WO2012099090A1 - Fe(II)置換ベータ型ゼオライト、それを含むガス吸着剤及びその製造方法、並びに一酸化窒素及びハイドロカーボンの除去方法 - Google Patents
Fe(II)置換ベータ型ゼオライト、それを含むガス吸着剤及びその製造方法、並びに一酸化窒素及びハイドロカーボンの除去方法 Download PDFInfo
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- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
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- F01N3/0842—Nitrogen oxides
Definitions
- the present invention relates to an Fe (II) -substituted beta zeolite, a gas adsorbent containing the same, and a method for producing the same.
- the present invention also relates to an adsorbent for adsorbing and removing nitrogen monoxide gas and hydrocarbon gas in a gas phase such as exhaust gas of an internal combustion engine, and a method for removing nitrogen monoxide gas and hydrocarbon gas from the gas phase.
- Patent Document 1 discloses a support obtained by ion-exchanging a beta zeolite having a SiO 2 / Al 2 O 3 molar ratio of 15 to 300 with 0.1 to 15% by mass of Fe 3+ ions, Denitration catalysts having ferric oxide supported on a support are described.
- Patent Document 2 has a skeletal structure in which the Si content attributed to Q 4 of the zeolite skeleton observed in a 29 Si MAS NMR spectrum is 35 to 47% by mass, and has a molar ratio of SiO 2 / Al 2 O 3 .
- ratio beta zeolite is less than 20 or more 100 by ion exchange by supporting Fe 3+, which has been described that contacting the exhaust gas containing nitrogen oxides.
- Patent Document 3 describes a method for producing a NO x adsorbent.
- a beta-type zeolite is impregnated with an iron chloride aqueous solution to form an iron chloride-containing zeolite, and the iron chloride-containing zeolite is heated at 330 ° C. to 500 ° C. in a moisture-free atmosphere to form Fe.
- the present invention is a Fe (II) -substituted beta zeolite ion-exchanged with Fe (II) ions
- the SiO 2 / Al 2 O 3 ratio is 10 to 18
- the BET specific surface area is 400 to 700 m 2 / g
- the micropore specific surface area is 290 to 500 m 2 / g
- the micropore volume is 0.15.
- the present invention provides an Fe (II) -substituted beta zeolite of ⁇ 0.25 cm 3 / g.
- the present invention also provides a gas adsorbent containing the Fe (II) -substituted beta zeolite.
- the SiO 2 / Al 2 O 3 ratio is 10 to 16
- the BET specific surface area measured in the sodium type state is 500 to 700 m 2 / g
- the micropore specific surface area is 350 to 500 m 2.
- Beta type zeolite having a micropore volume of 0.15 to 0.25 cm 3 / g is dispersed in an aqueous solution of a divalent iron water-soluble compound, and mixed and stirred to obtain the beta type
- the present invention provides a method for producing Fe (II) -substituted beta zeolite, which comprises a step of supporting Fe (II) ions on zeolite.
- the present invention is ion-exchanged with Fe (II) ions,
- the SiO 2 / Al 2 O 3 ratio is 10 to 18, the BET specific surface area is 400 to 700 m 2 / g, the micropore specific surface area is 290 to 500 m 2 / g, and the micropore volume is 0.15.
- ⁇ 0.25 cm 3 / g and is by Fe (II) is substituted beta zeolite is contacted with a gas containing nitric oxide or nitric oxide, one of the nitrogen monoxide is adsorbed on the Fe (II) substituted beta zeolite A method for removing nitric oxide is provided.
- the present invention is ion-exchanged with Fe (II) ions, A SiO 2 / Al 2 O 3 ratio of 10 ⁇ 18, BET specific surface area of 400 ⁇ 700m 2 / g, micropore specific surface area of 290 ⁇ 500m 2 / g, and micropore volume of 0.15
- BET specific surface area 400 ⁇ 700m 2 / g
- micropore specific surface area 290 ⁇ 500m 2 / g
- micropore volume of 0.15 Removal of hydrocarbons by adsorbing hydrocarbons to the Fe (II) -substituted beta zeolite by bringing the Fe (II) -substituted beta zeolite of ⁇ 0.25 cm 3 / g into contact with hydrocarbon or a gas containing hydrocarbon A method is provided.
- an Fe (II) -substituted beta zeolite useful for catalytic removal of various gases and a method for producing the same are provided.
- oxygen is present in a high concentration in the gas to be purified, or the temperature of the gas to be purified is low.
- nitrogen monoxide and hydrocarbons contained in the gas can be effectively adsorbed and removed.
- FIG. 1 is a process diagram for producing a pre-substitution beta zeolite used in the present invention.
- 2 is an X-ray diffraction pattern of the pre-substitution beta zeolite obtained in Example 1.
- FIG. 3 is an X-ray diffraction pattern of the Fe (II) -substituted beta zeolite obtained in Example 1.
- 4 is an X-ray diffraction pattern of the Fe (II) -substituted beta zeolite obtained in Example 2.
- FIG. FIG. 5 is an X-ray diffraction pattern of the Fe (II) -substituted beta zeolite obtained in Example 3.
- FIG. 6 is an X-ray diffraction pattern of the Fe (II) -substituted beta zeolite obtained in Example 4.
- FIG. 7A is an X-ray diffraction pattern of the beta zeolite before substitution used in Comparative Example 1
- FIG. 7B is an X-ray diffraction pattern of the Fe (II) beta zeolite used in Comparative Example 1.
