JPS6035176B2 - Steam reforming catalyst and its manufacturing method - Google Patents
Steam reforming catalyst and its manufacturing methodInfo
- Publication number
- JPS6035176B2 JPS6035176B2 JP54109385A JP10938579A JPS6035176B2 JP S6035176 B2 JPS6035176 B2 JP S6035176B2 JP 54109385 A JP54109385 A JP 54109385A JP 10938579 A JP10938579 A JP 10938579A JP S6035176 B2 JPS6035176 B2 JP S6035176B2
- Authority
- JP
- Japan
- Prior art keywords
- powder
- catalyst
- magnesia
- alumina
- carrier
- 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 title claims description 48
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 238000000629 steam reforming Methods 0.000 title claims 6
- 239000000843 powder Substances 0.000 claims description 45
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 41
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 30
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 24
- 239000000395 magnesium oxide Substances 0.000 claims description 20
- 229930195733 hydrocarbon Natural products 0.000 claims description 15
- 150000002430 hydrocarbons Chemical class 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 14
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 229910052596 spinel Inorganic materials 0.000 claims description 11
- 239000011029 spinel Substances 0.000 claims description 11
- 239000011812 mixed powder Substances 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- DJZHPOJZOWHJPP-UHFFFAOYSA-N magnesium;dioxido(dioxo)tungsten Chemical compound [Mg+2].[O-][W]([O-])(=O)=O DJZHPOJZOWHJPP-UHFFFAOYSA-N 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920001353 Dextrin Polymers 0.000 description 2
- 239000004375 Dextrin Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 235000019425 dextrin Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000264877 Hippospongia communis Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- -1 etc. Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000003502 gasoline 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
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 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
- 238000004064 recycling Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052566 spinel group Inorganic materials 0.000 description 1
- 238000010025 steaming Methods 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
- 239000002699 waste material Substances 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)
Description
【発明の詳細な説明】
本発明は、炭化水素の水蒸気故買用触媒およびその製造
方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a hydrocarbon steam recycling catalyst and a method for producing the same.
炭化水素を水蒸気教質して、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然ガスがその原
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
を損なってしまうおそれがある。When steaming hydrocarbons 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 or 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 catalyst surface, which may impair the catalytic activity.
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政質用触媒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・アルミナ
（ＭｇＡ１２０４）スピネルと、タングステン酸マグネ
シウム（ＭｇＷ０４）と、酸化タングステンとマグネシ
アおよびアルミナの一方又は双方とからなる多孔質担体
に、ニッケルを坦持してなることを特徴とする炭化水素
の水蒸気政質用触媒にある。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 catalyst for steam politics that does not cause carbon precipitation and exhibits excellent catalytic activity and durability. That is, the present invention is characterized in that nickel is supported on a porous carrier consisting of magnesia alumina (MgA1204) spinel, magnesium tungstate (MgW04), tungsten oxide, and one or both of magnesia and alumina. It is a catalyst for hydrocarbon steam chemistry.
本発明によれば、触媒表面への炭素の析出がなく、水蒸
気故買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。特に、本発明にかかる触媒は、
その担体としての前記多孔質体がマグネシア・アルミナ
（ＭｇＡ１２０４）スピネルを含有しているため、高温
における機械的強度も高く、また高温において使用して
もァ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。According to 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 against steam waste. In particular, the catalyst according to the invention is
Since the porous body as the carrier contains magnesia alumina (MgA1204) spinel, it has high mechanical strength at high temperatures, and even when used at high temperatures, the crystal structure of alumina does not change. There is no decrease in surface area or strength associated with this, and it exhibits excellent durability of catalyst activity at high temperatures.
また、本発明にかかる上記触媒においては、担体中にタ
ングステン酸マグネシウム（ＭｇＷ０４）が含有されて
いると共に、該担体にニッケルが担持されているので、
３００００という低温から１０００００という高温に至
る広範囲の温度範囲において、高い触媒活性を発揮する
と共に該触媒活性を長時間にわたり発揮する。Furthermore, in the above catalyst according to the present invention, magnesium tungstate (MgW04) is contained in the carrier, and nickel is supported on the carrier.
It exhibits high catalytic activity over a wide temperature range from a low temperature of 30,000 ℃ to a high temperature of 100,000 ℃, and exhibits this catalytic activity for a long time.
