Process for producing highly active denitrating catalysts

BACKGROUND OF THE INVENTION
This invention relates to a process for producing highly active denitrating catalysts, and more particularly to a process for producing catalysts useful in a reaction in which nitrogen oxides are selectively catalytically reduced with ammonia (NH.sub.3).
It is recognized that the nitrogen oxides (hereinafter referred to as "NO.sub.x ") released to the atmosphere from thermoelectric power stations, ironworks, chemical plants, motor vehicles, etc., cause photochemical smog, so that much attention has been given to the treatment of NO.sub.x in recent years.
Methods of removing NO.sub.x heretofore proposed include one in which NO.sub.x are catalytically reduced with the use of NH.sub.3 as a reducing agent. This method appears more advantageous than others since NH.sub.3 selectively reacts with NO.sub.x as represented by the following equations, even when the exhaust gas contains more than 1% by volume of oxygen.
6NO+4NH.sub.3 .fwdarw.5N.sub.2 +6H.sub.2 O
6NO.sub.2 +8NH.sub.3 .fwdarw.7N.sub.2 +12H.sub.2 O
The known catalysts useful in this method include those comprising a heavy metal compound supported on a carrier such as active alumina, silica alumina or zeolite. These catalysts are generally intended for use in fixed beds. Accordingly if it is attempted to achieve an increased space time yield (S.T.Y.), the emission will involve an increased pressure loss, while solid particles in the emission will clog up the catalyst layer. To overcome such drawbacks, it has been proposed to use carriers of porous structure.
Generally thermoelectric power stations and ironworks releases tremendous quantities of emissions which require large quantities of catalysts for treatment. Catalysts composed of porous carriers for this purpose therefore should preferably be large-sized and have high strength so as not to be fractured during charging. A catalyst is already known which fulfills such requirements and which is prepared by converting the surface layer of steel material to an aluminum alloy, immersing the resulting steel material in an aqueous alkali solution to dissolve out the aluminum and to thereby render the surface layer porous, and subjecting the resulting material to suitable oxidizing treatment. This catalyst is practically useful because the porous surface layer remains relatively intact and acts effectively even in the presence of SO.sub.2 or water vapor contained in the emission. However, the catalyst has the drawback that it exhibits seriously reduced denitrating activity at about 300.degree. C. and slighter lower temperatures.
SUMMARY OF THE INVENTION
The object of this invention which has been accomplished in view of the foregoing situations is to improve the conventional catalyst of porous steel material and to provide a process for producing denitrating catalyst having high activity even at relatively low temperatures. The process of this invention comprises the first step of converting the surface layer of steel material to an aluminum alloy, the second step of treating the resulting steel material with an aluminum dissolving solution to dissolve out the aluminum and to render the surface layer porous, and the third step of immersing the steel material having the porous surface layer in a solution containing a vanadium compound to cause the porous surface layer to support the vanadium compound.
The steel material, when rendered porous by the first and second steps, has catalytic activity for use in reactions in which NO.sub.x is selectively catalytically reduced with NH.sub.3. When the steel material is further subjected to the third step of this invention in which the porous surface layer is caused to support the vanadium compound, a denitrating catalyst is obtained which has high activity even at about 300.degree. C. and slightly lower temperatures.

BRIEF DESCRIPTION OF THE DRAWING
The drawing is a graph showing the relationship between the heat treating temperature for the production of the catalyst and the denitrating efficiency achieved by the catalyst.

PREFERRED EMBODIMENTS OF THE INVENTION
Examples of useful steel materials to be subjected to the first step are stainless steel, nickel steel, tungsten steel, molybdenum steel, etc. The surface layer of the steel material is converted to an aluminum alloy usually by coating the steel material with aluminum and heat-treating the aluminum-coated steel material. The steel material is coated with aluminum, for example, by hot dipping, cementation, vacuum evaporation, spray coating or like plating method. Preferably the heat treatment is conducted in a nitrogen gas or like inert gas atmosphere at a temperature of at least the melting point of aluminum (about 660.degree. C.) for 0.1 to 10 hours. The heat treatment causes the solid phases of steel and aluminum to diffuse through each other, forming an alloy.
