CN1157255C - Metal oxide catalyst for clearing halogenated aromatic through catalytic oxidation - Google Patents
Metal oxide catalyst for clearing halogenated aromatic through catalytic oxidation Download PDFInfo
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- CN1157255C CN1157255C CNB001102362A CN00110236A CN1157255C CN 1157255 C CN1157255 C CN 1157255C CN B001102362 A CNB001102362 A CN B001102362A CN 00110236 A CN00110236 A CN 00110236A CN 1157255 C CN1157255 C CN 1157255C
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- catalyst
- metal oxide
- oxide catalyst
- catalytic oxidation
- active component
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Abstract
The present invention relates to a metal oxide catalyst which is used for eliminating organic halogenated aryl hydrocarbon pollutants by catalytic combustion. The present invention is composed of a carrier and an active constituent, wherein the carrier is one or some of Al2O3, SiO2, TiO2, ZrO2 and CeO2; the active constituent is a valence-alternated transition metal element M which is one or some of Cu, Mn, V, Ce, Fe, Mo, W, Zn, Ni and Co, and the carrying capacity of the active constituent is from 0.1 to 30 wt%. The present invention has high catalytic activity and strong halogen poisoning resistance, and is particularly suitable for eliminating organic halogenated aryl hydrocarbon pollutants, particularly aromatic organic halogenated aryl hydrocarbon pollutants, by complete catalytic combustion.
Description
The present invention relates to the load metal oxide catalyst, provide a kind of especially and be used for the halogenated organic aromatic hydrocarbons pollutant that complete catalytic combustion is eliminated environment, and related to the catalyst of the complete catalytic combustion elimination process of halogenated organic aromatic hydrocarbons pollutant in waste gas, refuse, the waste water.
In recent years, the comprehensive regulation to volatile organic contaminant has received increasing concern.Flame combustion, catalytic combustion and absorption are to eliminate these pollutants method commonly used.Flame combustion need carry out under high temperature, and one-time investment is very big; If there is halogenated organic aromatic hydrocarbons pollutant to exist in the gas phase, flame combustion can also cause the more generation of high toxicity pollutant (Duo chlorodiphenyl Bing bioxin (PCDD) and polychlorinated dibenzo (PCDF), general designation bioxin (Dioxins)).In some cases, be that adsorbent adsorbs pollutant with the active carbon also be one of alternative processing method, still, this processing method only is to collect pollutant, but can not destroy their structure, and adsorption efficiency also is subjected to having a strong impact on of the fluctuation of pollutant levels in the fluid.
Advantages such as it is a kind of energy-conservation, economic, effective processing method that catalytic combustion is eliminated organic pollution, compares with flame combustion, and it has, and ignition temperature is low, the time of staying short, required reactor is little, and, also lower to the requirement of reactor material.
Catalytic combustion is used to eliminate halogenated organic aromatic hydrocarbons pollutant and is of long duration.As far back as 1975, G.C.Bond and N.Sadeghi delivered the article that is entitled as " CatalyzedDestruction of Chlorinated Hydrocarbons " just at J.Appl.Chem.Biotechnol.24 on the 241-248, reported Pt/ γ-Al
2O
3Catalyst is used for the catalytic combustion chlorohydrocarbon and generates HCl and CO
2Situation.
U.S.Patent 3 972 979 and 4 053 557 has narrated CrO
3Or the Pt catalyst of boehmite load is used for the situation of halogenated hydrocarbons catalytic combustion.
1987, Ind.Eng.Chem.Res. also delivered on the magazine and be entitled as " Complete Catalytic Oxidationof Volatile Organics " (James J.Spivy, 26,2165-2180 (1987)) survey article describes the result of study about heterogeneous catalysis burning elimination volatile organic contaminant in detail.
" Oxidative Catalysis of Chlorinated Hydrocarbons by Metal-Loaded AcidCatalysts (S.Chatterjee and H.L. Greene; J.Catal.; 130,76-85 (1991)) has reported that carried molecular sieve catalyst catalysis vinyl chloride carries out completing combustion in air.
