JPS6114861B2 - - Google Patents
Info
- Publication number
- JPS6114861B2 JPS6114861B2 JP54047113A JP4711379A JPS6114861B2 JP S6114861 B2 JPS6114861 B2 JP S6114861B2 JP 54047113 A JP54047113 A JP 54047113A JP 4711379 A JP4711379 A JP 4711379A JP S6114861 B2 JPS6114861 B2 JP S6114861B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- powder
- alumina
- cobalt
- magnesia
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000003054 catalyst Substances 0.000 claims description 49
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 36
- 239000000843 powder Substances 0.000 claims description 27
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- 239000000395 magnesium oxide Substances 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 17
- 229930195733 hydrocarbon Natural products 0.000 claims description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 238000000629 steam reforming Methods 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 18
- 230000000694 effects Effects 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 239000011029 spinel Substances 0.000 description 9
- 229910052596 spinel Inorganic materials 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000011812 mixed powder Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910020068 MgAl Inorganic materials 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- FQMNUIZEFUVPNU-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co] FQMNUIZEFUVPNU-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229920001353 Dextrin Polymers 0.000 description 2
- 239000004375 Dextrin Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 235000019425 dextrin Nutrition 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910020598 Co Fe Inorganic materials 0.000 description 1
- 229910002519 Co-Fe Inorganic materials 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 241000264877 Hippospongia communis Species 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000012050 conventional carrier Substances 0.000 description 1
- -1 etc. Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Classifications
-
- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Hydrogen, Water And Hydrids (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、炭化水素の水蒸気改質用触媒の製造
方法に関する。炭化水素を水蒸気改質して、合成
ガス、燃料ガス等を得る場合、従来はメタンを主
成分とする天燃ガスがその原料として使用されて
きたが、近年比較的重質の炭化水素類、あるいは
芳香族又は不飽和炭化水素を含む炭化水素類を原
料として使用することが望まれるようになつた。
しかしながら、これら炭化水素はその改質時に
おいて触媒表面上に炭素の析出を起し易く、その
ために触媒活性を損なつてしまうおそれがある。
そこで、改質時において原料炭化水素に対する水
蒸気の量を大過剰にする手段が提案されている
が、所望する効果を上げることができない。
本発明は、かかる問題点を解決し、炭素析出が
なく、触媒活性並びに耐久性に優れた効果を発揮
する水蒸気改質用触媒を製造する方法を提供しよ
うとするものである。
即ち、本発明は、マグネシア粉末と100ないし
15000オングストローム（Å）の平均粒径を有す
るアルミナ粉末とを混合し、所望の形状に成形
し；これを加熱して多孔質焼結体となし、次いで
該多孔質焼結体にコバルトおよび鉄よりなる触媒
成分を担持させることを特徴とする炭化水素の水
蒸気改質用触媒の製造方法にある。
本発明の製造法によれば、触媒表面への炭素の
析出がなく、水蒸気改質に対して高い触媒活性と
耐久性とを有する触媒を提供することができる。
また、本発明により得られた触媒は、その担体と
しての前記多孔質体がマグネシア・アルミナ
（MgAl2O4）スピネルであるため、高温における
機械的強度も高い。また、該触媒は高温において
使用してもアルミナの結晶構造の変化を生ぜず、
該変化に伴う表面積の減少、強度の低下がなく、
高温における触媒活性の耐久性に優れた効果を発
揮する。
また、本発明にかかる上記触媒においては、
300℃という低温から1000℃という高温に至る広
範囲の温度範囲においても高い上記活性を有す
る。しかして、比較的低温の範囲においては主と
してメタン、水素、炭酸ガスに富む生成ガスを生
成し、比較的高い温度範囲においては主として水
素、一酸化炭素などよりなる生成ガスを生成す
る。
また、上記スピネルは表面の化学特性がアルミ
ナより中性に近いため、特に炭化水素が関係する
水蒸気改質反応においてその活性が非常に高い。
本発明においては、前記アルミナ粉末は100な
いし15000Å（オングストローム）の粒径を有す
るものを用いる。この粒径の範囲外では、前記水
蒸気改質に関する触媒活性が低くなり、前記のご
