JP2023171427A - carbon dioxide reduction catalyst - Google Patents
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 239000003054 catalyst Substances 0.000 title claims abstract description 101
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 66
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 60
- 230000009467 reduction Effects 0.000 title claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 51
- 239000002184 metal Substances 0.000 claims abstract description 50
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 27
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 27
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 14
- 229910052742 iron Inorganic materials 0.000 claims abstract description 14
- 150000002739 metals Chemical class 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims description 27
- 230000003197 catalytic effect Effects 0.000 claims description 22
- 238000000975 co-precipitation Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
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- 239000002244 precipitate Substances 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 229910002651 NO3 Inorganic materials 0.000 claims description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 4
- 238000005984 hydrogenation reaction Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 13
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 31
- 238000006722 reduction reaction Methods 0.000 description 31
- 239000011734 sodium Substances 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 14
- -1 carbonate compound Chemical class 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
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- 238000003786 synthesis reaction Methods 0.000 description 6
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- 239000010419 fine particle Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 239000001257 hydrogen Substances 0.000 description 2
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- 239000007788 liquid Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 229910052701 rubidium Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Abstract
Description
本発明は、二酸化炭素還元触媒に関する。 The present invention relates to a carbon dioxide reduction catalyst.
従来、二酸化炭素を水素化反応させて燃料を生成する技術が知られている。例えば、二酸化炭素と水素の混合ガスからメタノールを合成する触媒として、Ｃｕ、Ｚｎ及びアルミナからなる触媒が提案されている（特許文献１参照）。 BACKGROUND ART Conventionally, a technique is known in which fuel is generated by subjecting carbon dioxide to a hydrogenation reaction. For example, a catalyst made of Cu, Zn, and alumina has been proposed as a catalyst for synthesizing methanol from a mixed gas of carbon dioxide and hydrogen (see Patent Document 1).
ところで、二酸化炭素を水素化反応させて得られる燃料として、液体燃料として使用可能な、炭素数が例えば５以上の炭化水素を生成できることが求められる。このような技術として、ＦＴ（フィッシャー・トロプシュ：Ｆｉｓｃｈｅｒ－Ｔｒｏｐｓｃｈ）合成反応におけるＦｅ触媒に対しカリウムを助触媒として用いることで、高度に分岐したＣ５以上の生成物を調製する方法が提案されている（特許文献２参照）。 By the way, as a fuel obtained by subjecting carbon dioxide to a hydrogenation reaction, it is required to be able to generate a hydrocarbon having, for example, 5 or more carbon atoms, which can be used as a liquid fuel. As such a technique, a method has been proposed to prepare highly branched C5 or higher products by using potassium as a cocatalyst for Fe catalyst in FT (Fischer-Tropsch) synthesis reaction. (See Patent Document 2).
特許文献２に開示された技術において助触媒として用いられるカリウムは、ＦＴ合成反応において二酸化炭素を捕捉する機能を有すると考えられる。しかし、助触媒としてのカリウムは、生成される炭化水素の炭素数の増大には直接寄与しないものと考えられる。このため、例えば内燃機関の排ガス等の高流速下で、炭素数が例えば５以上の炭化水素を高収率で生成することは不可能だった。
Potassium used as a promoter in the technique disclosed in
本発明は、上記課題に鑑みてなされたものであり、高流速下においても炭素数が５以上の炭化水素を高効率で生成可能な二酸化炭素還元触媒を提供することを目的とする。 The present invention has been made in view of the above problems, and an object of the present invention is to provide a carbon dioxide reduction catalyst that can generate hydrocarbons having 5 or more carbon atoms with high efficiency even at high flow rates.
（１） 本発明は、二酸化炭素を水素化反応させて二酸化炭素を還元し炭化水素を生成する二酸化炭素還元触媒であって、触媒金属として、Ｆｅ及びＧａを含み、前記触媒金属中に前記Ｇａは１０～３０質量％含まれる、二酸化炭素還元触媒に関する。 (1) The present invention relates to a carbon dioxide reduction catalyst that performs a hydrogenation reaction on carbon dioxide to reduce carbon dioxide and generate hydrocarbons, which contains Fe and Ga as catalytic metals, and wherein the catalytic metal contains Fe and Ga. relates to a carbon dioxide reduction catalyst containing 10 to 30% by mass.
（２） 前記触媒金属中に前記Ｇａは２０～３０質量％含まれる、（１）に記載の二酸化炭素還元触媒。 (2) The carbon dioxide reduction catalyst according to (1), wherein the catalytic metal contains 20 to 30% by mass of Ga.
（３） 前記触媒金属は、前記Ｆｅ及び前記Ｇａにより形成されるＦｅ－Ｇａ複合酸化物を含む、（１）又は（２）に記載の二酸化炭素還元触媒。 (3) The carbon dioxide reduction catalyst according to (1) or (2), wherein the catalyst metal includes a Fe-Ga composite oxide formed by the Fe and the Ga.
