JP2009247955A - Method of manufacturing catalyst - Google Patents
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- JP2009247955A JP2009247955A JP2008097080A JP2008097080A JP2009247955A JP 2009247955 A JP2009247955 A JP 2009247955A JP 2008097080 A JP2008097080 A JP 2008097080A JP 2008097080 A JP2008097080 A JP 2008097080A JP 2009247955 A JP2009247955 A JP 2009247955A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 22
- 239000001301 oxygen Substances 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 239000002923 metal particle Substances 0.000 claims abstract description 18
- 239000011261 inert gas Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- -1 polyethylene Polymers 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims 1
- 150000003949 imides Chemical class 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 47
- 238000000746 purification Methods 0.000 abstract description 28
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 12
- 239000002131 composite material Substances 0.000 abstract description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 11
- 229910052684 Cerium Inorganic materials 0.000 abstract description 3
- 229910052797 bismuth Inorganic materials 0.000 abstract description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 29
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 25
- 229910052799 carbon Inorganic materials 0.000 description 25
- 239000000843 powder Substances 0.000 description 23
- 229930195733 hydrocarbon Natural products 0.000 description 17
- 150000002430 hydrocarbons Chemical class 0.000 description 17
- 239000002245 particle Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 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
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
Description
本発明は、触媒の製造方法に関し、特に、ディーゼルエンジンの排ガス中の一酸化炭素および炭化水素の浄化に適した排ガス浄化触媒として使用可能な触媒の製造方法に関する。 The present invention relates to a method for producing a catalyst, and more particularly to a method for producing a catalyst that can be used as an exhaust gas purification catalyst suitable for purification of carbon monoxide and hydrocarbons in exhaust gas from a diesel engine.
従来、ディーゼルエンジンの排ガス中の一酸化炭素（ＣＯ）や炭化水素（ＨＣ）などの有害ガスを低温で効率的に酸化することができる排ガス浄化触媒として、アルミナからなる担体に貴金属が担持された排ガス浄化触媒や、チタニアとゼオライトを含有する担体に貴金属が担持された排ガス浄化触媒（例えば、特許文献１参照）などが提案されている。 Conventionally, a noble metal is supported on a support made of alumina as an exhaust gas purification catalyst capable of efficiently oxidizing harmful gases such as carbon monoxide (CO) and hydrocarbons (HC) in exhaust gas of a diesel engine at a low temperature. An exhaust gas purification catalyst, an exhaust gas purification catalyst in which a noble metal is supported on a carrier containing titania and zeolite (see, for example, Patent Document 1) have been proposed.
一方、ディーゼルエンジンの排ガスには、カーボンを主体とする粒子状物質（以下「ＰＭ」という）が含まれており、ディーゼルエンジンの排ガスからＰＭを除去する方法として、一般に、排気ガス流路に多孔質体セラミックスからなるディーゼル・パーティキュレート・フィルタ（以下、「ＤＰＦ」という）を設置してＰＭを捕集（トラップ）する方法が用いられている。ＤＰＦに捕集されたＰＭは間欠的または連続的に燃焼処理され、ＤＰＦはＰＭの捕集前の状態に再生される。このＤＰＦの再生処理には、一般に、電気ヒーターやバーナーなどによって外部から強制加熱してＰＭを燃焼させる方法や、ＤＰＦよりもエンジン側に酸化触媒を設置し、排ガス中に含まれるＮＯを酸化触媒によってＮＯ２にして、ＮＯ２の酸化力によってＰＭを燃焼させる方法などが用いられている。 On the other hand, the exhaust gas of a diesel engine contains particulate matter (hereinafter referred to as “PM”) mainly composed of carbon. As a method for removing PM from the exhaust gas of a diesel engine, the exhaust gas passage is generally porous. A method of collecting PM (trap) by installing a diesel particulate filter (hereinafter referred to as “DPF”) made of a material ceramic is used. The PM collected in the DPF is burned intermittently or continuously, and the DPF is regenerated to the state before the PM is collected. This DPF regeneration process is generally performed by a method of burning PM by forcibly heating from the outside with an electric heater, a burner, or the like, or by installing an oxidation catalyst on the engine side of the DPF, and converting NO contained in the exhaust gas into an oxidation catalyst. in the NO 2 by a method for combusting PM by the oxidation force of the NO 2 is used.
このようなディーゼルエンジンの排ガスからＰＭを低温で燃焼させることができる排ガス浄化触媒として、白金（Ｐｔ）などの貴金属元素を含まず、セリウム（Ｃｅ）とビスマス（Ｂｉ）と酸素から構成される複合酸化物を使用することが提案されている（例えば、特許文献２参照）。 As an exhaust gas purifying catalyst capable of burning PM from exhaust gas of such a diesel engine at a low temperature, it is a composite composed of cerium (Ce), bismuth (Bi) and oxygen without containing noble metal elements such as platinum (Pt). It has been proposed to use an oxide (for example, see Patent Document 2).
