CN100339152C - Trichloroethylene waste gas catalytic purification method - Google Patents
Trichloroethylene waste gas catalytic purification method Download PDFInfo
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- CN100339152C CN100339152C CNB2005101123086A CN200510112308A CN100339152C CN 100339152 C CN100339152 C CN 100339152C CN B2005101123086 A CNB2005101123086 A CN B2005101123086A CN 200510112308 A CN200510112308 A CN 200510112308A CN 100339152 C CN100339152 C CN 100339152C
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8659—Removing halogens or halogen compounds
- B01D53/8662—Organic halogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0325—Noble metals
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/28—Phosphorising
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2255/00—Catalysts
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- B01D2255/102—Platinum group metals
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2255/00—Catalysts
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- B01D2255/206—Rare earth metals
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/37—Acid treatment
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Abstract
The present invention discloses the trichloroethylene exhaust gas catalytic purification method which comprises the following steps that humid air is led to exhaust gas containing trichloroethylene for reaction under the condition that catalyst exists, and the catalyst is composed of a carrier which is stable in the humid air and rare metal, rare-earth oxides and phosphoric acid loaded on the carrier. The method of the present invention can be used for stably converting trichloroethylene in exhaust gas into CO2 and HCL for long in the humid air at a lower reaction temperature when the catalyst for oxidative decomposition exists, and the activity of the catalyst is not reduced. The content of noble metal in the catalyst is very low, and hydrocarbon containing chlorine in the exhaust gas is eliminated in a particularly economic method without the generation of poly-chlorine hydrocarbon by-products and secondary pollution. The present invention is a very effective method for processing the hydrocarbon containing the chlorine and has wide application prospect for environmental protection.
Description
Technical field
The present invention relates to a kind of processing method that contains trichloroethylene waste gas, relate in particular to a kind of catalytic combustion method, more specifically relate to the catalyst that is adopted.
Background technology
The harm of chlorine-containing organic compounds is not only human beings'health, and biosystem is caused influence lasting, accumulation property, and destroys the ozone of atmosphere.It all is chloride organic compound that 12 persistent organic pollutions of classifying the first place as are arranged in the united nations environment project international treaties
[2]Chlorinated hydrocarbon (CHC) divides the aromatic hydrocarbon chloride, as chlorobenzene, dichloro-benzenes, with the chloride of non-aromatic hydrocarbon class, as vinyl chloride, many vinyl chloride, chloromethanes and methane polychloride, the former results from waft white, the heat treatment of chlorine-containing compound and the recovery of metal of the wood pulp of chloro oxidant; The latter results from chlorine industry oxygen chlorine legal system and is equipped with the vinyl chloride process.Because the muriatic process of above-mentioned generation all relates to the industry of present stage China's national economy, the discharging of a large amount of chlorine-containing compounds is inevitable.Trichloro-ethylene is one of halogenated hydrocarbon of the most difficult oxidation Decomposition in the chlorinated hydrocarbon, and therefore, the exploitation of the catalysis and purification technology of trichloro-ethylene has important environmental protection meaning.
In recent years, adopt several different methods to eliminate chlorine-containing organic compounds both at home and abroad, and comprised hot elimination, biological processes, photocatalytic degradation, hydrogenation-dechlorination etc., wherein the catalysis null method is with low temperature conversion and high selectivity and most economical, the most reliable method that becomes.Be that exploitation is eliminated in the catalysis that the research group of representative is engaged in chlorinated hydrocarbon for a long time with Gutierrez-Ortiz, material with various acidic molecular sieves and carried noble metal thereof is a catalyst, chloralkane, chloro-alkenes catalytic oxidation process have been carried out comparatively extensive studies, comprised and kinetics, reaction mechanism and novel catalysis eliminate the exploitation of process (Stud.Surf.Sci.Catal.130 (2000) 893; Appl.Catal.B 19 (1998.189; Appl.Catal.B 30 (2001) 303; Stud.Surf.Sci.Catal.130 (2000) 1229; J.Catal.214 (2003) 130; Appl.Catal.B 41 (2003) 31); Wherein quite a few work is to eliminate about the oxidation of three chloro-alkenes, comprise the research of trichloro-ethylene and saturated hydrocarbons, unsaturated hydro carbons, water coexistence system, purpose is to reduce oxidizing temperature, reduces the discharging of tetrachloro-ethylene, improves ability of the anti-fluorine poisoning of catalyst or the like.BertM.Weckhuysen (Phys.Chem.Phys., 6 (2004) 5256) uses basic anhydride hydrolysis chlorinated hydrocarbon, generates carbon dioxide and hydrogen chloride.