（４） 前記触媒金属として更にＮａを含む、（１）～（３）のいずれかに記載の二酸化炭素還元触媒。 (4) The carbon dioxide reduction catalyst according to any one of (1) to (3), further containing Na as the catalyst metal.
（５） また、本発明は、（１）～（４）のいずれかに記載の二酸化炭素還元触媒の製造方法であって、前記Ｆｅの硝酸塩と前記Ｇａの硝酸塩とを所定量蒸留水に溶解させた水溶液から、共沈法により沈殿物を抽出する共沈工程を有する、二酸化炭素還元触媒の製造方法に関する。 (5) The present invention also provides a method for producing a carbon dioxide reduction catalyst according to any one of (1) to (4), wherein the Fe nitrate and the Ga nitrate are dissolved in a predetermined amount of distilled water. The present invention relates to a method for producing a carbon dioxide reduction catalyst, which includes a coprecipitation step of extracting a precipitate from an aqueous solution using a coprecipitation method.
（６） 前記共沈工程の次に、前記沈殿物にＮａを含む水溶液を滴下して所定期間乾燥させ、得られた粉末を所定の温度で焼成する含浸工程を有する、（５）に記載の二酸化炭素還元触媒の製造方法。 (6) Next to the coprecipitation step, there is an impregnation step of dropping an aqueous solution containing Na onto the precipitate, drying it for a predetermined period, and firing the obtained powder at a predetermined temperature. Method for producing carbon dioxide reduction catalyst.
（７） 前記共沈工程において、前記水溶液に対しＮａＣＯ３水溶液を滴下することで沈殿溶液を得る、（５）又は（６）に記載の二酸化炭素還元触媒の製造方法。 (7) The method for producing a carbon dioxide reduction catalyst according to (5) or (6), wherein in the coprecipitation step, a precipitation solution is obtained by dropping an aqueous NaCO 3 solution into the aqueous solution.
本発明によれば、高流速下においても炭素数が５以上の炭化水素を高効率で生成可能な二酸化炭素還元触媒を提供できる。 According to the present invention, it is possible to provide a carbon dioxide reduction catalyst that can generate hydrocarbons having 5 or more carbon atoms with high efficiency even at high flow rates.
以下、本発明の一実施形態について説明する。本実施形態に係る二酸化炭素還元触媒は、二酸化炭素を水素化反応させて二酸化炭素を還元するとともに炭化水素を生成することが可能な触媒である。特に、本実施形態に係る二酸化炭素還元触媒は、従来の触媒と比較して、炭素数が５以上の炭化水素の生成割合や生成率が高い。二酸化炭素の供給源としては特に限定されないが、本実施形態に係る二酸化炭素還元触媒は、内燃機関の排ガス等、高流速で二酸化炭素が供給される供給源に対しても、好ましく炭素数が５以上の炭化水素を生成できる。 An embodiment of the present invention will be described below. The carbon dioxide reduction catalyst according to the present embodiment is a catalyst capable of hydrogenating carbon dioxide to reduce carbon dioxide and generate hydrocarbons. In particular, the carbon dioxide reduction catalyst according to the present embodiment has a higher production rate and production rate of hydrocarbons having 5 or more carbon atoms than conventional catalysts. Although the supply source of carbon dioxide is not particularly limited, the carbon dioxide reduction catalyst according to the present embodiment is preferably used for sources where carbon dioxide is supplied at a high flow rate, such as exhaust gas of an internal combustion engine. It is possible to produce more than 1,000 hydrocarbons.
＜二酸化炭素還元触媒＞
本実施形態に係る二酸化炭素還元触媒（以下、単に「触媒」と記載する場合がある）は、触媒金属として、Ｆｅ（鉄）と、Ｇａ（ガリウム）と、を含む。また、Ｎａ（ナトリウム）を含むことが好ましい。本実施形態に係る触媒を用いた二酸化炭素還元反応は、Ｈ２（水素）とＣＯ２（二酸化炭素）の混合ガスを原料とし、ＣＯ２がＣＯ（一酸化炭素）に還元される逆シフト反応と、ＣＯが炭化水素へと転換されるＦＴ合成反応と、を一段で行うことにより炭化水素を生成する反応である。本実施形態に係る触媒は、上記逆シフト反応と、ＦＴ合成反応との両方に寄与する。本実施形態に係る触媒を用いた二酸化炭素還元反応は、従来のＦＴ合成反応と比較して、例えば空間速度ＳＶ（Ｓｐａｃｅ Ｖｅｌｏｃｉｔｙ）＝５０，０００ｈ－１程度の高流速下においても、炭素数が５以上の炭化水素を高効率に生成できる。
<Carbon dioxide reduction catalyst>
The carbon dioxide reduction catalyst (hereinafter sometimes simply referred to as "catalyst") according to the present embodiment includes Fe (iron) and Ga (gallium) as catalyst metals. Moreover, it is preferable that Na (sodium) is included. The carbon dioxide reduction reaction using the catalyst according to the present embodiment is a reverse shift reaction in which CO 2 is reduced to CO (carbon monoxide) using a mixed gas of H 2 (hydrogen) and CO 2 (carbon dioxide) as a raw material. This is a reaction in which hydrocarbons are produced by performing the following steps in one step: and an FT synthesis reaction in which CO is converted into hydrocarbons. The catalyst according to this embodiment contributes to both the reverse shift reaction and the FT synthesis reaction. Compared to the conventional FT synthesis reaction, the carbon dioxide reduction reaction using the catalyst according to the present embodiment reduces the number of carbon atoms even at a high flow rate of, for example, Space Velocity SV = 50,000 h -1 . 5 or more hydrocarbons can be produced with high efficiency.
