WO2006095392A1 - 排ガス処理用触媒の製造方法 - Google Patents
排ガス処理用触媒の製造方法 Download PDFInfo
- Publication number
- WO2006095392A1 WO2006095392A1 PCT/JP2005/003791 JP2005003791W WO2006095392A1 WO 2006095392 A1 WO2006095392 A1 WO 2006095392A1 JP 2005003791 W JP2005003791 W JP 2005003791W WO 2006095392 A1 WO2006095392 A1 WO 2006095392A1
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- WIPO (PCT)
- Prior art keywords
- metal
- exhaust gas
- catalyst
- solution
- gas treatment
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 74
- 239000002184 metal Substances 0.000 claims abstract description 74
- 150000003839 salts Chemical class 0.000 claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 claims abstract description 27
- 239000000243 solution Substances 0.000 claims abstract description 27
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 16
- 239000012266 salt solution Substances 0.000 claims abstract description 8
- 239000012855 volatile organic compound Substances 0.000 claims abstract description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 5
- 239000007853 buffer solution Substances 0.000 claims description 22
- 239000000084 colloidal system Substances 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 239000003638 chemical reducing agent Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 8
- 239000010953 base metal Substances 0.000 claims description 7
- 150000002739 metals Chemical class 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229910052741 iridium Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 239000011550 stock solution Substances 0.000 claims 1
- 239000006174 pH buffer Substances 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 22
- 238000012360 testing method Methods 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000011068 loading method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 235000011054 acetic acid Nutrition 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000003841 chloride salts Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
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- 238000005470 impregnation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- -1 jetyl ether Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000003826 tablet Substances 0.000 description 1
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- B01J21/04—Alumina
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
Definitions
- the present invention relates to a method for producing an exhaust gas treatment catalyst. More specifically, the present invention relates to a method for producing a catalyst for treating exhaust gas containing carbon monoxide and a volatile organic compound.
- Exhaust gas discharged from various industrial equipment such as automobiles, aircraft, and various factories contains NO, SO, CO (-acid carbon), unburned hydrocarbons, and the like.
- NO, SO, CO (-acid carbon), unburned hydrocarbons, and the like In order to treat such contents, exhaust gas treatment catalysts are used.
- JP-A-10-309462 describes an NMHC oxidation catalyst in which Pt (platinum) is supported on an alumina support.
- such a conventional exhaust gas treatment catalyst uses an expensive noble metal such as Pt.
- Pt is prepared as an aqueous solution in the form of nitrate or the like, and powdered alumina is added thereto and stirred appropriately. Then, after impregnating alumina with a platinum compound, it is dried and fired by a conventional method.
- Patent Document 1 Japanese Patent Laid-Open No. 10-309462
- the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing a catalyst for exhaust gas treatment that can reduce the amount of noble metal to be supported and can reduce the production cost.
- the present invention includes carbon monoxide and a volatile organic compound.
- a metal salt aqueous solution in which at least one metal salt is dissolved is prepared as a pH buffer solution, and the metal salt solution is reduced while maintaining the pH constant, thereby colloidal metal solution And immersing the carrier in the metal colloid solution, and supporting the metal on the carrier.
- a method for manufacturing a catalyst for exhaust gas treatment that enables a small amount of noble metal to be supported and reduces manufacturing costs. That is, in the method for producing an exhaust gas treatment catalyst according to the present invention, a metal salt aqueous solution is prepared as a pH buffer solution, and the pH can be maintained constant regardless of evaporation of the solution during colloid production. Also, in the loading process, the pH buffering action is inherited by the metal colloid solution, so that the pH can be kept constant regardless of the catalyst soaking process. As a result, the reduction rate of the metal and the loading rate of the metal on the colloidal carrier are stabilized, and it is possible to prepare very fine colloidal particles, while supporting the metal in a highly dispersed state.
- a catalyst for treating exhaust gas containing carbon monoxide and a volatile organic compound is produced. That is, the present invention is suitable for exhaust gas discharged from V, so-called lean combustion gas engine power.
- Volatile organic compounds generally refer to hydrocarbons other than methane and ethane.
- an aqueous metal salt solution in which at least one metal salt is dissolved is prepared as a pH buffer solution.