しかし、アルミナからなる担体に貴金属が担持された排ガス浄化触媒では、担体として使用するアルミナが、ディーゼルエンジンの排ガス中の硫黄化合物により被毒して劣化し易いという問題がある。また、特許文献１で提案されたチタニアとゼオライトを含有する担体に貴金属が担持された排ガス浄化触媒では、特許文献２で提案されたＣｅとＢｉと酸素から構成される複合酸化物を使用する排ガス浄化触媒と比べて、ディーゼルエンジンの排ガスからのＰＭの除去性能が格段に低くなる。
However, in an exhaust gas purification catalyst in which a noble metal is supported on a support made of alumina, there is a problem that alumina used as the support is easily poisoned and deteriorated by sulfur compounds in the exhaust gas of a diesel engine. Further, in the exhaust gas purifying catalyst proposed in Patent Document 1 in which a noble metal is supported on a support containing titania and zeolite, the exhaust gas using a composite oxide composed of Ce, Bi and oxygen proposed in
一方、特許文献２で提案されたＣｅとＢｉと酸素から構成される複合酸化物を使用する排ガス浄化触媒は、ディーゼルエンジンの排ガスからＰＭを低温で燃焼させることができるが、ディーゼルエンジンの排ガス中の一酸化炭素（ＣＯ）や炭化水素（ＨＣ）などの有害ガスも低温で効率的に酸化することができるようにするのが望ましい。
On the other hand, the exhaust gas purification catalyst using a composite oxide composed of Ce, Bi and oxygen proposed in
そこで、本発明者らは、ＣｅとＢｉと酸素から構成される複合酸化物を使用する排ガス浄化触媒のディーゼルエンジンの排ガス中の一酸化炭素（ＣＯ）や炭化水素（ＨＣ）などの浄化性能を向上させるために、ＣｅとＢｉと酸素から構成される複合酸化物からなる担体に、蒸発乾固法（担体に活性成分を含む過剰の溶液に加えて溶媒を加熱蒸発させる方法）やｉｎｃｉｐｉｅｎｔ ｗｅｔｎｅｓｓ法（ポアフィリング法）（活性成分を含む溶液をごく僅かずつ加えて担体表面が均一に濡れ始めた状態で含浸を終了する方法）などの従来の方法により、ＣｅとＢｉと酸素から構成される複合酸化物からなる担体にＰｔ、Ｐｄ、Ｒｈなどの貴金属が担持された触媒を製造することを試みたが、ディーゼルエンジンの排ガス中の一酸化炭素（ＣＯ）や炭化水素（ＨＣ）などの浄化性能を向上させることができなかった。 Therefore, the present inventors have a purification performance of carbon monoxide (CO), hydrocarbon (HC), etc. in the exhaust gas of a diesel engine of an exhaust gas purification catalyst using a composite oxide composed of Ce, Bi and oxygen. In order to improve, a carrier comprising a complex oxide composed of Ce, Bi and oxygen is evaporated to dryness (a method in which a solvent is heated and evaporated in addition to an excess solution containing an active ingredient in the carrier) or an incipient wetness method. (Pore-filling method) (composition composed of Ce, Bi and oxygen by a conventional method such as adding a solution containing an active ingredient little by little and ending the impregnation in a state where the surface of the carrier begins to get wet uniformly) An attempt was made to produce a catalyst in which a noble metal such as Pt, Pd, Rh, etc. was supported on an oxide carrier. Carbon monoxide (CO) in the exhaust gas of a diesel engine Could not be improved purification performance, such as hydrocarbons (HC).
また、触媒の活性は、原子状の触媒金属が高分散で担持された触媒よりも、触媒金属原子がナノクラスター状態で担持されている触媒の方が高いことが知られているが、上記の従来の方法によりＣｅとＢｉと酸素から構成される複合酸化物からなる担体に貴金属が担持された触媒を透過型電子顕微鏡（ＴＥＭ）で観察したところ、担体の表面に貴金属のクラスターは存在しなかった。この触媒では、貴金属が原子状で担持されているか、あるいは、担体の内部に取り込まれたことにより、貴金属が担持された効果が極めて低くなっていると考えられる。 Further, it is known that the catalyst activity is higher in the catalyst in which the catalyst metal atoms are supported in the nanocluster state than the catalyst in which the atomic catalyst metal is supported in a highly dispersed state. When a catalyst in which a noble metal is supported on a support made of a complex oxide composed of Ce, Bi, and oxygen by a conventional method is observed with a transmission electron microscope (TEM), no noble metal cluster exists on the surface of the support. It was. In this catalyst, it is considered that the effect of supporting the noble metal is extremely low because the noble metal is supported in an atomic form or taken into the support.