- FIG. 8A is an X-ray diffraction diagram of the pre-substitution beta zeolite used in Comparative Example 2
- FIG. 8B is an X-ray diffraction of the Fe (II) beta zeolite used in Comparative Example 2.
- the present invention relates to an Fe (II) -substituted beta zeolite obtained by ion exchange of beta zeolite with Fe (II) ions.
- the present invention also relates to a gas adsorbent containing the Fe (II) -substituted beta zeolite.
- Fe (II) ions, [AlO 2] in the beta zeolite - that is a cation ion exchange existing on the site, is supported on beta zeolite.
- the important point in the present invention is that the iron ion ion-exchanged with the cation contained in the beta zeolite is Fe (II) ion.
- the desired level of gas removal effect cannot be expressed. This is because the Fe (II) -substituted beta type used in the present invention is used. This does not prevent the zeolite from supporting Fe (III) ions. That is, it is permissible for Fe (II) -substituted beta zeolite to carry Fe (III) ions.
- examples of the gas to be adsorbed using the Fe (II) -substituted beta zeolite include nitrogen monoxide gas and hydrocarbon gas which are gases contained in the exhaust gas of an internal combustion engine.
- hydrocarbon gas alkanes such as methane, ethane, propane, butane, pentane, hexane, n-heptane and isooctane, alkenes such as ethylene, propylene, butene, pentene, methylpentene, hexene and methylhexene, benzene
- the Fe (II) -substituted beta zeolite of the present invention is effective for adsorption of aromatics such as toluene, xylene and trimethylbenzene.
- the amount of Fe (II) contained in the Fe (II) -substituted beta zeolite, that is, the supported amount is preferably 0.01 to 6.5% by mass with respect to the Fe (II) -substituted beta zeolite. It is more preferably 0.05 to 6.0% by mass, still more preferably 0.1 to 5.0% by mass, still more preferably 0.6 to 5.0% by mass.
- the amount of Fe (II) supported in the Fe (II) -substituted beta zeolite is measured by the following method. First, the Fe (II) -substituted beta zeolite to be measured is weighed. This Fe (II) -substituted beta zeolite is dissolved with hydrogen fluoride (HF), and the amount of divalent iron in the solution is quantified using an inductively coupled plasma emission spectrometer. By dividing the mass of the quantified divalent iron by the mass of the Fe (II) -substituted beta zeolite and multiplying by 100, the amount of Fe (II) supported in the Fe (II) -substituted beta zeolite ( %).
- HF hydrogen fluoride
- Beta-type zeolite is dispersed in an aqueous solution of a divalent iron water-soluble compound and mixed by stirring.
- the beta zeolite is preferably mixed at a ratio of 0.5 to 7 parts by mass with respect to 100 parts by mass of the aqueous solution. What is necessary is just to set the addition amount of the water-soluble compound of bivalent iron appropriately according to the grade of ion exchange.
- Mixing and stirring may be performed at room temperature or under heating.
- the liquid temperature is preferably set to 10 to 30 ° C.
- the mixing and stirring may be performed in an air atmosphere or in an inert gas atmosphere such as a nitrogen atmosphere.
- a compound that prevents divalent iron from being oxidized to trivalent iron may be added to water.
- ascorbic acid which is a compound that does not hinder the ion exchange of Fe (II) ions and can prevent the Fe (II) ions from being oxidized to Fe (III) ions.
- the amount of ascorbic acid to be added is 0.1 to 3 times, particularly 0.2 to 2 times the number of moles of divalent iron to be added, from the viewpoint of effectively preventing the oxidation of divalent iron. preferable.
- the solid content is suction filtered, washed with water and dried to obtain the target Fe (II) -substituted beta zeolite.
- the X-ray diffraction pattern of this Fe (II) -substituted beta zeolite is almost the same as the X-ray diffraction pattern of the beta zeolite before supporting Fe (II) ions. That is, the crystal structure of zeolite is not changed by ion exchange.
- the Fe (II) -substituted beta zeolite used in the present invention has a SiO 2 / Al 2 O 3 ratio of 10 to 18, preferably 10 to 17.
- the BET specific surface area is 400 to 700 m 2 / g, preferably 400 to 600 m 2 / g, and more preferably 400 to 520.
- the micropore specific surface area is 290 to 500 m 2 / g, preferably 300 to 480 m 2 / g, and the micropore volume is 0.15 to 0.25 cm 3 / g, preferably 0.16 to 0.24 cm. 3 / g.
- the Fe (II) -substituted beta zeolite used in the present invention is particularly excellent in trapping properties of nitrogen monoxide and hydrocarbons discharged at the cold start of the internal combustion engine.
- the temperature of the three-way catalyst is not high enough at the cold start of the gasoline engine or diesel engine.
- beta zeolite having a specific physical property value as the beta zeolite that is ion-exchanged with Fe (II) ions.
- the beta zeolite used in the present invention (hereinafter, this zeolite is referred to as “pre-substitution beta zeolite” in comparison with the Fe (II) -substituted beta zeolite) is SiO 2 / Al 2.
- pre-substitution beta zeolite SiO 2 / Al 2.
- One of the characteristics is that it has a high BET specific surface area, a high micropore specific surface area, and a high micropore volume, despite the fact that it is aluminum-rich with a low O 3 ratio.