The second step in which aluminum is dissolved out from the steel material having the alloy layer is carried out by immersing the steel material in a solution capable of dissolving aluminum or by spraying an aluminum dissolving solution against the alloy layer of the steel material. Useful aluminum dissolving solutions are aqueous acid or alkali solutions. Examples of useful acids are mineral acids such as hydrochloric acid and nitric acid. Examples of useful alkalis are sodium hydroxide and like alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides. Aqueous solutions of alkali metal hydroxides are especially preferable to use. The temperature of the aluminum dissolving solutions, although not particularly limited, is preferably room temperature to 100.degree. C. The dissolving out of the aluminum from the surface layer renders the surface layer porous. The steel material having the resulting porous surface layer is washed with water and dried in the usual manner. It is not always required to completely dissolve out the aluminum; good results are achievable if at least 50% of the aluminum is dissolved out.
Preferably the porous surface layer resulting from the second step is oxidized with an oxygen-containing gas before being subjected to the third step. More preferably the porous surface layer is sulfated with a gas containing sulfur dioxide gas (SO.sub.2) after or simultaneously with the oxidizing treatment.
The oxidizing treatment is carried out by contacting the porous surface layer with a gas containing 0.1 to 20.8% by volume of oxygen under mild conditions, for example at approximate room temperature to 400.degree. C. for 0.1 to 20 hours. The oxidizing treatment imparts enhanced catalytic activity to the surface layer.
The sulfating treatment is effected by bringing the porous surface layer into contact with an SO.sub.2 containing gas. The conditions under which this treatment is carried out, such as the temperature, duration and gas composition, are not limited. Usually the treatment is conducted at approximate room temperature to 400.degree. C. for 0.1 to 20 hours with the use of a gas containing at least 100 ppm of SO.sub.2. The treating conditions are suitably determined within the above-mentioned ranges. For example, when the SO.sub.2 -containing gas has a low temperature and a low SO.sub.2 concentration, the contact is effected for a prolonged period of time. This treatment sulfates the surface of the porous portion, consequently preventing the catalytic decomposition of NH.sub.3 in the denitrating reaction.
H.sub.2 O, CO.sub.2, N.sub.2, combustible gas or like gas, even if contained in the oxidizing gas and in the sulfating gas, will produce little or no influence on the effects achieved by the treatments. Further when the exhaust gas to be treated contains oxygen and/or SO.sub.2 in the specified concentrations, the oxidizing and sulfating treatments may be omitted, since the catalyst comes into contact with such gases during use in the denitrating reaction.
The third step is carried out immediately after the second step or after the oxidizing treatment and/or the sulfating treatment following the second step, by immersing the steel material having the porous surface layer in a solution containing a vanadium compound, such as aqueous solution or oxalic acid solution of ammonium metavanadate, oxalic acid solution of vanadium pentoxide, aqueous solution of vanadyl sulfate or the like. When the aqueous solution of vanadyl sulfate is used, the steel material withdrawn from the solution is heated for 1-4 hours at a temperature of at least 400.degree. C. to decompose the vanadyl sulfate. When the other vanadium compound-containing solutions are used, the steel material withdrawn from the solution is dried at about 100.degree. C. The temperature of the solution for the third step is not limited and may be room temperature. The duration of the immersion, although not limited, is preferably 0.1 to 1 hour. These treating conditions are suitably determined so that the resulting catalyst will contain the desired amount of the vanadium compound. In this way a catalyst is obtained in which the vanadium compound is supported on the porous surface layer. The catalysts in which the ratio of the content of the vanadium compound to the amount of the active layer is at least 0.01 have high denitrating activity. The amount of the active layer mentioned is expressed in terms of the weight of the porous active layer per unit surface area of the steel material before it is rendered porous.