したがって、本発明は、このような従来の問題点に鑑み、ＣｅとＢｉと酸素から構成される複合酸化物からなる担体の表面に貴金属ナノクラスターを形成して、ディーゼルエンジンの排ガス中の一酸化炭素（ＣＯ）や炭化水素（ＨＣ）などの有害ガスの浄化性能を向上させる排ガス浄化触媒として使用可能な触媒を製造することができる、触媒の製造方法を提供することを目的とする。 Therefore, in view of such a conventional problem, the present invention forms a noble metal nanocluster on the surface of a support composed of a composite oxide composed of Ce, Bi and oxygen, and thereby monoxide in the exhaust gas of a diesel engine. An object of the present invention is to provide a catalyst production method capable of producing a catalyst that can be used as an exhaust gas purification catalyst that improves the purification performance of harmful gases such as carbon (CO) and hydrocarbons (HC).
本発明者らは、上記課題を解決するために鋭意研究した結果、ＣｅとＢｉと酸素を構成元素として含む複合酸化物からなる担体に貴金属粒子を分散して担持させた後、貴金属粒子を有機分子で保護し、その後、不活性ガス雰囲気中で熱処理することにより、ＣｅとＢｉと酸素から構成される複合酸化物からなる担体の表面に貴金属ナノクラスターを形成して、ディーゼルエンジンの排ガス中の一酸化炭素（ＣＯ）や炭化水素（ＨＣ）などの有害ガスの浄化性能を向上させる排ガス浄化触媒として使用可能な触媒を製造することができることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have dispersed noble metal particles on a support made of a composite oxide containing Ce, Bi, and oxygen as constituent elements, and then supported the noble metal particles in an organic form. By protecting with molecules and then heat-treating in an inert gas atmosphere, noble metal nanoclusters are formed on the surface of the support composed of a composite oxide composed of Ce, Bi and oxygen, and in the exhaust gas of diesel engines It has been found that a catalyst that can be used as an exhaust gas purification catalyst that improves the purification performance of harmful gases such as carbon monoxide (CO) and hydrocarbons (HC) can be produced, and the present invention has been completed.
すなわち、本発明による触媒の製造方法は、ＣｅとＢｉと酸素を構成元素として含む複合酸化物からなる担体に貴金属粒子を分散して担持させた後、貴金属粒子を有機分子で保護し、その後、不活性ガス雰囲気中で熱処理することを特徴とする。この触媒の製造方法において、不活性ガス雰囲気中で熱処理した後、水素雰囲気中および空気または酸素雰囲気中の少なくとも一方の雰囲気中で熱処理してもよい。また、不活性ガス雰囲気中で熱処理する温度が、有機分子を焼成して炭化させる温度であるのが好ましい。さらに、有機分子が、ポリビニルピロリドン、ポリビニルアルコール、ポリエチレンイミド、ポリアクリル酸、シュウ酸、クエン酸、マレイン酸およびこれらの混合物からなる群から選ばれるのが好ましく、貴金属粒子が、Ｐｔ、ＰｄおよびＲｈからなる群から選ばれる貴金属の粒子であるのが好ましい。 That is, in the method for producing a catalyst according to the present invention, after precious metal particles are dispersed and supported on a support made of a composite oxide containing Ce, Bi and oxygen as constituent elements, the precious metal particles are protected with organic molecules, and then Heat treatment is performed in an inert gas atmosphere. In this catalyst manufacturing method, after heat treatment in an inert gas atmosphere, heat treatment may be performed in a hydrogen atmosphere and / or an atmosphere of air or oxygen. Moreover, it is preferable that the temperature which heat-processes in inert gas atmosphere is a temperature which bakes and carbonizes an organic molecule. Furthermore, the organic molecule is preferably selected from the group consisting of polyvinylpyrrolidone, polyvinyl alcohol, polyethyleneimide, polyacrylic acid, oxalic acid, citric acid, maleic acid and mixtures thereof, and the noble metal particles are Pt, Pd and Rh. The particles are preferably noble metal particles selected from the group consisting of:
本発明によれば、ＣｅとＢｉと酸素から構成される複合酸化物からなる担体の表面に貴金属ナノクラスターを形成して、ディーゼルエンジンの排ガス中の一酸化炭素（ＣＯ）や炭化水素（ＨＣ）などの有害ガスの浄化性能を向上させる排ガス浄化触媒として使用可能な触媒を製造することができる。 According to the present invention, noble metal nanoclusters are formed on the surface of a support composed of a complex oxide composed of Ce, Bi and oxygen, and carbon monoxide (CO) and hydrocarbon (HC) in exhaust gas from a diesel engine. Thus, it is possible to produce a catalyst that can be used as an exhaust gas purification catalyst that improves the purification performance of harmful gases.
