JP5252453B2 - CO selective oxidation catalyst - Google Patents
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- JP5252453B2 JP5252453B2 JP2009153927A JP2009153927A JP5252453B2 JP 5252453 B2 JP5252453 B2 JP 5252453B2 JP 2009153927 A JP2009153927 A JP 2009153927A JP 2009153927 A JP2009153927 A JP 2009153927A JP 5252453 B2 JP5252453 B2 JP 5252453B2
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- 239000003054 catalyst Substances 0.000 title claims description 46
- 238000007254 oxidation reaction Methods 0.000 title claims description 25
- 230000003647 oxidation Effects 0.000 title claims description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 33
- 229910052697 platinum Inorganic materials 0.000 claims description 17
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 229910052707 ruthenium Inorganic materials 0.000 claims description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 7
- 239000000446 fuel Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000005518 polymer electrolyte Substances 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 56
- 229910002091 carbon monoxide Inorganic materials 0.000 description 56
- 238000006243 chemical reaction Methods 0.000 description 33
- 239000007864 aqueous solution Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- -1 aluminum silicate compound Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- FOSZYDNAURUMOT-UHFFFAOYSA-J azane;platinum(4+);tetrachloride Chemical compound N.N.N.N.[Cl-].[Cl-].[Cl-].[Cl-].[Pt+4] FOSZYDNAURUMOT-UHFFFAOYSA-J 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
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- 239000000047 product Substances 0.000 description 2
- 239000005297 pyrex Substances 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RHERIKDJZAOBAO-UHFFFAOYSA-N N.[N+](=O)([O-])[Pt][N+](=O)[O-] Chemical compound N.[N+](=O)([O-])[Pt][N+](=O)[O-] RHERIKDJZAOBAO-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229910000929 Ru alloy Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 239000002737 fuel gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical compound [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
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- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Description
本発明は、水素中の一酸化炭素除去に有用な、選択酸化触媒（ＰＲＯＸ触媒）等への応用が期待される、新規な高選択性触媒に関するものである。 The present invention relates to a novel highly selective catalyst that is expected to be applied to a selective oxidation catalyst (PROX catalyst) useful for removing carbon monoxide in hydrogen.
水素中に微量に混入する一酸化炭素（ＣＯ）を酸化除去する反応は、たとえば、固体高分子型燃料電池（ＰＥＦＣ）アノードの白金に対する被毒を軽減し、電池の長寿命化を実現するものとして重要である。家庭用の定置型燃料電池の場合では、原料となる都市ガスを４００〜７００℃の温度下で水蒸気改質することにより、燃料となる水素ガスを得る（反応式１）。 The reaction that oxidizes and removes carbon monoxide (CO) mixed in a trace amount in hydrogen, for example, reduces the poisoning of platinum on the anode of a polymer electrolyte fuel cell (PEFC) and realizes a longer battery life. As important. In the case of a stationary fuel cell for home use, hydrogen gas serving as fuel is obtained by steam reforming the city gas serving as a raw material at a temperature of 400 to 700 ° C. (Reaction Formula 1).
CH4+H2O → CO+3H2 （反応式1）
この際、副生成物として、１０ｖｏｌ％程度のＣＯが生成する。
CH 4 + H 2 O → CO + 3H 2 (Scheme 1)
At this time, CO of about 10 vol% is generated as a by-product.
この後、さらに２００〜４００℃の温度下で、水性ガスシフト反応により、燃料ガス中の水素濃度を上昇するとともに、ＣＯを１ｖｏｌ％以下まで酸化除去する（反応式２）。 Thereafter, the hydrogen concentration in the fuel gas is increased by a water gas shift reaction at a temperature of 200 to 400 ° C., and CO is oxidized and removed to 1 vol% or less (Reaction Formula 2).
CO+H2O → CO2+H2 (反応式2)
最終段階では、微量の空気を導入することにより、８０〜２００℃で、ＣＯを１０ｐｐｍ以下まで酸化除去する（ＰＲＯＸ反応、反応式３）。
CO + H 2 O → CO 2 + H 2 (Scheme 2)
In the final stage, CO is oxidized and removed to 80 ppm or less at 80 to 200 ° C. by introducing a small amount of air (PROX reaction, reaction formula 3).
CO+1/2O2 → CO2 (反応式3)
しかしながら、このとき反応式４に示す副反応が起こり、燃料である水素が酸化される。
CO + 1 / 2O 2 → CO 2 (Reaction formula 3)
However, at this time, a side reaction shown in the reaction formula 4 occurs, and hydrogen as a fuel is oxidized.