- beta zeolite was also known in the past, but such BET specific surface area and micropore specific surface area of beta-type zeolite, micropore volume was not high.
- the SiO 2 / Al 2 O 3 ratio has to be increased.
- the pre-substitution beta zeolite has an SiO 2 / Al 2 O 3 ratio of 10 to 16, preferably 10 to 14, and is rich in aluminum.
- Such an aluminum-rich pre-substitution beta zeolite has a high BET specific surface area measured in the sodium form of 500 to 700 m 2 / g, preferably 550 to 700 m 2 / g.
- the micropore specific surface area measured in a sodium type state has a high value of 350 to 500 m 2 / g, preferably 380 to 500 m 2 / g.
- the micropore volume measured in the sodium type state has a high value of 0.15 to 0.25 cm 3 / g, preferably 0.18 to 0.25 cm 3 / g.
- the values of SiO 2 / Al 2 O 3 ratio, BET specific surface area, micropore specific surface area and micropore volume in the beta zeolite before substitution are the corresponding values in the Fe (II) substituted beta zeolite. It does n’t change much.
- Pre-substitution beta-type zeolite includes sodium-type zeolite, and further includes sodium-ion-exchanged protons to form H + type.
- the beta zeolite is of the H + type, the measurement of the specific surface area and the like is performed after the proton is replaced with sodium ions.
- the sodium type beta zeolite is dispersed in an aqueous ammonium salt solution such as ammonium nitrate, and the sodium ions in the zeolite are replaced with ammonium ions. By calcining this ammonium type beta zeolite, an H + type beta zeolite can be obtained.
- the beta-type zeolite before substitution used in the present invention is different from the conventional beta-type zeolite in that the SiO 2 / Al 2 O 3 ratio, the BET specific surface area, the micropore specific surface area and the micropore volume are different from those of the conventional beta-type zeolite, X-ray diffractograms are also characterized by differences.
- the aluminum-rich pre-substitution beta zeolite having the above-mentioned physical properties is suitably produced by the production method described later.
- the reason why the pre-substitution beta-type zeolite can achieve the above-mentioned physical properties is that the production method can suppress the occurrence of defects that may occur in the crystal structure of the obtained pre-substitution-type beta zeolite. The details are not clear, although it is presumed that it was because of this.
- the conventional synthesis method of beta zeolite using organic SDA is performed in the order of ⁇ 1>, ⁇ 2>, ⁇ 3>.
- a method carried out in the order of ⁇ 1>, ⁇ 2>, ⁇ 3>, ⁇ 4>, ⁇ 5>, ⁇ 6>, ⁇ 9> for example, Chinese Patent Application No. 10129968A). (Hereinafter also referred to as “conventional method”).
- the use of a seed crystal is essential, and for the production of the seed crystal, an organic compound called tetraethylammonium ion and a structure directing agent (hereinafter also referred to as “SDA”) are essential.
- SDA structure directing agent
- the beta-type zeolite obtained by the conventional method it is necessary to remove tetraethylammonium ion by high temperature baking.
- pre-substitution beta zeolite can be produced by six methods.
- the first method is the same method as the conventional method ⁇ 1>, ⁇ 2>, ⁇ 3>, ⁇ 4>, ⁇ 5>, ⁇ 6>, ⁇ 9>.
- the SiO 2 / Al 2 O 3 ratio of the seed crystal and the composition of the reaction mixture are different from those of the conventional method. Therefore, according to the present invention, pre-substitution beta zeolite having a wide range of SiO 2 / Al 2 O 3 ratio can be produced.
- the second method is a method performed in the order of ⁇ 1>, ⁇ 2>, ⁇ 3>, ⁇ 4>, ⁇ 5>, ⁇ 7>, ⁇ 6>, ⁇ 9>.
- a seed crystal having a low SiO 2 / Al 2 O 3 ratio can be effectively used by standing and heating after aging.
- the third method is a method performed in the order of ⁇ 1>, ⁇ 2>, ⁇ 3>, ⁇ 4>, ⁇ 5>, ⁇ 7>, ⁇ 8>, ⁇ 9>.
- the SiO 2 / Al 2 O 3 ratio of the seed crystal and the reaction mixture composition are different from the conventional method.
- the following three orders are also possible.
- the SiO 2 / Al 2 O 3 ratio of the seed crystal and the composition of the reaction mixture are different from those of the conventional method.
- the pre-substitution beta zeolite obtained by the method of the present invention is used as a seed crystal to be used. That is, in these three production methods, seed crystals can be used repeatedly, and thus organic SDA is essentially not used. In short, these three production methods can be said to be methods for producing a beta zeolite by a green process that has an extremely low environmental load.
- the method of the beta zeolite before substitution used in the present invention will be described in more detail.
- the method in the order of ⁇ 1>, ⁇ 2>, and ⁇ 3> in FIG. 1 is the same as the conventional method using organic SDA.
- the SiO 2 / Al 2 O 3 ratio range of the seed crystal is limited to a narrow range of 22-25.