A significant disadvantages of the chlorinated hydrocarbon removing method of above-mentioned proposition is all to have the polychlorocarbon class to produce in the process, causes secondary pollution.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of trichloroethylene waste gas catalytic purification method, to overcome the shortcoming of the generation polychlorocarbon class that prior art exists.
Method of the present invention comprises the steps:
In the presence of catalyst, in containing the waste gas of trichloro-ethylene, feed malaria, react, trichloro-ethylene is transformed into carbon dioxide and hydrogen chloride non-toxic gas, the chlorine that produces in the elimination process makes catalyst can steady in a long-termly keep oxidation activity.When reaction temperature during at 450 ℃, the conversion ratio of trichloro-ethylene can reach more than 95%, and no polychlorocarbon class generates.
Reaction pressure is 0.1-1Mpa, preferred 0.1-0.5Mpa, especially 0.1Mpa, and near normal pressure, temperature is 300～600 ℃, is preferably 400～500 ℃, especially 450 ℃.
Said catalyst is by to constituting at the stable carrier of malaria and the rare metal, rare earth oxide and the phosphoric acid that are carried on this carrier;
Said rare metal comprises one or more in palladium or the platinum, preferred platinum, and its amount is the 0.08-5wt% of total catalyst weight;
Said rare earth oxide is one or more in the oxide of the oxide of lanthanum or cerium, and its amount is the 1-10wt% of total catalyst weight;
Said carrier is a carrier well known in the art, and preferred mesoporous silicon oxide, silica or other pure silicon molecular screen materials, preferred carrier are the Metaporous silicon dioxide material on big surface.
Said mesoporous silicon oxide MCM-41 can adopt document (Nature, 1992,359:710) disclosed method is prepared;
Catalyst preferred ingredients and weight content are:
Palladium 0.1-2wt%, platinum 0.08-2wt%, lanthana 3-10wt%, cerium oxide 3-10wt%, phosphatase 11 wt%～20wt%, all the other are carrier silica.
Said Preparation of catalysts can be divided into for two steps, and the first step is an impregnation of phosphoric acid solution on silica, drying, roasting, its method can adopt incipient impregnation method well known in the art to be prepared, as document (J.Mater.Chem., 2002,12:1582) disclosed method; Second step load rare metal and the rare earth element, the salt solution impregnation method of mentioning usually as document.
Catalyst consumption, must be enough to make trichloro-ethylene in the existing under the situation of humid air, change into carbon dioxide and hydrogen chloride, generally speaking, the concentration of trichloro-ethylene is 0.05-0.2vol% in the waste gas of trichloro-ethylene, and every gram catalyst treatment exhausted air quantity is 10-30L per hour.
Said humid air is the air that contains steam, and its water concentration must satisfy the chlorine that reaction is generated and all be converted into hydrogen chloride, but can not make water become the mortifier of reaction, and in the air, the concentration of suitable water is 0.1～1vol%;
The mol ratio of water and trichloro-ethylene is 2～5: 1;
Adopt method of the present invention, in humid air, under lower reaction temperature, in the presence of oxidation decomposing catalyst, can long-term and stably the trichloro-ethylene in the waste gas be transformed into carbon dioxide and hydrogen chloride, activity of such catalysts does not reduce; The content of noble metal is low especially in the catalyst; eliminate chloride hydro carbons in the waste gas with economic especially method, do not have the generation of polychlorocarbon class accessory substance, do not cause secondary pollution; be the method for highly effective chloride hydro carbons exhaust-gas treatment, have bigger environmental protection application prospect.