H2+1/2O2 → H2O (反応式4)
従って、水素を酸化せずにＣＯのみを選択的に酸化する、高い選択反応活性を持つ触媒が望まれることになる。
H 2 + 1 / 2O 2 → H 2 O (Scheme 4)
Therefore, a catalyst having high selective reaction activity that selectively oxidizes only CO without oxidizing hydrogen is desired.
理論的には反応式３で、選択性が１００％の場合、導入されるべき酸素とＣＯの比（Ｏ２／ＣＯ）は０．５であるが、現状で実際に用いられている触媒では、ＣＯ酸化選択性が低いために、１．５〜２．５程度の範囲で運転されている。このような過剰量の酸素の導入は、前記反応式４による副反応での水素消費の要因となる。 Theoretically, when the selectivity is 100% and the selectivity is 100%, the ratio of oxygen to CO to be introduced (O 2 / CO) is 0.5, but the catalyst actually used at present is Because of low CO oxidation selectivity, it is operated in the range of about 1.5 to 2.5. The introduction of such an excessive amount of oxygen becomes a factor of hydrogen consumption in the side reaction according to the reaction formula 4.
また、一方で、現状での前記反応式３でのＰＲＯＸ触媒は典型的には１５０℃程度の温度で使用されているが、このような温度下では、メタン化反応（反応式５）が起きる可能性がある。かつまた、ＰＥＦＣ自体の動作温度は８０℃付近であるので、これに近い温度で運転できる触媒であることが望まれている。このようなことからは、低温下でのＣＯ酸化選択性の高い触媒が求められていることがわかる。しかしながら、アルミナ担持白金触媒のような典型的な酸化触媒においては、ＣＯ酸化選択性は、高温ほど高くなる傾向がある。 On the other hand, the current PROX catalyst in the reaction formula 3 is typically used at a temperature of about 150 ° C. Under such a temperature, a methanation reaction (reaction formula 5) occurs. there is a possibility. Moreover, since the operating temperature of PEFC itself is around 80 ° C., a catalyst that can be operated at a temperature close to this is desired. From this, it can be seen that there is a demand for a catalyst having high CO oxidation selectivity at low temperatures. However, in a typical oxidation catalyst such as an alumina-supported platinum catalyst, CO oxidation selectivity tends to be higher at higher temperatures.
CO+3H2 → CH4+H2O （反応式5）
従来では、ＣＯの酸化に対して高い選択性を有する触媒としては、白金-ルテニウム合金をアルミナに担持した触媒（特許文献１）や、白金と鉄等の遷移金属によるバイメタルをアルミナに担持した触媒（特許文献２、３）、ルテニウムとチタン等の複合酸化物を担持した触媒（特許文献４）、酸化コバルトおよびその複合酸化物を用いる触媒（特許文献５）などが知られているが、低い温度域でのＣＯ酸化選択性は、さらに改善する必要がある。
CO + 3H 2 → CH 4 + H 2 O (Scheme 5)
Conventionally, as a catalyst having high selectivity to CO oxidation, a catalyst in which a platinum-ruthenium alloy is supported on alumina (Patent Document 1), or a catalyst in which a bimetal made of a transition metal such as platinum and iron is supported on alumina. (Patent Documents 2 and 3), a catalyst carrying a composite oxide such as ruthenium and titanium (Patent Document 4), a catalyst using cobalt oxide and its composite oxide (Patent Document 5), etc. are known, but low The CO oxidation selectivity in the temperature range needs to be further improved.
また、近年、ＦＳＭ−１６等のメソポーラスシリカに担持した白金触媒が、高い選択性を有することが明らかになってきた（非特許文献１）。この触媒は、助触媒等を用いることなく、非常に高いＣＯ酸化選択性を発現することから、有望視されている。 In recent years, it has become clear that platinum catalysts supported on mesoporous silica such as FSM-16 have high selectivity (Non-patent Document 1). This catalyst is considered promising because it exhibits a very high CO oxidation selectivity without using a cocatalyst or the like.
しかしながら、ＦＳＭ−１６やＭＣＭ−４１などのメソポーラスシリカは、それ自体を作製するために、テンプレートとなる有機物を大量に使用し、最終的にそれらを燃焼除去することが必要なため、環境負荷が大きく、また、製造コストも高い。 However, mesoporous silicas such as FSM-16 and MCM-41 use a large amount of organic substances as a template to produce themselves, and ultimately they must be burned and removed. Large and also expensive to manufacture.