- Beta-type zeolite having a seed crystal SiO 2 / Al 2 O 3 ratio of less than 8 is generally not used because it is extremely difficult to synthesize. If the SiO 2 / Al 2 O 3 ratio of the seed crystal exceeds 30, the product tends to be ZSM-5 regardless of the composition of the reaction mixture. Further, the amount of seed crystals added in this production method is in the range of 0.1 to 20% by mass with respect to the silica component contained in the reaction mixture. The amount added is preferably small, but is determined in consideration of the reaction rate and the effect of suppressing impurities. A preferable addition amount is 1 to 20% by mass, and a more preferable addition amount is 1 to 10% by mass.
- the average particle size of the beta-type zeolite seed crystal used in this production method is 150 nm or more, preferably 150 to 1000 nm, and more preferably 200 to 600 nm.
- the size of the pre-substitution beta zeolite obtained by synthesis is generally not uniform and has a certain particle size distribution, and it is not difficult to determine the crystal particle size having the highest frequency among them. .
- the average particle diameter refers to the maximum particle diameter of crystals in observation with a scanning electron microscope. Beta-type zeolite using organic SDA generally has a small average particle size and is generally in the range of 100 nm to 1000 nm. However, the particle diameter is unclear due to the aggregation of small particles, or there are those exceeding 1000 nm.
- beta zeolite having an average particle size of 150 nm or more is used as a seed crystal. Since the pre-substitution beta zeolite obtained by this production method also has an average particle diameter in this range, it can be suitably used as a seed crystal.
- the reaction mixture to which the seed crystal is added is obtained by mixing a silica source, an alumina source, an alkali source, and water so as to have a composition represented by the molar ratio shown below. If the composition of the reaction mixture is outside this range, the intended pre-substitution beta zeolite cannot be obtained.
- silica source used for obtaining the reaction mixture having the above molar ratio examples include silica itself and silicon-containing compounds capable of generating silicate ions in water. Specific examples include wet method silica, dry method silica, colloidal silica, sodium silicate, aluminosilicate gel, and the like. These silica sources can be used alone or in combination of two or more. Among these silica sources, it is preferable to use silica (silicon dioxide) in that a zeolite can be obtained without unnecessary by-products.
- alumina source for example, a water-soluble aluminum-containing compound can be used. Specific examples include sodium aluminate, aluminum nitrate, and aluminum sulfate.
- Aluminum hydroxide is also a suitable alumina source. These alumina sources can be used alone or in combination of two or more. Of these alumina sources, it is preferable to use sodium aluminate or aluminum hydroxide because zeolite can be obtained without unnecessary by-products (for example, sulfate, nitrate, etc.).
- the alkali source for example, sodium hydroxide can be used.
- sodium silicate is used as the silica source or sodium aluminate is used as the alumina source
- sodium which is an alkali metal component contained therein is simultaneously regarded as NaOH and is also an alkali component.
- NaOH sodium hydroxide
- the method of adding the raw materials when preparing the reaction mixture may be a method that facilitates obtaining a uniform reaction mixture.
- a uniform reaction mixture can be obtained by adding and dissolving an alumina source in an aqueous sodium hydroxide solution at room temperature, then adding a silica source and stirring and mixing.
- the seed crystals are added with mixing with the silica source or after the silica source is added. Thereafter, stirring and mixing are performed so that the seed crystals are uniformly dispersed.
- the temperature at which the reaction mixture is prepared and generally the reaction may be performed at room temperature (20 to 25 ° C.).
- the reaction mixture containing seed crystals is placed in a closed container and heated to react to crystallize the beta zeolite.
- This reaction mixture does not contain organic SDA.
- One method of crystallizing is to heat by standing method without aging as shown in the conventional method ( ⁇ 4>, ⁇ 5>, ⁇ 6>, ⁇ 9> procedure) ).
- aging refers to an operation of maintaining the temperature at a temperature lower than the reaction temperature for a certain period of time. In aging, generally, it is left without stirring. It is known that effects such as prevention of by-product impurities, enabling heating under stirring without by-product impurities, and increasing the reaction rate can be achieved by aging. However, the mechanism of action is not always clear.
- the temperature and time for aging are set so that the above-mentioned effects are maximized. In this production method, aging is preferably carried out at 20 to 80 ° C., more preferably 20 to 60 ° C., and preferably in the range of 2 hours to 1 day.
- the following three methods are methods for producing a pre-substitution beta zeolite by the green process, which is a feature of this production method. According to these three methods, infinite self-reproduction using the pre-substitution beta zeolite obtained by the present production method as a seed crystal is possible, and a production process using no organic SDA is possible. That is, a method in the order ⁇ 10>, ⁇ 5>, ⁇ 6>, ⁇ 9>, a method in the order ⁇ 10>, ⁇ 5>, ⁇ 7>, ⁇ 6>, ⁇ 9>, ⁇ 10>, It is a method in the order of ⁇ 5>, ⁇ 7>, ⁇ 8>, ⁇ 9>. The characteristics of each process are as described above.
- the SiO 2 / Al 2 O 3 ratio of the pre-substitution beta zeolite obtained by this production method is preferably in the range of 8-30.
- the pre-substitution beta-type zeolite obtained by this production method is used as a seed crystal, in the case of static synthesis, the beta-type zeolite can be used without aging even though the SiO 2 / Al 2 O 3 ratio is low. Crystallization is possible.
- a beta zeolite synthesized using organic SDA is used as a seed crystal, a calcined product is used.
- a pre-substitution beta zeolite obtained by this production method is used, the calcining is not necessary. It is estimated that this difference appears in the difference in effect as a seed crystal, but details are not clear.