とき優れた触媒を得難い。なお、本発明において
「粒径」とは重量平均粒径を意味する。アルミナ
粉末と混合するマグネシア粉末は、アルミナ粉末
の最適な接合剤とも言うべきもので、その粒径は
特に限定するものではないが、アルミナ粉末とほ
ぼ均等に混合し合い、アルミナとスピネを形成す
ると共に、得られる多孔質焼結体（担体）の孔径
をほぼ均一なものとするためには、0.1ないし500
ミクロン（μ）の粒径のものを用いるのが好まし
い。
マグネシア粉末に対するアルミナ粉末の混合割
合（アルミナ／マグネシア）は、1.5ないし10重
量倍であることが好ましい。1.5重量倍未満で
は、マグネシアの量が多すぎ、焼成時の加熱によ
つてマグネシア同志が結晶化を起し、マグネシア
のみの大きな結晶が生成してしまい、担体の孔の
数が少なくなつてしまう。また、多量のマグネシ
アによつてアルミナが包み込まれた状態となる恐
れがある。また、10重量倍よりも大きいとマグネ
シアの量が少な過ぎて、アルミナの結合が弱くな
り、担体の強度が低下するおそれがある。
アルミナ粉末とマグネシア粉末との混合粉末を
加熱焼結するための温度は、1000℃ないし1600℃
が好ましい。1000℃よりも低い温度では焼結が十
分でないと共にMgAl2O4スピネルの量が少な
く、触媒の強度が弱くなるおそれがある。また、
1600℃より高くなるとMgAl2O4スピネルの粒子
が成長しすぎて細孔容積量が減少してしまう。こ
の場合、1200ないし1600℃において焼成するとき
には、マグネシアとアルミナとが反応して、これ
らの75％以上がMgAl2O4スピネルとなり、最終
的に優れた耐熱性、強度を有する触媒を得ること
ができる。
なお、前記混合粉末の焼結に当つては、上記混
合粉末に少量のデキストリン等の有機糊を添加、
混合し、これらの混合物を錠剤成形機等により所
望の大きさに成形し、これを電気炉等により焼成
する。
上記のごとき粒径のアルミナ粉末を用いて得ら
れた多孔質焼結体は、その平均孔径が約200Åな
いし15000Åである。
次に、上記多孔質焼結体を担体とし、これに前
記触媒成分たるコバルトおよび鉄を担持させる。
この担持に当たつては、通常の触媒成分の担持の
場合と同様に行い、例えば硝酸コバルト、硝酸鉄
等の触媒成分を形成するための原料の溶液中に上
記担体を浸漬し、乾燥、焼成する。
上記において、触媒成分中のコバルトと鉄との
割合は、鉄の量がコバルトの量に対して0.01ない
し1.0重量倍であることが望ましい。この範囲外
では本発明の効果を達成し難い。また、触媒成分
中のコバルトの量は、スピネル担体に対して1.0
ないし10重量％であることが好ましい。１％以下
のコバルト量では本発明の効果を達成し難いし、
10％以上担持させてもそれに見合うだけの効果は
得難い。
なお、前記混合粉末の成形は、粒状、柱状、ハ
ニカム状等所望の形状に行なう。また、本発明に
おいては、前記微細アルミナ粉末の節約のため
に、本発明とは別に作製したアルミナ等の粒状
体、ハニカム状体を用い、これを母体とし、これ
に前記本発明にかかる混合粉末を被覆して任意の
形状に成形、加熱し、その担体の表層部分を前記
スピネルとなし、これに前記触媒成分を担持する
方法を採ることもできる。
実施例 １
平均粒径が400、1500、5000、10000Åの４種類
のアルミナ粉末を準備し、これら粉末にそれぞれ
平均粒径0.5μのマグネシア粉末を添加すると共
に、これら混合粉末に対して１重量％のデキスト
リンを加え、これらを十分に混合し、次いでマル
メライザー（錠剤成形機）により、約３mmの直径
を有する球状ペレツトに成形した。なお、上記の
マグネシア粉末に対するアルミナ粉末との混合割
合は、2.8重量倍であつた。
次に、上記のペレツトを電気乾燥器により110
℃で約12時間乾燥し、その後これを電気炉に入
れ、1350℃で10時間加熱、焼結し、担体としての
多孔質焼結体を作製した。これらの焼結体の性質
を第１表に示した。
次いで、上記担体を硝酸コバルト70％（重量
比、以下同じ）と硝酸鉄9.7％とを含有する水溶
液に浸漬し、乾燥後、600℃、空気中で３時間焼
成し、コバルト−鉄（Co−Fe）触媒を製造した
（第２表参照）。
次に、これらの触媒の活性を評価するため、触
媒を石英管に充填し、500℃に加熱保持してお
き、これに水蒸気とｎ（ノルマル）−ヘプタンと
の混合ガスを導入した。上記混合ガスは、ｎ−ヘ
プタンに対する水蒸気の比が24.4モル／モルのも
のを用いた。空間速度（SV）は15000（１／時）
とした。
上記の触媒活性は、初期と５時間後における上
記ｎ−ヘプタンの転化率により評価した。その結
果を第３表に示す。
なお、上記の「初期」とは反応開始の時点を言
い、「５時間後」とは「初期」の開始時から５時
間後の時点のことを言う。
また、上記転化率とは、ｎ−ヘプタンが水蒸気
と反応した割合（％）である。
また、比較のために粒子径25000Åのアルミナ
粉末と0.5μのマグネシア粉末とを用い他は上記
と同様にして作製した担体（No.S1）、および従
来市販されているδ．アルミナのみの焼結体から
なる担体（No.S2）を用い、他は上記と同様にし
て調製したコバルト鉄触媒（No.C1、C2）を製造
し、上記と同様に評価を行なつた。これらについ
ても、上記と同様に第１表ないし第３表に併示し
た。
The present invention relates to a method for producing a catalyst for steam reforming of hydrocarbons. When hydrocarbons are steam reformed to obtain synthesis gas, fuel gas, etc., natural gas, whose main component is methane, has traditionally been used as the raw material, but in recent years relatively heavy hydrocarbons, Alternatively, it has become desirable to use hydrocarbons including aromatic or unsaturated hydrocarbons as raw materials. However, when these hydrocarbons are reformed, carbon tends to be deposited on the surface of the catalyst, which may impair the catalytic activity.
Therefore, a method has been proposed in which the amount of steam relative to the raw material hydrocarbon is greatly exceeded during reforming, but the desired effect cannot be achieved. The present invention aims to solve these problems and provide a method for producing a steam reforming catalyst that is free from carbon precipitation and exhibits excellent catalytic activity and durability. That is, in the present invention, magnesia powder and 100 to 100%