- the metal salt is preferably a metal salt of a noble metal that exhibits catalytic activity.
- a plurality of kinds of noble metal salts may be used.
- Suitable salts of noble metals are nitrates, chlorides, acetates, and complex salts of Ir, Rh, Ru, Pt, Pd, Ag, and Au. Among these, Ir, Pt, Pd nitrates, chlorides, acetates, and complex salts are more preferable.
- the pH buffer solution (metal salt aqueous solution to be reduced) is prepared, for example, by a suitable one of the following procedures.
- An aqueous solution of the metal salt is prepared by dissolving the metal salt.
- a reducing agent is charged.
- a pH buffer solution is mixed with the obtained metal salt aqueous solution to prepare a pH buffer solution containing the target metal salt.
- the above pH buffer solution and a mixture of this in a metal salt aqueous solution are also pH buffer solutions.
- the reducing agent and the pH buffer solution may be added simultaneously to the initially prepared metal salt aqueous solution, or the reducing agent may be added after mixing the pH buffer solution.
- a metal salt and a pH buffer solution may be mixed in a mixed solution of water such as ion-exchanged water and a reducing agent.
- the water used in any procedure is preferably used after boiling to remove dissolved oxygen.
- organic acids are preferred, such as sodium citrate, potassium citrate, carboxylic acids such as acetic acid, formic acid and malic acid, methanol, ethanol, propanol and the like. Mention may be made of alcohols, ethers such as jetyl ether, and ketones such as methyl ethyl ketone.
- Typical pH buffer solutions are a mixture of weak acid and strong base, weak base and strong acid, or weak acid and weak base.
- Examples of the pH buffer solution that can be used in the present invention include ammonia water / salt ammonium buffer solution and acetic acid Z acetate Na buffer solution.
- a metal colloid solution is prepared by reducing the metal salt aqueous solution prepared as a pH buffer solution to be obtained.
- the reduction reaction proceeds by heating a pH buffer (aqueous metal salt solution) to about 80 ° C.
- the pH buffer can maintain P H regardless evaporation of the solution in a colloidal manufacturing constant (1 one 14).
- metal colloidal particles are generated by the reduction reaction of the metal dissolved as ions, and the metal colloid solution is prepared by completing the reaction.
- the carrier can be immersed in the metal colloid solution, and the metal can be supported on the carrier.
- the following processing can be performed according to the form of the final product.
- a monolithic carrier such as powder, granules, pellets, tablets, or hercum is immersed in a metal colloid solution, and then dried and fired if necessary. To obtain the final catalyst product.
- the powdered catalyst obtained as described above is subjected to a force for granulating or granulating to a predetermined particle size, or pressure molding or extrusion molding. In addition, the molded product is cut into a predetermined length to make a pellet.
- the metal reduction rate and the metal support rate to the colloidal carrier are stable, and it is possible to prepare very fine colloidal particles, while the metal is in a highly dispersed state. It can be supported on a carrier.
- a plurality of active metals can be supported on the obtained catalyst. That is, one or more kinds of noble metals and Z or base metals can be included as active metals. A sufficient effect can be exhibited even if the loading amount per kind of these metals is 0.7 gZL or less.
- the noble metal to be supported is preferably at least one selected from the group consisting of Ir, Rh, Ru, Pt, Pd, Ag, Au, and their oxides.
- the supported base metal is selected from the group consisting of Cr, Mn, Fe, Co, Cu, Ce, La, Ba, Na, Ca, K, W, Mo, V, P metals and their oxides. It is preferable that it is at least one kind.
- the compounds constituting the carrier include SiO, AlO, TiO, ZrO, SiOAlO, Ti
- the 2 2 2 2 2 3 2 2 4 2 4 2 4 2 o force is preferably at least one selected from the group consisting of forces.
- the base metal and Z or their oxides are preferably supported on a catalyst for treating exhaust gas after supporting colloidal particles (noble metal).
- Table 1 shows the effect of the method for producing an exhaust gas treatment catalyst according to the present invention. Such tests and comparisons were performed. No. 1—No. 54 show Test Examples 1-154 according to the present invention, and also show the results of Comparative Examples 1-3.