- aging is preferably performed.
- the heating temperature is in the range of 100 to 200 ° C., preferably 120 to 180 ° C., and heating is performed under an autogenous pressure. If the temperature is lower than 100 ° C., the crystallization rate becomes extremely slow, so that the production efficiency of the beta zeolite is deteriorated. On the other hand, when the temperature exceeds 200 ° C., an autoclave having a high pressure resistance is required, which is not economical, and the generation rate of impurities increases.
- the heating time is not critical in the present production method, and it may be heated until a beta zeolite with sufficiently high crystallinity is produced. In general, a pre-substitution beta zeolite with satisfactory crystallinity can be obtained by heating for about 5 to 150 hours.
- Pre-substitution beta-type zeolite crystals are obtained by the heating described above. After completion of the heating, the produced crystal powder is separated from the mother liquor by filtration, washed with water or warm water and dried. Since it does not contain organic substances in a dry state, there is no need for firing.
- the beta zeolite before substitution thus obtained is ion-exchanged with Fe (II) ions as described above to become Fe (II) substituted beta zeolite.
- the Fe (II) -substituted beta zeolite may be used as it is as an adsorbent for various gases such as nitric oxide and hydrocarbons, or as a gas adsorbent containing the Fe (II) -substituted beta zeolite. May be.
- the Fe (II) -substituted beta zeolite is brought into solid-gas contact with various gases such as nitrogen monoxide and hydrocarbons, whereby the gas is converted into Fe (II).
- gases such as nitrogen monoxide and hydrocarbons, whereby the gas is converted into Fe (II).
- II) Can be adsorbed on substituted beta zeolite.
- the nitric oxide gas or hydrocarbon gas in addition to adsorbing the nitric oxide gas or hydrocarbon gas by bringing the nitric oxide gas or hydrocarbon gas itself into contact with the Fe (II) substituted beta zeolite, the nitric oxide gas or hydrocarbon gas is adsorbed.
- a gas containing gas may be brought into contact with the Fe (II) -substituted beta zeolite to adsorb nitrogen monoxide gas or hydrocarbon gas in the gas and remove nitrogen monoxide gas or hydrocarbon gas from the gas.
- Examples of such gas include exhaust gas of an internal combustion engine using hydrocarbons such as gasoline and light oil as fuel, exhaust gas generated from various boilers and incinerators, and the like.
- Powder X-ray diffractometer manufactured by Mac Science Co., Ltd., powder X-ray diffractometer MO3XHF 22 , using Cuk ⁇ ray, voltage 40 kV, current 30 mA, scan step 0.02 °, scan speed 2 ° / min SiO 2 / Al 2 O 3 ratio: Beta-type zeolite was dissolved using hydrogen fluoride (HF), and the solution was analyzed using ICP to quantify Al. Beta-type zeolite was dissolved using potassium hydroxide (KOH), and the solution was analyzed using ICP to quantify Si. The SiO 2 / Al 2 O 3 ratio was calculated based on the determined amounts of Si and Al. BET surface area, micropore specific surface area, and micropore volume measuring device: ANTOSORB-1 manufactured by Cantachrome Instruments
- This reaction mixture was placed in a 60 cc stainless steel sealed container and left to stand at 140 ° C. for 46 hours under autogenous pressure without aging and stirring. After cooling the sealed container, the product was filtered and washed with warm water to obtain a white powder. The X-ray diffraction pattern of this product is shown in FIG. As can be seen from the figure, this product was a beta zeolite containing no impurities such as SDA. Table 1 shows the physical property values of the pre-substitution beta zeolite thus obtained.
- Fe (II) -substituted beta-type zeolite After adding 40 ml of distilled water, 1.00 g of beta-type zeolite before substitution and ascorbic acid twice the number of moles of iron compound to be added to a polypropylene container, Fe (II ) SO 4 ⁇ 7H 2 O was added in an amount of 1% by mass with respect to the pre-substitution beta-type zeolite, followed by stirring at room temperature for 1 day in a nitrogen atmosphere. Thereafter, the precipitate was filtered by suction, washed with distilled water, and dried to obtain Fe (II) -substituted beta zeolite carrying 0.04% by mass of Fe 2+ .
- FIG. 3 shows an X-ray diffraction pattern of the obtained Fe (II) -substituted beta zeolite.
- the amount of nitric oxide gas that has come out of the quartz glass tube without being adsorbed is measured using the peak area of a thermal conductivity gas chromatograph (GC-TCD, manufactured by Shimadzu Corporation, GC-8A) and a chemiluminescent NO analyzer (NOx). It was calculated from the value detected by analyzer, manufactured by Yanagimoto Seisakusho, ECL-77A).
- the measurement conditions of the thermal conductivity gas chromatograph (GC-TCD) are as shown below.
- the amount of nitrogen monoxide gas adsorbed on the Fe (II) -substituted beta zeolite per unit mass was determined by subtracting the calculated value from the supply amount of nitric oxide gas. The results are shown in Table 1 below.
- Toluene gas adsorption evaluation Toluene which is a typical hydrocarbon contained in exhaust gas discharged from an internal combustion engine, was used as an adsorption target gas. 20 mg of Fe (II) -substituted beta zeolite was put in a quartz tube having an inner diameter of 4 mm and held between quartz wool and glass beads. Helium was used as the mobile phase and the sample was activated at 390 ° C. for about 1 hour. After cooling the column to 50 ° C., toluene was injected until saturated.