以下、図１を参照して、本発明による触媒の製造方法の実施の形態について説明する。 Hereinafter, an embodiment of a method for producing a catalyst according to the present invention will be described with reference to FIG.
まず、ＣｅとＢｉと酸素から構成される複合酸化物からなる担体１が分散した分散液中において担体１の表面電位を利用して、担体１に貴金属錯イオンを静電的に吸着させ、その後、還元剤で化学的に還元すると、図１（ａ）に示すように、担体１に貴金属粒子２が分散して担持された状態になる。次に、貴金属に配位し易い有機分子を投入して攪拌すると、図１（ｂ）に示すように、貴金属粒子２に有機分子３が選択的に配位した状態になる。このようにして得られた触媒前駆体の分散液を濾過し、洗浄し、乾燥した後、不活性ガス雰囲気中で焼成すると、図１（ｃ）に示すように、有機分子３が炭化してそのまま残留するため、熱処理中の貴金属粒子２の移動が抑制され、貴金属粒子２が担体１の表面にナノサイズで固定される。その後、水素雰囲気中および空気または酸素雰囲気中の少なくとも一方の雰囲気中で熱処理することによって、図１（ｄ）に示すように、炭化物４を除去した状態にしてもよい。なお、空気または酸素雰囲気中で熱処理する場合は、３００〜４００℃程度で燃焼させて除去するのが好ましい。
First, a noble metal complex ion is electrostatically adsorbed on the carrier 1 using the surface potential of the carrier 1 in a dispersion in which the carrier 1 made of a complex oxide composed of Ce, Bi and oxygen is dispersed. When chemically reduced with a reducing agent, the
このように、本発明による触媒の製造方法の実施の形態では、貴金属に選択的に配位する性質をもつ有機分子を添加することによって、ＣｅとＢｉと酸素から構成される複合酸化物からなる担体に担持されている貴金属粒子を保護し、その後の熱処理工程における貴金属の熱移動を抑制して、担体の表面に貴金属ナノクラスターを形成することができる。 As described above, in the embodiment of the method for producing a catalyst according to the present invention, an organic molecule having a property of selectively coordinating to a noble metal is added to form a composite oxide composed of Ce, Bi, and oxygen. It is possible to protect the noble metal particles supported on the carrier, suppress the heat transfer of the noble metal in the subsequent heat treatment step, and form noble metal nanoclusters on the surface of the carrier.
一般に、触媒は、反応条件によって決定される反応系の化学平衡に達するまでの反応速度を変化させるので、反応速度を向上させるために反応系の温度や圧力を上昇させる。そのため、ナノサイズの粒子が担体の表面に担持された触媒では、反応系の温度や圧力が上昇した環境下においてナノサイズの粒子の焼結（シンタリング）が進行し、反応に寄与する触媒の表面積や活性点が減少して、触媒の活性が次第に低下する。しかし、本発明による触媒の製造方法の実施の形態では、担体の表面に分散して担持されたナノサイズの貴金属粒子をポリビニルピロリドン（ＰＶＰ）などの有機分子で保護し、その後、高温で熱処理して有機分子を焼成して炭化することによって、触媒の活性点を表面に露出させるとともに、生成した炭素による粒子の焼結を防止して、ナノサイズの粒子が担体の表面に担持された触媒の劣化を防止することができる。したがって、本発明による触媒の製造方法の実施の形態によって製造された触媒は、ディーゼルエンジンの排ガス中の一酸化炭素および炭化水素の浄化に適した排ガス浄化触媒として使用することができるだけでなく、化学工学や石油化学などの高温や高圧における触媒反応に使用する触媒としても使用することができる。 In general, the catalyst changes the reaction rate until the chemical equilibrium of the reaction system determined by the reaction conditions is reached, so that the temperature and pressure of the reaction system are increased in order to improve the reaction rate. For this reason, in a catalyst in which nano-sized particles are supported on the surface of the support, sintering (sintering) of the nano-sized particles proceeds in an environment in which the temperature and pressure of the reaction system are increased, and the catalyst contributing to the reaction. The surface area and active sites decrease, and the activity of the catalyst gradually decreases. However, in the embodiment of the method for producing a catalyst according to the present invention, nano-sized noble metal particles dispersed and supported on the surface of the support are protected with organic molecules such as polyvinyl pyrrolidone (PVP), and then heat-treated at a high temperature. By calcination and carbonization of organic molecules, the active sites of the catalyst are exposed to the surface, and sintering of the particles by the generated carbon is prevented, so that the nano-sized particles are supported on the surface of the support. Deterioration can be prevented. Therefore, the catalyst produced by the embodiment of the method for producing a catalyst according to the present invention can be used not only as an exhaust gas purification catalyst suitable for purification of carbon monoxide and hydrocarbons in exhaust gas of a diesel engine, but also as a chemical. It can also be used as a catalyst used in catalytic reactions at high temperatures and high pressures such as engineering and petrochemistry.