- Test Examples 1-11 13 and Test Examples 35-54 were conducted by preparing a metal colloid solution containing a single noble metal or a noble metal oxide. These were performed according to the following procedure.
- Ion exchange water from which dissolved oxygen was removed by boiling for 1 hour was prepared.
- Test Examples 14 to 34 are test examples in which other noble metals or base metals are further supported. Corresponding metal salts were prepared, and an aqueous metal salt solution (including a reducing agent) was prepared in the same manner as described above, and all the aqueous metal salt solutions were mixed and subjected to the same reduction treatment and immersion treatment. The amount of catalyst supported is shown in Table 1 as the active component composition (active metal 1 1 2 or 1 1 3).
- Comparative Example 1 was carried out by the impregnation method, and Comparative Examples 2 and 3 were the same as in the test example, but were carried out without using a pH buffer solution.
- 0.5 liter of ethanol was added to 0.5 liter of ion-exchanged water to prepare 1 liter of a mixed solution. Dissolved oxygen was removed by boiling the mixture for 1 hour.
- To this mixture add 2.4 g of salt iridium acid and 0.02 liters of acetic acid Z aqueous solution of sodium acetate, and mix with pH buffer solution.
- a solution (Ir is lmmol) was prepared. These were kept at 80 ° C. and reduced for 1 hour. The pH of the solution during the reduction was kept at 2. After confirming that the solution changed from red to black, the solution was cooled on ice to obtain a metal colloid solution.
- Test Example 1 It was soaked and loaded with a predetermined amount of Ir. The pH during loading was also the same as above.
- the supported catalyst was dried at 110 ° C. and then calcined at 500 ° C. for 5 hours. The resulting catalyst was designated as Test Example 1.
- Catalyst layer temperature 300 ° C
- the gas reaction rate is expressed by the following equation.
- the exhaust gas treatment catalyst obtained by the method for producing an exhaust gas treatment catalyst according to the present invention can be used for exhaust gas discharged from various industrial equipment such as automobiles, airplanes, and various factories.