The catalyst resulting from the third step is preferably treated by being heated advantageously at a temperature of 450.degree. to 700.degree. C., more advantageously at the temperature (640.degree. C.) at which iron oxide and vanadium pentoxide form a eutectic mixture. H.sub.2 O, CO.sub.2, N.sub.2, combustible gas or like gas, even if contained in the atmosphere for the treatment, will produce little or no influence on the effects achieved by this treatment. The heat treatment gives the catalyst remarkable improved resistance to SO.sub.3.
EXAMPLE 1
First step:
A panel of SUS 304 (JIS) steel, 2 mm.times.33 mm.times.50 mm, was immersed in a molten bath of aluminum at 680.degree. C. for 20 minutes. The aluminum-coated steel panel was then heat-treated in a nitrogen atmosphere at 800.degree. C. for 1 hour to convert the surface layer of the steel panel to an aluminum alloy.
Second step:
The steel panel having the alloy layer was immersed in 200 ml of aqueous solution containing 10% by weight of NaOH at about 20.degree. C. for 2 hours to dissolve out the aluminum from the alloy layer, thereby rendering the surface layer porous. Subsequently, the steel panel was washed with water treated with ion exchange resin and was dried in the atmosphere.
After the second step, the porous surface layer of the steel panel was oxidized with nitrogen gas containing 3% by volume of oxygen at 300.degree. C. for 1 hour.
Third step:
The resulting steel panel was immersed in 200 ml of oxalic acid solution containing 1 mole of ammonium metavanadate per liter of the solution at room temperature for 30 minutes, thereafter withdrawn from the solution and dried at about 100.degree. C., whereby a catalyst containing the vanadium compound was obtained.
EXAMPLE 2
A catalyst was produced in the same manner as in Example 1 except that the material of the steel panel used was SUS 316 (JIS) in place of SUS 304.
EXAMPLES 3 TO 9
First and second steps:
The surface layer of each panel was rendered porous by repeating the same procedures as in the first and second steps of Example 1 except that the material of the panel used was SS 41 (JIS) in place of SUS 304.
After the second step, the porous surface layer formed was oxidized in the same manner as in the oxidizing treatment of Example 1.
Third step:
Following a procedure similar to that of the third step of Example 1, the steel panels were caused to support vanadium compounds by immersing the panels respectively in an oxalic acid solution of ammonium metavanadate, aqueous solution of ammonium metavanadate and aqueous solution of vanadyl sulfate having varying concentrations whereby catalysts were prepared. The steel panel immersed in the aqueous solution of vanadyl sulfate was heat-treated at about 500.degree. C. for 2 hours after having been withdrawn from the solution.
COMPARISON EXAMPLE 1
The same procedures as in the first and second steps of Example 1 were repeated to form a porous surface layer on a steel panel.
The porous surface layer was oxidized in the same manner as in the oxidizing treatment of Example 1 to obtain a catalyst.
COMPARISON EXAMPLES 2 AND 3
Catalysts in the form of a steel panel having a porous surface layer were produced by following procedures similar to those of Comparison Example 1, namely by repeating the first and second steps and the subsequent oxidizing treatment of Example 2 and by repeating the first and second steps and the subsequent oxidizing treatment of Example 3, respectively.
Table 2 shows the amount of the active layer of each of the catalysts obtained in Examples 1 to 9 and the content of the vanadium compound thereof as well as the amount of active layer of each of the catalysts prepared in Comparison Examples 1 to 3.
Activity test
The denitration efficiency of each of the catalysts produced in Examples 1 to 9 and in Comparison Examples 1 to 3 was determined in the following manner.
Panels of the catalyst were charged into the catalyst accommodating portion, in the form of a rectangular parallelepiped, of a reactor tube. With use of a usual flow system, a simulated exhaust gas having the composition shown in Table 1 was passed through the reactor tube at a flow rate of 1 liter per minute for denitration reaction while controlling the reaction temperature. During the reaction, the concentration of NO.sub.x was measured at the inlet and outlet of the reactor tube. The same procedure as above was repeated for each catalyst to determine the denitration efficiency. Table 2 shows the results.
