CN102353064A - Method for eliminating chlorinated aromatic hydrocarbons through low temperature catalytic combustion - Google Patents
Method for eliminating chlorinated aromatic hydrocarbons through low temperature catalytic combustion Download PDFInfo
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- CN102353064A CN102353064A CN2011101796965A CN201110179696A CN102353064A CN 102353064 A CN102353064 A CN 102353064A CN 2011101796965 A CN2011101796965 A CN 2011101796965A CN 201110179696 A CN201110179696 A CN 201110179696A CN 102353064 A CN102353064 A CN 102353064A
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- chlorine
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a method for eliminating volatile chlorinated aromatic hydrocarbon pollutants in environment through complete catalytic combustion. In the method, cerium oxide-supported ruthenium oxide is taken as a combustion catalyst, and is carried into a reactor by air serving as an oxidant, chlorine-containing volatile aromatic hydrocarbons are completely combusted under the action of the catalyst, and are converted into carbon dioxide, hydrogen chloride and chlorine, and tail gas (acid gas such as hydrogen chloride, chlorine and the like) obtained after complete combustion can be absorbed by a dilute alkaline solution and is discharged. The catalyst is high in activity, byproducts are not generated, secondary pollution is avoided, chlorine poisoning resistance is high, the catalyst is long in service life, and the method is particularly suitable for eliminating halogen-containing organic compounds, particularly the volatile chlorinated aromatic hydrocarbon pollutants, through low temperature complete catalytic combustion.
Description
Technical field
The invention belongs to the catalytic combustion environmental protection technical field, specially refer to a kind of method that the easy-to-volatile chloroarene low-temperature catalytic burning is eliminated that is used for.
Background technology
The chlorine-containing volatile hydro carbons not only can cause serious harm to human beings'health, also can cause influence lasting, accumulation property to biosystem, and can destroy atmospheric ozone layer.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.The chlorine-containing volatile hydro carbons divides the aromatic hydrocarbon chloride; Like chlorobenzene, dichloro-benzenes; And non-fragrant fat hydrocarbon chloride; Like dichloroethanes, trichloro-ethylene, tetrachloro-ethylene, chloromethanes and methane polychloride etc., the former results from the bleaching of the wood pulp of chloro oxidant, the heat treatment of chlorine-containing compound and the recovery of metal; The latter mainly results from chlorine industry oxygen chlorine legal system and is equipped with industries such as vinyl chloride process, process hides, washing, pharmacy.Because the muriatic process of above-mentioned generation all relates to the industry of present stage national economy, the discharging of a large amount of chlorine-containing compounds is inevitable.Therefore, also do not possess the possibility of pollution that elimination chlorine-containing volatile hydro carbons is caused from the source at present.And the pollution that the method elimination chlorine-containing volatile hydro carbons of taking post processing is brought becomes unique feasible approach and method.
In recent years, the comprehensive regulation to volatile organic compound (VOCs) had received concern more and more widely.Methods such as flame combustion, catalytic combustion and absorption are to eliminate the common method of these pollutants.But flame combustion need carry out under higher temperature (1000 ℃), and energy consumption is big; And this method is also causing more highly toxic bioxin (Dioxins) pollutant aspect the chloride hydro carbons of processing, like many chlorodiphenyls and bioxin (PCDD) and polychlorinated dibenzo (PCDF).Absorption method as one of organic pollution common method is unsatisfactory for the treatment effect of low concentration pollutant, and its adsorption efficiency is extremely low.For the elimination of the chloride aromatic hydrocarbon of effumability, the method for multiple novelty has been proposed recently in succession, like biological processes, photocatalytic degradation, hydrogenation-dechlorination etc.But these methods are not to have defective technically, are exactly that disposal cost is high, all are in the laboratory research state mostly, are difficult for realizing industrialization, industrialization.
Advantages such as the pollution that catalytic combustion is eliminated organic compound is a kind of energy-conservation, economic, effective processing method, compares with flame combustion, and it has, and ignition temperature is low, the time of staying short, required reactor is little, secondary pollution is few.Therefore, catalytic combustion is obtaining using widely aspect the elimination volatile organic compound.