以下、本発明による触媒の製造方法の実施例について詳細に説明する。 Examples of the method for producing a catalyst according to the present invention will be described in detail below.
［実施例１］
まず、ＣｅとＢｉと酸素から構成される複合酸化物としてＣｅ０．９Ｂｉ０．１Ｏ２７ｇを蒸留水３０ｍＬに入れて超音波で１時間分散させた後、一晩攪拌して溶液中にＣｅ０．９Ｂｉ０．１Ｏ２を十分に分散させた。また、この攪拌中の溶液にＰｔ前駆溶液（Ｋ２ＰｔＣｌ４）と錯化剤（ＮａＣｌ）を投入した後、ｐＨを３に調整して、表面がプラスにチャージされたＣｅ０．９Ｂｉ０．１Ｏ２にＰｔ錯イオン（［Ｐｔ２＋（Ｃｌ−）４］）を静電的に吸着させた。
[Example 1]
First, 7 g of Ce 0.9 Bi 0.1 O 2 as a composite oxide composed of Ce, Bi, and oxygen was placed in 30 mL of distilled water and dispersed with ultrasound for 1 hour, and then stirred overnight in the solution. Ce 0.9 Bi 0.1 O 2 was sufficiently dispersed in the mixture. In addition, after adding a Pt precursor solution (K 2 PtCl 4 ) and a complexing agent (NaCl) to this stirring solution, the pH was adjusted to 3 and the surface was positively charged with Ce 0.9 Bi 0. .1 Pt complex ions ([Pt 2+ (Cl − ) 4 ]) were electrostatically adsorbed on O 2 .
次に、ｐＨを３に調整したヒドラジン溶液２ｍＬを添加し、さらに１時間攪拌して、Ｐｔ錯イオンを還元した後、ＰＶＰ５００ｍｇを添加して、さらに３０分間攪拌し、得られた溶液を濾過し、洗浄し、乾燥して粉末を得た。
Next, 2 mL of a hydrazine solution adjusted to
この粉末を窒素気流中において４００℃で１時間熱処理した後、窒素気流中において８００℃で１時間熱処理して、１質量％のＰｔを含むＣｅ０．９Ｂｉ０．１Ｏ２粉末を得た。 This powder was heat-treated at 400 ° C. for 1 hour in a nitrogen stream, and then heat-treated at 800 ° C. for 1 hour in a nitrogen stream to obtain Ce 0.9 Bi 0.1 O 2 powder containing 1% by mass of Pt. .
このようにして得られた１質量％のＰｔを含むＣｅ０．９Ｂｉ０．１Ｏ２粉末（触媒粉末）の貴金属粒子の粒径を測定した。この貴金属粒子の粒径を測定するために、次のようにＴＥＭ−ＥＤＸ（透過型電子顕微鏡−エネルギー分散型Ｘ線検出器）による測定を行った。まず、触媒粉末をメタノールに入れて超音波で十分に分散させた後、ＴＥＭグリッドに滴下して測定試料を用意した。この測定試料について、透過型電子顕微鏡（ＴＥＭ）（日立製作所製のＨＦ−２０００）により加速電圧２００ｋＶで観察し、結晶粒の分散状態を調べた。この観察で得られた映像中においてコントラストの部分に焦点をあてて金属種を限定し、その金属の粒径を測定した。このＴＥＭ−ＥＤＸ測定により、図２のＴＥＭ写真に示すように、Ｃｅ０．９Ｂｉ０．１Ｏ２の表面に粒径２〜５ｎｍのＰｔクラスターが（丸印で囲んだ位置に）明瞭に分散しているのが観察された。このように８００℃の熱処理を行っても、Ｃｅ０．９Ｂｉ０．１Ｏ２の表面にＰｔクラスターが熱処理前と同等の粒径２〜５ｎｍを維持したまま分散して担持されていることから、本実施例のように、有機分子としてＰＶＰを添加することによって、熱処理の有無にかかわらず、Ｃｅ０．９Ｂｉ０．１Ｏ２の表面に粒径２〜５ｎｍのＰｔクラスターを安定して形成することができることがわかった。 The particle diameter of the noble metal particles of Ce 0.9 Bi 0.1 O 2 powder (catalyst powder) containing 1% by mass of Pt thus obtained was measured. In order to measure the particle size of the noble metal particles, measurement was performed with a TEM-EDX (transmission electron microscope-energy dispersive X-ray detector) as follows. First, the catalyst powder was put in methanol and sufficiently dispersed with ultrasonic waves, and then dropped onto a TEM grid to prepare a measurement sample. This measurement sample was observed with a transmission electron microscope (TEM) (HF-2000 manufactured by Hitachi, Ltd.) at an acceleration voltage of 200 kV to examine the dispersion state of the crystal grains. In the image obtained by this observation, the metal type was limited by focusing on the contrast portion, and the particle size of the metal was measured. By this TEM-EDX measurement, as shown in the TEM photograph of FIG. 2, a Pt cluster having a particle diameter of 2 to 5 nm is clearly formed on the surface of Ce 0.9 Bi 0.1 O 2 (at a position surrounded by a circle). Dispersion was observed. Thus, even when heat treatment at 800 ° C. is performed, the Pt clusters are dispersed and supported on the surface of Ce 0.9 Bi 0.1 O 2 while maintaining the same particle diameter of 2 to 5 nm as before the heat treatment. Thus, as in this example, by adding PVP as an organic molecule, a Pt cluster having a particle size of 2 to 5 nm is stabilized on the surface of Ce 0.9 Bi 0.1 O 2 regardless of the presence or absence of heat treatment. It was found that can be formed.