本実施形態に係る触媒金属に含有されるＦｅは、酸化物、炭酸化合物、硝酸化合物、硫酸化合物等の化合物であってもよく、酸化物であることが好ましい。これらの化合物は２種以上含有されてもよい。また、Ｆｅは、Ｆｅ及びＧａにより形成されるＦｅ－Ｇａ複合酸化物として触媒金属に含有されることがより好ましい。Ｆｅ－Ｇａ複合酸化物は、鉄酸化物等の化合物と比較して、微粒子化されるため、Ｆｅ触媒の反応サイトが増大することで、ＦＴ合成反応の反応時間、即ち生成される炭化水素の炭素鎖が成長する時間を確保できる。従って、高流速下においても炭素数が５以上の炭化水素の収率を向上させることができる。 Fe contained in the catalyst metal according to the present embodiment may be a compound such as an oxide, a carbonate compound, a nitric acid compound, or a sulfuric acid compound, and is preferably an oxide. Two or more kinds of these compounds may be contained. Further, it is more preferable that Fe is contained in the catalyst metal as a Fe--Ga composite oxide formed by Fe and Ga. Compared to compounds such as iron oxides, Fe-Ga composite oxides are made into fine particles, so the number of reaction sites for the Fe catalyst increases, which reduces the reaction time of the FT synthesis reaction, that is, the amount of hydrocarbons produced. This allows time for the carbon chain to grow. Therefore, even at high flow rates, the yield of hydrocarbons having 5 or more carbon atoms can be improved.
本実施形態に係る触媒金属に含有されるＧａは、Ｆｅと同様に、酸化物、炭酸化合物、硝酸化合物、硫酸化合物等の化合物であってもよく、酸化物であることが好ましい。これらの化合物は２種以上含有されてもよい。Ｇａは、Ｆｅ及びＧａにより形成されるＦｅ－Ｇａ複合酸化物として触媒金属に含有されることがより好ましい。 Like Fe, Ga contained in the catalyst metal according to this embodiment may be a compound such as an oxide, a carbonate compound, a nitric acid compound, or a sulfuric acid compound, and is preferably an oxide. Two or more types of these compounds may be contained. More preferably, Ga is contained in the catalyst metal as a Fe--Ga composite oxide formed by Fe and Ga.
本実施形態に係る触媒金属中におけるＧａの含有量は、金属原子換算で１０～３０質量％である。上記Ｇａの含有量は、２０～３０質量％であることが好ましい。Ｇａの含有量が１０質量％未満である場合、触媒金属の微粒子化が十分ではない場合がある。Ｇａの含有量が３０質量％を超える場合、ＧａがＦｅの反応サイトを被覆することで、触媒活性が低下する場合がある。 The content of Ga in the catalyst metal according to this embodiment is 10 to 30% by mass in terms of metal atoms. The content of Ga is preferably 20 to 30% by mass. When the Ga content is less than 10% by mass, the catalytic metal may not be sufficiently made into fine particles. When the Ga content exceeds 30% by mass, the catalytic activity may decrease due to Ga covering Fe reaction sites.
本実施形態に係る触媒金属は、更にＮａを含むことが好ましい。Ｎａは、Ｆｅ及びＧａを含む触媒金属において助触媒として機能し、ＣＯ２をＮａ２ＣＯ３として捕捉することで、Ｈ２及びＣＯ２からＣＯが生成する逆シフト反応を進行させ、ＣＯ２変換率を向上させることができる。Ｎａは、Ｆｅ－Ｇａ複合酸化物とは別に、酸化物等の形態でＦｅ－Ｇａ複合酸化物の表面上に存在することが好ましい。なお、触媒金属は、Ｎａに代えて、又はＮａと共に、Ｌｉ、Ｋ、Ｒｂ、Ｃｓ等のアルカリ金属を含有していてもよい。 It is preferable that the catalyst metal according to this embodiment further contains Na. Na functions as a co-catalyst in catalytic metals including Fe and Ga, and by capturing CO2 as Na2CO3 , advances the reverse shift reaction in which CO is produced from H2 and CO2 , resulting in CO2 conversion. rate can be improved. Separate from the Fe-Ga composite oxide, Na is preferably present on the surface of the Fe-Ga composite oxide in the form of an oxide or the like. Note that the catalytic metal may contain an alkali metal such as Li, K, Rb, or Cs instead of or together with Na.