本発明にかかる触媒は、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。The catalyst according to the present invention produces a product gas mainly rich in methane, hydrogen, and carbon dioxide in a relatively low temperature range, and produces a product gas mainly consisting of hydrogen, carbon monoxide, etc. in a relatively high temperature range. .
上記触媒において、多孔質担体は、少なくともＭｇＡ１
２０４スピネルを５０なし、し７０モル％，ＭｇＷ０４
５なし、し３０モル％含有していることが好ましい。In the above catalyst, the porous carrier comprises at least MgA1
204 spinel 50%, 70mol%, MgW04
Preferably, the content is 30 mol %.
この場合には、上記した、これらの存在による効果が一
層良く発揮される。また、触媒成分としてのニッケル（
Ｎｉ）の量は上言己多孔質担体に対して１．０なし、し
１０重量％であることが好ましい。In this case, the above-mentioned effects due to their presence are better exhibited. In addition, nickel as a catalyst component (
The amount of Ni) is preferably between 1.0% and 10% by weight based on the porous carrier.
１％以下のニッケル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。If the amount of nickel is less than 1%, it is difficult to achieve the effects of the present invention, and even if the amount of nickel is 10% or more, it is difficult to obtain the corresponding effect.
本発明にかかる触媒を用いて、水蒸気故質を行なう際に
は、水蒸気は炭化水素の１炭素原子当り１なし、し７モ
ル使用することが好ましい。When carrying out steam latexing using the catalyst according to the present invention, it is preferable to use 1 to 7 moles of steam per carbon atom of the hydrocarbon.
また、本発明にかかる触媒は、内燃機関等の排気ガスに
ガソリンのごとき炭化水素を添加し、排気ガス中の水蒸
気によって上記炭化水素を改質する場合にも使用できる
。次に、上記触媒を製造する方法としては、マグネシア
粉末と酸化タングステン粉末と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給体と
なし、次いで該多孔質体にニッケルを触媒成分として担
持させる方法がある。The catalyst according to the present invention can also be used when hydrocarbons such as gasoline are added to the exhaust gas of an internal combustion engine or the like and the hydrocarbons are reformed by water vapor in the exhaust gas. Next, as a method for producing the above catalyst, magnesia powder, tungsten oxide powder, and alumina powder are mixed, molded into a desired shape, heated to form a porous combustion body, and then the porous There is a method of supporting nickel as a catalyst component in the body.
この方法においては、前記アルミナ粉末は１００ないし
１５０００Ａ（オングストローム）の粒径を有するもの
を用いるのが好ましい。この粒径の範囲外では、前記水
葵気改質に関する触媒活性が低くなり、前誌のごとき優
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。マグネシァ粉末は、アルミナ
粉末と反応してＭｇＡ１２０４スピネルを生成すると共
に、酸化タングステン粉末と反応してＭｇＷ０４を生成
するものである。In this method, the alumina powder preferably has a particle size of 100 to 15,000 Angstroms. If the particle size is outside this range, the catalytic activity for the water-oil reforming will be low, making it difficult to obtain an excellent catalyst such as the one described above. In addition, in the present invention, "particle size" means a weight average particle size. Magnesia powder reacts with alumina powder to produce MgA1204 spinel, and reacts with tungsten oxide powder to produce MgW04.
しかして、該粉末の粒径は特に限定するものではないが
、アルミナ粉末と、酸化タングステン粉末とほぼ均等に
混合し合い、目的とする多孔質焼縞体（担体）の孔径を
ほぼ均一なものとするためには、０．１なし、し５００
ミクロン（山）の粒座のものを用いるのが好ましい。酸
化タングステン粉末は、上記のごとく
ＭｇＷ０４を生成するための原料となるものであるが、
担体の孔径をほど均一なものとするためには０．１なし
、し５００ミクロンの粒径のものを用いるのが好ましい
。Although the particle size of the powder is not particularly limited, it is preferable to mix the alumina powder and tungsten oxide powder almost evenly, so that the pore size of the target porous fried stripe (carrier) is almost uniform. In order to make it, 0.1 none, then 500
It is preferable to use grain size of micron (mountain). Tungsten oxide powder is a raw material for producing MgW04 as mentioned above,
In order to make the pore size of the carrier fairly uniform, it is preferable to use particles with a particle size of 0.1 to 500 microns.
