CN100398184C - Process for low-temperature catalytically burning chlorinated aliphatics - Google Patents
Process for low-temperature catalytically burning chlorinated aliphatics Download PDFInfo
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- CN100398184C CN100398184C CNB2006100293046A CN200610029304A CN100398184C CN 100398184 C CN100398184 C CN 100398184C CN B2006100293046 A CNB2006100293046 A CN B2006100293046A CN 200610029304 A CN200610029304 A CN 200610029304A CN 100398184 C CN100398184 C CN 100398184C
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Abstract
The invention relates to a method for low-temperature catalyzing and burning chloro aliphatic hydrocarbon, wherein it is characterized in that: with catalyst, burning the air with water and the mixture with chlorine volatile aliphatic hydrocarbon; said catalyst is formed by rare-earth oxide, or rare-earth oxide and one or several oxides of order-variable transient metals; the doping amount of said transient metal is 0.1-30wt% at oxide; the invention has simple preparation, without side product and secondary pollution; and the catalyst has long service, to be completely catalyze and burn halide organic compound, with low cost.
Description
Technical field
The present invention relates to a kind of method of low-temperature catalytically burning chlorinated aliphatics, relate in particular to a kind of catalyst of low-temperature catalytically burning chlorinated aliphatics.
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, as chlorobenzene, dichloro-benzenes, and non-aromatic face cream fat hydro carbons chloride, as dichloroethanes, trichloro-ethylene, tetrachloro-ethylene, chloromethanes and methane polychloride etc., 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 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, the pollution that is caused from source elimination chlorine-containing volatile hydro carbons does not also possess possibility at present.And the pollution that the method elimination chlorine-containing volatile hydro carbons of taking post processing is brought becomes unique feasible approaches and methods.
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, as 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 aliphatic hydrocarbon of effumability, the method for multiple novelty has been proposed recently in succession, as biological processes, photocatalytic degradation, hydrogenation-dechlorination, steam reforming 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.
The method that catalytic combustion is used to eliminate effumability chloro-hydrocarbons pollutant is of long duration, as far back as 1975, G.C.Bond and N.Sadeghi are in J.Appl.Chem.Biotechnol.24 (1975): delivered the article that is entitled as " Catalyzed Destruction of Chlorinated Hydrocarbons " on 24, specifically reported Pt/ γ-Al
2O
3Catalyst burns chlorohydrocarbon and is translated into 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.
U.S.Patent 4 059 675,4 059 676 and 4 059 683 has narrated the catalytic combustion of halogenated hydrocarbons on noble metal catalysts such as Ru, Ru-Pt and Pt and has decomposed.
U.S.Patent 5 283 041 has reported a kind of catalyst that is used for halogenated hydrocarbons and other organic compound 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.
Gutierrez-Ortiz is engaged in the catalysis of chlorinated hydrocarbon for a long time and eliminates exploitation, material with various acidic molecular sieves and carried noble metal thereof is a catalyst, chloralkane, chloro-alkenes catalytic oxidation process are carried out comparatively extensive studies, comprised the exploitation (Stud.Surf.Sci.Catal.130 (2000): 893 of kinetics, reaction mechanism and novel catalysis elimination process; 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).
H.L.Greene has reported that also carried molecular sieve catalyst is used for the catalytic combustion of trichloro-ethylene (S.Chatterjee and H.L.Greene, J.Catal.130 (1991): 76).
Kie β ing, people such as Wendt, Schneider have studied the catalytic combustion (R.Schneider on the Ca-Ti ore type composite metal catalyst such as chloromethanes, chloroethanes, vinyl chloride, D.Kie β ing and G.Wendt, Catal.Today, 47 (1999): 429; R.Schneider, D.Kie β ing and P.Kraak, Chem.Techn.47 (1995): 199; R.Schneider, D.Kie β ing and R.Herzschuh, React.Kinet.Catal.Lett.61 (1997): 245).
All there is shortcoming more or less in the catalyst that above-mentioned chlorine-containing volatile hydro carbons catalytic combustion elimination is adopted, low as catalytic combustion activity, have the polychlorocarbon class to produce, easily 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 method of low-temperature catalytically burning chlorinated aliphatics, to overcome the above-mentioned defective that prior art exists.
