CN1342522A - Catalyst for eliminating haloaromatic contaminant by catalytic combustion - Google Patents
Catalyst for eliminating haloaromatic contaminant by catalytic combustion Download PDFInfo
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- CN1342522A CN1342522A CN 00122988 CN00122988A CN1342522A CN 1342522 A CN1342522 A CN 1342522A CN 00122988 CN00122988 CN 00122988 CN 00122988 A CN00122988 A CN 00122988A CN 1342522 A CN1342522 A CN 1342522A
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- tio
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Abstract
A catalyst for eliminating haloaromatic contaminant by catalytic combustion is composed of composite TiO2-Al2O3 carrier, manganese oxide as active component (0.1-0.3 wt.%), and transition metal M as assistant (0.1-20 wt.%) chosen from one or several kinds of Cu, V, Ce, Fe, Mo, Zn and Ni. It features high performance to catalytic condustion of chlorobenzene of dichlorobenzene.
Description
The present invention relates to a kind of based on TiO
2-Al
2O
3The manganese Base Metal oxide catalyst of complex carrier and other carrier is used for complete catalytic oxidation and eliminates environment halogenated aromatic pollutant, and relates to such Preparation of catalysts method.
The conventional method of eliminating the halogenated aromatic pollutant is direct flame combustion, this method often needs 1000 ℃ even higher ignition temperature, caused the more generation of high toxicity pollutant (Duo chlorodiphenyl Bing bioxin (PCDD) and polychlorinated dibenzo (PCDF), general designation bioxin (Dioxins)).Catalytic combustion can carry out under lower temperature, it is a kind of energy-conservation, economic, effective processing method, the more important thing is that this method can handle the organic pollution of content very low (＜1%) effectively, and this organic pollution can not be handled not having under the situation of extra fuel with direct flame combustion.Therefore, catalytic combustion is considered to " end-of-pipe " the most feasible pollutant processing method.
In general, noble metal catalyst has very high complete catalytic combustion activity to volatile organic contaminant, yet, they are eliminated for the catalytic oxidation of halogenated aromatic pollutant, and but effect is bad, this mainly is because the poisoning that halogen that the halogenated aromatic pollutant produces in the process of catalytic combustion or hydrogen halides cause noble metal catalyst, thereby catalyst activity is reduced even lose activity (Catal.Today 11 (1992) 465 for J.J.Spivey, J.B.Butt).Therefore, people shift to metal oxide catalyst to interest, for example Cr
2O
3, CuO, U
3O
8, Co
3O
4, WO
3, TiO
2, V
2O
5Deng (U.S.Patent 3 972 979; U.S.Patent 4 053557; U.S.Patent 5 283 041; G.J.Hutchings, C.S.Heneghan, I.D.Hudson, S.H.Taylor, Nature 384 (1996) 341; S.L.Hung, L.D.Pferfferle, Environ.Sci.Tech.23 (9) (1989) 1085; P.Subbanna, H.Greene, F.Desal, Environ. Sci.Technol.22 (1988) 557; S.Krishnamoorthy, M.D.Amiridis, Catal.Today 51 (1999) 203).
Manganese oxide catalyst is as one of the most effective combustion catalyst (A.Nishino, Catal.Today, 10 (1991) 107; H.G.Stenger, G.E.Buzan, J.M.Berty, Appl.Catal.B, 2 (1993) 117), also receiving increasing concern (U.S.Patent 5,283 041) aspect the catalytic combustion elimination of halogenated aromatic pollutant.We have also carried out research work (Yan Liu, Mengfei Luo, ZhaobinWei, et al., Appl.Catal.B, the in press of this respect; Chinese patent, application number 00 1 10236.2).
The object of the present invention is to provide a kind of based on TiO
2-Al
2O
3Manganese Base Metal oxide catalyst of complex carrier and other carrier and preparation method thereof, its catalytic activity height, anti-halogen poisoning capability are strong, are particularly suitable for complete catalytic combustion and eliminate halogenated organic pollutant, especially halogenated aromatic pollutant.
The catalytic combustion that the invention provides a kind of halogenated aromatic pollutant is eliminated catalyst, is made up of carrier and active component, and it is characterized in that: carrier is TiO
2-Al
2O
3Complex carrier, TiO
2Disperse to be covered in Al
2O
3The surface, TiO
2Content accounts for 0.1～50% of vehicle weight, preferably accounts for 3～40% of vehicle weight; Active component is a manganese oxide, and loading is 0.1～30%wt.