本発明は、以上のとおりの背景から、従来技術の問題点を解消し、環境負荷の小さい製造プロセスによる担体を用いて、簡便な方法で調製可能な、水素中の一酸化炭素の酸化反応に、より低い温度域においても高い反応選択性を有する触媒を提供することを課題とする。 From the background as described above, the present invention eliminates the problems of the prior art and uses a carrier produced by a manufacturing process with a low environmental load to prepare an oxidation reaction of carbon monoxide in hydrogen that can be prepared by a simple method. Another object of the present invention is to provide a catalyst having high reaction selectivity even in a lower temperature range.
本発明の触媒は、前記課題を解決するものとして以下のことを特徴としている。 The catalyst of the present invention is characterized by the following in order to solve the above problems.
第１：Ｈ２（水素）とＣＯ（一酸化炭素）を含むガスからＣＯを酸化除去するための、非晶質アルミニウムケイ酸塩に白金、ルテニウム及び鉄の少なくとも１種の金属を担持したＣＯ選択酸化触媒である。 First: CO in which at least one metal of platinum, ruthenium and iron is supported on amorphous aluminum silicate for oxidizing and removing CO from a gas containing H 2 (hydrogen) and CO (carbon monoxide) It is a selective oxidation catalyst.
第２：前記ガスは、固体高分子型燃料電池に用いられる改質ガスである。 Second: The gas is a reformed gas used in a polymer electrolyte fuel cell.
第３：前記非晶質アルミニウムケイ酸塩は、Ｓｉ／Ａｌ比が０．７〜１で、かつ、29Ｓｉ固体高分解能ＮＭＲスペクトルにおいて、−７８ｐｐｍおよび−８７ｐｐｍ付近にピークを有するものである。 Third: The amorphous aluminum silicate has a Si / Al ratio of 0.7 to 1 and peaks in the vicinity of -78 ppm and -87 ppm in a 29 Si solid high-resolution NMR spectrum.
そして、本発明は、以上の触媒を用いての、Ｈ２とＣＯを含むガスからの選択的なＣＯ酸化除去反応の方法も提供する。 Then, the present invention is to use the above catalyst, also provides a method for selective CO oxidation reaction of removing from a gas containing H 2 and CO.
以上の例で説明したように、本発明による触媒を用いた場合、Ｈ２中のＣＯを高い選択性で酸化除去することが出来る。また、反応選択性は低温で、より増大する傾向があり、ＰＥＦＣの動作温度である８０℃付近で動作するＣＯ選択酸化触媒として有効である。 As described in the above example, when the catalyst according to the present invention is used, CO in H 2 can be oxidized and removed with high selectivity. In addition, the reaction selectivity tends to increase at low temperatures, and is effective as a CO selective oxidation catalyst that operates near 80 ° C., which is the operating temperature of PEFC.
本発明においては、前記のとおり、非晶質のアルミニウムケイ酸化合物を担体として用い、これに、周期律表８〜１０族元素、たとえばＰｔ，Ｒｕ，Ｐｄ，Ｒｈ，Ｎｉ，Ｃｏ，Ｆｅ等の元素のうちのすくなくとも種もしくはこれらの合金を担持した触媒であることを特徴としている。この特徴によって、たとえば、白金化合物を含浸・焼成して作製した触媒をもちいた場合、水素中の一酸化炭素の酸化反応に対して、低温ほど高い反応選択性を発現することを見いだしている。 In the present invention, as described above, an amorphous aluminum silicate compound is used as a carrier, and this includes elements of groups 8 to 10 of the periodic table, such as Pt, Ru, Pd, Rh, Ni, Co, and Fe. The catalyst is characterized in that it is a catalyst supporting at least one of the elements or an alloy thereof. With this feature, for example, when a catalyst prepared by impregnating and calcining a platinum compound is used, it has been found that a higher reaction selectivity is exhibited at a lower temperature with respect to an oxidation reaction of carbon monoxide in hydrogen.
本発明の担体として用いられる非晶質アルミニウムケイ酸塩は、従来公知のように調製することができ、たとえば、本発明においてより好適なものとしては、モノケイ酸水溶液とアルミニウム水溶液をＳｉ／Ａｌ比が０．７〜１となるように混合し、酸またはアルカリによってｐＨ６〜８に調製し、その後、脱塩処理し、１１０℃以下で加熱することにより得ることができる（特開２００８−１７９５３３参照）。 The amorphous aluminum silicate used as the carrier of the present invention can be prepared as conventionally known. For example, in the present invention, a monosilicate aqueous solution and an aluminum aqueous solution are mixed with a Si / Al ratio. Is adjusted to pH 6-8 with an acid or alkali, then desalted and heated at 110 ° C. or lower (see JP 2008-179533 A). ).