- the amount of toluene gas that was not adsorbed and emerged from the quartz glass tube was calculated from the value detected by the peak area of the thermal conductivity gas chromatograph (GC-TCD, manufactured by Shimadzu Corporation, GC-8A).
- the measurement conditions of the thermal conductivity gas chromatograph (GC-TCD) are as shown below.
- the amount of toluene gas adsorbed on the Fe (II) -substituted beta zeolite per unit mass was determined by subtracting the calculated value from the supply amount of toluene gas. The results are shown in Table 1 below.
- Example 2 Fe (II) SO 4 .7H 2 O was added except that 5% by mass (Example 2), 10% by mass (Example 3) and 20% by mass (Example 4) were added to the pre-substitution beta-type zeolite.
- Example 2 an Fe (II) -substituted beta zeolite was obtained.
- the amount of Fe 2+ supported was as shown in Table 1.
- the X-ray diffraction patterns of the obtained Fe (II) -substituted beta zeolite are as shown in FIGS.
- the obtained Fe (II) -substituted beta zeolite was evaluated in the same manner as in Example 1. The results are shown in Table 1.
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Abstract
Description
SiO2/Al2O3比が10~18であり、BET比表面積が400~700m2/gであり、ミクロ孔比表面積が290~500m2/gであり、かつミクロ孔容積が0.15~0.25cm3/gであるFe(II)置換ベータ型ゼオライトを提供するものである。
SiO2/Al2O3比が10~18であり、BET比表面積が400~700m2/gであり、ミクロ孔比表面積が290~500m2/gであり、かつミクロ孔容積が0.15~0.25cm3/gであるFe(II)置換ベータ型ゼオライトを一酸化窒素又は一酸化窒素を含むガスと接触させて、一酸化窒素を該Fe(II)置換ベータ型ゼオライトに吸着させる一酸化窒素の除去方法を提供するものである。
SiO2/Al2O3比が10~18であり、BET比表面積が400~700m2/gであり、ミクロ孔比表面積が290~500m2/gであり、かつミクロ孔容積が0.15~0.25cm3/gであるFe(II)置換ベータ型ゼオライトをハイドロカーボン又はハイドロカーボンを含むガスと接触させて、ハイドロカーボンを該Fe(II)置換ベータ型ゼオライトに吸着させるハイドロカーボンの除去方法を提供するものである。
・<10>、<5>、<6>、<9>
・<10>、<5>、<7>、<6>、<9>
・<10>、<5>、<7>、<8>、<9>
これらの場合も種結晶のSiO2/Al2O3比や、反応混合物の組成が従来法と異なる。その上、これらの三通りの方法では、使用する種結晶として、本発明の方法によって得られた置換前ベータ型ゼオライトを用いている。すなわち、この三通りの製造方法では種結晶が繰り返し使用可能なので、本質的に有機SDAを使用しない。要するに、この三通りの製造方法は、環境負荷が究極的に小さいグリーンプロセスによるベータ型ゼオライトの製造方法ということができる。
・SiO2/Al2O3=40~200
・Na2O/SiO2=0.22~0.4
・H2O/SiO2=10~50
・SiO2/Al2O3=44~200
・Na2O/SiO2=0.24~0.35
・H2O/SiO2=15~25
・SiO2/Al2O3=10~40
・Na2O/SiO2=0.05~0.25
・H2O/SiO2=5~50
・SiO2/Al2O3=12~40
・Na2O/SiO2=0.1~0.25
・H2O/SiO2=10~25
SiO2/Al2O3比:ベータ型ゼオライトを、フッ化水素(HF)を用いて溶解させ、溶解液を、ICPを用いて分析しAlを定量した。またベータ型ゼオライトを、水酸化カリウム(KOH)を用いて溶解させ、溶解液を、ICPを用いて分析しSiを定量した。定量したSi及びAlの量に基づきSiO2/Al2O3比を算出した。
BET表面積、ミクロ孔比表面積及びミクロ孔容積測定装置:(株)カンタクローム インスツルメンツ社製 AUTOSORB-1
(1)置換前ベータ型ゼオライトの製造