本実施形態に係る触媒金属中におけるＮａの含有量は、０．５～１．５質量％であることが好ましく、１．０質量％であることがより好ましい。Ｎａの含有量が０．５質量％未満である場合、炭素数が５以上の炭化水素の十分な生成効率が得られない。Ｎａの含有量が１．５質量％を超える場合、ＮａがＦｅの反応サイトを被覆することで触媒活性が低下する。 The content of Na in the catalyst metal according to this embodiment is preferably 0.5 to 1.5% by mass, more preferably 1.0% by mass. When the Na content is less than 0.5% by mass, sufficient production efficiency of hydrocarbons having 5 or more carbon atoms cannot be obtained. When the Na content exceeds 1.5% by mass, the catalyst activity decreases because Na covers Fe reaction sites.
本実施形態に係る二酸化炭素還元触媒は、例えば、触媒金属の粉体であってもよいし、触媒金属を加圧成型することで形成されるペレット状の成型体であってもよい。また、シリカ等の公知の触媒担体に触媒金属が担持されたものであってもよい。本実施形態に係る二酸化炭素還元触媒は、上記以外に、触媒製造工程等で混入する不可避的不純物を含んでもよいが、できるだけ不純物を含まないことが好ましい。 The carbon dioxide reduction catalyst according to the present embodiment may be, for example, a catalytic metal powder, or a pellet-shaped molded body formed by pressure molding a catalytic metal. Alternatively, a catalyst metal may be supported on a known catalyst carrier such as silica. In addition to the above, the carbon dioxide reduction catalyst according to the present embodiment may contain unavoidable impurities mixed in during the catalyst manufacturing process, etc., but it is preferable to contain as few impurities as possible.
＜二酸化炭素還元触媒の製造方法＞
本実施形態に係る二酸化炭素還元触媒の製造方法は、共沈工程を有する。また、共沈工程の次に、含侵工程を有することが好ましい。
<Method for producing carbon dioxide reduction catalyst>
The method for producing a carbon dioxide reduction catalyst according to this embodiment includes a coprecipitation step. Moreover, it is preferable to have an impregnation process next to the coprecipitation process.
（共沈工程）
共沈工程は、Ｆｅの硝酸塩とＧａの硝酸塩とを所定量蒸留水に溶解させた水溶液から、共沈法により触媒前駆体である沈殿物を抽出する工程である。共沈工程により、Ｆｅ－Ｇａ複合酸化物が形成される。共沈工程において、ＦｅとＧａを含む上記水溶液に対し、Ｎａ２ＣＯ３水溶液を滴下することで、沈殿溶液が得られる。その後、沈殿溶液からろ過・洗浄等によって沈殿物を分離し、乾燥させることで、触媒前駆体である沈殿物（Ｆｅ－Ｇａ複合酸化物）が得られる。
(co-precipitation process)
The coprecipitation process is a process of extracting a precipitate, which is a catalyst precursor, by a coprecipitation method from an aqueous solution in which predetermined amounts of Fe nitrate and Ga nitrate are dissolved in distilled water. A Fe--Ga composite oxide is formed by the coprecipitation process. In the coprecipitation step, a precipitation solution is obtained by dropping an aqueous Na 2 CO 3 solution into the aqueous solution containing Fe and Ga. Thereafter, the precipitate is separated from the precipitate solution by filtration, washing, etc., and dried to obtain a precipitate (Fe--Ga composite oxide) that is a catalyst precursor.
（含侵工程）
含侵工程は、共沈工程により得られた沈殿物にＮａを含む水溶液を滴下して所定時間乾燥させ、得られた粉末を所定の温度で焼成する工程である。含侵工程により、Ｆｅ－Ｇａ複合酸化物の表面付近にＮａ化合物を偏在させることができる。Ｎａを含む水溶液としては、例えば、ＮａＮＯ３水溶液が挙げられる。ＮａＮＯ３水溶液は、超音波加振の下、滴下することができる。これにより、Ｆｅ－Ｇａ複合酸化物の表面付近にＮａ化合物を均一に偏在させることができる。焼成温度は、例えば５５０℃、焼成時間は４時間とすることができる。
(impregnation process)
The impregnation step is a step in which an aqueous solution containing Na is dropped onto the precipitate obtained in the coprecipitation step, dried for a predetermined period of time, and the resulting powder is fired at a predetermined temperature. The impregnation step allows the Na compound to be unevenly distributed near the surface of the Fe--Ga composite oxide. An example of the aqueous solution containing Na is an aqueous NaNO 3 solution. The NaNO 3 aqueous solution can be dropped under ultrasonic vibration. Thereby, the Na compound can be uniformly distributed near the surface of the Fe--Ga composite oxide. The firing temperature can be, for example, 550° C. and the firing time can be 4 hours.