The specific embodiment
Embodiment 1
Get the deionized water that 3.0g softex kw (CTMAB) adds 105ml,, produce transparent template solution 30 ℃ of dissolvings down; Ethylenediamine (EDA) with 35ml adds in the flask with template solution under condition of stirring again, keeps 30 ℃; Then the mixed liquid of 15ml ethyl orthosilicate (TEOS) and 50ml deionized water is slowly splashed into above-mentioned containing in the system that template agent, ethylenediamine and water constitutes, make each amount of system satisfy: n (TEOS): n (CTMAB): n (EDA): n (H
2O)=and 1: 0.12: 9.7: 130, stir 15min, pH with the acetate regulation system is 10.5, continue to stir behind the 1.5h collosol intermixture changed over to and have in the teflon-lined 100ml stainless steel cauldron, static crystallization 72h under self pressure in 120 ℃ of baking ovens, spend deionised water, suction filtration, absolute ethanol washing, suction filtration after taking out cooling, 50 ℃ of oven dry of spending the night obtain the not mesopore molecular sieve sample of removed template method.The sample roasting in Muffle furnace-50 of not deviating from the template agent ℃ is begun heating, and every 0.5h heats up 50 ℃, up to 550 ℃, keeps 550 ℃ of 8h then, obtains the MCM-41 mesopore molecular sieve.
MCM-41/PO
3Traditional immersion process for preparing is adopted in the preparation of H: step is as follows: take by weighing the mesopore molecular sieve MCM-41 after the above-mentioned roasting of 1g, add 1.125,1.5,2.25,4.5 respectively, the H of 11.25ml
3PO
4In the solution and vigorous stirring, maintenance system under certain temperature fast with the moisture content evaporate to dryness.Then, 100 ℃ of following dry 8h, 400 ℃ of following roasting 3h get MCM-41/PO
3H, the carrier of phosphoric acid is carried in acquisition, and its Si/P (atom) is 100,75,50,25,15,10 than respectively.Different Si/P measure examination according to method NH well known in the art than its acid of carrier
3-TPD carries out, its result such as table 1.The test of pyridine In-situ Infrared can determine that it is B acid that phosphoric acid is modified the acidity that causes.
Dipping noble metal active component on above-mentioned carrier, at first chloroplatinic acid is mixed with the aqueous solution, its concentration is 0.00638M, regulate its pH to 4.7 with ammoniacal liquor then, above-mentioned carrier is respectively got 1g, under each comfortable condition of stirring the 2mL chloroplatinic acid aqueous solution is slowly joined in the carrier, staticly spend the night in air at room temperature then, 50 ℃ of dryings, 550 ℃ of roasting 4h, obtain various carrier loaded Pt catalyst.Recording each catalyst by atomic absorption spectrum, to contain Pt amount be about 0.16wt%.In the same way, be the 0.00319M chloroplatinic acid aqueous solution with concentration, make another serial catalyst, containing the Pt amount is about 0.08%.
The catalyst activity evaluation is carried out at fixed bed reactors.The test of the trichloro-ethylene of all catalyst (TCE) combustion activity is all carried out in U-shaped quartzy little anti-(internal diameter 6mm), and catalyst consumption is 200mg, and reaction temperature is 500 ℃, and temperature adopts K type thermocouple to control automatically.Trichloro-ethylene adopts 100 serial KDS120 type micro-injection pumps injections of U.S. Stoelting company to enter vaporizer, is that the humid air of 0.15vol% is mixed into reactor and burns with water concentration then.The humid air total flow adopts mass flowmenter control, and the concentration of trichloro-ethylene is controlled at 0.05vol%, and the amount that every gram catalyst is per hour handled waste gas is 15L, is 120m/h through the gas line speed of reactor.The mol ratio of water and trichloro-ethylene is 3: 1; Reaction pressure is 0.1Mpa, and temperature is 450 ℃.The conversion ratio of trichloro-ethylene sees Table 1, and product is the chlorine of carbon dioxide, hydrogen chloride and trace.