混合粉末の混合割合は、マグネシア粉末４０ないし６０
モル％、酸化タングステン粉末５なし、し１５モル％、
アルミナ粉末３０なし、し６０モル％であることが好ま
しい。The mixing ratio of the mixed powder is 40 to 60% magnesia powder.
Mol%, no tungsten oxide powder 5, 15 mol%,
Preferably, the alumina powder is 30% by mole and 60% by mole.
マグネシア粉末の量が上記より多すぎると、焼成時の加
熱によっ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
なくなってしまう。If the amount of magnesia powder is larger than the above, the magnesia particles will crystallize due to heating during firing, resulting in the formation of large crystals of magnesia alone, resulting in a decrease in the number of pores in the carrier.
また、多量のマグネシアによって酸化タングステンおよ
びアルミナの粉末が包み込まれた状態となる恐れがある
。また、マグネシアの量が上記よりも少ない場合には、
焼結体の結合が弱くなり、担体の強度が低下するおそれ
がある。酸化タングステン粉末およびアルミナ粉末は、
ＭｇＷ０４およびＭｇＡ１２０４スピネルを生成させて
、これら生成物の存在による前記効果を一層発揮させる
ために、上記範囲で用いることが好ましい。Furthermore, there is a possibility that the tungsten oxide and alumina powders will be wrapped in a large amount of magnesia. Also, if the amount of magnesia is less than the above,
There is a possibility that the bond between the sintered bodies becomes weak and the strength of the carrier decreases. Tungsten oxide powder and alumina powder are
In order to generate MgW04 and MgA1204 spinels and further exhibit the effects of the presence of these products, it is preferable to use them within the above ranges.
アルミナ粉末とマグネシア粉末との混合粉末を加熱競結
するための温度は、１００００・０ないし１６００００
が好ましい。１０００ｏｏよりも低い温度では暁結が十
分でないと共に、ＭｇＷ０４およびＭｇＮ２０４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。The temperature for heating and bonding the mixed powder of alumina powder and magnesia powder is 10,000.0 to 160,000.
is preferred. At a temperature lower than 1000 oo, the crystallization is not sufficient and the amount of MgW04 and MgN204 spinel is small, which may weaken the strength of the catalyst.
また、１６００００より高くなるとＭｇＡ１２０４スピ
ネルの粒子が成長しすぎて紬孔容積量が減少してしまう
。この場合、１２００ないし１６００ｏＣ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ＭｇＡ１２０４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。上記方法により得られた焼絹体は、上記各粉末が
反応して生成したＭｇＮ２０４スピネルと、ＭｇＷ０４
と、未反応のＷ０３，ＡＩ２０３およびＭざ０とを含有
している。Moreover, if it becomes higher than 160,000, the MgA1204 spinel particles will grow too much and the pongee hole volume will decrease. In this case, when calcining at 1200 to 1600oC, magnesia and alumina react, and more than 75% of them become MgA1204 spinel, and finally a catalyst with excellent heat resistance and strength can be obtained. The sintered silk body obtained by the above method contains MgN204 spinel produced by the reaction of the above powders, and MgW04 spinel.
and unreacted W03, AI203 and Mza0.
この中、Ｎ２０３とＭｇ０とは、そのいずれかが原料粉
末の使用割合によって、焼結体中に殆んど存在しない場
合がある。なお、前記混合粉末の焼結に当っては、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。Among these, either N203 or Mg0 may be hardly present in the sintered body depending on the proportion of the raw material powder used. In addition, in sintering the mixed powder, a small amount of organic glue such as dextrin is added and mixed with the mixed powder, the mixture is molded into a desired size using a tablet molding machine, etc., and this is electrically heated. Fired in a furnace, etc.
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
質焼給体は、その平均孔径が約２００△ないし１５００
０△である。The porous combustion body obtained using the alumina powder having the above particle size has an average pore size of about 200△ to 1500.
It is 0△.
次に、上記多孔質競結体を担体とし、これに前記触媒成
分たるニッケルを担持させるに当っては、通常の触媒成
分の担特の場合と同様に行ない、例えば硝酸ニッケル等
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
浸潰し、乾燥、焼成する。Next, using the porous composite as a carrier, supporting nickel as the catalyst component is carried out in the same manner as in the case of supporting a normal catalyst component, for example, a catalyst component such as nickel nitrate is supported. The carrier is immersed in a solution of raw materials for formation, dried, and fired.