Chlorination aromatic hydrocarbon such as chlorobenzene, dichlorobenzene, dioxin, its catalytic combustion is mainly used in the exhaust-gas treatment of incinerator, and the research work of this direction and the exploitation of technology concentrate on Japan.Representational patent has Jpn.Kokai Tokkyo Koho JP 2001286729A2, Jpn.Kokai Tokkyo Koho JP2001286730A2, Jpn.Kokai Tokkyo Koho JP 2001286734A2, Jpn.Kokai Tokkyo Koho JP 10085559A2 etc.Use fuel gas and air to burn.The main catalyst activity component of using is transition metal and noble metal, and carrier is SiO
2, Al
2O
3, TiO
2, ZrO
2Though precious metal catalyst is active higher, is easy to fluorine poisoning; The anti-poisoning capability of non-precious metal catalyst is stronger, but selectivity is lower, often has polystream to produce.
Part chlorination aromatic hydrocarbon catalytic combustion granted patent has:
[1]Nawama，Junichi；Moriya，Yoshifumi；Suzuki，Tadashi；Kuchino，Kunikazu，Jpn.Kokai?Tokkyo?Koho?JP?2002219364A2
[2]Kiyono，Kenichi；Uchida，Masaaki；Adachi，Kentaro；Nishii，Kazuhiro，Jpn.Kokai?Tokkyo?Koho?JP?2001286729A2
[3]Kiyono，Kenichi；Uchida，Masaaki；Adachi，Kentaro；Nishii，Kazuhiro，Jpn.Kokai?Tokkyo?Koho?JP?2001286730A2
[4]Kajikawa，Osamu；Wang，Hsiang?Sheng；Kawase，Noboru；Maeda，Takeshi，Jpn.Kokai?Tokkyo?Koho?JP?2001009284A2.
[5]Kiyono，Kenichi；Uchida，Masaaki；Adachi，Kentaro；Nishii，Kazuhiro，Jpn.Kokai?Tokkyo?Koho?JP?2001286734A2
[6]Moriya，Yoshifumi；Nawama，Junichi；Tokumitsu，Shuzo，Jpn.Kokai?Tokkyo?Koho?JP?2001327869A2
These patent works mainly are to be active component with the transition metal, and catalytic combustion purifies De bioxin in the incinerator.
Above-mentioned chlorine-containing volatile hydro carbons catalytic combustion is eliminated the catalyst that is adopted and is all had shortcoming more or less; Low like catalytic combustion activity; Have the polychlorocarbon class to produce, be prone to cause secondary pollution in the catalyticing combustion process, the catalyst activity component runs off easily, catalyst life short.
Summary of the invention
The objective of the invention is to disclose a kind of easy-to-volatile chloroarene low-temperature catalytic burning method that is used for; This method is a combustion catalyst with the ruthenium-oxide of cerium oxide load; Its activity is high, no coupling product generates, do not cause secondary pollution, anti-fluorine poisoning ability is strong, catalyst life is long; Be specially adapted to complete catalytic combustion and eliminate halogen-containing organic compound, especially effumability chloro-hydrocarbons pollutant.
The invention provides a kind of catalyst that the easy-to-volatile chloroarene low-temperature catalytic burning is eliminated that is used for, this catalyst mainly is made up of cerium oxide and ruthenium-oxide, and wherein the content of ruthenium-oxide is 0.5～3%, and all the other are cerium oxide.
Infusion process well known in the art is adopted in the preparation of the ruthenium oxide catalysts of cerium oxide load.The presoma of cerium oxide is selected from the cerous nitrate of rare earth, the presoma of ruthenium-oxide is selected from ruthenic chloride.
The invention provides a kind of method that complete catalytic combustion is eliminated environment easy-to-volatile chloroarene pollutant that is used for; It is characterized in that; In the presence of catalyst; Employing is brought reactor into as the air of oxidant; Make the completing combustion under the effect of catalyst of chlorine-containing volatile aromatic hydrocarbon, chlorine-containing volatile aromatic hydrocarbon is transformed into carbon dioxide, hydrogen chloride and chlorine.Completing combustion tail gas can adopt dilute alkaline soln to absorb back emptying such as (hydrogen chloride/chlorine sour gas);
Reaction pressure is 0.1～1Mpa, preferred 0.1～0.5Mpa, especially 0.1Mpa, and near normal pressure, temperature is 100～400 ℃, is preferably 150～350 ℃, especially 320 ℃;
Catalyst consumption; Must be enough to make chlorine-containing volatile aromatic hydrocarbon existing under the situation at air; Change into carbon dioxide and hydrogen chloride; Generally speaking; The concentration of chlorine-containing volatile aromatic hydrocarbon is 0.05～0.2vol% in the waste gas of chlorine-containing volatile aromatic hydrocarbon, and every gram catalyst treatment exhausted air quantity is 5～16L per hour.