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Abstract
担持する貴金属の少量化を可能とし、製造コストの低減させる排ガス処理用触媒の製造方法を提供する。
一酸化炭素及び揮発性有機化合物を含有する排ガス処理用触媒の製造方法において、少なくとも一種の金属塩を溶解した金属塩水溶液をｐＨ緩衝液として調製し、ｐＨを一定に維持しつつ上記金属塩水溶液を還元処理して金属コロイド溶液を調製し、該金属コロイド溶液中に担体を浸漬させ、該担体に金属を担持させることとした。上記金属の一種当たりの担持量は、０．７ｇ／Ｌ以下とすることができる。
Description
排ガス処理用触媒の製造方法
技術分野
[0001] 本発明は、排ガス処理用触媒の製造方法に関する。さらに詳細には、一酸化炭素 及び揮発性有機化合物を含有する排ガスの処理用触媒の製造方法に関する。 背景技術
[0002] 各種産業機器、例えば、自動車、航空機、各種工場等から排出される排ガス中に は、 NO、 SO、 CO (—酸ィ匕炭素）、未燃焼の炭化水素等が含まれている。このよう な含有物を処理するために、排ガス処理用触媒が用いられて 、る。
例えば、特開平 10-309462号公報には、アルミナ担体に Pt (白金）を担持した N MHC酸化触媒が記載されて ヽる。
[0003] ここで、このような従来の排ガス処理用触媒は、 Ptのような高価な貴金属を用いて いる。 Ptを、例えば、含浸法で担体であるアルミナに担持するには、 Ptを硝酸塩等の 形態の水溶液として調製し、これに粉末状のアルミナを投入し、適宜攪拌する。そし て、アルミナに白金化合物を含浸させた後、常法により乾燥、焼成させることとしてい る。
[0004] しかし、従来の方法では、高価な Pt等の貴金属を多量に担持するため、製造コスト が高力つた。また、製造コストを減らすため貴金属量を低減すると、処理対象物の燃 焼速度が低下し、十分な性能が得られな力つた。
特許文献 1：特開平 10- 309462号公報
発明の開示
発明が解決しょうとする課題
[0005] 本発明は、上記事情に鑑みてなされたもので、担持する貴金属の少量化を可能と し、製造コストの低減させる排ガス処理用触媒の製造方法を提供することを目的とす る。
課題を解決するための手段
[0006] 上記目的を達成するために、本発明は、一酸化炭素及び揮発性有機化合物を含
有する排ガスの処理用触媒の製造方法において、少なくとも一種の金属塩を溶解し た金属塩水溶液を pH緩衝液として調製し、 pHを一定に維持しつつ上記金属塩水 溶液を還元処理して金属コロイド溶液を調製し、該金属コロイド溶液中に担体を浸漬 させ、該担体に金属を担持させることを含む。
発明の効果
[0007] 本発明によれば、担持する貴金属の少量ィ匕を可能とし、製造コストの低減させる排 ガス処理用触媒の製造方法が提供される。すなわち、本発明に係る排ガス処理用触 媒の製造方法では、 pH緩衝液として金属塩水溶液を調製し、コロイド製造中の溶液 の蒸発にかかわらず pHを一定に維持することができる。また、担持工程においても、 金属コロイド溶液に pH緩衝作用が受け継がれるので、触媒の浸漬経過にかかわら ず、 pHを一定に維持することができる。これによつて、金属の還元速度及びコロイド 担体への金属の担持速度が安定し、非常に微細なコロイド粒子を調製可能としつつ 、金属を高分散の状態で担体に担
持することができる。
発明を実施するための最良の形態
[0008] 以下に本発明に係る排ガス処理用触媒の製造方法をさらに詳細に説明する。
本発明に係る排ガス処理用触媒の製造方法では、一酸化炭素及び揮発性有機化 合物を含有する排ガスを処理するための触媒が製造される。すなわち、本発明は、 V、わゆる希薄燃焼ガスエンジン力 排出される排ガスに適合して 、る。「揮発性有機 化合物」は、一般的にメタン、エタン以外の炭化水素を指す。
[0009] 本発明に係る排ガス処理用触媒の製造方法では、少なくとも一種の金属塩を溶解 した金属塩水溶液を pH緩衝液として調製する。金属塩は、触媒活性を具現する貴 金属の金属塩が好適である。複数種の貴金属の塩を用いることもできる。貴金属の 塩として好適なものは、 Ir、 Rh、 Ru、 Pt、 Pd、 Ag、 Auの硝酸塩、塩化物、酢酸塩、 錯塩である。これらのうち、さらに好適なものは、 Ir、 Pt、 Pdの硝酸塩、塩化物、酢酸 塩、錯塩である。
[0010] pH緩衝液 (還元処理の対象となる金属塩水溶液）は、例えば以下のような手順のう ち好適なもので調製される。