U.S.Patent 4 059 675, and 4 059 676 and 4 059 683 have narrated halogenated hydrocarbons at Ru, carry out combustion decomposition on the noble metal catalysts such as Ru-Pt and Pt, and its minimum completing combustion temperature is 350 ℃.
U.S.Patent 5 283 041 has disclosed a kind of catalyst that is used for halogenated hydrocarbons and other organic matter or its mixture completing combustion, and catalyst is with ZrO
2With one or more oxides of Mn, Ce, Co, V be carrier, the platinum family element of high dispersive is an active component.
The object of the present invention is to provide a kind of metal oxide catalyst that is used for the elimination of halogenated organic aromatic hydrocarbons pollutant catalytic combustion and preparation method thereof, its catalytic activity height, anti-halogen poisoning capability are strong, be particularly suitable for complete catalytic combustion and eliminate halogenated organic aromatic hydrocarbons pollutant, especially aromatics halogenated organic aromatic hydrocarbons pollutant.
The invention provides the catalytic combustion elimination that a kind of metal oxide catalyst is used for halogenated organic aromatic hydrocarbons pollutant, be made up of carrier and active component, carrier is selected from Al
2O
3, SiO
2, TiO
2, ZrO
2, CeO
2One or more, active component is that the transition metal M that appraises at the current rate is selected from one or more of Mn, Ce, Fe, Zn; The active component loading is 0.1～30%wt; Be selected from Al at carrier
2O
3, SiO
2, ZrO
2, CeO
2The time, transition metal M can also be one or more of Cu, Co.
Catalyst activity component of the present invention adopts the preparation of incipient impregnation method.The active component precursor is selected from nitrate, oxalates, acetate, hydroxide, the carbonate of metal M; Maceration extract is the aqueous solution or the ammonia spirit of metallic salt.Bicomponent catalyst provided by the invention adopts equal-volume dipping method preparation altogether.
The halogenated organic aromatic compound is the pollutant that class harm is very big, chemical stability is very strong.Not only have strong toxicity, refractory organics, and have very strong biological concentration, extensively exist in waste gas, refuse, waste water, its content is generally ppm, the ppb order of magnitude, and the concentration of pollutant is very low, recycles relatively difficulty, uneconomical.Therefore, the invention provides following technology path and be used for the elimination that halogenated organic aromatic hydrocarbons pollutes.
1. technology path and the embodiment that halogenated organic aromatic hydrocarbons pollutant is eliminated in the gas phase
Traditional removing method of solid waste is directly burning in incinerator, and ignition temperature generally surpasses 1273K, and in this process, the existence of Halogen pollutant can cause the more generation of high toxicity accessory substance bioxin.Therefore, the technology path that the halogenated organic aromatic hydrocarbons pollutant in refuse, the waste gas is eliminated can reduce the elimination of halogenated organic aromatic hydrocarbons pollutant in the gas phase, the invention provides following technology path:
Before the tail gas emptying of industrial waste gas and incinerator, add a catalytic combustion burner, make the completing combustion under the effect of catalyst of halogenated organic aromatic hydrocarbons pollutant.This process need not any separation means, and method is effective and feasible, and the environmental pollution that halogenated organic aromatic hydrocarbons pollutant causes is extremely important for alleviating even eliminating.Combustion furnace tail gas can absorb (HCl/Cl by sig water
2Deng sour gas) back emptying.
2. technology path and the embodiment that halogenated organic aromatic hydrocarbons pollutant is eliminated in the waste water
Halogenated organic aromatic hydrocarbons pollutant load in the waste water is very low, eliminates with catalytic oxidation if adopt directly to heat up, need be with the main component-water in the waste water-also be heated to equivalent temperature, because the thermal capacitance of water is very big, therefore, need to supply with sizable heat, energy consumption height; On the other hand, water does not change in whole catalytic oxidation process, there is no need water is heated to equivalent temperature yet.Therefore, the invention provides following technology path:
Earlier with the halogenated aromatic organic pollution with suitable adsorbent, as high-ratio surface materials such as active carbons, adsorbing separation from waste water makes its desorption with inert gas then under heating condition, and brings catalytic combustion burner into and make its completing combustion.Tail gas can absorb back emptying by sig water.