金属を該担体に担持する方法としては、金属イオンを担体に含浸した後、空気中焼成および還元雰囲気下で焼成する方法が想定されるが、金属微粒子が該担体上に担持される方法であれば、この方法に限定されるものではない。金属の担持量については、特に限定的ではないが、一般的目安として、触媒の全体量の０．１〜２０質量％の範囲とすることが考慮される。 As a method of supporting the metal on the carrier, a method of impregnating the metal ion with the carrier and then firing in air and in a reducing atmosphere is assumed, but any method in which metal fine particles are supported on the carrier. For example, it is not limited to this method. The amount of metal supported is not particularly limited, but as a general guideline, it is considered that the amount is 0.1 to 20% by mass of the total amount of the catalyst.
本発明の触媒では、最初に仕込む金属の量や、焼成温度を変化させることにより、金属微粒子のサイズを変化させることが可能である。金属微粒子の粒径としては、まず一般的な目安としては０．５〜１０ｎｍの範囲とすることが考慮される。金属微粒子のサイズは反応選択性の重要なパラメータの一つであるので、これを変化させることで、種々の反応系において、従来触媒とは異なる選択性を発現することも期待できる。 In the catalyst of the present invention, it is possible to change the size of the metal fine particles by changing the amount of metal initially charged and the firing temperature. As a particle size of the metal fine particles, it is considered that a range of 0.5 to 10 nm is a general guideline. Since the size of the metal fine particles is one of the important parameters of the reaction selectivity, it can be expected that the selectivity different from that of the conventional catalyst is expressed in various reaction systems by changing the size.
次に、実施例により本発明をさらに詳細に説明する。もちろん、本発明はこれらの例によってなんら限定されるものではない。
＜担体の調製＞
担体となる非晶質アルミニウムケイ酸化合物を公知の方法で作製した（特許文献６）。すなわち、Ｓｉ濃度が、３８３ｍｍｏｌ／Ｌになるように、純水で希釈したオルトケイ酸ナトリウム水溶液４００ｍｌを調製した。また、これとは別に、塩化アルミニウムを純水に溶解させ、Ａｌ濃度が４５０ｍｍｏｌ／Ｌの水溶液４００ｍｌを調製した。次に、塩化アルミニウム水溶液にオルトケイ酸ナトリウム水溶液を混合し、マグネティックスターラーで撹拌した。このときのケイ素／アルミニウム比は０．８５であった。更に、この混合溶液に、１Ｎ水酸化ナトリウム水溶液１８ｍｌを滴下しｐＨを７とした。この溶液から遠心分離により前駆体を回収し、４Ｌの純水中に分散させた。室温下で１時間攪拌した後、４Ｌの密閉容器に移し替え、恒温槽にて９８℃で２日間加熱を行った。冷却後、遠心分離により３回洗浄後、６０℃で乾燥を行った。
Next, the present invention will be described in more detail with reference to examples. Of course, the present invention is not limited to these examples.
<Preparation of carrier>
An amorphous aluminum silicate compound as a carrier was produced by a known method (Patent Document 6). That is, 400 ml of a sodium orthosilicate aqueous solution diluted with pure water was prepared so that the Si concentration was 383 mmol / L. Separately, aluminum chloride was dissolved in pure water to prepare 400 ml of an aqueous solution having an Al concentration of 450 mmol / L. Next, the sodium orthosilicate aqueous solution was mixed with the aluminum chloride aqueous solution and stirred with a magnetic stirrer. The silicon / aluminum ratio at this time was 0.85. Further, 18 ml of 1N aqueous sodium hydroxide solution was added dropwise to the mixed solution to adjust the pH to 7. The precursor was recovered from this solution by centrifugation and dispersed in 4 L of pure water. After stirring at room temperature for 1 hour, the mixture was transferred to a 4 L sealed container and heated at 98 ° C. for 2 days in a thermostatic bath. After cooling, it was washed three times by centrifugation and then dried at 60 ° C.
得られたアルミニウムケイ酸塩について、Ｘ線回折、および、29Ｓｉ固体高分解能ＮＭＲ測定をおこなった。Ｘ線回折パターンにおいては、２θ＝２７°および４０°にブロードなピークが観測されるのみの、非晶質アルミニウムケイ酸塩に特徴的なパターンであった。この結果から、この物質は非晶質のアルミニウムケイ酸塩であることが確認された。 The obtained aluminum silicate was subjected to X-ray diffraction and 29 Si solid high-resolution NMR measurement. The X-ray diffraction pattern was a pattern characteristic of amorphous aluminum silicate, with only broad peaks observed at 2θ = 27 ° and 40 °. From this result, it was confirmed that this material was an amorphous aluminum silicate.