金属塩を溶解して金属塩の水溶液を調製する。次いで、還元剤を投入する。得ら れる金属塩水溶液に、 pH緩衝液を混合し、目的とする金属塩を含む pH緩衝液を調 製する。先の pH緩衝液も、これを金属塩水溶液に混合したものも pH緩衝液である。 なお、最初に調製した金属塩水溶液に、還元剤と pH緩衝液とを同時に投入すること としてもよく、又は pH緩衝液混合後に還元剤を投入してもよい。または、イオン交換 水等の水と還元剤の混合液に金属塩と、 pH緩衝液を混合するようにしてもよい。い ずれの手順でも使用する水は、沸騰させて溶存酸素を除去した後、用いることが好 適である。
[0011] 「還元剤」として用いることができる化合物としては、有機酸が好ましぐクェン酸ナト リウム、クェン酸カリウム、酢酸、ギ酸、りんご酸等のカルボン酸、メタノール、エタノー ル、プロパノール等のアルコール類、ジェチルエーテル等のエーテル類、メチルェチ ルケトン等のケトン類を挙げることができる。
[0012] 酸または塩基を加えたとき、又は希釈したときに、 pHの変化を緩める作用を緩衝作 用（buffer action) t 、 、、 このような作用を備えた水溶液を pH緩衝液 (buffer solution)という。弱酸と強塩基、弱塩基と強酸、弱酸と弱塩基の混合 液が代表的 な pH緩衝液である。本発明に採用可能な pH緩衝液としては、例えば、アンモニア 水/塩ィ匕アンモ-ゥム緩衝液、酢酸 Z酢酸 Na緩衝液を挙げることができる。
[0013] 本発明では、得られる pH緩衝液として調製した金属塩水溶液を還元処理して金属 コロイド溶液を調製する。一般的に、還元反応は、 pH緩衝液 (金属塩水溶液)を約 8 0°Cに加熱することによって進行する。 pH緩衝液では、コロイド製造中の溶液の蒸発 にかかわらず PHを一定（1一 14)に維持することができる。還元反応では、イオンとし て溶解している金属の還元反応によって、金属コロイド粒子が生成し、反応が終了す ることによって金属コロイド溶液が調製される。
[0014] そして、該金属コロイド溶液中に担体を浸漬させ、該担体に金属を担持させること ができる。最終製品の形態に合わせて以下のような処理を行うことができる。
(1)金属コロイド溶液中に、粉末状、粒状、ペレット状、タブレット状又はハ-カム等の モノリス体の担体 (基材ともいう）を浸漬し、しかる後に乾燥させ、必要な場合焼成を 行って最終触媒製品を得る。
(2)上記のようにして得られた粉末状の触媒を所定粒度に整粒する力もしくは造粒し 、又は加圧成形もしくは押出成形を行う。また、成形品を所定長さに切断してペレット 化する。
[0015] ここで、このような担持工程においても、金属コロイド溶液に pH緩衝作用が受け継 がれるので、触媒の浸漬経過にかかわらず、 pHを一定（1一 14)に維持することがで きる。
[0016] 以上のような結果、本発明では、金属の還元速度及びコロイド担体への金属の担 持速度が安定し、非常に微細なコロイド粒子を調製可能としつつ、金属を高分散の 状態で担体に担持することができる。
[0017] なお、本発明では、得られる触媒に複数の活性金属を担持させることができる。す なわち、活性金属として、一種又は二種以上の貴金属及び Z又は卑金属を含ませる ことができる。そして、これらの金属の一種当たりの担持量を 0. 7gZL以下としても十 分な効果を発揮させることができる。
なお、本明細書及び特許請求の範囲の記載で、上記のような「及び Z又は」の表現 は、 JISZ 8301 「規格票の様式」に従って、並列する二つの語句の両者を併合し たもの、及びいずれか一方ずつの三通りを、一括して厳密に示すのに用いている。
[0018] 上記担持される貴金属としては、 Ir、 Rh、 Ru、 Pt、 Pd、 Ag、 Au及びそれらの酸ィ匕 物から成る群より選ばれる少なくとも一種以上であることが好適であり。上記担持され る卑金属としては、 Cr、 Mn、 Fe、 Co、 Cu、 Ce、 La、 Ba、 Na、 Ca、 K、 W、 Mo、 V、 Pの金属及びその酸ィ匕物から成る群より選ばれる少なくとも一種以上であることが好 適である。
[0019] 上記担体を構成する化合物としては、 SiO、 Al O、 TiO、 ZrO、 SiO Al O、 Ti
2 2 3 2 2 2 2 3
O -SiO、 TiO— Al O、 TiO—ZrO、 SO /ZrO、 SO /TiO、 SO /TiO— Zr
2 2 2 2 3 2 2 4 2 4 2 4 2 o力も成る群より選ばれる少なくとも一種であることが好適である。
2
卑金属及び Z又はその酸化物は、コロイド粒子 (貴金属)担持後の排ガス処理用触 媒に担持することが好適である。
実施例 1
[0020] 本発明に係る排ガス処理用触媒の製造方法の効果を確認するために、表 1に示す
ような試験及び比較を行った。 No. 1— No. 54は、本発明に係る試験例 1一 54を示 し、比較例 1一 3の結果も示す。
[0021] 試験例 1一 13及び試験例 35— 54は、単一の貴金属又は貴金属の酸化物を含む 金属コロイド溶液を調製して行った。これらは、以下の手順に従って行った。