次に、本実施例で得られた触媒粉末の排ガス浄化触媒としての性能を評価した。まず、固定床流通系反応器に１〜２ｍｍの触媒ペレット１．８４ｇを充填し、表１に示す組成のディーゼル排ガスの模擬混合ガスを室温において全ガス流量８Ｌ／分で流通させた。次に、出口側のＣＯ濃度を赤外分析計（堀場製作所製のＶＩＡ−５１０）、Ｃ３Ｈ６濃度を水素イオン化法分析計（堀場製作所製のＦＩＡ−５１０）によってそれぞれモニタリングしながら、触媒充填層の温度を室温から５００℃まで昇温し、ＣＯ転化率（％）＝（入口ＣＯ濃度−出口ＣＯ濃度）×１００／入口ＣＯ濃度、Ｃ３Ｈ６転化率（％）＝（入口Ｃ３Ｈ６濃度−出口Ｃ３Ｈ６濃度）×１００／入口Ｃ３Ｈ６濃度から、ＣＯ転化率（％）およびＣ３Ｈ６転化率（％）を求めた。その結果、表２に示すように、ＣＯ転化率は、２００℃で８４．９％、２５０℃で９３．１％であり、Ｃ３Ｈ６転化率は、２００℃で５４．９％、２５０℃で７７．２％であった。なお、担体としてのＣｅ０．９Ｂｉ０．１Ｏ２のＣＯ転化率は、２００℃で７８．１％、２５０℃で８４．１％であり、Ｃ３Ｈ６転化率は、２００℃で４６．６％、２５０℃で５６．３％であった。 Next, the performance of the catalyst powder obtained in this example as an exhaust gas purification catalyst was evaluated. First, 1.84 g of 1 to 2 mm catalyst pellets were charged into a fixed bed flow system reactor, and a simulated mixed gas of diesel exhaust gas having the composition shown in Table 1 was passed at room temperature at a total gas flow rate of 8 L / min. Next, while monitoring the CO concentration on the outlet side by an infrared analyzer (VIA-510 manufactured by Horiba, Ltd.) and the C 3 H 6 concentration by a hydrogen ionization analyzer (FIA-510 manufactured by Horiba, Ltd.), the catalyst The temperature of the packed bed is raised from room temperature to 500 ° C., CO conversion (%) = (inlet CO concentration−outlet CO concentration) × 100 / inlet CO concentration, C 3 H 6 conversion (%) = (inlet C The CO conversion rate (%) and the C 3 H 6 conversion rate (%) were determined from 3 H 6 concentration−outlet C 3 H 6 concentration) × 100 / inlet C 3 H 6 concentration. As a result, as shown in Table 2, the CO conversion rate was 84.9% at 200 ° C. and 93.1% at 250 ° C., and the C 3 H 6 conversion rate was 54.9%, 250 at 200 ° C. It was 77.2% at ° C. The CO conversion rate of Ce 0.9 Bi 0.1 O 2 as a carrier is 78.1% at 200 ° C. and 84.1% at 250 ° C., and the C 3 H 6 conversion rate is 200 ° C. It was 46.6% and 56.3% at 250 ° C.
［実施例２］
窒素気流中において８００℃で１時間熱処理した後に、水素気流中において４００℃で２時間還元処理した以外は、実施例１と同様の方法により、Ｐｔを含むＣｅ０．９Ｂｉ０．１Ｏ２粉末を得た。
[Example 2]
Ce 0.9 Bi 0.1 O 2 containing Pt was produced in the same manner as in Example 1 except that heat treatment was performed at 800 ° C. for 1 hour in a nitrogen stream and then reduction treatment was performed at 400 ° C. for 2 hours in a hydrogen stream. A powder was obtained.