担体に対する触媒成分の担持量は前記した。なお、前記
混合物末の成形は、粒状、柱状、ハニカム状等所望の形
状に行なう。The amount of catalyst component supported on the carrier was described above. The powder mixture may be shaped into a desired shape such as granules, columns, or honeycombs.
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多孔質焼結体となし、
これに前記触媒成分を担持する方法を探ることもできる
。実施例 １
平均粒蓬が４００，１５００，５０００，１００００△
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１山のマグネシア粉末と同粒径の酸化タング
ステン粉末とを添加すると共に、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、次いでマルメラィザー（錠剤成形機）により、約３
側の直径を有する球状べレットに成形した。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. is coated, molded into an arbitrary shape, heated, and the surface layer portion of the carrier is made into the porous sintered body,
It is also possible to explore a method of supporting the catalyst component on this. Example 1 Average grain size is 400, 1500, 5000, 10000△
Prepare four types of alumina powder, add magnesia powder with an average particle size of one mountain and tungsten oxide powder with the same particle size to each of these powders, and add 1% by weight of dextrin to these mixed powders, Mix these thoroughly and then use a marmerizer (tablet press) to
Formed into a spherical pellet with a side diameter.
なお、上記粉末の混合割合は、マグネシア粉末４７モル
％、酸化タングステン粉末１３モル％、アルミナ粉末４
０モル％であった。次に、上記のべレットを電気乾燥器
により１１０℃で約１幼時間乾燥し、その後これを電気
炉に入れ、１３００ｏＣで６時間加熱、焼結し、担体と
しての多孔質凝結体を作製した。これらの焼結体の性質
を第１表に示した。次いで、上言己坦体を硝酸ニッケル
７０％（重量比、以下同じ）を含有する水溶液に浸潰し
、乾燥後、６００００、空気中で３時間焼成し、本発明
にかかる触媒を製造した（第２表参照）。The mixing ratio of the above powders is 47 mol% magnesia powder, 13 mol% tungsten oxide powder, and 4 mol% alumina powder.
It was 0 mol%. Next, the above pellet was dried in an electric dryer at 110° C. for about 1 hour, and then placed in an electric furnace and heated and sintered at 1300° C. for 6 hours to produce a porous aggregate as a carrier. . The properties of these sintered bodies are shown in Table 1. Next, the above-mentioned self-supporting material was immersed in an aqueous solution containing 70% nickel nitrate (weight ratio, same hereinafter), dried, and then calcined in air at 60,000 ℃ for 3 hours to produce a catalyst according to the present invention (No. (See Table 2).
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、５００ｏ０に加熱保持しておき、これに水
蒸気とｎ（ノルマル）−へブタンとの混合ガスを導入し
た。Next, in order to evaluate the activity of these catalysts, the catalysts were filled in a quartz tube, heated and maintained at 500o0, and a mixed gas of water vapor and n (normal) hebutane was introduced into the tube.
上記混合ガスは、ｎーヘフ。タンに対する水蒸気の比が
２４．４モルノモルのものを用いた。空間速度（ＳＶ）
は１５００戊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−へブタンの転化率により
評価した。The above mixed gas is n-hef. The ratio of water vapor to tongue was 24.4 molar. Space velocity (SV)
was set at 1500 1/hour). . The above catalyst activity was evaluated based on the conversion rate of n-hebutane at the initial stage and after 5 hours.
その結果を第３表に示す。なお、上言己の「初期」とは
反応開始の時点を言い、「５時間後」とはｒ初期」の開
始時から５時間後の時点のことを言う。The results are shown in Table 3. Note that the term "initial stage" as used above refers to the time point at which the reaction begins, and the term "5 hours later" refers to the time point 5 hours after the start of the "r initial period".
また、上記転化率とは、ｎ−へブタンが水蒸気と反応し
た割合（％）である。Moreover, the above-mentioned conversion rate is the ratio (%) of n-hebutane reacted with water vapor.
また、比較のために、前記Ｎ０３の担体を用い、上記の
ニッケル担特の場合と同様にして、コバルト（Ｃｏ）４
重量％を担持させたコバルト触媒（Ｎｏ．Ｃ，）を製造
した。For comparison, using the N03 carrier, cobalt (Co4) was added in the same manner as in the case of the nickel carrier.
A cobalt catalyst (No. C,) supported by % by weight was produced.