Alumina powder having an average particle size of 15,000 angstroms (Å) is mixed and formed into the desired shape; this is heated to form a porous sintered body, and then the porous sintered body is injected with cobalt and iron. The present invention provides a method for producing a catalyst for steam reforming of hydrocarbons, which comprises supporting a catalyst component. According to the production method of the present invention, it is possible to provide a catalyst that does not deposit carbon on the catalyst surface and has high catalytic activity and durability for steam reforming.
Further, the catalyst obtained according to the present invention has high mechanical strength at high temperatures because the porous body serving as the carrier is magnesia alumina (MgAl 2 O 4 ) spinel. In addition, the catalyst does not cause any change in the crystal structure of alumina even when used at high temperatures,
There is no decrease in surface area or decrease in strength due to this change,
Demonstrates excellent durability of catalyst activity at high temperatures. Furthermore, in the above catalyst according to the present invention,
It has the above-mentioned high activity even in a wide temperature range from a low temperature of 300°C to a high temperature of 1000°C. Therefore, in a relatively low temperature range, a product gas mainly rich in methane, hydrogen, and carbon dioxide gas is produced, and in a relatively high temperature range, a product gas mainly consisting of hydrogen, carbon monoxide, etc. is produced. In addition, since the surface chemical properties of spinel are closer to neutrality than alumina, its activity is particularly high in steam reforming reactions involving hydrocarbons. In the present invention, the alumina powder used has a particle size of 100 to 15,000 angstroms. Outside this particle size range, the catalyst activity for the steam reforming will be low, making it difficult to obtain the excellent catalyst described above. In addition, in the present invention, "particle size" means a weight average particle size. Magnesia powder mixed with alumina powder can be said to be the best bonding agent for alumina powder, and its particle size is not particularly limited, but it mixes almost evenly with alumina powder to form alumina and spine. At the same time, in order to make the pore diameter of the obtained porous sintered body (carrier) almost uniform, it is necessary to
It is preferable to use particles with a particle size of microns (μ). The mixing ratio of alumina powder to magnesia powder (alumina/magnesia) is preferably 1.5 to 10 times by weight. If it is less than 1.5 times the weight, the amount of magnesia is too large, and the heating during firing causes magnesia to crystallize, producing large crystals of only magnesia, and the number of pores in the carrier decreases. . Furthermore, there is a possibility that alumina may be wrapped in a large amount of magnesia. On the other hand, if it is more than 10 times the weight, the amount of magnesia is too small, which weakens the bonding of alumina and may reduce the strength of the carrier. The temperature for heating and sintering the mixed powder of alumina powder and magnesia powder is 1000℃ to 1600℃.