Can also add the transition metal M that appraises at the current rate among the present invention is auxiliary agent, and M is selected from one or more of Cu, V, Ce, Fe, Mo, Zn, Ni, and loading is 0.1～20%wt.
The present invention also provides the catalytic combustion of above-mentioned halogenated aromatic pollutant to eliminate the Preparation of catalysts method, it is characterized in that: in the preparation of carrier, and TiO
2Introduce Al by the method that the titanium species precursor disperses
2O
3The surface; Active component adopts the dipping method preparation, and the active component precursor is selected from nitrate, oxalates, acetate, hydroxide, the carbonate of manganese metal or metal M, and maceration extract is the aqueous solution or the ammonia spirit of metallic salt
Below by example the present invention is given to illustrate in further detail.
Example 1
TiO
2-Al
2O
3The preparation of complex carrier:
Titanium precursors such as a certain amount of butyl titanate, titanyl sulfate or titanium tetrachloride are made into the ethanol or the aqueous solution, insert Al
2O
3Carrier, in Rotary Evaporators dipping, behind the evaporate to dryness, separate in water in air and to spend the night, after oven dry, the roasting, can make TiO again
2-Al
2O
3Complex carrier.Look TiO
2What of content are made the TiO of different coverages respectively
2-Al
2O
3Complex carrier.TA-0.25, TA-0.5, TA-1.0.TA-1.5 represent Al
2O
3TiO on the carrier
2Overlay capacity be respectively 4.25wt%, 8.5wt%, 17wt%, 23.5wt%.
Example 2
Metallic salt is mixed with maceration extract in the water-soluble or ammoniacal liquor, adds TiO
2-Al
2O
3, Al
2O
3, SiO
2, TiO
2, CeO
2Or ceramic honeycomb, to flood according to a conventional method, after the oven dry, roasting, the difference of looking catalyst precarsor is made one pack system or bi-component supported manganese Base Metal oxide catalyst respectively.
Example 3
The complete catalytic combustion properties evaluation of halogenated aromatic pollutant is carried out in atmospheric fixed bed quartz tube reactor.1.0 milliliters of catalyst amounts, granularity 40-60 order, halogenated organic aromatic hydrocarbons pollutant pass through inert gas (as N
2, Ar etc.) bubbling brings beds (content of chlorobenzene or dichloro-benzenes is 1300ppm) into, used oxidant is an oxygen, gas space velocity is 8000h
-1Studied the complete catalytic combustion properties of chlorobenzene of the manganese-based catalyst of different carriers load, test result is listed in table 1.
The catalytic performance of the manganese-based catalyst catalysis chlorobenzene completing combustion of table 1 different carriers load
Chlorobenzene?conv.(％Catalyst
Temperature(℃)
200 250 300 350 400 450 500 550 MnO
x/ SiO
20000 50.60 98.41 100 MnO
x/ Al
2O
36.74 20.34 17.4 21.8 59.43 99.2 100 MnO
x/ TiO
26.77 37.18 52.76 61.69 100 MnO
x/ CeO
255.26 91.90 97.10 98.99 100MnO
x/ ceramic honeycomb 8.11 10.40 16.14 34.01 73.49 100 MnO
x/ TA-1 1.87 3.43 54.36 96.94 100
The result shows, with TiO
2, CeO
2, TiO
2-Al
2O
3For the manganese-based catalyst of carrier all has catalytic activity preferably, wherein with CeO
2Active best for the manganese-based catalyst of carrier, especially low temperature active.But this catalyst has a certain amount of polystream accessory substance to generate in the catalytic oxidation process of chlorobenzene, therefore, is not desirable complete catalyst for catalytic combustion.With TiO
2-Al
2O
3For the activity of the manganese-based catalyst of carrier is better than separately with TiO
2And Al
2O
3Manganese-based catalyst for carrier.
Example 4
Manganese-based catalyst to the different loads amount under the reaction condition identical with example 3 has carried out the complete catalytic combustion experiment of chlorobenzene, and its comparative result is listed in table 2.