また、平均粒径５０００△のアルミナ粉末５５モル％と
平均粒径１仏のマグネシア粉末４５モル％とを用い他は
上言己と同様にして作製した担体（Ｎｏ．Ｓ．）を用い
、該担体Ｓ，に上記と同様にして、ニッケル（Ｎｉ）４
重量％を担持してなるニッケル触媒（Ｎｏ．Ｃ２）を製
造した。しかして、これら比較触媒についても上記と同
機に評価を行なった。これらについても、上言己と同様
に第１表ないし第３表に併示した。なお、上記Ｎｏ．Ｓ
，の坦体は、本発明にかかる触媒の担体に比して、Ｍｇ
Ｗ０４，Ｗ０２を含んでいないものである。In addition, a carrier (No. Nickel (Ni)4 was added to the support S in the same manner as above.
A nickel catalyst (No. C2) in which % by weight of nickel was supported was produced. Therefore, these comparative catalysts were also evaluated on the same machine as above. These are also listed in Tables 1 to 3, as in the case above. In addition, the above No. S
, compared to the carrier of the catalyst according to the present invention, the carrier of Mg
This does not include W04 and W02.
第１表
第２表
第３表
上記より知られるごとく、本発明にかる触媒（Ｎｏ．１
〜４）は、コバルトを担持させた比較触媒Ｎｏ．Ｃ，に
比して高い触媒活性を長時間維持していることが分る。Table 1 Table 2 Table 3 As is known from the above, the catalyst of the present invention (No. 1
~4) are comparative catalysts No. 4 on which cobalt is supported. It can be seen that high catalytic activity is maintained for a long time compared to C.
また、担体の原料としてＷ０３を用いていないもの、即
ち担体にＭｇＷ０４を含んでいないＮｏ．Ｃ２触媒は、
触媒成分としてＮｉを用いているものの５時間の使用中
にその表面に炭素が析出し触媒活性が減少してしまった
。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。In addition, No. 1 that does not use W03 as a raw material for the carrier, that is, the carrier that does not contain MgW04. The C2 catalyst is
Although Ni was used as a catalyst component, carbon was deposited on its surface during 5 hours of use, resulting in a decrease in catalytic activity. Furthermore, ``No carbon was observed to be deposited on the surface of any of the catalysts according to the present invention in the above reaction.
実施例 ２
担体原料粉末の混合割合、触媒成分の担持量を、異にす
る触媒を製造し、その活性を測定した。Example 2 Catalysts were produced with different mixing ratios of carrier raw material powder and different supported amounts of catalyst components, and their activities were measured.
平均粒径が５０００Ａ（０．５山）のｙーアルミナ粉末
と、平均粒径１仏のマグネシア粉末と、同数径の酸化タ
ングステン粉末とを混合し、実施例１と同様にして直径
約３側の球状べレットを作成した。Y-alumina powder with an average particle size of 5000A (0.5 peaks), magnesia powder with an average particle size of 1 French, and tungsten oxide powder with the same number of diameters were mixed, and in the same manner as in Example 1, the diameter side of about 3 mm was mixed. A spherical pellet was created.
次に、上記べレットを電気炉に入れ、１３００つ○で６
時間加熱、焼結し、坦体とした。Next, put the above pellets into an electric furnace and 6
It was heated and sintered for a period of time to form a carrier.
上記三種の粉末の混合割合を、第４表に示す。Table 4 shows the mixing ratio of the above three types of powder.
また、得られた損体の組成および紬孔容積（地／夕）を
第５表に示す。次に、上記担体を所定濃度の硝酸ニッケ
ル水溶液に浸潰し、乾燥後、６００００、空気中で３時
間焼成し、本発明にかかる触媒を調製した。In addition, Table 5 shows the composition of the resulting damaged body and the pongee hole volume (earth/yellow). Next, the above-mentioned carrier was immersed in a nickel nitrate aqueous solution of a predetermined concentration, dried, and then calcined at 60,000 in air for 3 hours to prepare a catalyst according to the present invention.
これを第６表に示す。また、上記各触媒について、実施
例１と同機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」を上記第６表に示した。第４表
第 ５ 表
６ 表
第４表ないし第６表より知られるごとく、本発明にかか
る触媒は「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。This is shown in Table 6. In addition, the catalytic activity of each of the above catalysts was evaluated on the same machine as in Example 1, and the conversion rates at the initial stage and after 5 hours, and the ratio of the conversion rate after 5 hours to the initial conversion rate were shown in Table 6 above. It was shown to. Table 4 Table 5 Table 6 As can be seen from Tables 4 to 6, the catalyst according to the present invention has a high "conversion rate ratio", indicating that it is a catalyst with excellent durability. I understand.