29Ｓｉ固体高分解能ＮＭＲスペクトルにおいては、−７８ｐｐｍおよび−８７ｐｐｍ付近にピークが見られる。このことから、生成物は、−７８ｐｐｍにピークを示す、ＯＨ−Ｓｉ−（ＯＡｌ）３の配位を含むイモゴライトに特徴的な構造と、−８７ｐｐｍにピークを示す、Ｓｉ−Ｏ−Ｓｉの重合構造を併せ持つ物質であることが確認された。 In the 29 Si solid high-resolution NMR spectrum, peaks are observed around -78 ppm and -87 ppm. From this, the product has a characteristic structure of imogolite including the coordination of OH—Si— (OAl) 3, which shows a peak at −78 ppm, and polymerization of Si—O—Si which shows a peak at −87 ppm. The substance was confirmed to have a structure.
＜実施例１＞ <Example 1>
作製したアルミニウムケイ酸塩０．３ｇを蒸留水２ｍｌに分散し、白金量５ｗｔ％の亜硝酸ジニトロ白金アンモニア水溶液６０．６μｌを混合し、室温で２４時間撹拌した。その後、蒸気浴で混合液を加熱しながら撹拌し、水を蒸発させ、さらに１１０℃に加熱した乾燥機で２時間乾燥させた。このようにして得られた粉体を、３００ｍｌ／ｍｉｎの空気気流中４００℃で焼成した後、さらに、５０ｍｌ／ｍｉｎのＨ２／Ａｒ（１：１）混合気流中、４００℃で２時間熱処理し、触媒試料とした。白金仕込み量は１ｗｔ％である。 0.3 g of the produced aluminum silicate was dispersed in 2 ml of distilled water, 60.6 μl of dinitroplatinum ammonia aqueous solution having a platinum amount of 5 wt% was mixed, and stirred at room temperature for 24 hours. Thereafter, the mixed solution was stirred while being heated in a steam bath to evaporate water, and further dried for 2 hours in a dryer heated to 110 ° C. The powder thus obtained was calcined at 400 ° C. in an air stream of 300 ml / min, and further heat-treated at 400 ° C. for 2 hours in a mixed air stream of H 2 / Ar (1: 1) at 50 ml / min. And used as a catalyst sample. The amount of platinum charged is 1 wt%.
この様にして作製した触媒試料（白金仕込み量１ｗｔ％）０．１ｇをパイレックス（登録商標）ガラス製の反応管に詰め、固定床流通式反応装置を用いて、水素中でのＣＯ酸化反応の転換率を種々の温度下にて測定した。用いた混合ガスの組成はＣＯ：Ｏ２：Ｈ２＝１：０．５：９８．５であり、ガスの流量は１６．７ｍｌ／ｍｉｎである。触媒層通過前後のＣＯおよびＯ２の濃度をガスクロマトグラフにより検出した。 0.1 g of the catalyst sample (platinum charge 1 wt%) prepared in this way is packed in a Pyrex (registered trademark) glass reaction tube, and CO oxidation reaction in hydrogen using a fixed bed flow type reactor. Conversion was measured at various temperatures. The composition of the mixed gas used is CO: O 2 : H 2 = 1: 0.5: 98.5, and the gas flow rate is 16.7 ml / min. The concentrations of CO and O 2 before and after passing through the catalyst layer were detected by gas chromatography.
図１にＣＯおよびＯ２の転換率（それぞれ○および●）、ＣＯ酸化選択性（＋）を温度の関数として示す。ＣＯおよびＯ２の転換率は、触媒層通過前のＣＯおよびＯ２の濃度を［ＣＯ］０、［Ｏ２］０、通過後のＣＯおよびＯ２の濃度を［ＣＯ］、［Ｏ２］とした時、それぞれ、｛１−（［ＣＯ］／［ＣＯ］０）｝＊１００、および、｛１−（［Ｏ２］／［Ｏ２］０）｝＊１００で表される。また、ＣＯ酸化選択性は、消費されたＯ２のうちの何割がＣＯの酸化に使われたかを示す量であり、１／２×（［ＣＯ］０−［ＣＯ］）／（［Ｏ２］０−［Ｏ２］）で定義される。 FIG. 1 shows the CO and O 2 conversions (◯ and ●, respectively) and CO oxidation selectivity (+) as a function of temperature. The conversion of CO and O 2 is the concentration of CO and O 2 of the front catalyst layer pass [CO] 0, [O 2 ] 0, the concentration of CO and O 2 after passing through [CO], [O 2] Are represented by {1-([CO] / [CO] 0 )} * 100 and {1-([O 2 ] / [O 2 ] 0 )} * 100, respectively. The CO oxidation selectivity is an amount indicating what percentage of the consumed O 2 was used for the oxidation of CO. 1/2 × ([CO] 0 − [CO]) / ([O 2 ] 0- [O 2 ]).