このようにして得られた触媒粉末について、実施例１と同様の方法により、排ガス浄化触媒としての性能を評価した。その結果、表２に示すように、ＣＯ転化率は、２００℃で８５．３％、２５０℃で９２．５％であり、Ｃ３Ｈ６転化率は、２００℃で５５．９％、２５０℃で７３．８％であった。 With respect to the catalyst powder thus obtained, the performance as an exhaust gas purification catalyst was evaluated by the same method as in Example 1. As a result, as shown in Table 2, the CO conversion was 85.3% at 200 ° C. and 92.5% at 250 ° C., and the C 3 H 6 conversion was 55.9% at 250 ° C. It was 73.8% at ° C.
［比較例１］
有機分子としてのＰＶＰを添加せず、窒素気流中において４００℃で１時間熱処理した後に窒素気流中において８００℃で１時間熱処理する代わりに、空気中において８００℃で２時間焼成（昇温速度５℃／分）した以外は、実施例１と同様の方法により、１質量％のＰｔを含むＣｅ０．９Ｂｉ０．１Ｏ２粉末を得た。
[Comparative Example 1]
Instead of adding PVP as an organic molecule and heat-treating at 400 ° C. for 1 hour in a nitrogen stream and then heat-treating at 800 ° C. for 1 hour in a nitrogen stream, firing in air at 800 ° C. for 2 hours (heating rate 5) (C / min), a Ce 0.9 Bi 0.1 O 2 powder containing 1% by mass of Pt was obtained in the same manner as in Example 1.
このようにして得られた触媒粉末について、実施例１と同様の方法により、排ガス浄化触媒としての性能を評価した。その結果、表２に示すように、ＣＯ転化率は、２００℃で７２．０％、２５０℃で７６．２％であり、Ｃ３Ｈ６転化率は、２００℃で４１．４％、２５０℃で４９．８％であった。 With respect to the catalyst powder thus obtained, the performance as an exhaust gas purification catalyst was evaluated by the same method as in Example 1. As a result, as shown in Table 2, the CO conversion was 72.0% at 200 ° C. and 76.2% at 250 ° C., and the C 3 H 6 conversion was 41.4% at 250 ° C. It was 49.8% at ° C.
［比較例２］
まず、Ｐｔ濃度８．４８６質量％のＰｔ（ＮＨ３）２（ＮＯ２）２溶液３．５７１ｇに純水１８０ｍＬを加えて金属塩溶液を製造した。この溶液をマグネティックスターラーで攪拌しながら、溶液中にＣｅ０．９Ｂｉ０．１Ｏ２３０ｇを投入した後、さらに１時間攪拌した。
[Comparative Example 2]
First, 180 mL of pure water was added to 3.571 g of a Pt (NH 3 ) 2 (NO 2 ) 2 solution having a Pt concentration of 8.486% by mass to produce a metal salt solution. While stirring this solution with a magnetic stirrer, 30 g of Ce 0.9 Bi 0.1 O 2 was added to the solution, and the mixture was further stirred for 1 hour.
得られた溶液をエバポレーターに移し、温度８０℃、回転速度２５ｒｐｍで溶媒を除去して粉末を得た。この粉末を１３０℃で一晩乾燥させた後、空気中において５００℃で２時間焼成（昇温速度５℃／分）して、１質量％のＰｔを含むＣｅ０．９Ｂｉ０．１Ｏ２粉末を得た。 The obtained solution was transferred to an evaporator, and the solvent was removed at a temperature of 80 ° C. and a rotation speed of 25 rpm to obtain a powder. This powder was dried at 130 ° C. overnight and then calcined in air at 500 ° C. for 2 hours (heating rate: 5 ° C./min) to obtain Ce 0.9 Bi 0.1 O containing 1% by mass of Pt. Two powders were obtained.
このようにして得られた触媒粉末について、実施例１と同様の方法により、ＴＥＭ−ＥＤＸ測定を行った。その結果、Ｃｅ０．９Ｂｉ０．１Ｏ２の表面にＰｔのクラスターは観察されず、ＰｔマッピングからＰｔが担体酸化物中に均質に（原子状に近い状態で）存在していた。 The catalyst powder thus obtained was subjected to TEM-EDX measurement by the same method as in Example 1. As a result, no Pt cluster was observed on the surface of Ce 0.9 Bi 0.1 O 2 , and Pt was present homogeneously (in an atomic state) in the support oxide from the Pt mapping.
また、本比較例で得られた触媒粉末について、実施例１と同様の方法により、排ガス浄化触媒としての性能を評価した。その結果、表２に示すように、ＣＯ転化率は、２００℃で６３．１％、２５０℃で７８．０％であり、Ｃ３Ｈ６転化率は、２００℃で２７．２％、２５０℃で４４．３％であった。 Moreover, about the catalyst powder obtained by this comparative example, the performance as an exhaust gas purification catalyst was evaluated by the method similar to Example 1. FIG. As a result, as shown in Table 2, the CO conversion was 63.1% at 200 ° C. and 78.0% at 250 ° C., and the C 3 H 6 conversion was 27.2% at 250 ° C., 250 It was 44.3% at ° C.