Table 1______________________________________Components of gas Composition (vol %)______________________________________NO 0.05NH.sub.3 0.05CO.sub.2 13.0H.sub.2 O 10.0O.sub.2 3.6SO.sub.2 0.025N.sub.2 Balance______________________________________
Table 2__________________________________________________________________________ Amount of Content of Denitration efficiencyMaterial of V compd-contg soln and active V compd (%) at reaction temp of:Ex No. steel panel its concn (mole/l) layer(g/m.sup.2) (g/m.sup.2) 300.degree. C. 350.degree. C. 400.degree. C.__________________________________________________________________________1 SUS 304 Oxalic acid soln of NH.sub.4 VO.sub.3 1.0 141 3.2 55.4 74.1 83.62 SUS 316 " 138 3.0 50.7 72.5 82.03 SS-41 A9 soln of NH.sub.4 VO.sub.3 0.1 130 0.53 49.0 71.2 83.04 " Oxalic acid soln of NH.sub.4 VO.sub.3 0.1 132 0.42 38.1 66.2 82.05 " " 0.5 135 1.8 53.2 72.0 80.06 " " 1.0 138 3.0 56.1 72.5 80.07 " " 1.5 141 4.1 70.4 82.5 87.58 " " 2.0 145 5.0 71.5 83.2 87.09 " Aq soln of vanadyl sulfate 1.0 135 2.8 56.0 70.0 78.8CompEx No.1 SUS 304 -- 125 -- 25.5 60.4 85.02 SUS 316 -- 131 -- 23.7 54.5 82.53 SS-41 -- 128 -- 21.5 55.1 80.0__________________________________________________________________________
(The amount of the active layer was determined by rubbing the surface of the steel panel with absorbent cotton impregnated with 6 N aqueous solution of nitric acid to remove the porous portion and dividing the resulting reduction (g) in the weight of the panel by the surface area (m.sup.2) of the steel panel before it was rendered porous. The content of the vanadium (i.e., V) compound is the value obtained by dividing the weight (g) of the vanadium compound supported on the steel panel by the surface area (m.sup.2) of the steel panel before it was rendered porous.)
Table 2 reveals that the catalysts containing the vanadium compounds have higher activity even at temperatures of around 300.degree. C. than those containing no vanadium compound.
EXAMPLES 10 TO 15
First and second steps:
The same procedures as in the first and second steps of Example 1 were repeated to form a porous surface layer on each steel panel.
After the second step, the porous surface layer was oxidized in the same manner as in the oxidizing treatment of Example 1.
The oxidized porous surface layer was then treated with an SO.sub.2 -containing gas under the conditions (temperature, time and gas composition) listed in Table 3 to sulfate the surface of the porous layer.
Third step:
The steel panel having the porous surface layer thus treated was further treated in the same manner as in the third step of Example 1 to obtain a catalyst. Table 3 shows the amount of the active layer and the content of the vanadium compound of the catalyst.
Activity test
The catalysts produced in Examples 10 to 15 were tested in the same manner as above for denitration efficiency, with the results shown in Table 3.
Table 3__________________________________________________________________________ Concn of V compd-SO.sub.2 treatment conditions contg soln Amount ofTemperature (oxalic acid soln active Content of Denitration efficiencyTime of NH.sub.4 VO.sub.3) layer V compd (%) at reaction temp of:Ex. No. Compn of gas (vol) (mol/l) (g/m.sup.2) (g/m.sup.2) 250.degree. C. 300.degree. C. 350.degree. C. 400.degree.__________________________________________________________________________ C. Room temperature10 2 hours 1 137 2.9 45.0 83.1 96.2 99.0 N.sub.2 gas contg 250 ppm SO.sub.2 300.degree. C.11 2 hours 1 135 3.1 43.8 81.5 95.8 98.0 N.sub.2 gas contg 250 ppm SO.sub.2 300.degree. C. 2 hours12 SO.sub.2 (250 ppm) + H.sub.2 O(10%) 0.5 135 2.7 39.2 78.5 95.0 97.8 O.sub.2 (3.6%) + N.sub.2 (86.4%)13 " 1 137 3.3 45.5 82.1 96.1 98.814 " 1.5 137 3.6 50.3 80.6 93.8 96.515 " 2 140 4.2 46.0 77.2 87.1 88.8__________________________________________________________________________
(The amount of active layer and the content of V compound in Table 3 have the same meanings as in Table 2.)