純水13.9gに、アルミン酸ナトリウム0.235gと、36%水酸化ナトリウム1.828gとを溶解した。微粉状シリカ2.024gと、SiO2/Al2O3比=24.0のベータ型ゼオライト種結晶0.202gを混合したものを、少しずつ前記の水溶液に添加して攪拌混合し、SiO2/Al2O3=40、Na2O/SiO2=0.275、H2O/SiO2=25の組成の反応混合物を得た。このベータ型ゼオライト種結晶は、SDAを用いて以下に述べる方法で得られたものである。この反応混合物を60ccのステンレス製密閉容器に入れて、熟成及び攪拌することなしに140℃で46時間、自生圧力下で静置加熱した。密閉容器を冷却後、生成物を濾過、温水洗浄して白色粉末を得た。この生成物のX線回折図を図2に示す。同図から判るように、この生成物はSDA等の不純物を含まないベータ型ゼオライトであった。このようにして得られた置換前ベータ型ゼオライトの物性値を表1に示す。
テトラエチルアンモニウムヒドロキシドをSDAとして用い、アルミン酸ナトリウムをアルミナ源、微粉状シリカ(Mizukasil P707)をシリカ源とする従来公知の方法により、165℃、96時間、攪拌加熱を行って、SiO2/Al2O3比が24.0のベータ型ゼオライトを合成した。これを電気炉中で空気を流通しながら550℃で10時間焼成して、有機物を含まない結晶を製造した。X線回折の結果から、この結晶はベータ型ゼオライトであることが確認された。この結晶を走査型電子顕微鏡により観察した結果、平均粒子径は280nmであった。このベータ型ゼオライトは、SDAを含まないものであった。
ポリプロピレン容器に40mlの蒸留水、置換前ベータ型ゼオライト1.00g及び加える鉄化合物の2倍のモル数のアスコルビン酸を加えた後、Fe(II)SO4・7H2Oを、置換前ベータ型ゼオライトに対して1質量%加え、窒素雰囲気下、室温で1日撹拌した。その後、沈殿物を吸引濾過し、蒸留水で洗浄後、乾燥させFe2+を0.04質量%担持したFe(II)置換ベータ型ゼオライトを得た。Fe2+の担持量は、誘導結合プラズマ発光分光分析装置(ICP-AES、(株)バリアン製、LIBERTY SeriesII)を用いて求めた。得られたFe(II)置換ベータ型ゼオライトのX線回折図を図3に示す。図3(Fe(II)置換ベータ型ゼオライト)と図2(置換前ベータ型ゼオライト)とを対比すると、ピーク位置及びピーク強度がほぼ変わらないので、イオン交換後もベータ型ゼオライトの構造を維持していることが確認された。
Fe(II)置換ベータ型ゼオライト20mgを電子天秤で正確に秤量した後、希釈剤としてシリコンカーバイトを180mg用いて、両者を均等になるように混合した。混合物を、内径6mmの石英ガラス管に詰めた。混合中の吸着水をマントルヒーターで加温して除去した後、室温まで冷却した。次に、石英ガラス管内に2分おきに1030ppmの一酸化窒素ガスを、室温で、5cm3パルスした。吸着されずに石英ガラス管から出てきた一酸化窒素ガスの量を、熱伝導度型ガスクロマトグラフ(GC-TCD、島津製作所製、GC-8A)のピーク面積及び化学発光式NO分析装置(NOx analyzer、柳本製作所製、ECL-77A)で検出される値から算出した。熱伝導度型ガスクロマトグラフ(GC-TCD)の測定条件は、以下に示すとおりである。そして、算出した値を、一酸化窒素ガスの供給量から差し引くことで、単位質量あたりのFe(II)置換ベータ型ゼオライトに吸着した一酸化窒素ガスの量を求めた。その結果を以下の表1に示す。
・キャリアガス:Heガス
・キャリアガス流量:30cm3・min-1 ・検出部温度:100℃
・検出部電流:80mA
内燃機関から排出される排気ガスに含まれるハイドロカーボンの典型であるトルエンを吸着の対象ガスとして用いた。Fe(II)置換ベータ型ゼオライト20mgを内径4mmの石英管に入れ、石英ウールとガラスビーズとの間に保持した。移動相としてヘリウムを用い、試料を390℃で約1時間活性化させた。カラムを50℃に冷却した後、トルエンを飽和状態になるまで注入した。吸着されずに石英ガラス管から出てきたトルエンガスの量を、熱伝導度型ガスクロマトグラフ(GC-TCD、島津製作所製、GC-8A)のピーク面積で検出される値から算出した。熱伝導度型ガスクロマトグラフ(GC-TCD)の測定条件は、以下に示すとおりである。そして、算出した値を、トルエンガスの供給量から差し引くことで、単位質量あたりのFe(II)置換ベータ型ゼオライトに吸着したトルエンガスの量を求めた。その結果を以下の表1に示す。
・キャリアガス:Heガス
・キャリアガス流量:30cm3・min-1 ・検出部温度:150℃
・検出部電流:50mA
Fe(II)SO4・7H2Oを、置換前ベータ型ゼオライトに対して5質量%(実施例2)、10質量%(実施例3)及び20質量%(実施例4)加える以外は実施例1と同様にしてFe(II)置換ベータ型ゼオライトを得た。Fe2+の担持量は表1に示すとおりとなった。また得られたFe(II)置換ベータ型ゼオライトのX線回折図は図4~図6に示すとおりである。得られたFe(II)置換ベータ型ゼオライトについて実施例1と同様の評価を行った。その結果を表1に示す。
置換前ベータ型ゼオライトとして東ソー(株)製のH+型ベータ型ゼオライト(型番HSZ-940HOA、SDAを用いて合成)を用いた。このゼオライトのX線回折図を図7(a)に示す。これ以外は実施例1と同様にしてFe(II)置換ベータ型ゼオライトを得た。得られたFe(II)置換ベータ型ゼオライトのX線回折図を図7(b)に示す。得られたFe(II)置換ベータ型ゼオライトについて、実施例1と同様にして一酸化窒素ガス及びトルエンガス吸着の評価を行った。その結果を表1に示す。
置換前ベータ型ゼオライトとして東ソー(株)製のNH4 +型ベータ型ゼオライト(型番HSZ-930NHA、SDAを用いて合成)を用いた。このゼオライトのX線回折図を図8(a)に示す。これ以外は実施例1と同様にしてFe(II)置換ベータ型ゼオライトを得た。得られたFe(II)置換ベータ型ゼオライトのX線回折図を図8(b)に示す。得られたFe(II)置換ベータ型ゼオライトについて、実施例1と同様にして一酸化窒素ガス及びトルエンガス吸着の評価を行った。その結果を表1に示す。