The method of low-temperature catalytically burning chlorinated aliphatics of the present invention comprises the steps:
The mixture that will contain the air of moisture content and chlorine-containing volatile aliphatic hydrocarbon is in the presence of catalyst, carry out combustion reaction, make the chlorine-containing volatile aliphatic hydrocarbon transform into carbon dioxide, hydrogen chloride and chlorine, sour gas in the product, as hydrogen chloride/chlorine etc., adopt dilute alkaline soln to absorb back emptying;
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 200 ℃;
Contain in the air of moisture content, 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 the volumetric concentration of suitable water is 0.1～15% in the air;
Contain in the mixture of the air of moisture content and chlorine-containing volatile aliphatic hydrocarbon, the volumetric concentration of chlorine effumability aliphatic hydrocarbon is 0.05～5%;
Catalyst consumption must be enough to make the chlorine-containing volatile aliphatic hydrocarbon to change into carbon dioxide and hydrogen chloride in containing the air of moisture content, and the air capacity that every gram catalyst treatment contains moisture content is 10～30L per hour.
The catalyst that is used for the elimination of volatile chloro fat hydrocarbon low-temperature catalytic burning provided by the invention, mainly by rare earth oxide, or the oxide of rare earth oxide and one or more transition metals that appraise at the current rate is formed;
Said rare earth oxide is selected from one or more in the oxide of the oxide of oxide, Pr of oxide, the La of Ce or Nd, the said transition metal that appraises at the current rate is selected from Cu, Fe, V, Mn, Mo, Co or W, the appraise at the current rate doping of transition metal is counted 0.1～30wt% with oxide;
The general structure of said chloro fat hydro carbons is as follows:
C
nH
2n+2-xCl
xN=1～4, preferred n=1～2, x=1～4; Or C
nH
2n-xCl
xN=2～4, preferred n=2, x=1～4.
One pack system rare earth oxide catalyst of the present invention adopts nitrate of rare earth element roasting direct method to make;
Add the bicomponent catalyst of the transition metal that appraises at the current rate, adopt coprecipitation to make;
The presoma of transition-metal catalyst of appraising at the current rate is selected from nitrate, oxalates, acetate or the carbonate of the transition metal that appraises at the current rate;
Adopt method of the present invention, can long-term and stably the chlorine-containing volatile aliphatic hydrocarbon be transformed into carbon dioxide and hydrogen chloride under lower reaction temperature, activity of such catalysts does not reduce.
Catalyst provided by the invention has that preparation technology is simple, 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, while is cheap, technology path is convenient and practical, and the catalytic combustion that can be widely used in the chlorine-containing volatile fat hydrocarbon pollutant in papermaking, pharmacy, process hides, washing and chemical industry (as chlorine industry) and the petrochemical industry waste gas is eliminated.
Description of drawings
Catalyst life when Fig. 1 is anhydrous steam.
Fig. 2 catalyst life when containing 3% steam.
The specific embodiment
Embodiment 1
Commercially available 100g cerous nitrate is placed in the heating furnace, temperature programming in air atmosphere, 1 ℃ of per minute is raised to 180 ℃, is incubated 2 hours; Temperature programming again, 10 ℃ of per minutes are raised to 550 ℃ with temperature, are incubated 4 hours, can make CeO
2Catalyst.
Embodiment 2
Commercially available 100g lanthanum nitrate is placed in the heating furnace, temperature programming in air atmosphere, 1 ℃ of per minute is raised to 180 ℃, is incubated 2 hours; Temperature programming again, 10 ℃ of per minutes are raised to 550 ℃ with temperature, are incubated 4 hours, can make La
2O
3Catalyst.