本発明は上記実施形態に限定されるものではなく、本発明の目的を達成できる範囲での変形、改良は本発明に含まれる。 The present invention is not limited to the above-described embodiments, and the present invention includes modifications and improvements within the scope that can achieve the purpose of the present invention.
次に、本発明の実施例について説明するが、本発明はこの実施例に限定されるものではない。 Next, examples of the present invention will be described, but the present invention is not limited to these examples.
［実施例１］
表１に示す触媒金属１としてのＦｅの硝酸塩（Ｆｅ（ＮＯ３）３・９Ｈ２Ｏ）と、同じく触媒金属２としてのＧａの硝酸塩（Ｇａ（ＮＯ３）３・６Ｈ２Ｏとを、金属原子換算でＦｅ：Ｇａの質量比が８：２となるように秤量し、蒸留水に溶解させた。次いで、上記水溶液を撹拌しながら、１．０Ｍ ＮａＮＯ３水溶液を２ｍｌ／ｍｉｎ滴下し、ｐＨ８．５に固定することで、ＦｅとＧａを沈殿物として含む沈殿溶液を得た。次いで、沈殿溶液を室温下、２４時間エージングさせた後、ろ過、洗浄を繰り返すことで沈殿物を分離した。分離した沈殿物を６０℃×１２時間乾燥させることで、Ｆｅ－Ｇａ触媒前駆体を得た。
[Example 1]
Fe nitrate (Fe( NO 3 ) 3.9H 2 O) as
上記Ｆｅ－Ｇａ触媒前駆体に対し、ＮａＮＯ３水溶液を９２ｋＨｚ超音波加振の下、Ｎａ含有量が１．０質量％となるように滴下した。次いで、５０００Ｐａの真空下で１時間乾燥させ、更に常圧下で６０℃×１２時間乾燥させ、粉末を得た。得られた粉末を５５０℃×４時間焼成することで、実施例１に係る触媒を得た。 An aqueous NaNO 3 solution was added dropwise to the Fe--Ga catalyst precursor under 92 kHz ultrasonic vibration so that the Na content was 1.0% by mass. Next, it was dried under a vacuum of 5000 Pa for 1 hour, and further dried at 60° C. for 12 hours under normal pressure to obtain a powder. The catalyst according to Example 1 was obtained by calcining the obtained powder at 550° C. for 4 hours.
［実施例２～３、比較例１～９］
触媒金属１（Ｆｅ）、及び触媒金属２の種類及び量を、それぞれ表１に示すものとしたこと以外は、実施例１と同様として、実施例２～３、及び比較例１～９に係る触媒を得た。比較例１は触媒金属２を用いず、Ｆｅの硝酸塩のみを用いた。なお、表１に触媒金属１と触媒金属２の質量部を示しているが、各実施例及び比較例に係る触媒金属には、表１に示す触媒金属１と触媒金属２以外に１．０質量％のＮａが含有される。
[Examples 2-3, Comparative Examples 1-9]
Examples 2 to 3 and Comparative Examples 1 to 9 were carried out in the same manner as in Example 1, except that the types and amounts of catalyst metal 1 (Fe) and
［評価］
実施例１～３、及び比較例１～９の二酸化炭素還元触媒について、以下の方法で二酸化炭素還元反応を行った。装置は、固定床流通式の反応装置を使用し、反応ガスはＣＯ２ ２．８ＮＬ／ｈ、Ｈ２ ８．４ＮＬ／ｈ（ＣＯ２／Ｈ２＝１／３）とした。各実施例及び比較例に係る二酸化炭素触媒は０．４～０．８ｍｍ角のペレット状としたものを０．２５ｇ用いた。上記ペレットを、反応管（内径６ｍｍ）に５ｃｍの長さで充填して用いた。Ｗ／Ｆ（触媒重量／ガス流量）は０．５ｇ・ｈ／ｍｏｌ、空間速度ＳＶ（Ｓｐａｃｅ Ｖｅｌｏｃｉｔｙ）＝５０，０００ｈ－１とした。反応条件は温度３８０℃、圧力３ＭＰａ、反応時間４時間とした。触媒反応後のガス成分を、オンラインでのガスクロマトグラフィー（Ｓｈｉｍａｄｚｕ，ＧＣ－２０１４ＡＴ、検出器：熱伝導度検出器（ＴＣＤ））及び水素炎イオン化検出器（ＦＩＤ）（Ｓｈｉｍａｄｚｕ，ＧＣ－２０１４ＡＦ）により定性・定量分析した。また触媒反応後の液体成分もオフラインでのガスクロマトグラフィー（Ｓｈｉｍａｄｚｕ，ＧＣ－２０１４ＡＦ、検出器：水素炎イオン化検出器（ＦＩＤ））により定性・定量分析した。
[evaluation]
Carbon dioxide reduction reactions were carried out using the carbon dioxide reduction catalysts of Examples 1 to 3 and Comparative Examples 1 to 9 in the following manner. A fixed bed flow reactor was used as the apparatus, and the reaction gases were CO 2 2.8 NL/h and H 2 8.4 NL/h (CO 2 /H 2 =1/3). The carbon dioxide catalyst used in each of the Examples and Comparative Examples was 0.25 g of pellets of 0.4 to 0.8 mm square. The above pellets were used by filling a reaction tube (inner diameter 6 mm) with a length of 5 cm. W/F (catalyst weight/gas flow rate) was 0.5 g·h/mol, and space velocity SV (Space Velocity) was 50,000 h −1 . The reaction conditions were a temperature of 380°C, a pressure of 3 MPa, and a reaction time of 4 hours. The gas components after the catalytic reaction were analyzed by online gas chromatography (Shimadzu, GC-2014AT, detector: thermal conductivity detector (TCD)) and flame ionization detector (FID) (Shimadzu, GC-2014AF). Qualitative and quantitative analysis was performed. The liquid components after the catalytic reaction were also qualitatively and quantitatively analyzed by off-line gas chromatography (Shimadzu, GC-2014AF, detector: flame ionization detector (FID)).