The complete catalytic combustion properties of chlorobenzene of table 2 different loads amount manganese-based catalyst
Chlorobenzene?conv.(％)Catalyst
Temperature(℃)
200 250 300 350 400 450Mn(1.9)-TA-1 0 1.2 31.14 73.94 99.5 100Mn(3.2)-TA-1 1.87 3.43 54.36 96.94 100Mn(4.5)-TA-1 7.89 13.07 65.82 99.61 100Mn(5.8)-TA-1 25.24 47.91 92.17 100Mn(6.3)-TA-1 20.24 59.07 100Mn(9.6)-TA-1 36.79 74.70 100
The result shows that the increase of active component content can improve the complete catalytic combustion properties of chlorobenzene of catalyst effectively.
Example 5
Under the reaction condition identical, investigated different Ti O with example 3
2-Al
2O
3The carrier loaded complete catalytic combustion properties of manganese-based catalyst o-dichlorohenzene the results are shown in Table 3.
The complete catalytic combustion properties of manganese-based catalyst o-dichlorohenzene of table 3 different carriers load
o-Dichlorobenzene?conv.(％)Catalyst
Temperature(℃)
200 250 300 350 400 450Mn(5)-TA-0.25 21.78 49.76 96.56 99.5 100Mn(5)-TA-0.5 21.08 50.93 96.51 100Mn(5)-TA-1 31.67 69.40 99.70 100Mn(5)-TA-1.5 22.38 62.47 99.12 100
The result shows, different amount TiO
2The TiO that modifies
2-Al
2O
3Carrier loaded manganese-based catalyst is also little to the influence of the complete catalytic combustion properties of o-dichlorohenzene.
Example 6
Under the reaction condition identical with example 3, investigated the complete catalytic combustion properties of manganese-based catalyst o-dichlorohenzene of different loads amount, the results are shown in Table 4.
The complete catalytic combustion properties of o-dichlorohenzene of table 4 different loads amount manganese-based catalyst
o-Dichlorobenzene?conv.(％)Catalyst
Temperature(℃)
200 250 300 350 400 450Mn (1)-TA-1 10.50 31.47 56.30 87.27 99.30 100Mn (3)-TA-1 19.99 46.43 90.55 99.2 100Mn (5)-TA-1 31.67 69.40 99.70 100Mn (7)-TA-1 46.00 95.07 100Mn (12)-100Mn (15)-TA-1 88.25 100 as seen for TA-1 57.76 99.19, manganese-based catalyst also has extraordinary complete catalytic combustion properties to o-dichlorohenzene, get final product complete catalytic combustion under quite low temperature, the experimental result of gained is apparently higher than bibliographical information.
Comparative example 1
Precious metals pt/Al
2O
3Catalyst (0.6ml), at 0.1MPa, 10000h
-1, in the feeding gas under the reaction condition of chlorobenzene concentration 1000ppm, chlorobenzene is in 400 ℃ of catalytic combustions fully.And accessory substance generations such as phenyl polychloride are arranged in the combustion process.(seeing document Ruud W.van den Brink, Robert Louw, PeterMulder, Appl.Catal.B, 16,219 (1998)).
Comparative example 2
V
2O
5/ TiO
2Catalyst (0.5g), at 0.1MPa, 450scm
3/ min, under the reaction condition of dichloro-benzenes concentration 600ppm, dichloro-benzenes only is about 95% in 450 ℃ conversion ratio in the feeding gas.(seeing document S.Krishnamoorthy, J.P.Baker, M.D.Amiridis, Catal.Today, 40,39 (1998)).
Claims (4)
1, a kind of catalytic combustion of halogenated aromatic pollutant is eliminated catalyst, is made up of carrier and active component, and it is characterized in that: carrier is TiO
2-Al
2O
3Complex carrier, TiO
2Disperse to be covered in Al
2O
3The surface, TiO
2Content accounts for 0.1～50% of vehicle weight; Active component is a manganese oxide, and loading is 0.1～30%wt.
2, eliminate catalyst according to the catalytic combustion of the described halogenated aromatic pollutant of claim 1, it is characterized in that: adding the transition metal M that appraises at the current rate is auxiliary agent, M is selected from one or more of Cu, V, Ce, Fe, Mo, Zn, Ni, and loading is 0.1～20%wt.
3, eliminate catalyst according to the catalytic combustion of the described halogenated aromatic pollutant of claim 1, it is characterized in that: TiO
2Content accounts for 3～40% of vehicle weight.
4, the catalytic combustion of the described halogenated aromatic pollutant of a kind of claim 1 is eliminated the Preparation of catalysts method, it is characterized in that: in the preparation of carrier, and TiO
2Introduce Al by the method that the titanium species precursor disperses
2O
3The surface; Active component adopts the dipping method preparation, and the active component precursor is selected from nitrate, oxalates, acetate, hydroxide, the carbonate of manganese metal or metal M, and maceration extract is the aqueous solution or the ammonia spirit of metallic salt.