is preferred. At a temperature lower than 1000°C, sintering is not sufficient and the amount of MgAl 2 O 4 spinel is small, which may weaken the strength of the catalyst. Also,
If the temperature is higher than 1600°C, MgAl 2 O 4 spinel particles grow too much and the pore volume decreases. In this case, when calcined at 1200 to 1600°C, magnesia and alumina react, and more than 75% of them become MgAl 2 O 4 spinel, making it possible to finally obtain a catalyst with excellent heat resistance and strength. can. In addition, when sintering the mixed powder, a small amount of organic glue such as dextrin is added to the mixed powder,
The mixture is then molded into a desired size using a tablet molding machine or the like, and then fired using an electric furnace or the like. A porous sintered body obtained using alumina powder having the above particle size has an average pore size of about 200 Å to 15,000 Å. Next, the porous sintered body is used as a carrier, and cobalt and iron, which are the catalyst components, are supported on the porous sintered body.
This support is carried out in the same manner as in the case of normal catalyst component support; for example, the above-mentioned carrier is immersed in a solution of raw materials for forming catalyst components such as cobalt nitrate and iron nitrate, and then dried and calcined. do. In the above, the ratio of cobalt and iron in the catalyst components is preferably such that the amount of iron is 0.01 to 1.0 times the amount of cobalt by weight. Outside this range, it is difficult to achieve the effects of the present invention. Also, the amount of cobalt in the catalyst component is 1.0 with respect to the spinel support.
The amount is preferably from 10% to 10% by weight. It is difficult to achieve the effects of the present invention with a cobalt content of 1% or less,
Even if it is loaded more than 10%, it is difficult to obtain a commensurate effect. The mixed powder is shaped into a desired shape such as granules, columns, or honeycombs. In addition, in the present invention, in order to save the fine alumina powder, a granular body or a honeycomb-shaped body of alumina, etc. produced separately from the present invention is used, and this is used as a matrix, and the mixed powder according to the present invention is added to the base body. It is also possible to adopt a method in which the spinel is coated, molded into an arbitrary shape, and heated, the surface layer of the carrier is made into the spinel, and the catalyst component is supported on this. Example 1 Four types of alumina powders with average particle sizes of 400, 1500, 5000, and 10000 Å were prepared, and magnesia powder with an average particle size of 0.5μ was added to each of these powders, and 1% by weight of the mixed powder was added. of dextrin were added, these were thoroughly mixed and then formed into spherical pellets with a diameter of about 3 mm using a marmerizer (tablet press). The mixing ratio of the alumina powder to the magnesia powder was 2.8 times by weight. Next, the above pellets were heated to 110% by electric dryer.
It was dried at ℃ for about 12 hours, and then placed in an electric furnace and heated and sintered at 1350 ℃ for 10 hours to produce a porous sintered body as a carrier. The properties of these sintered bodies are shown in Table 1. Next, the above carrier was immersed in an aqueous solution containing 70% cobalt nitrate (weight ratio, same hereinafter) and 9.7% iron nitrate, dried, and then calcined in air at 600°C for 3 hours to form a cobalt-iron (Co- Fe) catalyst was prepared (see Table 2). Next, in order to evaluate the activity of these catalysts, the catalysts were filled in a quartz tube, heated and maintained at 500° C., and a mixed gas of water vapor and n-heptane was introduced into the tube. The mixed gas used had a ratio of water vapor to n-heptane of 24.4 mol/mol. Space velocity (SV) is 15000 (1/hour)
And so. The above catalyst activity was evaluated based on the conversion rate of n-heptane at the initial stage and after 5 hours. The results are shown in Table 3. In addition, the above-mentioned "initial stage" refers to the time point at which the reaction starts, and "5 hours later" refers to the time point 5 hours after the start time of the "initial stage". Moreover, the above-mentioned conversion rate is the ratio (%) of n-heptane reacted with water vapor. For comparison, a support (No. S 1 ) prepared using alumina powder with a particle size of 25,000 Å and magnesia powder with a particle size of 0.5 μm in the same manner as above, and a conventional commercially available δ. Cobalt iron catalysts (Nos. C 1 and C 2 ) were prepared using a carrier made of a sintered body of alumina only (No. S 2 ), and the rest were prepared in the same manner as above, and the evaluation was performed in the same manner as above. Summer. These are also listed in Tables 1 to 3 in the same way as above.