（ＣＯ２変換率）
上記二酸化炭素還元反応によるＣＯ２の変換率を、以下の式（１）により求めた。結果を図１に示す。
ＣＯ２変換率（％）＝（（反応前のＣＯ２濃度）－（反応後のＣＯ２濃度））／（反応前のＣＯ２濃度）×１００ …（１）
( CO2 conversion rate)
The conversion rate of CO 2 due to the carbon dioxide reduction reaction was determined using the following equation (1). The results are shown in Figure 1.
CO 2 conversion rate (%) = ((CO 2 concentration before reaction) - (CO 2 concentration after reaction)) / (CO 2 concentration before reaction) × 100 ... (1)
（炭化水素選択率）
上記二酸化炭素還元反応により生成された炭化水素（ＣＯ、ＣＨ４、Ｃ２－４、Ｃ５＋）の選択率を、以下の式（２）により求めた。なおＣ２－４は、炭素数２～４の炭化水素を示し、Ｃ５＋は、炭素数５以上の炭化水素を示す。結果を図２に示す。
炭化水素選択率（％）＝（炭化水素濃度）／（（（反応前のＣＯ２濃度）－（反応後のＣＯ２濃度））×１００ …（２）
(Hydrocarbon selectivity)
The selectivity of hydrocarbons (CO, CH 4 , C 2-4 , C 5+ ) produced by the carbon dioxide reduction reaction was determined using the following equation (2). Note that C 2-4 represents a hydrocarbon having 2 to 4 carbon atoms, and C 5+ represents a hydrocarbon having 5 or more carbon atoms. The results are shown in Figure 2.
Hydrocarbon selectivity (%) = (hydrocarbon concentration) / (((CO 2 concentration before reaction) - (CO 2 concentration after reaction)) × 100 ... (2)
（Ｃ５＋生成率）
上記二酸化炭素還元反応により生成されたＣ５＋（炭素数５以上の炭化水素）の生成率を、以下の式（３）により求めた。結果を図３に示す。
Ｃ５＋生成率（％）＝ＣＯ２変換率×Ｃ５＋選択率／１００ …（３）
(C5 + generation rate)
The production rate of C 5+ (hydrocarbon having 5 or more carbon atoms) produced by the carbon dioxide reduction reaction was determined using the following equation (3). The results are shown in Figure 3.
C 5 + production rate (%) = CO 2 conversion rate x C 5 + selectivity / 100...(3)
（Ｇａ含有量とＣＯ２変換率との関係）
次に、表１に示すように触媒金属中のＦｅとＧａとの質量割合を変化させた実施例１～３及び、Ｇａ含有量をそれぞれ４０質量％、５０質量、６０質量％（Ｆｅ含有量約６０質量％、約５０質量％、約４０質量％）とした触媒と、Ｇａを含有しない比較例１の触媒を用いた二酸化炭素還元反応における、Ｇａ含有量とＣＯ２変換率との関係を調べた。結果を図４に示す。図４の縦軸は上記式（１）により求められるＣＯ２変換率（％）を示し、図４の横軸はＧａ含有量（質量％）を示す。なお、各触媒には、Ｎａが１．０質量％含有されるが、Ｇａ含有量としては触媒金属中のＦｅとＧａとの合計に対するＧａの質量割合を近似値として用いることができる（以下同様）。
(Relationship between Ga content and CO 2 conversion rate)
Next, Examples 1 to 3 in which the mass ratio of Fe and Ga in the catalyst metal was changed as shown in Table 1, and the Ga content was 40 mass%, 50 mass%, and 60 mass%, respectively (Fe content The relationship between the Ga content and the CO 2 conversion rate in the carbon dioxide reduction reaction using a catalyst containing (approximately 60 mass %, approximately 50 mass %, approximately 40 mass %) and the catalyst of Comparative Example 1 that does not contain Ga. Examined. The results are shown in Figure 4. The vertical axis of FIG. 4 shows the CO 2 conversion rate (%) determined by the above formula (1), and the horizontal axis of FIG. 4 shows the Ga content (mass %). Each catalyst contains 1.0% by mass of Na, but the mass ratio of Ga to the total of Fe and Ga in the catalyst metal can be used as an approximate value for the Ga content (hereinafter, the same applies). ).