Trichloro-ethylene conversion ratio (500 ℃) after the acid amount of the MCM-41 carrier of the different Si/P ratios of table 1 and the supporting Pt thereof
| Si/P(atom) | Without phosphorus | 100 | 75 | 50 | 25 | 15 | 10 | |
| Acid amount (mmol/g) | 0 | 0.15 | 0.2 | 0.25 | 0.3 | 0.45 | 0.55 | |
| Conversion ratio (%) | 0.08wt％Pt | 25 | 70 | 82 | 99 | 65 | 65 | 15 |
| 0.16wt％Pt | 40 | 80 | 85 | 99 | 99 | 85 | 30 | |
Embodiment 2
With concentration is that 0.00319M chloroplatinic acid aqueous solution 1ml and concentration are that 0.01275M palladium chloride aqueous solution 1ml is mixed, is immersed in the MCM-41/PO of the various phosphorus acid contents that make among the embodiment 1 respectively with the mixed liquid of 2mL
3On the H carrier, subsequent treatment is pressed the method for embodiment 1, obtains 0.08wt%Pt-0.5wt%Pd/MCM-41/PO
3The H catalyst series.Take by weighing this catalyst 100mg, reaction temperature is 500 ℃, and water content is 0.2vol% in the humid air, trichloro-ethylene concentration be 0.1vol%, the mol ratio of water and trichloro-ethylene is 2: 1; The amount that every gram catalyst is per hour handled waste gas is 30L, and reaction pressure is 0.1Mpa.The remaining reaction condition is with embodiment 1, and the conversion ratio of trichloro-ethylene sees Table 2, and product is the chlorine of carbon dioxide, hydrogen chloride and trace.
Trichloro-ethylene conversion ratio (500 ℃) after the acid amount of the MCM-41 carrier of the different Si/P ratios of table 2 and the supporting Pt thereof
| Si/P(atom) | 100 | 75 | 50 | 25 | 15 | 10 |
| Conversion ratio (%) | 85 | 85 | 99.5 | 99.5 | 87 | 43 |
Embodiment 3
Use commercially available SiO
2Surface area is 303m
2/ g presses embodiment 1 impregnation of phosphoric acid, makes the SiO of various phosphorus acid contents
2/ PO
3The H carrier.Be the 0.00319M chloroplatinic acid aqueous solution with 2ml concentration, be immersed on the various carriers that subsequent treatment is undertaken by the method for embodiment 1, obtains 0.08wt%Pt/SiO respectively
2/ PO
3The H catalyst.Take by weighing each 200mg of this catalyst series, reaction temperature is 450 ℃, reaction pressure is 0.5Mpa, water content is 0.15vpl% in the humid air, the concentration of trichloro-ethylene is 0.05vol%, and the amount that every gram catalyst is per hour handled waste gas is 15L, and the remaining reaction condition is with embodiment 1, the conversion ratio of trichloro-ethylene sees Table 3, and product is the chlorine of carbon dioxide, hydrogen chloride and trace.
After the acid amount of the MCM-41 carrier of the different Si/P ratios of table 3 and the supporting Pt thereof at trichloro-ethylene conversion ratio (450 ℃)
| Si/P(atom) | 100 | 75 | 50 | 25 | 15 | 10 |
| Conversion ratio (%) | 35 | 42 | 67 | 41 | 28 | 15 |
Embodiment 4
Be the 0.1M lanthanum nitrate and the cerous nitrate aqueous solution with 5mL concentration respectively, the MCM-41 carrier that excessive dipping makes by embodiment 1, solution slowly joins in the carrier under condition of stirring; Staticly spend the night in air at room temperature then, low temperature (50 ℃) is dry, 550 ℃ of roasting 4h, obtains the MCM-41 carrier modified with La and Ce, the load capacity of La and Ce is about 10wt%.Be the 0.00319M chloroplatinic acid aqueous solution with 2ml concentration respectively, be immersed on above-mentioned Ce-MCM-41 that makes and the La-MCM-41 carrier, carry out subsequent treatment, obtain the 0.08wt%Pt catalyst by the method for embodiment 1.Take by weighing each 200mg of this catalyst series, reaction temperature is 450 ℃, water content is 0.1vol% in the humid air, the concentration of trichloro-ethylene is 0.5ol%, the amount that every gram catalyst is per hour handled waste gas is 15L, the remaining reaction condition is with embodiment 1, and the conversion ratio of trichloro-ethylene sees Table 4, and product is the chlorine of carbon dioxide, hydrogen chloride and trace.