As apparent from Table 3, the catalysts obtained in Examples 10 to 15 have high activity not only at high temperatures of around 400.degree. C. as well as at low temperatures of around 250.degree. C.
EXAMPLE 16
First and second steps:
The same procedures as in the first and second steps of Example 1 were repeated to form a porous surface layer on a steel panel.
Third step:
The steel panel having the porous surface layer was immersed in 200 ml of oxalic acid solution containing 1 mole of ammonium metavanadate per liter of the solution at room temperature for 0.1 hour. The steel panel was then withdrawn from the solution and dried at about 100.degree. C., whereby a catalyst containing the vanadium compound was prepared.
After the third step, the catalyst was heattreated in the atmosphere at 680.degree. C. for 1 hour.
EXAMPLES 17 TO 34
First and second steps:
The same procedures as in the first and second steps of Example 1 were repeated to form a porous surface layer on each steel panel.
The porous surface layer of the steel panel resulting from the second step was subjected to oxidizing treatment and/or sulfating treatment under the conditions listed in Table 4.
Third step:
The treated steel panel was immersed in the solution containing a vanadium compound listed in Table 4 under the conditions given in the same table, then withdrawn from the solution and dried, whereby a catalyst was produced with the vanadium compound supported thereon.
Subsequent to the third step, the catalyst was heat-treated under the conditions indicated in Table 4.
COMPARISON EXAMPLE 4
In the same manner as in the first and second steps of Example 1, a catalyst in the form of a steel panel having a porous surface layer was obtained. The catalyst was oxidized and sulfated under the conditions shown in Table 4.
Table 4 also shows the amount of active layer and the content of V compound of each of the catalysts prepared in Examples 16 to 34 and Comparison Example 4.
Activity test
The catalysts obtained in Examples 16 to 34 and in Comparison Example 4 were also tested for denitration efficiency in the following manner.
Panels of the catalyst were charged into the catalyst accommodating portion, in the form of a rectangular parallelepiped, of a reactor tube. With use of a usual flow system, air containing 2500 ppm by volume of SO.sub.3 and 3% by volume of water vapor was passed through the reactor tube at a flow rate of 1 liter per minute for 1 hour to treat the catalyst with SO.sub.3 while controlling the reaction temperature. Subsequently a simulated exhaust gas having the composition shown in Table 1 was passed through the reactor tube at a flow rate of 1 liter per minute for denitration reaction while controlling the temperature. During the reaction, the concentration of NO.sub.x was measured at the inlet and outlet of the reactor tube. The same procedure as above was repeated for each catalyst to determine the denitration efficiency. Table 4 shows the results.