【表】【table】
【表】【table】
【表】
上記より知られるごとく、本発明にかかるCo
−Fe触媒は、比較触媒No.C1に比して高い触媒活
性を有していることが分る。また、従来の担体を
用いたNo.C2触媒は、その表面に炭素が析出し触
媒が崩壊してしまつた。
また、本発明にかかる触媒はいずれも上記反応
においてその表面への炭素の析出は見受けられな
かつた。
なお、上記の触媒活性は、前記のごとくｎ−ヘ
プタンの転化率で示したが、この水蒸気改質反応
によつて生成した改質ガスの組成（即ち、ｎ−ヘ
プタンから転化、生成した成分を100％とする）
は、上記触媒No.1〜４、C1のいずれを用いた場
合も、水素73〜75％、一酸化炭素19〜23％、炭酸
ガス３〜６％、メタン及びエタンの合計0.4％以
下であつた。このように、改質ガスの組成はほぼ
同じである故、本発明における触媒活性は上記転
化率によつて評価することができる。
実施例 ２
触媒成分の担持量、混合割合を異にする触媒を
製造し、その活性を測定した。
平均粒径が１μのγ−アルミナ粉末と、平均粒
径１μのマグネシア粉末とを混合し、実施例１と
同様にして直径約３mmの球状ペレツトを作成し
た。上記のマグネシア粉末に対するアルミナ粉末
の混合割合は、2.8重量倍であつた。
また、上記ペレツトを電気炉に入れ、1350℃で
６時間加熱、焼結し、担体とした。
次に、上記担体を所定濃度の硝酸コバルト水溶
液に浸漬し、乾燥後、600℃、空気中で３時間焼
成した。次いで、これを所定濃度の硝酸第二鉄水
溶液に浸漬し、乾燥後、600℃空気中で３時間焼
成し、コバルト−鉄触媒を製造した。得られた触
媒の触媒成分の担持量、コバルトに対する鉄の割
合は第４表に示した。
上記各触媒について、実施例１と同様に触媒活
性の評価をし、初期および５時間後の各転化率、
初期転化率に対する５時間後の「転化率の比」を
第５表に示した。
また、第５表には比較例として、コバルトの
み、又は鉄のみを前記スピネル担体に担持した触
媒についての結果を併記した。これら触媒の担持
量は第４表に示した（触媒No.C3〜C6）。[Table] As is known from the above, Co according to the present invention
It can be seen that the -Fe catalyst has higher catalytic activity than Comparative Catalyst No. C1 . In addition, in the No. C 2 catalyst using a conventional carrier, carbon was deposited on the surface and the catalyst collapsed. In addition, no carbon was observed to be deposited on the surface of any of the catalysts according to the present invention in the above reaction. The catalytic activity described above is indicated by the conversion rate of n-heptane as described above, but the composition of the reformed gas produced by this steam reforming reaction (i.e., the components converted and produced from n-heptane) (100%)
When using any of the above catalysts No. 1 to 4 and C 1 , hydrogen is 73 to 75%, carbon monoxide is 19 to 23%, carbon dioxide is 3 to 6%, and the total of methane and ethane is 0.4% or less. It was hot. As described above, since the compositions of the reformed gases are almost the same, the catalytic activity in the present invention can be evaluated based on the conversion rate. Example 2 Catalysts with different supported amounts and mixing ratios of catalyst components were produced, and their activities were measured. γ-Alumina powder with an average particle size of 1 μm and magnesia powder with an average particle size of 1 μm were mixed, and spherical pellets with a diameter of about 3 mm were prepared in the same manner as in Example 1. The mixing ratio of alumina powder to the above magnesia powder was 2.8 times by weight. Further, the above pellets were placed in an electric furnace and heated and sintered at 1350°C for 6 hours to form a carrier. Next, the above carrier was immersed in an aqueous cobalt nitrate solution of a predetermined concentration, dried, and then calcined at 600° C. in air for 3 hours. Next, this was immersed in a ferric nitrate aqueous solution of a predetermined concentration, dried, and then calcined in air at 600°C for 3 hours to produce a cobalt-iron catalyst. Table 4 shows the amount of catalyst components supported on the obtained catalyst and the ratio of iron to cobalt. For each of the above catalysts, the catalytic activity was evaluated in the same manner as in Example 1, and the conversion rates at the initial stage and after 5 hours,
The "ratio of conversion rate" after 5 hours to the initial conversion rate is shown in Table 5. Table 5 also shows, as comparative examples, the results of catalysts in which only cobalt or only iron was supported on the spinel carrier. The supported amounts of these catalysts are shown in Table 4 (Catalyst Nos. C3 to C6 ).