Trichloro-ethylene conversion ratio (450 ℃) after the acid amount of the MCM-41 carrier of the different Si/P ratios of table 4 and the supporting Pt thereof
| Catalyst | Ce-MCM-41 | La-MCM-41 | Pt/Ce-MCM-41 | Pt/La-MCM-41 |
| Conversion ratio (%) | 60 | 65 | 95 | 95 |
Embodiment 5
Be the 0.1M lanthanum nitrate and the cerous nitrate aqueous solution with 5mL concentration respectively, the MCM-41/PO that excessive dipping makes by embodiment 1
3The H serial carrier, solution slowly joins in the carrier under condition of stirring; Staticly spend the night in air at room temperature then, low temperature (50 ℃) is dry, 550 ℃ of roasting 4h, obtains the MCM-41/PO that modifies with La and Ce
3Two serial carriers of H, the load capacity of La and Ce is about 10wt%.Flood this two serial carriers with 2ml concentration for the 0.00319M chloroplatinic acid aqueous solution respectively, carry out subsequent treatment, obtain the 0.08wt%Pt catalyst by embodiment 1.Take by weighing each 100mg of this two catalyst series, reaction temperature is 450 ℃, water content is 0.5vol% in the humid air, the concentration of trichloro-ethylene is 0.1vol%, the amount that every gram catalyst is per hour handled waste gas is that 30L remaining reaction condition is with embodiment 1, the conversion ratio of trichloro-ethylene sees Table 5, and product is the chlorine of carbon dioxide, hydrogen chloride and trace.
Table 5 embodiment 5 makes trichloro-ethylene conversion ratio on each catalyst (450 ℃)
| Si/P(atom) | 100 | 75 | 50 | 25 |
| Ce/MCM-41/PO 3H | 47 | 62 | 77 | 51 |
| La/MCM-41/PO 3H | 45 | 59 | 80 | 48 |
| Pt-Ce/MCM-41/PO 3H | 83 | 89 | 98 | 76 |
| Pt-La/MCM-41/PO 3H | 81 | 85 | 95 | 71 |
Embodiment 6
Be 0.01275M and 0.0255M palladium chloride aqueous solution with 2ml concentration respectively, be immersed in the MCM-41/PO of the various phosphorus acid contents that make among the embodiment 1
3On the H carrier, subsequent treatment is undertaken by embodiment 1, obtains 0.5wt%Pd/MCM-41/PO
3H and 1wt%Pd/MCM-41/PO
3Two catalyst series of H.Take by weighing each 200mg of this catalyst series, reaction temperature is 450 ℃, water content is 0.2vol% in the humid air, trichloro-ethylene concentration be 0.1vol%, the amount that every gram catalyst is per hour handled waste gas is 15L, the remaining reaction condition is with embodiment 1, and the conversion ratio of trichloro-ethylene sees Table 6, and product is the chlorine of carbon dioxide, hydrogen chloride and trace.
Trichloro-ethylene conversion ratio (450 ℃) behind the acid amount of the MCM-41 carrier of the different Si/P ratios of table 6 and the load P d thereof
| Si/P(atom) | 100 | 75 | 50 | 25 | 15 | 10 |
| 0.5wt％Pd/MCM-41/PO 3H | 75 | 81 | 90 | 86 | 77 | 32 |
| 1wt％Pd/MCM-41/PO 3H | 80 | 87 | 93 | 89 | 78 | 40 |
Claims (6)
1. a catalytic purification method that contains trichloroethylene waste gas is characterized in that, comprises the steps:
In the presence of catalyst, in containing the waste gas of trichloro-ethylene, feed malaria, react;
Said humid air is the air that contains steam, and its water concentration is 0.1～1vol%; The mol ratio of water and trichloro-ethylene is 2～5: 1;
Said catalyst is by to constituting at the stable carrier of malaria and the rare metal, rare earth oxide and the phosphoric acid that are carried on this carrier;
Said rare metal comprises one or more in palladium or the platinum, and its amount is the 0.08-5wt% of total catalyst weight;
Said rare earth oxide is one or more in the oxide of the oxide of lanthanum or cerium, and its amount is the 1-10wt% of total catalyst weight;
Phosphoric acid is the 1wt%～20wt% of total catalyst weight;
All the other are carrier.
2. method according to claim 1 is characterized in that, reaction pressure is 0.1-1Mpa, and temperature is 300～600 ℃.
3. method according to claim 1 is characterized in that, said rare metal is a platinum.