(1) 1時間煮沸させることによって溶存酸素を除去したイオン交換水を調製した。
(2)還元剤を準備した。表 1中、還元剤の仕様は、全てイオン交換水/還元剤の体積 比が 1Z1となるように調製した。
[0022] (3)イオン交換水 0. 5リットルに還元剤（還元剤溶液) 0. 5リットルを混合して 1リットル の混合液とした。
[0023] (4)各々の活性金属に対応する金属塩及び酢酸 Z酢酸 Na水溶液 (pH2) 0. 02リツ トルを、上記混合液に加え、活性金属が lmmol含まれる pH緩衝液を調製した。
[0024] (5) pH緩衝液を 80°Cに保持して 1時間還元処理を行った。還元中の溶液の pHは 2 に維持された。これによつて金属コロイド溶液を得た。
[0025] (6)この金属コロイド溶液 250ccに担体を浸漬し、表 1中のような割合で、活性金属を 担持した。担持する際も pHを 2に維持した。担持後、触媒を 110°Cで乾燥し、 500°C で焼成した。触媒の担持量を、表 1に活性成分組成 (活性金属 1)として示す。
[0026] 試験例 14から 34は、他の貴金属、又は卑金属をさらに担持した試験例である。対 応する金属塩を準備し、上記と同様にして金属塩水溶液 (還元剤を含む)を調製し、 全部の金属塩水溶液を混合して同様の還元処理、浸漬処理を行った。触媒担持量 を表 1に活性成分組成 (活性金属 1一 2又は 1一 3)として示す。
比較例 1は含浸法により、比較例 2, 3は、試験例と同様であるが、 pH緩衝液を用 いないで実施した。
[0027] なお、試験例 1について、手順をさらに詳細に示す。
試験例 1
金属コロイド溶液の調製：
イオン交換水 0.5リットルにエタノール 0.5リットルをカ卩え、混合液 1リットルを調製した 。この混合液を 1時間沸騰させることにより溶存酸素を除去した。この混合液に、塩ィ匕 イリジウム酸 2. 4gと酢酸 Z酢酸 Na水溶液を 0. 02リットルカ卩え、 pH緩衝液の混合水
溶液 (Irが lmmol)を調製した。これらを 80°Cに保持して 1時間還元処理を行った。 還元中の溶液の pHは 2に保持した。溶液が赤色から黒色に変色するのを確認後氷 冷し、金属コロイド溶液とした。
[0028] 金属コロイドの担体への担持：
250ccの金属コロイド溶液に、 γ AI Oを lOOgZm2コートしたハ-カム基材を浸
2 3
漬させ、所定量の Irを担持した。担持する際の pHも上記と同じとした。担持後の触媒 は、 110°Cで乾燥した後 500°C5時間焼成し、得られた触媒を試験例 1とした。
[0029] 反応率評価条件：
以上のようにして調製した試験例及び比較例について反応率評価試験を以下の条 件で行った。結果は、表 1に示すとおりである。本発明に係る試験例では、少量の触 媒担持量にかかわらず、十分な触媒活性を得られていることが了解される。
CO： 65ppm、 C以上の炭ィ匕水素： 30ppm、 NOx ： 65ppm
O
ガス量 200NLZh、
触媒層温度： 300°C
なお、ガスの反応率は下記式にて表される。
•COの反応率（％) = (1 出口 CO濃度 Z入口 CO濃度） X 100
•C
2以上の炭化水素の反応率 (％)
= (1 出口 c以上の炭化水素濃度 炭化水素濃度） X 100
2 Z入口 c以上の
2
[表 1]
讓
本発明に係る排ガス処理用触媒の製造方法によって得られる排ガス処理用触媒は 、各種産業機器、例えば、自動車、航空機、各種工場等から排出される排ガスに用 いることがでさる。
Claims
[1] 一酸化炭素及び揮発性有機化合物を含有する排ガスの処理用触媒の製造方法に お ヽて、少なくとも一種の金属塩を溶解した金属塩水溶液を pH緩衝液として調製し
、pHを一定に維持しつつ上記金属塩水溶液を還元処理して金属コロイド溶液を調 製し、該金属コロイド溶液中に担体を浸漬させ、該担体に金属を担持させることを含 む排ガス処理用触媒の製造方法。
[2] 活性金属として、一種又は二種以上の貴金属及び Z又は卑金属を含み、上記金 属の一種当たりの担持量を 0. 7gZL以下とした排ガス処理用触媒を製造することを 含む請求項 1に記載の排ガス処理用触媒の製造方法。
[3] 金属塩水溶液に、有機酸からなる還元剤及び pH緩衝液を混合し、金属コロイド溶 液の原液となる金属塩水溶液を調製することを含む請求項 1又は 2に記載の排ガス 処理用触媒の製造方法。
[4] 上記貴金属が、 Ir、 Rh、 Ru、 Pt、 Pd、 Ag、 Au及びそれらの酸化物から成る群より 選ばれる少なくとも一種以上である請求項 2又は 3に記載の排ガス処理用触媒の製 造方法。
[5] 上記卑金属が Cr、 Mn、 Fe、 Co、 Cu、 Ce、 La、 Ba、 Na、 Ca、 K、 W、 Mo、 V、 Pの 金属及びその酸ィ匕物力 成る群より選ばれる少なくとも一種以上である請求項 2ない し 3のいずれかに記載の排ガス処理用触媒の製造方法。