ＰＥＦＣにおいて好適な、ＣＯ酸化触媒の動作温度は８０℃〜１５０℃程度であるが、この温度領域において、作製した非晶質アルミニウムケイ酸塩担持の白金触媒は、６０％以上の反応選択性を示した。
＜実施例２＞
The operating temperature of the CO oxidation catalyst suitable for PEFC is about 80 ° C. to 150 ° C. In this temperature range, the produced platinum catalyst supported on amorphous aluminum silicate has a reaction selectivity of 60% or more. Indicated.
<Example 2>
該アルミニウムケイ酸塩０．５ｇを蒸留水２ｍｌに分散し、ルテニウム量１．６ｗｔ％の塩化ルテニウム水溶液３０５μｌを混合し、室温で２４時間撹拌した。その後、蒸気浴で混合液を加熱しながら撹拌し、水を蒸発させ、さらに１１０℃に加熱した乾燥機で２時間乾燥させた。このようにして得られた粉体を、３００ｍｌ／ｍｉｎの空気気流中２００℃で焼成した後、さらに、５０ｍｌ／ｍｉｎのＨ２／Ａｒ（１：１）混合気流中、２００℃で２時間熱処理し、触媒試料とした。ルテニウム担持量は、仕込みで１．０ｗｔ％である。
＜実施例３＞
0.5 g of the aluminum silicate was dispersed in 2 ml of distilled water, mixed with 305 μl of a ruthenium chloride aqueous solution having a ruthenium content of 1.6 wt%, and stirred at room temperature for 24 hours. Thereafter, the mixed solution was stirred while being heated in a steam bath to evaporate water, and further dried for 2 hours in a dryer heated to 110 ° C. The powder thus obtained was calcined at 200 ° C. in an air stream of 300 ml / min, and further heat-treated at 200 ° C. for 2 hours in a mixed air stream of H 2 / Ar (1: 1) at 50 ml / min. And used as a catalyst sample. The amount of ruthenium supported is 1.0 wt% in preparation.
<Example 3>
該アルミニウムケイ酸塩０．５ｇを蒸留水２ｍｌに分散し、白金量２．１ｗｔ％のテトラアンミン白金塩化物水溶液２２２μｌとルテニウム量１．６ｗｔ％の塩化ルテニウム水溶液１５３μｌを混合し、室温で２４時間撹拌した。その後、蒸気浴で混合液を加熱しながら撹拌し、水を蒸発させ、さらに１１０℃に加熱した乾燥機で２時間乾燥させた。このようにして得られた粉体を、３００ｍｌ／ｍｉｎの空気気流中２００℃で焼成した後、さらに、５０ｍｌ／ｍｉｎのＨ２／Ａｒ（１：１）混合気流中、２００℃で２時間熱処理し、触媒試料とした。白金およびルテニウム担持量は、仕込みで１．９および１．０ｗｔ％である（モル比で１：１）。
＜実施例４＞
0.5 g of the aluminum silicate is dispersed in 2 ml of distilled water, and 222 μl of a tetraammineplatinum chloride aqueous solution with a platinum amount of 2.1 wt% and 153 μl of a ruthenium chloride aqueous solution with a ruthenium amount of 1.6 wt% are mixed and stirred at room temperature for 24 hours. did. Thereafter, the mixed solution was stirred while being heated in a steam bath to evaporate water, and further dried for 2 hours in a dryer heated to 110 ° C. The powder thus obtained was calcined at 200 ° C. in an air stream of 300 ml / min, and further heat-treated at 200 ° C. for 2 hours in a mixed air stream of H 2 / Ar (1: 1) at 50 ml / min. And used as a catalyst sample. The loadings of platinum and ruthenium are 1.9 and 1.0 wt% in the charge (1: 1 in molar ratio).