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|---|---|---|---|
| CNB001229885A CN1170636C (en) | 2000-09-13 | 2000-09-13 | Catalyst for eliminating haloaromatic contaminant by catalytic combustion |
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|---|---|---|---|
| CNB001229885A CN1170636C (en) | 2000-09-13 | 2000-09-13 | Catalyst for eliminating haloaromatic contaminant by catalytic combustion |
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|---|---|
| CN1342522A true CN1342522A (en) | 2002-04-03 |
| CN1170636C CN1170636C (en) | 2004-10-13 |
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|---|---|---|---|
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101703932B (en) * | 2009-10-23 | 2011-07-27 | 北京工业大学 | Method for preparing Pd and Pt loaded mesoporous manganese oxide for catalytically eliminating VOCs |
| CN102698751A (en) * | 2012-06-26 | 2012-10-03 | 华东理工大学 | Catalyst for eliminating chlorine-containing volatile organic compounds by low-temperature catalytic combustion |
| CN103357415A (en) * | 2013-06-27 | 2013-10-23 | 浙江工业大学 | Catalyst for catalytic combustion of chlorine-containing organic waste gas |
| CN103801323A (en) * | 2014-01-06 | 2014-05-21 | 中国科学院过程工程研究所 | Catalyst for controlling nitric oxide and chlorinated benzenes pollutants in coupling manner, preparation method and application thereof |
| CN106215950A (en) * | 2016-07-18 | 2016-12-14 | 浙江师范大学 | A kind of for catalyst eliminating chlorinated organics and preparation method thereof |
| CN111203241A (en) * | 2020-02-16 | 2020-05-29 | 山东迅达化工集团有限公司 | Organic chlorine-containing waste gas treatment catalyst and preparation method thereof |
| CN114425313A (en) * | 2020-10-14 | 2022-05-03 | 中国石油化工股份有限公司 | Titanium dioxide-aluminum oxide composite oxide and preparation and application thereof |
-
2000
- 2000-09-13 CN CNB001229885A patent/CN1170636C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101703932B (en) * | 2009-10-23 | 2011-07-27 | 北京工业大学 | Method for preparing Pd and Pt loaded mesoporous manganese oxide for catalytically eliminating VOCs |
| CN102698751A (en) * | 2012-06-26 | 2012-10-03 | 华东理工大学 | Catalyst for eliminating chlorine-containing volatile organic compounds by low-temperature catalytic combustion |
| CN103357415A (en) * | 2013-06-27 | 2013-10-23 | 浙江工业大学 | Catalyst for catalytic combustion of chlorine-containing organic waste gas |
| CN103357415B (en) * | 2013-06-27 | 2015-06-03 | 浙江工业大学 | Catalyst for catalytic combustion of chlorine-containing organic waste gas |
| CN103801323A (en) * | 2014-01-06 | 2014-05-21 | 中国科学院过程工程研究所 | Catalyst for controlling nitric oxide and chlorinated benzenes pollutants in coupling manner, preparation method and application thereof |
| CN106215950A (en) * | 2016-07-18 | 2016-12-14 | 浙江师范大学 | A kind of for catalyst eliminating chlorinated organics and preparation method thereof |
| CN106215950B (en) * | 2016-07-18 | 2018-10-26 | 浙江师范大学 | It is a kind of to be used to eliminate catalyst of chlorinated organics and preparation method thereof |
| CN111203241A (en) * | 2020-02-16 | 2020-05-29 | 山东迅达化工集团有限公司 | Organic chlorine-containing waste gas treatment catalyst and preparation method thereof |
| CN111203241B (en) * | 2020-02-16 | 2022-05-27 | 山东迅达化工集团有限公司 | Organic chlorine-containing waste gas treatment catalyst and preparation method thereof |
| CN114425313A (en) * | 2020-10-14 | 2022-05-03 | 中国石油化工股份有限公司 | Titanium dioxide-aluminum oxide composite oxide and preparation and application thereof |
| CN114425313B (en) * | 2020-10-14 | 2023-09-29 | 中国石油化工股份有限公司 | Titanium dioxide-aluminum oxide composite oxide and preparation and application thereof |
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|---|---|
| CN1170636C (en) | 2004-10-13 |
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