（Ｇａ含有量とＣ５＋選択率との関係）
次に、図４と同様に実施例１～３等及び比較例１の触媒を用いた二酸化炭素還元反応における、Ｇａ含有量とＣ５＋選択率との関係を調べた。結果を図５に示す。図５の縦軸は上記式（２）により求められるＣ５＋選択率（％）を示し、図５の横軸はＧａ含有量（質量％）を示す。
(Relationship between Ga content and C5 + selectivity)
Next, as in FIG. 4, the relationship between Ga content and C 5+ selectivity in the carbon dioxide reduction reaction using the catalysts of Examples 1 to 3 and Comparative Example 1 was investigated. The results are shown in Figure 5. The vertical axis of FIG. 5 shows the C 5+ selectivity (%) determined by the above formula (2), and the horizontal axis of FIG. 5 shows the Ga content (mass %).
（Ｇａ含有量とＣ５＋生成率との関係）
次に、図４と同様に実施例１～３等及び比較例１の触媒を用いた二酸化炭素還元反応における、Ｇａ含有量とＣ５＋生成率との関係を調べた。結果を図６に示す。図６の縦軸は上記式（３）により求められるＣ５＋生成率（％）を示し、図５の横軸はＧａ含有量（質量％）を示す。
(Relationship between Ga content and C5 + production rate)
Next, as in FIG. 4, the relationship between Ga content and C 5+ production rate in the carbon dioxide reduction reaction using the catalysts of Examples 1 to 3 and Comparative Example 1 was investigated. The results are shown in FIG. The vertical axis of FIG. 6 shows the C 5+ production rate (%) determined by the above formula (3), and the horizontal axis of FIG. 5 shows the Ga content (mass %).
（Ｇａ含有量と触媒金属粒子径との関係）
次に、図４と同様に実施例１～３等及び比較例１の触媒のＧａ含有量と触媒金属粒子径（ｎｍ）との関係を調べた。結果を図７に示す。図７の縦軸は触媒金属粒子径（ｎｍ）を示し、図７の横軸はＧａ含有量（質量％）を示す。触媒金属粒子径（ｎｍ）は、Ｘ線回折強度測定装置を用い、Ｘ線源をＣｕＫα線、出力を４０ｋＶ、５０ｍＡとして、２θ＝３５．６°付近で得られるピークに対して、以下の式（４）に示すシェラーの式を用いて算出した。なお式（４）におけるＫはシェラー定数を、λはＸ線波長（ｎｍ）を、βはピークの半値幅を、θは回折角度をそれぞれ示す。
粒子径（ｎｍ）＝Ｋ＝Ｋ×λ／（β×ｃｏｓθ） …（４）
(Relationship between Ga content and catalyst metal particle size)
Next, similarly to FIG. 4, the relationship between the Ga content and the catalyst metal particle diameter (nm) of the catalysts of Examples 1 to 3 and Comparative Example 1 was investigated. The results are shown in FIG. The vertical axis in FIG. 7 shows the catalyst metal particle diameter (nm), and the horizontal axis in FIG. 7 shows the Ga content (mass %). The catalyst metal particle diameter (nm) is calculated using the following formula using an X-ray diffraction intensity measuring device, using the CuKα ray source as the X-ray source, and the output as 40 kV and 50 mA, for the peak obtained around 2θ = 35.6°. Calculated using Scherrer's equation shown in (4). In equation (4), K represents the Scherrer constant, λ represents the X-ray wavelength (nm), β represents the half-width of the peak, and θ represents the diffraction angle.
Particle diameter (nm)=K=K×λ/(β×cosθ)…(4)
（Ｎａ含有量とＣＯ２変換率、Ｃ５＋選択率、Ｃ５＋生成率との関係）
次に、触媒金属中のＧａ含有量を３０質量％とした触媒において、Ｎａ含有量を０質量％、０．５質量％、１．０質量％、１．５質量％、２．０質量％とし、残りの触媒金属中の成分をＦｅとした触媒をそれぞれ調製し、図４～図６と同様の条件で、ＣＯ２変換率、Ｃ５＋選択率、Ｃ５＋生成率をそれぞれ測定及び算出して、Ｎａ含有量との関係を調べた。結果をそれぞれ図８～図１０に示す。
(Relationship between Na content and CO 2 conversion rate, C 5+ selectivity, and C 5+ production rate)
Next, in the catalyst where the Ga content in the catalyst metal is 30% by mass, the Na content is 0% by mass, 0.5% by mass, 1.0% by mass, 1.5% by mass, and 2.0% by mass. Then, catalysts were prepared with Fe as the component in the remaining catalytic metal, and the CO 2 conversion rate, C 5+ selectivity, and C 5+ production rate were measured and calculated under the same conditions as in Figures 4 to 6. The relationship with Na content was investigated. The results are shown in FIGS. 8 to 10, respectively.