<Example 4>
該アルミニウムケイ酸塩０．５ｇを蒸留水２ｍｌに分散し、白金量２．１ｗｔ％のテトラアンミン白金塩化物水溶液４４３μｌと鉄量１．３ｗｔ％の酢酸鉄水溶液２１７μｌを混合し、室温で２４時間撹拌した。その後、蒸気浴で混合液を加熱しながら撹拌し、水を蒸発させ、さらに１１０℃に加熱した乾燥機で２時間乾燥させた。このようにして得られた粉体を、３００ｍｌ／ｍｉｎの空気気流中２００℃で焼成した後、さらに、５０ｍｌ／ｍｉｎのＨ２／Ａｒ（１：１）混合気流中、２００℃で２時間熱処理し、触媒試料とした。白金および鉄担持量は、仕込みで３．８および１．１ｗｔ％である（モル比で１：１）。 0.5 g of the aluminum silicate is dispersed in 2 ml of distilled water, 443 μl of a tetraammine platinum chloride aqueous solution with a platinum amount of 2.1 wt% and 217 μl of an iron acetate aqueous solution with an iron amount of 1.3 wt% are mixed and stirred at room temperature for 24 hours. did. Thereafter, the mixed solution was stirred while being heated in a steam bath to evaporate water, and further dried for 2 hours in a dryer heated to 110 ° C. The powder thus obtained was calcined at 200 ° C. in an air stream of 300 ml / min, and further heat-treated at 200 ° C. for 2 hours in a mixed air stream of H 2 / Ar (1: 1) at 50 ml / min. And used as a catalyst sample. The loadings of platinum and iron are 3.8 and 1.1 wt% in the charge (1: 1 in molar ratio).
実施例２〜４の試料を０．１ｇをパイレックス（登録商標）ガラス製の反応管に詰め、固定床流通式反応装置を用いて、水素中でのＣＯ酸化反応の転換率を種々の温度下にて測定した。用いた混合ガスの組成はＣＯ：Ｏ２：Ｈ２＝１：０．５：９８．５であり、ガスの流量は１６．７ｍｌ／ｍｉｎである。触媒層通過前後のＣＯおよびＯ２の濃度をガスクロマトグラフにより検出した。 0.1 g of the samples of Examples 2 to 4 were packed in a Pyrex (registered trademark) glass reaction tube, and the conversion rate of the CO oxidation reaction in hydrogen at various temperatures using a fixed bed flow reactor. Measured with The composition of the mixed gas used is CO: O 2 : H 2 = 1: 0.5: 98.5, and the gas flow rate is 16.7 ml / min. The concentrations of CO and O 2 before and after passing through the catalyst layer were detected by gas chromatography.
いずれの場合にも、低温ほど高いＣＯ酸化選択性を示した（下記、表１参照）。
＜比較例１＞
アルミナを担体とした場合と比較した。実施例１と同様の方法で、アルミナ（触媒学会参照触媒ＪＲＣ−ＡＬＯ−１）担体とした触媒を作製し、触媒反応特性を比較した。
In either case, the lower the temperature, the higher the CO oxidation selectivity (see Table 1 below).
<Comparative Example 1>
The comparison was made with alumina as a carrier. In the same manner as in Example 1, a catalyst using alumina (catalyst society reference catalyst JRC-ALO-1) support was prepared, and the catalytic reaction characteristics were compared.
結果を図２に示す。８０℃〜１５０℃の温度範囲において、ＣＯ酸化反応選択性は４０％以下であり、また、選択性は低温ほど低くなった。
＜比較例２＞
シリカを担体とした場合と比較した。テトラメチルシリケイト５１ｇをメタノール１０７ｇと混合し、撹拌した。その後撹拌しながら溶液中にアンモニア水３６ｇを加えた。この時、テトラメチルシリケイトとメタノール、水の比はモル比で１：１０：６であった。１分ほど撹拌した後、混合液を円柱形の型（直径４０ｍｍ，深さ１０ｍｍ）に流し込んだ。約１時間放置し反応液がゼリー状に固まっていることを確認してから、乾燥するのを防ぐためポリ塩化ビニリデンフィルムで密封をした。その後１日放置しゲル化を進行させた。その後、型から取り出し、エタノールに浸して１日以上放置した。ゲル中に残存する水やアンモニアを完全に除去するため、その後エタノールの取替えを２回おこなった。得られたバルク体を空気中で乾燥し、粉砕した。このようにして得られたシリカ粉体に、実施例１と同様の方法で白金を担持した。
The results are shown in FIG. In the temperature range of 80 ° C. to 150 ° C., the CO oxidation reaction selectivity was 40% or less, and the selectivity became lower as the temperature was lower.