4. according to claim 1,2 or 3 described methods, it is characterized in that said carrier is selected from silica.
5. method according to claim 4 is characterized in that said carrier is selected from mesoporous silicon oxide.
6. method according to claim 4 is characterized in that, the component of catalyst and weight content are: palladium 0.1～2wt%, platinum 0.08-2wt%, lanthana 3-10wt%, and cerium oxide 3-10wt%, phosphatase 11 wt%～20wt%, all the other are carrier silica.
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| CNB2005101123086A CN100339152C (en) | 2005-12-29 | 2005-12-29 | Trichloroethylene waste gas catalytic purification method |
| PCT/CN2006/000361 WO2007073631A1 (en) | 2005-12-29 | 2006-03-10 | A catalytic purifying method for a waste gas containing trichloroethylene |
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| CNB2005101123086A CN100339152C (en) | 2005-12-29 | 2005-12-29 | Trichloroethylene waste gas catalytic purification method |
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| CN101185796A (en) * | 2007-12-11 | 2008-05-28 | 华东理工大学 | Chlorination aromatic hydrocarbon waste gases catalytic purification method |
| CN102211028B (en) * | 2010-04-08 | 2014-01-29 | 中化蓝天集团有限公司 | Hydrogenation dechlorinating catalyst for synthesizing trifluoroethylene and novel preprocessing process of carrier of catalyst |
| JP5859366B2 (en) * | 2011-09-06 | 2016-02-10 | 三井金属鉱業株式会社 | Exhaust gas purification catalyst and exhaust gas purification catalyst structure |
| CN103691464B (en) * | 2013-12-17 | 2015-10-28 | 华东理工大学 | A kind of catalyst for the low-temperature catalyzed hydrogenation elimination of chlorophenol compounds in water and preparation and application thereof |
| CN109603869B (en) * | 2019-01-23 | 2020-07-07 | 浙江大学 | Phosphoric acid modified cerium oxide catalyst and preparation method and application thereof |
| CN110917871B (en) * | 2019-11-05 | 2022-03-25 | 河北科技大学 | Method for absorbing and catalytically oxidizing halogenated hydrocarbon by using metal simple substance and/or metal oxide |
| CN113976125B (en) * | 2021-08-30 | 2023-05-12 | 郑州大学 | Co-doped ZnO catalyst and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5716590A (en) * | 1993-12-17 | 1998-02-10 | Wacker-Chemie Gmbh | Catalytic hydrodehalogenation of halogen-containing compounds of group IV elements |
| CN1157255C (en) * | 2000-03-22 | 2004-07-14 | 中国科学院大连化学物理研究所 | Metal oxide catalyst for clearing halogenated aromatic through catalytic oxidation |
| US20050069478A1 (en) * | 2002-01-14 | 2005-03-31 | Bert Weckhuysen | Catalytic destruction of halogenated hydrocarbons |
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| JP3598539B2 (en) * | 1994-08-09 | 2004-12-08 | 住友金属鉱山株式会社 | Catalyst for decomposition of volatile organic chlorine compounds |
| JPH0852361A (en) * | 1994-08-11 | 1996-02-27 | Sumitomo Metal Mining Co Ltd | Catalyst for decomposition of volatile organic chlorine compound |
| JPH0857323A (en) * | 1994-08-15 | 1996-03-05 | Sumitomo Metal Mining Co Ltd | Catalyst for decomposition of volatile organic halogen compound and production thereof |
| JPH0857322A (en) * | 1994-08-19 | 1996-03-05 | Sumitomo Metal Mining Co Ltd | Catalyst for decomposition of volatile organic halogen compound and production thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5716590A (en) * | 1993-12-17 | 1998-02-10 | Wacker-Chemie Gmbh | Catalytic hydrodehalogenation of halogen-containing compounds of group IV elements |
| CN1157255C (en) * | 2000-03-22 | 2004-07-14 | 中国科学院大连化学物理研究所 | Metal oxide catalyst for clearing halogenated aromatic through catalytic oxidation |
| US20050069478A1 (en) * | 2002-01-14 | 2005-03-31 | Bert Weckhuysen | Catalytic destruction of halogenated hydrocarbons |
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| WO2007073631A1 (en) | 2007-07-05 |
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