Adopt method of the present invention, in air, under lower reaction temperature, in the presence of catalyst, can long-term and stably the chlorine-containing volatile aromatic hydrocarbon in the waste gas be transformed into carbon dioxide and hydrogen chloride, activity of such catalysts does not reduce.
Catalyst provided by the invention has characteristics such as preparation technology is simple, cheap, catalytic activity is high, anti-fluorine poisoning ability is strong, the life-span is long; Technology path is convenient and practical, and the catalytic combustion that can be widely used in the chlorine-containing volatile arene pollutant in papermaking, pharmacy, process hides, washing and the chemical industry waste gas is eliminated.
The specific embodiment
Embodiment 1
With commercially available 4000g cerous nitrate (Ce (NO
3)
3) 6H
2O puts into the Muffle furnace roasting, and its concrete roasting process is: 50 ℃ begin heating, carry out temperature programming with the heating rate of 4.2 ℃/min, keep 4h at 550 ℃, obtain flaxen CeO
2Powder.
With commercially available RuCl
3.3H
2O is configured to the aqueous solution of 20g/L, and this solution of 400mL is joined in the 300mL deionized water, is configured to maceration extract.This maceration extract is poured into the CeO of the above-mentioned preparation of 800g
2In the powder; Stir; In the air at room temperature static 10 hours; Place 110 ℃ of baking ovens to carry out drying 12 hours; Put into the Muffle furnace roasting again, its concrete roasting process is: 30 ℃ begin heating, carry out temperature programming with the heating rate of 4 ℃/min; Keep 4h at 550 ℃, the ruthenium-oxide amount that obtains the cerium oxide load is 1wt% catalyst (1wt%Ru/CeO
2).
Embodiment 2
The ruthenium-oxide amount for preparing the cerium oxide load by embodiment 1 same method is 3wt% catalyst (3wt%Ru/CeO
2).
Embodiment 3
All catalyst chlorobenzene combustion activities are estimated in fixed bed (internal diameter 100mm is quartzy) and are carried out, and catalyst consumption is 200g, and temperature adopts K type thermocouple to control automatically.Chlorobenzene adopts SY-02 double plunger micro pump (manufacturing of Beijing Orient scientific instrument factory) injection to get into vaporizer.Total flow adopts mass flowmenter control, and the concentration of chlorobenzene is controlled at 0.1vol%, and the amount that every gram catalyst is per hour handled waste gas is 16L, is 1000m/h through the gas line speed of reactor.Reaction pressure is 0.1Mpa, and the conversion ratio of chlorobenzene and the relation of reaction temperature are seen table 1, T in the table
10%, T
50%, T
90%Be respectively conversion ratio and reach 10%, 50%, 90% o'clock required reaction temperature.The key reaction product is the chlorine of carbon dioxide, hydrogen chloride and trace.
Chlorobenzene catalytic combustion properties on table 1 different catalysts
Embodiment 4
Change every gram catalyst and per hour handle the amount of waste gas, reaction pressure is at 0.1Mpa, and the concentration of chlorobenzene is 0.1vol%, uses air to be oxidizing gas, and air is a dry air, at embodiment 1 catalyst 1wt%Ru/CeO
2On, having investigated of the influence of different air speeds to the chlorobenzene catalytic combustion properties, the result sees table 3.
Table 3 air speed is to 1wt%Ru/CeO
2The influence of catalyst combustibility
The result shows, 1wt%Ru/CeO
2Exhaust-gas treatment amount hourly can be up to 16L/g catalyst (pressing 80% chlorobenzene by conversion calculations) down at 300 ℃ on the catalyst, and this commercial Application for catalyst is very crucial and important beyond doubt.
Embodiment 5
The amount that every gram catalyst is per hour handled waste gas is fixed as 5L, and reaction pressure is at 0.1Mpa, and reaction temperature is decided to be 280 ℃, and the concentration of chlorobenzene is 0.1vol%, uses air to be oxidizing gas, and air is a dry air, at embodiment 1 catalyst 1wt%Ru/CeO
2On, the conversion ratio of chlorobenzene maintains more than 99% in several hours, does not see catalyst poisoning.