【表】【table】
【表】【table】
【表】
第４表および第５表より知られるごとく、本発
明にかかるCo−Fe触媒は比較触媒に比して、「転
化率の比」が高い値を示しており、耐久性に優れ
た触媒であることが分る。また、鉄のみを担持し
てなる触媒は殆んど活性を有していないことが分
る。
なお、改質ガスの組成は、触媒No.5〜14、C3
〜C4いずれを用いた場合も、前記実施例１にお
いて述べたものと同じであつた。[Table] As is known from Tables 4 and 5, the Co-Fe catalyst according to the present invention has a higher "conversion rate ratio" than the comparative catalyst, and has excellent durability. It turns out that it is a catalyst. Furthermore, it can be seen that the catalyst supporting only iron has almost no activity. The composition of the reformed gas is catalyst No. 5 to 14, C 3
-C4 The results were the same as those described in Example 1 above.
Claims (1)
ローム（Å）の平均粒径を有するアルミナ粉末と
を混合し、所望の形状に成形し、これを加熱して
多孔質焼結体となし、次いで該多孔質焼結体にコ
バルトおよび鉄よりなる触媒成分を担持させるこ
とを特徴とする炭化水素の水蒸気改質用触媒の製
造方法。 ２ 粉末成形体を1200ないし1600℃において加
熱、焼結することを特徴とする特許請求の範囲第
１項に記載の炭化水素の水蒸気改質用触媒の製造
方法。[Claims] 1. Mixing magnesia powder and alumina powder having an average particle size of 100 to 15,000 angstroms (Å), forming it into a desired shape, and heating it to form a porous sintered body, A method for producing a catalyst for steam reforming of hydrocarbons, characterized in that a catalyst component consisting of cobalt and iron is then supported on the porous sintered body. 2. The method for producing a catalyst for steam reforming of hydrocarbons according to claim 1, which comprises heating and sintering the powder compact at 1200 to 1600°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4711379A JPS55139836A (en) | 1979-04-16 | 1979-04-16 | Catalyst for steam modification and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4711379A JPS55139836A (en) | 1979-04-16 | 1979-04-16 | Catalyst for steam modification and its production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS55139836A JPS55139836A (en) | 1980-11-01 |
| JPS6114861B2 true JPS6114861B2 (en) | 1986-04-21 |
Family
ID=12766113
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4711379A Granted JPS55139836A (en) | 1979-04-16 | 1979-04-16 | Catalyst for steam modification and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS55139836A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02245239A (en) * | 1989-03-20 | 1990-10-01 | Ube Ind Ltd | High-active nickel catalyser and its production |
| DE10011738A1 (en) * | 2000-03-13 | 2002-03-28 | Porzellanwerk Kloster Veilsdor | Ceramic shaped catalyst bodies and method for producing such shaped catalyst bodies |
| JP5446060B2 (en) * | 2006-06-09 | 2014-03-19 | 戸田工業株式会社 | Porous material for honeycomb, porous material mixture, suspension for supporting honeycomb, catalyst body, and method for producing mixed reaction gas using the catalyst body |
| WO2009110241A1 (en) * | 2008-03-06 | 2009-09-11 | 戸田工業株式会社 | A porous catalytic body that decomposes hydrocarbons and a manufacturing method thereof, a method for manufacturing mixed reformed gas that comprises hydrogen from hydrocarbon, and a fuel cell system |
-
1979
- 1979-04-16 JP JP4711379A patent/JPS55139836A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS55139836A (en) | 1980-11-01 |
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