Embodiment 3
With commercially available 50g cerous nitrate (Ce (NO
3)
3) 6H
2O and 6g copper nitrate Cu (NO
3)
2) 3H
2O is dissolved in the 500ml ionized water, and this solution places 50 ℃ constant temperature water bath to stir 0.5h; Drip the oxalic acid aqueous solution 200ml of 0.5N then with per minute 1ml flow velocity, constantly stir in the process, treat that oxalate precipitation fully after, continue down to stir 2～4h at 50 ℃, static, suction filtration, each adds the 500ml absolute ethanol washing once, suction filtration again with the hot deionized water washed twice of 500ml, 100 ℃ of dry 24h in baking oven then, move in the roaster temperature programming in air atmosphere, 1 ℃ of per minute, be raised to 180 ℃, insulation 2h; Temperature programming again, 10 ℃ of per minutes are raised to 550 ℃ with temperature, during insulation 4h, can obtain 10CuO-90CeO
2(CuO: CeO by weight
2Be 1: 9) catalyst.
Embodiment 4
Make 10Fe with the 3 identical methods of enforcement
2O
3-90CeO
2(Fe by weight
2O
3: CeO
2It is 1: 9).
Embodiment 5
With implement 3 method make 10MnO
2-90CeO
2(MnO by weight
2: CeO
2It is 1: 9).
Embodiment 6
With commercially available 50g lanthanum nitrate (La (NO
3)
3) xH
2O and 6.5g copper nitrate (Cu (NO
3)
2) 3H
2O is dissolved in the 500ml ionized water, and this solution places 50 ℃ constant temperature water bath to stir 0.5h; Drip the NH of 0.1N then with per minute 0.5ml flow velocity
4OH aqueous solution 1500ml, process constantly stirs, and waits to dropwise, stir 1h again, static spending the night, suction filtration, each adds the 500ml absolute ethanol washing once, suction filtration again with 500ml deionized water washed twice, 100 ℃ of dry 24h in baking oven move in the roaster temperature programming in air atmosphere then, 10 ℃ of per minutes, temperature is raised to 550 ℃, is incubated 4 hours, can obtain 10CuO-90La
2O
3(CuO: La by weight
2O
3Be 1: 9) catalyst.
Embodiment 7
With implement 6 method make NiO-La
2O
3(NiO: La by weight
2O
3It is 1: 9).
Embodiment 8
With implement 6 method make Co
2O
3-La
2O
3(Co by weight
2O
3: La
2O
3It is 1: 9).
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 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 dry air, water concentration respectively then.Total flow adopts mass flowmenter control, and the volumetric concentration of trichloro-ethylene is controlled at 0.1%, 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.Reaction pressure is 0.1Mpa, and the conversion ratio of trichloro-ethylene and the relation of reaction temperature see Table 1, T in the table
10%, T
50%, T
98%Be respectively conversion ratio and reach 10%, 50%, 98% o'clock required reaction temperature.Product is the chlorine of carbon dioxide, hydrogen chloride and trace.
Trichloro-ethylene catalytic combustion properties on table 1 different catalysts
The volumetric concentration of chlorinated organics is controlled at 1.5%, is that 0.51% humid air is mixed into reactor and burns with the volumetric concentration of dry air, water respectively, and the amount that every gram catalyst is per hour handled waste gas is 10L, at embodiment 1CeO
2On the catalyst catalytic combustion properties of dissimilar chlorine-containing volatile fat hydrocarbons (CVOCs) is investigated, be the results are shown in Table 2.
The catalytic combustion result of the different chlorine-containing volatile fat hydrocarbons of table 2
The result shows, CeO
2Rare earth oxide catalyst all has good catalytic combustion properties to dissimilar chlorine-containing volatile fat hydrocarbons, and wherein with complete Catalytic Combustion Effect the best of dichloroethanes, trichloro-ethylene, tetrachloro-ethylene take second place.
Embodiment 11
Change the concentration of trichloro-ethylene, the volumetric concentration that water in air is divided is controlled at 0.7%, the amount that every gram catalyst is per hour handled waste gas is 20L, reaction pressure is at 0.3Mpa, on embodiment 1 and enforcement 2 catalyst, investigated of the influence of variable concentrations trichloro-ethylene, the results are shown in Table 3 catalytic combustion properties.
Table 3 variable concentrations trichloro-ethylene is to CeO
2And La
2O
3The influence of catalyst combustibility
The result shows, one pack system CeO
2And La
2O
3Catalyst has good catalytic combustion properties for the TCE of low concentration.Thus, the catalyst among the present invention can be widely used in the catalytic combustion elimination of variable concentrations (organic pollution that comprises low concentration and high concentration) chlorine-containing volatile fat hydrocarbon.