Claims (4)
1. one kind is used for the method that chlorine-containing volatile organic compound by low-temperature catalytic combustion is eliminated; It is characterized in that; In the presence of catalyst; Employing is brought reactor into as the air of oxidant; Make chlorine-containing volatile organic compound completing combustion under the effect of catalyst, chlorine-containing volatile organic compound is transformed into carbon dioxide, hydrogen chloride and chlorine.Completing combustion tail gas can adopt dilute alkaline soln to absorb back emptying such as (hydrogen chloride/chlorine sour gas);
Reaction pressure is 0.1～1Mpa, preferred 0.1～0.5Mpa, especially 0.1Mpa, and near normal pressure, temperature is 100～400 ℃, is preferably 150～350 ℃, especially 320 ℃;
Catalyst consumption; Must be enough to make chlorine-containing volatile organic compound existing under the situation at humid air; Change into carbon dioxide and hydrogen chloride; Generally speaking; The concentration of pollutant is 0.05～0.2vol% in the chlorine-containing volatile organic compound waste gas, and every gram catalyst treatment exhausted air quantity is 5～16L per hour;
Said catalyst mainly is made up of the ruthenium-oxide of cerium oxide load, and wherein the content of ruthenium-oxide is 0.5～3% (weight), and all the other are cerium oxide.
2. according to the said Preparation of catalysts method of claim 1, it is characterized in that: combustion method well known in the art is adopted in the preparation of carrier cerium oxide.
3. according to the said Preparation of catalysts method of claim 1, it is characterized in that: the ruthenium oxide catalysts of cerium oxide load adopts dipping method well known in the art, and the presoma of ruthenium-oxide is selected from ruthenic chloride.
4. catalyst according to claim 1 can be widely used in the low-temperature catalytic burning of chlorine-containing volatile organic compound in industrial waste gas, refuse, the waste water and eliminate, especially the chloride arene pollutant of the effumability in the industrial waste gas.
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| CN2011101796965A CN102353064A (en) | 2011-06-28 | 2011-06-28 | Method for eliminating chlorinated aromatic hydrocarbons through low temperature catalytic combustion |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106731563A (en) * | 2015-11-19 | 2017-05-31 | 中国石油化工股份有限公司 | A kind of processing method and processing device of chloride organic exhaust gas |
| CN108906044A (en) * | 2018-06-15 | 2018-11-30 | 中国科学院过程工程研究所 | A kind of manganese cerium ruthenium composite oxide catalysts and its preparation method and application |
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| CN101693198A (en) * | 2009-09-30 | 2010-04-14 | 广州科城环保科技有限公司 | Catalyst for reducing dioxin emission in waste incineration |
| CN101767011A (en) * | 2008-12-30 | 2010-07-07 | 华东理工大学 | Low-temperature catalytic combustion eliminating method of volatile chloro aryl hydrocarbons |
| CN101862593A (en) * | 2010-06-22 | 2010-10-20 | 华东理工大学 | Low-temperature catalytic combustion elimination method for chlorine-containing volatile organic compounds |
| CN101929682A (en) * | 2010-06-22 | 2010-12-29 | 华东理工大学 | Method for eliminating chlorine-containing volatile organic compound by low-temperature catalytic combustion |
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2011
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Patent Citations (4)
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| CN101767011A (en) * | 2008-12-30 | 2010-07-07 | 华东理工大学 | Low-temperature catalytic combustion eliminating method of volatile chloro aryl hydrocarbons |
| CN101693198A (en) * | 2009-09-30 | 2010-04-14 | 广州科城环保科技有限公司 | Catalyst for reducing dioxin emission in waste incineration |
| CN101862593A (en) * | 2010-06-22 | 2010-10-20 | 华东理工大学 | Low-temperature catalytic combustion elimination method for chlorine-containing volatile organic compounds |
| CN101929682A (en) * | 2010-06-22 | 2010-12-29 | 华东理工大学 | Method for eliminating chlorine-containing volatile organic compound by low-temperature catalytic combustion |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106731563A (en) * | 2015-11-19 | 2017-05-31 | 中国石油化工股份有限公司 | A kind of processing method and processing device of chloride organic exhaust gas |
| CN106731563B (en) * | 2015-11-19 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of processing method and processing device of the organic exhaust gas containing chlorine |
| CN108906044A (en) * | 2018-06-15 | 2018-11-30 | 中国科学院过程工程研究所 | A kind of manganese cerium ruthenium composite oxide catalysts and its preparation method and application |
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Application publication date: 20120215 |