［比較例３］
まず、Ｐｔ濃度８．４８６質量％のＰｔ（ＮＨ３）２（ＮＯ２）２溶液２．３８１ｇに純水４ｍＬを加えて金属塩溶液を製造した。この溶液をＣｅ０．９Ｂｉ０．１Ｏ２２０ｇにスポイトで滴下して含浸させた後、１３０℃で一晩乾燥させて粉末を得た。この粉末を空気中において５００℃で２時間焼成（昇温速度５℃／分）して、１質量％のＰｔを含むＣｅ０．９Ｂｉ０．１Ｏ２粉末を得た。
[Comparative Example 3]
First, 4 mL of pure water was added to 2.381 g of a Pt (NH 3 ) 2 (NO 2 ) 2 solution having a Pt concentration of 8.486% by mass to produce a metal salt solution. The solution was dropped into 20 g of Ce 0.9 Bi 0.1 O 2 with a dropper and impregnated, and then dried at 130 ° C. overnight to obtain a powder. This powder was calcined in air at 500 ° C. for 2 hours (heating rate 5 ° C./min) to obtain Ce 0.9 Bi 0.1 O 2 powder containing 1% by mass of Pt.
このようにして得られた触媒粉末について、実施例１と同様の方法により、排ガス浄化触媒としての性能を評価した。その結果、表２に示すように、ＣＯ転化率は、２００℃で６２．０％、２５０℃で７２．９％であり、Ｃ３Ｈ６転化率は、２００℃で２５．７％、２５０℃で４０．４％であった。 With respect to the catalyst powder thus obtained, the performance as an exhaust gas purification catalyst was evaluated by the same method as in Example 1. As a result, as shown in Table 2, the CO conversion was 62.0% at 200 ° C. and 72.9% at 250 ° C., and the C 3 H 6 conversion was 25.7% at 250 ° C. It was 40.4% at ° C.
このように、実施例１および２の触媒粉末では、ＣＯ転化率およびＣ３Ｈ６転化率がいずれも担体と比べて大幅に向上しているのがわかった。これは、担体の表面に形成されたＰｔナノクラスターによって酸化反応が促進されたことによるものであると考えられる。一方、比較例１〜３では、ＣＯ転化率およびＣ３Ｈ６転化率がいずれも担体と比べて低い値を示し、担体にＰｔが担持されたことによって、逆にＣＯ転化率やＣ３Ｈ６転化率が低下する結果となることがわかった。これは、担体自体の活性点とＰｔの間に何らかの相互作用が起こり、活性点が変質したと考えられる。 Thus, in the catalyst powders of Examples 1 and 2, it was found that both the CO conversion rate and the C 3 H 6 conversion rate were significantly improved as compared with the support. This is considered to be because the oxidation reaction was promoted by the Pt nanoclusters formed on the surface of the support. On the other hand, in Comparative Examples 1 to 3, the CO conversion rate and the C 3 H 6 conversion rate both showed lower values than that of the carrier, and Pt was supported on the carrier, so that the CO conversion rate and C 3 H were reversed. It was found that the 6- conversion rate was reduced. This is considered that some interaction occurred between the active site of the carrier itself and Pt, and the active site was altered.
本発明による触媒の製造方法では、ディーゼルエンジンの排ガス中の一酸化炭素および炭化水素の浄化に適した排ガス浄化触媒として使用可能な触媒の他、化学工学や石油化学などの高温や高圧における触媒反応に使用可能な触媒を製造することができる。 In the method for producing a catalyst according to the present invention, in addition to a catalyst that can be used as an exhaust gas purification catalyst suitable for the purification of carbon monoxide and hydrocarbons in exhaust gas from a diesel engine, a catalytic reaction at high temperatures and high pressures such as chemical engineering and petrochemistry. A usable catalyst can be produced.
１ 担体
２ 貴金属粒子
３ 有機分子
４ 炭化物
1
Claims (5)
The method for producing a catalyst according to any one of claims 1 to 4, wherein the noble metal particles are noble metal particles selected from the group consisting of Pt, Pd and Rh.
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| CN108672717A (en) * | 2018-05-25 | 2018-10-19 | 苏州大学 | The method of one-step synthesis cluster type palladium copper nano-particle and the application of cluster type palladium copper nano-particle |
| CN118507754A (en) * | 2024-07-18 | 2024-08-16 | 长春黄金研究院有限公司 | Platinum-based intermetallic compound catalyst and preparation method and application thereof |
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