Embodiment 12
Change every gram catalyst and per hour handle the amount of waste gas, reaction pressure is at 0.1Mpa, the volumetric concentration of trichloro-ethylene is 0.1%, use air to be oxidizing gas, air is a dry air, on embodiment 3 catalyst, investigated of the influence of different air speeds to the trichloro-ethylene catalytic combustion properties, the results are shown in Table 4.
Table 4 air speed CeO
2The influence of catalyst combustibility
The result shows, CeO
2Exhaust-gas treatment amount hourly can be up to 45L/g catalyst (pressing 90% trichloro-ethylene by conversion calculations) down at 325 ℃ on the catalyst, and this commercial Application for catalyst is very crucial and important beyond doubt.
Embodiment 13
With embodiment 3 same reaction conditions under, be the chlorine-containing volatile aliphatic hydrocarbon with trichloro-ethylene (TCE), investigated steam respectively to the CeO among the embodiment 1
2With the CuO-CeO among the embodiment 2
2The influence of the complete catalytic combustion activity of catalyst the results are shown in Table 5.
Table 5 steam is to the influence of the complete catalytic combustion activity of trichloro-ethylene
The result shows that steam is to one pack system CeO
2Activity of such catalysts has certain inhibitory action, and adds the bi-component CuO-CeO of Cu
2Catalyst but is not subjected to the influence of steam substantially, and especially in the temperature that is higher than more than 225 ℃, the existence of water vapour also helps the conversion of trichloro-ethylene.The commercial Application that this point is eliminated for chlorine-containing volatile fat hydrocarbon catalytic combustion is particularly important, because the waste gas of industrial chlorine-containing volatile fat hydrocarbon all contains a large amount of steam.
Embodiment 14
The reaction unit of enumerating by embodiment 9, water in air partial volume concentration is controlled at 0% or 1%, the amount that every gram catalyst is per hour handled waste gas is 20L, reaction pressure is at 0.15Mpa, the volumetric concentration of trichloro-ethylene is controlled at 0.1%, reaction temperature is set at 400 ℃, investigates the anti-fluorine poisoning ability of embodiment 3 catalyst, the results are shown in Figure 1.As seen from Figure 1, the catalyst of the present invention development has good anti-fluorine poisoning ability, and no matter being is not having under the condition of steam or under the existence condition of steam, does not become substantially in the activity of 50-70h inner catalyst.
Claims (6)
1. the method for a low-temperature catalytically burning chlorinated aliphatics is characterized in that, the mixture that comprises the steps: to contain the air of moisture content and chlorine-containing volatile aliphatic hydrocarbon carries out combustion reaction in the presence of catalyst;
Said catalyst, mainly by rare earth oxide, or the oxide of rare earth oxide and one or more transition metals that appraise at the current rate is formed;
The appraise at the current rate doping of transition metal is counted 0.1～30wt% with oxide;
Said rare earth oxide is selected from one or more in the oxide of the oxide of oxide, Pr of oxide, the La of Ce or Nd;
The said transition metal that appraises at the current rate is selected from Cu, Fe, V, Mn, Mo, Co or W;
The general structure of said chloro fat hydro carbons is as follows:
C
nH
2n+2-xCl
xN=1～4, x=1～4; Or C
nH
2n-xCl
xN=2～4, x=1～4.
2. method according to claim 1 is characterized in that, reaction pressure is 0.1～1Mpa, and temperature is 100～400 ℃.
3. method according to claim 1 is characterized in that, the volumetric concentration that contains the water in air of moisture content is 0.1～15%.
4. method according to claim 1 is characterized in that, contains in the mixture of the air of moisture content and chlorine-containing volatile aliphatic hydrocarbon, and the volumetric concentration of chlorine effumability aliphatic hydrocarbon is 0.05～5%.
5. method according to claim 1 is characterized in that, the air capacity that every gram catalyst treatment contains moisture content is 10～30L per hour.
6. method according to claim 1 is characterized in that, the general structure of said chloro fat hydro carbons is as follows:
C
nH
2n+2-xCl
xN=1～2, or C
nH
2n-xCl
xN=2.
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