特に、実施例1ないし実施例4の対比から明らかなように、Fe(II)の担持量が増加するに連れて一酸化窒素ガス及びトルエンガスの吸着量が増加することが判る。
Claims (11)
- Fe(II)イオンによってイオン交換されたFe(II)置換ベータ型ゼオライトであって、
SiO2/Al2O3比が10~18であり、BET比表面積が400~700m2/gであり、ミクロ孔比表面積が290~500m2/gであり、かつミクロ孔容積が0.15~0.25cm3/gであるFe(II)置換ベータ型ゼオライト。 - Fe(II)の担持量が、Fe(II)置換ベータ型ゼオライトに対して0.01~6.5質量%である請求項1に記載のFe(II)置換ベータ型ゼオライト。
- Fe(II)イオンによってイオン交換される前のベータ型ゼオライトとして、SiO2/Al2O3比が10~16であり、ナトリウム型の状態で測定されたBET比表面積が500~700m2/gであり、ミクロ孔比表面積が350~500m2/gであり、かつミクロ孔容積が0.15~0.25cm3/gであるものを用いた請求項1又は2に記載のFe(II)置換ベータ型ゼオライト。
- (1)以下に示すモル比で表される組成の反応混合物となるように、シリカ源、アルミナ源、アルカリ源、及び水を混合し、
SiO2/Al2O3=40~200
Na2O/SiO2=0.22~0.4
H2O/SiO2=10~50
(2)SiO2/Al2O3比が8~30であり、且つ平均粒子径が150nm以上である有機化合物を含まないベータ型ゼオライトを種結晶として用い、これを、前記反応混合物中のシリカ成分に対して0.1~20質量%の割合で該反応混合物に添加し、
(3)前記種結晶が添加された前記反応混合物を100~200℃で密閉加熱することで得られたベータ型ゼオライトを、Fe(II)イオンによってイオン交換される前のベータ型ゼオライトとして用いる請求項3に記載のFe(II)置換ベータ型ゼオライト。 - 請求項1ないし4のいずれか一項に記載のFe(II)置換ベータ型ゼオライトを含むガス吸着剤。
- 一酸化窒素の吸着に用いられる請求項5に記載のガス吸着剤。
- ハイドロカーボンの吸着に用いられる請求項5に記載のガス吸着剤。
- SiO2/Al2O3比が10~16であり、ナトリウム型の状態で測定されたBET比表面積が500~700m2/gであり、ミクロ孔比表面積が350~500m2/gであり、かつミクロ孔容積が0.15~0.25cm3/gであるベータ型ゼオライトを、二価の鉄の水溶性化合物水溶液中に分散し、混合撹拌することで、該ベータ型ゼオライトにFe(II)イオンを担持させる工程を有する、Fe(II)置換ベータ型ゼオライトの製造方法。
- 前記混合撹拌に際し、前記水溶液に、前記二価の鉄のモル数の0.1~3倍のアスコルビン酸を添加する請求項8に記載の製造方法。
- Fe(II)イオンによってイオン交換されており、
SiO2/Al2O3比が10~18であり、BET比表面積が400~700m2/gであり、ミクロ孔比表面積が290~500m2/gであり、かつミクロ孔容積が0.15~0.25cm3/gであるFe(II)置換ベータ型ゼオライトを一酸化窒素又は一酸化窒素を含むガスと接触させて、一酸化窒素を該Fe(II)置換ベータ型ゼオライトに吸着させる一酸化窒素の除去方法。 - Fe(II)イオンによってイオン交換されており、
SiO2/Al2O3比が10~18であり、BET比表面積が400~700m2/gであり、ミクロ孔比表面積が290~500m2/gであり、かつミクロ孔容積が0.15~0.25cm3/gであるFe(II)置換ベータ型ゼオライトをハイドロカーボン又はハイドロカーボンを含むガスと接触させて、ハイドロカーボンを該Fe(II)置換ベータ型ゼオライトに吸着させるハイドロカーボンの除去方法。
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DE112012000495.7T DE112012000495B4 (de) | 2011-01-18 | 2012-01-17 | Fe(II)-substituierter Beta-Typ-Zeolith und Verfahren zur Herstellung desselben |
CN201280011170.9A CN103402918B (zh) | 2011-01-18 | 2012-01-17 | Fe(II)置换β型沸石、包含其的气体吸附剂及其制造方法、以及一氧化氮及烃的除去方法 |
US13/979,670 US9108187B2 (en) | 2011-01-18 | 2012-01-17 | Fe(II)-substituted beta type zeolite, gas adsorbent containing same and method for producing same, and method for removing nitrogen monoxide and hydrocarbon |
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JP5116880B2 (ja) | 2013-01-09 |
US9108187B2 (en) | 2015-08-18 |
JP2012162446A (ja) | 2012-08-30 |
DE112012000495B4 (de) | 2019-01-10 |
DE112012006703A5 (de) | 2015-06-25 |
CN103402918B (zh) | 2016-01-20 |
DE112012000495T5 (de) | 2013-10-24 |
CN103402918A (zh) | 2013-11-20 |
US20140157987A1 (en) | 2014-06-12 |
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