a kind of that aluminium-nano-TiO is activated with Ni-2For the efficient elctro-catalyst of active centre |
| CN105964308A (en) * | 2016-05-27 | 2016-09-28 | 东莞市联洲知识产权运营管理有限公司 | Preparation method of carrier material for catalyst for sewage treatment |
| CN106582711A (en) * | 2016-11-25 | 2017-04-26 | 南宁市黑晶信息技术有限公司 | Wastewater precipitation and purification method |
| CN106745958A (en) * | 2016-11-25 | 2017-05-31 | 南宁市黑晶信息技术有限公司 | A kind of method for processing organic wastewater |
| CN109701551A (en) * | 2018-12-12 | 2019-05-03 | 佛山科学技术学院 | A kind of loaded catalyst and preparation method thereof, treatment method of printing and dying wastewater |
| CN111420665A (en) * | 2020-04-26 | 2020-07-17 | 万华化学集团股份有限公司 | Modified Fenton-like catalyst, preparation method and application |
| CN111420665B (en) * | 2020-04-26 | 2022-09-20 | 万华化学集团股份有限公司 | Modified Fenton-like catalyst, preparation method and application |
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Application publication date: 20110622 |