［考察］
図１～図３から、実施例１の触媒は、従来の触媒金属としてＦｅのみを用いた触媒や、触媒金属としてＧａの代わりに他の金属元素を用いた各比較例に係る触媒と比較して、炭素数５以上の炭化水素の選択率及び生成率が高く、かつＣＯ２変換率も比較的高い結果が明らかであった。
[Consideration]
From FIGS. 1 to 3, the catalyst of Example 1 was compared with the conventional catalyst using only Fe as the catalytic metal and the catalyst of each comparative example using other metal elements instead of Ga as the catalytic metal. As a result, it was clear that the selectivity and production rate of hydrocarbons having 5 or more carbon atoms were high, and the CO 2 conversion rate was also relatively high.
また、図４～図６から、触媒金属としてのＧａの含有量は、１０～３０質量％の範囲が好ましく、２０～３０質量％の範囲がより好ましい結果が明らかであった。Ｇａ添加量を増加させると、Ｃ５＋を生成する触媒活性は向上するが、Ｇａ含有量が３０質量％を超える場合、ＧａがＦｅの反応サイトを被覆することで、結果的に触媒活性が低下しているものと考えられる。 Furthermore, from FIGS. 4 to 6, it was clear that the content of Ga as a catalytic metal is preferably in the range of 10 to 30% by mass, and more preferably in the range of 20 to 30% by mass. Increasing the amount of Ga added improves the catalytic activity that generates C 5+ , but when the Ga content exceeds 30% by mass, Ga covers Fe reaction sites, resulting in a decrease in catalytic activity. It is thought that this is the case.
また、図７から、Ｇａの含有量が１０～３０質量％の範囲内である場合、触媒金属が微粒子化されている結果が明らかであった。図４～図６の結果と併せて考察すると、触媒金属にＧａを添加することによるＣ５＋生成率等の触媒活性の向上は、触媒金属が微粒子化されていることによるものと推察される。 Further, from FIG. 7, it was clear that when the Ga content was within the range of 10 to 30% by mass, the catalyst metal was made into fine particles. When considered in conjunction with the results of FIGS. 4 to 6, it is inferred that the improvement in catalytic activity such as C 5+ production rate by adding Ga to the catalyst metal is due to the fine particles of the catalyst metal.
また、図８～図１０から、触媒金属としてのＧａの含有量が、１０～３０質量％の範囲内である場合において、触媒金属としてのＮａの含有量は、０．５～１．５質量％の範囲が好ましく、１．０質量％の範囲がより好ましい結果が明らかであった。Ｎａ含有量を増やすほど、Ｃ５＋生成活性は向上するが、Ｎａ含有量が１．０質量％を超える場合、ＮａがＦｅ触媒の反応サイトを被覆するため、触媒活性が低下するものと考えられる。 Furthermore, from FIGS. 8 to 10, when the content of Ga as a catalytic metal is within the range of 10 to 30% by mass, the content of Na as a catalytic metal is 0.5 to 1.5% by mass. It was clear that a range of 1.0% by mass was preferable, and a range of 1.0% by mass was more preferable. As the Na content increases, the C 5+ production activity improves, but when the Na content exceeds 1.0% by mass, it is thought that the catalytic activity decreases because Na covers the reaction sites of the Fe catalyst. .
Claims (7)
触媒金属として、Ｆｅ及びＧａを含み、
前記触媒金属中に前記Ｇａは１０～３０質量％含まれる、二酸化炭素還元触媒。 A carbon dioxide reduction catalyst that performs a hydrogenation reaction on carbon dioxide to reduce carbon dioxide and generate hydrocarbons,
Contains Fe and Ga as catalyst metals,
A carbon dioxide reduction catalyst, wherein the catalytic metal contains 10 to 30% by mass of Ga.
前記Ｆｅの硝酸塩と前記Ｇａの硝酸塩とを所定量蒸留水に溶解させた水溶液から、共沈法により沈殿物を抽出する共沈工程を有する、二酸化炭素還元触媒の製造方法。 A method for producing a carbon dioxide reduction catalyst according to any one of claims 1 to 4, comprising:
A method for producing a carbon dioxide reduction catalyst, comprising a coprecipitation step of extracting a precipitate by a coprecipitation method from an aqueous solution in which a predetermined amount of the Fe nitrate and the Ga nitrate are dissolved in distilled water.
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