[6] 上記担体が、 SiO、 Al O、 TiO、 ZrO、 SiO—Al O、 TiO— SiO、 TiO—Al O
2 2 3 2 2 2 2 3 2 2 2 2 3
、 TiO -ZrO、 SO /ZrO、 SO /TiO、 SO /TiO—ZrOから成る群より選ば
2 2 4 2 4 2 4 2 2
れる一種である請求項 2な ヽし 5の ヽずれかに記載の排ガス処理用触媒の製造方法
[7] 卑金属又はその酸ィ匕物を、コロイド粒子担持後の排ガス処理用触媒に担持するこ とを含む請求項 2な 、し 6の 、ずれかに記載の排ガス処理用触媒の製造方法。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/576,041 US20080176742A1 (en) | 2005-03-04 | 2005-03-04 | Method For Producing Catalyst For Treating Exhaust Gas |
| PCT/JP2005/003791 WO2006095392A1 (ja) | 2005-03-04 | 2005-03-04 | 排ガス処理用触媒の製造方法 |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2005/003791 WO2006095392A1 (ja) | 2005-03-04 | 2005-03-04 | 排ガス処理用触媒の製造方法 |
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Family
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|---|---|---|---|
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| Country | Link |
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| US (1) | US20080176742A1 (ja) |
| WO (1) | WO2006095392A1 (ja) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008041756A1 (en) | 2006-10-05 | 2008-04-10 | Nippon Shokubai Co., Ltd. | Catalyst for treating an exhaust gas containing organic acid, and method for treating an exhaust gas containing organic acid |
| CN112588285A (zh) * | 2020-12-14 | 2021-04-02 | 西安凯立新材料股份有限公司 | 一种水热稳定的丙烯酸废气催化燃烧催化剂及其制备方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI121531B (fi) * | 2007-07-23 | 2010-12-31 | Ecocat Oy | Katalyytti poiste- tai prosessikaasuissa olevien haitallisten hiilivetyjen poistamiseksi sekä menetelmä tällaisen katalyytin valmistamiseksi ja käyttämiseksi |
| CN101829568B (zh) * | 2010-05-07 | 2012-01-04 | 广东工业大学 | 锰氧化物原位掺杂型钯基整体式催化剂的制备方法及其应用 |
| JP2014069151A (ja) * | 2012-09-28 | 2014-04-21 | Daihatsu Motor Co Ltd | 排ガス浄化用触媒 |
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| EP2066441A4 (en) * | 2006-10-05 | 2011-11-23 | Nippon Catalytic Chem Ind | CATALYST FOR TREATING AN EXHAUST WITH ORGANIC ACID AND PROCESS FOR TREATING AN EXHAUST WITH ORGANIC ACID |
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| CN112588285B (zh) * | 2020-12-14 | 2023-02-10 | 西安凯立新材料股份有限公司 | 一种水热稳定的丙烯酸废气催化燃烧催化剂及其制备方法 |
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