Characteristics such as that metal oxide catalyst provided by the invention has is cheap, catalytic activity is high, anti-halogen poisoning capability is strong; Technology path is convenient and practical, except that catalytic combustion burner, substantially do not need additional investment, can be widely used in the complete catalytic combustion elimination of halogenated organic aromatic hydrocarbons pollutant in papermaking, pharmacy, printing and dyeing industry and chemical industry and petrochemical industry waste gas, refuse, the waste water.
Accompanying drawing 1 concerns over time for the catalytic performance of catalyst.
Below by example the present invention is given to illustrate in further detail.
Example 1
Metallic salt is mixed with maceration extract in the water-soluble or ammoniacal liquor, adds Al
2O
3, SiO
2, TiO
2, ZrO
2Or CeO
2, fully stir dipping and spend the night; Then, under stirring condition, in the water-bath with the maceration extract evaporate to dryness, in 130 ℃ of bakings 3 hours, 500 ℃ of roastings 2 hours.Look the difference of catalyst precarsor, make one pack system or bi-component supported metal oxide catalyst respectively.
Example 2
The complete catalytic combustion properties evaluation of halogenated organic aromatic hydrocarbons pollutant is carried out in atmospheric fixed bed quartz tube reactor.0.5 milliliter of catalyst amount, granularity 40～60 orders, halogenated organic aromatic hydrocarbons pollutant pass through inert gas (as N
2, Ar etc.) bubbling brings beds (chlorobenzene content 1300ppm) into, used oxidant is an oxygen, gas space velocity is 8000h
-1Studied the complete catalytic combustion properties of chlorobenzene of different catalysts under the reaction condition identical with example 2, test result is listed in table 1.
The performance of the complete catalytic combustion of chlorobenzene on table 1 different catalysts
Chlorobenzene?conv.(％)
Catalyst Temperature(℃)
200 250 300 350 400 450 500 550 600
Fe/Al
2O
3 9.5 16.3 20.3 22.6 37.7 56 83.3 93.8 100
Zn/Al
2O
3 1.01 4.69 2.75 4.47 24.45 50.03 49.64 71.58 77.88
Cu/Al
2O
3 3.7 5.1 24.09 40.61 73.93 98.61 100
Ni/Al
2O
3 2.13 6.28 11.4 25.08 59.4 60.7 92.12 97.58
Mn/Al
2O
3 8.3 12.6 37.2 63.2 93.4 100
Mo/Al
2O
3 0 0 0 2.98 22.6 25.74 50.28 77.48
The result shows that Mn, Cu, Fe catalyst have reasonable catalytic performance, modifies the combustion catalyst that available can be good by different modulations and catalyst.
Example 3
Mn catalyst to the different carriers load under the reaction condition identical with example 2 has carried out the complete catalytic combustion experiment of chlorobenzene, and its comparative result is listed in table 2.
Table 2 carrier is to Mn catalyst chlorobenzene completing combustion Effect on Performance
Chlorobenzene?conv.(％)
Catalyst Temperature(℃)
200 250 300 350 400 450 500 550
MnO
2/SiO
2 0 0 0 0 50.60 98.41 100
MnO
2/Al
2O
3?8.3 12.6 37.2 63.2 93.4 100
MnO
2/TiO
2 6.77 37.18 52.76 61.69 100
The result shows, with TiO
2For the Mn catalyst of carrier has higher catalytic performance.
Example 4
Under the reaction condition identical with example 2, investigated the catalytic combustion properties of bi-component supported catalyst, the results are shown in Table 3.
The catalytic combustion properties of table 3 bicomponent catalyst
Chlorobenzene?conv.(％)
Catalyst Temperature(℃)
200 250 300 350 400
Mn-Cu/TiO
2 10.89 40.6 73.84 99.16 100
Mn-Ce/TiO
2 0.83 24.96 62.62 74.52 100
Mn-V/TiO
2 0 20.19 33.92 75.2 100
As seen, can obviously change the low temperature active of catalytic combustion properties, the especially catalyst of catalyst by the adding of second component, this commercial Application for combustion catalyst is very important beyond doubt.