<Comparative example 2>
Comparison was made with silica as the carrier. 51 g of tetramethyl silicate was mixed with 107 g of methanol and stirred. Thereafter, 36 g of aqueous ammonia was added to the solution while stirring. At this time, the ratio of tetramethyl silicate to methanol and water was 1: 10: 6 in molar ratio. After stirring for about 1 minute, the mixture was poured into a cylindrical mold (
反応試験の結果を図３に示す。８０℃〜１５０℃の温度範囲において、ＣＯ酸化反応選択性は３０％以下であり、また、選択性は低温ほど低くなった。
＜比較例３＞
チューブ状アルミニウムケイ酸塩である、イモゴライトを担体とした場合と比較した。Ｓｉ濃度が６０ｍｍｏｌ／Ｌになるように純水で希釈したオルトケイ酸ナトリウム水溶液２００ｍｌを調製した後。また、これとは別に塩化アルミニウムを純水に溶解させ、Ａｌ濃度が１５０ｍｍｏｌ／Ｌ水溶液２００ｍｌを調製した。塩化アルミニウム水溶液にオルトケイ酸ナトリウム水溶液を混合し、マグネティックスターラーで撹拌した。このときのケイ素／アルミニウム比は０．４である。この混合溶液に、１Ｎ水酸化ナトリウム水溶液４４．８ｍｌを滴下しｐＨを６とした。この溶液から遠心分離により前駆体を回収し、更に、純水で前駆体を２回遠心分離により洗浄した後、２Ｌの純水中に分散させた。この前駆体の懸濁液２Ｌに、１Ｎ塩酸を１０ｍｌ加えｐＨを４．２とした後、室温下で１時間攪拌した後、テフロン（登録商標）製の２Ｌ密閉容器に移し替え、恒温槽にて１００℃で４日間加熱を行った。こうしてイモゴライトを含む水溶液を得た。冷却後、この水溶液を６０℃で乾燥させた後、孔径０．２μｍのフィルターを用いて洗浄を行った。
The results of the reaction test are shown in FIG. In the temperature range of 80 ° C. to 150 ° C., the CO oxidation reaction selectivity was 30% or less, and the selectivity was lower at lower temperatures.
<Comparative Example 3>
This was compared with the case where imogolite, which is a tubular aluminum silicate, was used as a carrier. After preparing 200 ml of a sodium orthosilicate aqueous solution diluted with pure water so that the Si concentration becomes 60 mmol / L. Separately, aluminum chloride was dissolved in pure water to prepare 200 ml of an aqueous solution having an Al concentration of 150 mmol / L. A sodium orthosilicate aqueous solution was mixed with the aluminum chloride aqueous solution and stirred with a magnetic stirrer. The silicon / aluminum ratio at this time is 0.4. To this mixed solution, 44.8 ml of 1N aqueous sodium hydroxide solution was added dropwise to adjust the pH to 6. The precursor was recovered from this solution by centrifugation, and the precursor was washed twice with pure water by centrifugation, and then dispersed in 2 L of pure water. To 2 L of this precursor suspension, 10 ml of 1N hydrochloric acid was added to adjust the pH to 4.2, and the mixture was stirred at room temperature for 1 hour, and then transferred to a 2 L sealed container made of Teflon (registered trademark). And heated at 100 ° C. for 4 days. Thus, an aqueous solution containing imogolite was obtained. After cooling, the aqueous solution was dried at 60 ° C. and then washed using a filter having a pore size of 0.2 μm.
得られた生成物について、その粉末Ｘ線回折を測定したところ、２θ＝４，９．５，１４，２７，４０°付近にピークを有する、チューブ状アルミニウムケイ酸塩特有のＸ線回折パターンを示した。 When the powder X-ray diffraction of the obtained product was measured, an X-ray diffraction pattern peculiar to tubular aluminum silicate having a peak in the vicinity of 2θ = 4, 9.5, 14, 27, and 40 ° was obtained. Indicated.
このようにして得られたイモゴライト粉体に、実施例１と同様の方法で白金を担持した。図４に触媒反応試験の結果を示す。８０℃〜１５０℃の温度範囲において、ＣＯ酸化反応選択性は４０％以下であり、また、選択性は低温ほど低くなった。 The imogolite powder thus obtained was loaded with platinum in the same manner as in Example 1. FIG. 4 shows the results of the catalytic reaction test. In the temperature range of 80 ° C. to 150 ° C., the CO oxidation reaction selectivity was 40% or less, and the selectivity became lower as the temperature was lower.
実施例１〜４、および、比較例１〜３の１００℃および１５０℃における、Ｏ２およびＣＯの転換率、反応選択性を表１にまとめて示した。 The conversion rates of O 2 and CO and reaction selectivity at 100 ° C. and 150 ° C. of Examples 1 to 4 and Comparative Examples 1 to 3 are summarized in Table 1.
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