Table 4__________________________________________________________________________Treating conditions Amount ofOxidizing Sulfating Heat activetreatment treatment treatment layerTemp Temp Immersion treatment Temp (g/m.sup.2) Time Time V compd solution Time Content of Denitration efficiency (%)Ex Compn of Compn of atm Concn of solution Compn of V compd at reaction temp of:No. atm (vol) (vol) Temp Time atm (vol) (g/m.sup.2) 275.degree. C. 325.degree. 375.degree.__________________________________________________________________________ C. Oxalic acid soln of 680.degree. C. NH.sub.4 VO.sub.3 14716 -- -- 23.4 66.0 83.6 1.0 mole/l 1 hr 6.6 Room temp 0.1 hr Air 300.degree. C. 3 hr 14217 -- " " 28.0 67.0 85.8 O.sub.2 (3%) + H.sub.2 O(3%) + 6.2 N.sub.2 (balance) 300.degree. C. 3 hr 14018 N.sub.2 gas contg " " 16.5 64.7 81.0 SO.sub.2 (5000 ppm) 8.3 Room temp 14619 20 hr " " " 21.4 66.5 83.2 Air 8.5 300.degree. C. 300.degree. C. 3 hr 3 hr 14320 O.sub.2 (3%) + SO.sub.2 (250 ppm) + " " 24.2 69.6 82.3 H.sub.2 O(3%) + H.sub.2 O(5%) + O.sub.2 (4%) 8.4 N.sub.2 (balance) + N.sub.2 (balance) Room temp21 " 10 hr " " 145 26.4 64.2 82.7 N.sub.2 gas contg SO.sub.2 8.0 (5000 ppm) 300.degree. C. Oxalic acid soln of NH.sub.4 VO.sub.3 15222 " 3 hr 1.0 mole/l " 19.6 66.3 81.9 N.sub.2 gas contg 60.degree. C. 1 hr 10.6 SO.sub.2 (5000 ppm) 300.degree. C. Oxalic acid soln of NH.sub.4 VO.sub.3 15123 3 hr 1.0 mole/l " 23.7 65.2 82.3 O.sub.2 (4%) + SO.sub.2 (250 ppm) Room temp 0.1 hr 8.7 + N.sub.2 (balance) 300.degree. C. 300.degree. C. Aq soln of NH.sub.4 VO.sub.3 14024 3 hr 3 hr 0.1 mole/l " 19.5 68.5 88.3 O.sub.2 (3%) + N.sub.2 gas contg Room temp 0.1 hr 2.5 H.sub.2 O(3%) + SO.sub.2 (5000 ppm) N.sub.2 (balance) Oxalic acid soln of 14525 " " vanadium pentoxide " 23.8 65.2 81.6 1.0 mole/l 8.4 Room temp 0.1 hr Aq soln of vanadyl 680.degree. C. sulfate 14726 " " 25.0 68.3 84.5 1.0 mole/l 1 hr 6.5 Room temp 0.1 hr Air Oxalic acid soln of NH.sub.4 VO.sub.3 14227 " " " 18.5 57.5 77.4 0.5 mole/l 6.4 Room temp 0.1 hr Oxalic acid soln of NH.sub.4 VO.sub.3 14828 " " " 24.8 57.0 81.3 0.1 mole/l 1.2 Room temp 0.1 hr Oxalic acid soln of 400.degree. C. NH.sub.4 VO.sub.3 14329 " " 9.2 45.3 64.2 1.0 mole/l 1 hr 8.4 Room temp 0.1 hr Air 500.degree. C. 15030 " " " 1 hr 8.7 28.1 62.9 78.0 Air 600.degree. C. 14531 " " " 1 hr 30.0 69.0 81.8 Air 8.6 700.degree. C. 14132 " " " 1 hr 17.5 51.3 73.3 Air 8.3 800.degree. C. 14333 " " " 1 hr 4.8 20.0 41.3 Air 8.5 680.degree. C. 1 hr 14734 " " " O.sub.2 (5%) + 23.4 70.2 82.6 H.sub.2 O(5%) + 8.5 N.sub.2 (balance)CompEx " " -- -- 150 2.5 13.7 37.54 --__________________________________________________________________________
(The amount of active layer and the content of V compound in Table 4 have the same meanings as above.)
As will be apparent from Table 4, the catalysts obtained in Examples 16 to 34 have high activity at high temperatures and also at temperatures slightly lower than 300.degree. C. and possess outstanding resistance to SO.sub.3. The graph of the drawing shows the relationship between the heat treating temperature and the denitration efficiency determined in respect of the catalysts prepared in Examples 18 and 29 to 33. The graph reveals that the catalysts heat-treated at a temperature of 450.degree. to 700.degree. C., especially at about 640.degree. C. have high activity even after the forced treatment with SO.sub.3.

Number	Date	Country
51-134860	Nov 1976	JPX
51-134861	Nov 1976	JPX
52-24165	Mar 1977	JPX

Number	Name	Date
3712856	Betz	Jan 1973
3939097	Takeoka et al.	Feb 1976
4040981	Inaba et al.	Aug 1977
4048112	Matsushita et al.	Sep 1977

Process for producing highly active denitrating catalysts

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