Example 5
Change the concentration of halogenated organic aromatic hydrocarbons pollutant in the reaction system, other condition is with example 2, studied the catalytic performance of the urging situation of change with pollutant levels, the results are shown in Table 4.
The catalytic performance of table 4 catalyst is with the situation of change of pollutant levels
Chlorobenzene?conv.(％)
CB?content Temperature(℃)
(ppm)
200 250 300 350 400 450
1300 1.67 30.91 55.44 65.26 100
2300 6.79 19.56 35.57 43.4 91.27 100
3000 0 10.98 22.28 26.55 72.09 100
4100 0 3.86 11.69 26.08 58.69 100
Example 6
Increase the concentration (chlorobenzene content 2300ppm) of halogenated organic aromatic hydrocarbons pollutant, 400 ℃ of temperature, other condition have been investigated the anti-fluorine poisoning ability of catalyst with example 2, the results are shown in Figure 1.
As seen from Figure 1, the catalyst of the present invention's development has good anti-fluorine poisoning ability, does not change the active basic of 82 hours time inner catalysts.This commercial Application for catalyst also is very important.
Comparative example 1
Under the reaction condition identical with example 2, the Mn catalyst code name that catalyst is carried out making behind the further modulation is that the catalytic performance of CB-I and noble metal catalyst contrasts, and sees Table 5.
The contrast of table 5 Mn-Cu catalyst and noble metal catalyst catalytic performance
Chlorobenzene?conv.(％)
Catalyst Temperature(℃)
200 250 300 350 400
CB-I 20.2 42.8 95.1 100
Pt/Al
2O
3 3.8 4.2 47.3 98.53 100
As can be seen, the catalytic combustion properties of the metal oxide catalyst of the present invention's development can match in excellence or beauty with noble metal catalyst fully.
Claims (4)
1. one kind is used for the metal oxide catalyst that halogenated aromatic through catalytic oxidation is eliminated, and is made up of carrier and active component, and it is characterized in that: carrier is selected from Al
2O
3, SiO
2, TiO
2, ZrO
2, CeO
2One or more, active component is that the transition metal M that appraises at the current rate is selected from one or more of Mn, Ce, Fe, Zn; The active component loading is 0.1～30%wt.
2. according to the described metal oxide catalyst that is used for the halogenated aromatic through catalytic oxidation elimination of claim 1, it is characterized in that: be selected from Al at carrier
2O
3, SiO
2, ZrO
2, CeO
2The time, transition metal M can also be one or more of Cu, Co.
3. according to the described preparation method who is used for the metal oxide catalyst of halogenated aromatic through catalytic oxidation elimination of claim 1, it is characterized in that: active component adopts impregnated load type method for preparing catalyst altogether, and the active component precursor is selected from nitrate, oxalates, acetate, hydroxide, the carbonate of metal M; Maceration extract is the aqueous solution or the ammonia spirit of metallic salt.
4. according to the described application of metal oxide catalyst in the complete catalytic combustion of waste gas, refuse, waste water halogenated organic aromatic hydrocarbons pollutant is eliminated that is used for the halogenated aromatic through catalytic oxidation elimination of claim 1.
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|---|---|---|---|
| CNB001102362A CN1157255C (en) | 2000-03-22 | 2000-03-22 | Metal oxide catalyst for clearing halogenated aromatic through catalytic oxidation |
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|---|---|---|---|
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| CN1157255C true CN1157255C (en) | 2004-07-14 |
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2000
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100339152C (en) * | 2005-12-29 | 2007-09-26 | 华东理工大学 | Trichloroethylene waste gas catalytic purification method |
| CN110961117A (en) * | 2019-12-06 | 2020-04-07 | 山西大学 | Cu-Mn-O-SiO2-Al2O3Preparation method and application of catalyst |
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| CN1314206A (en) | 2001-09-26 |
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