Claims (1)
酸マグネシウムと、酸化タングステンと、マグネシアお
よびアルミナの一方又は双方とからなる多孔質担体に、
ニツケルを担持させてなることを特徴とする炭化水素の
水蒸気改質用触媒。 ２ 多孔質担体は、少なくともマグネシア・アルミナ・
スピネルを５０ないし７０モル％、タングステン酸マグ
ネシウムを５ないし３０モル％含有していることを特徴
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。 ３ 担体に対するニツケルの担持量は、担体に対して１
ないし１０重量％であ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。 ４ マグネシア粉末と酸化タングステン粉末と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
体にニツケルを担持す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。 ５ 混合粉末は、マグネシア粉末４０ないし６０モル％
、酸化タングステン粉末５ないし１５モル％、アルミナ
粉末３０ないし６０モル％であることを特徴とする特許
請求範囲第４項に記載の炭化水素の水蒸気改質用触媒の
製造方法。 ６ 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４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. A porous carrier consisting of magnesia-alumina-spinel, magnesium tungstate, tungsten oxide, and one or both of magnesia and alumina,
A hydrocarbon steam reforming catalyst characterized by supporting nickel. 2 The porous carrier is made of at least magnesia, alumina,
The catalyst for steam reforming of hydrocarbons according to claim 1, which contains 50 to 70 mol% of spinel and 5 to 30 mol% of magnesium tungstate. 3 The amount of nickel supported on the carrier is 1
The catalyst for steam reforming of hydrocarbons according to claim 1, characterized in that the amount is from 10% by weight to 10% by weight. 4 Magnesia powder, tungsten oxide powder, and alumina powder having an average particle size of 100 to 15,000 angstroms (Å) are mixed, formed into a desired shape, heated to form a porous sintered body, and then A method for producing a catalyst for steam reforming of hydrocarbons, characterized by supporting nickel on a porous sintered body. 5 The mixed powder contains 40 to 60 mol% of magnesia powder.
5 to 15 mol % of tungsten oxide powder and 30 to 60 mol % of alumina powder. 6. The method for producing a catalyst for steam reforming of hydrocarbons according to claim 4, wherein the powder compact is heated and sintered at 1200 to 1600°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP54109385A JPS6035176B2 (en) | 1979-08-27 | 1979-08-27 | Steam reforming catalyst and its manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP54109385A JPS6035176B2 (en) | 1979-08-27 | 1979-08-27 | Steam reforming catalyst and its manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5633036A JPS5633036A (en) | 1981-04-03 |
| JPS6035176B2 true JPS6035176B2 (en) | 1985-08-13 |
Family
ID=14508887
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP54109385A Expired JPS6035176B2 (en) | 1979-08-27 | 1979-08-27 | Steam reforming catalyst and its manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6035176B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2507294Y2 (en) * | 1992-03-11 | 1996-08-14 | 公一 矢野 | Prize machine |
| EP1013603A1 (en) * | 1998-12-22 | 2000-06-28 | Haldor Topsoe A/S | Process for catalytical steam reforming of a hydrocarbon feedstock |
| KR100448683B1 (en) * | 2002-04-18 | 2004-09-16 | 한국과학기술연구원 | POX reforming catalysts of gasoline for fuel-cell powered vehicles applications and methods for preparing catalysts |
| JP5354142B2 (en) * | 2006-01-16 | 2013-11-27 | 戸田工業株式会社 | Steam reforming catalyst and reaction gas production method |
| CN103055874A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Methanation catalyst used for preparing substitute natural gas from synthesis gas, and preparation method and application thereof |
| CN103055884A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Supported sulfur and heat resistant methanation catalyst and preparation method and application thereof |
-
1979
- 1979-08-27 JP JP54109385A patent/JPS6035176B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5633036A (en) | 1981-04-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4367166A (en) | Steam reforming catalyst and a method of preparing the same | |
| US4906176A (en) | High temperature stable catalyst, process for preparing same, and process for conducting chemical reaction using same | |
| JP2818171B2 (en) | Catalyst for steam reforming reaction of hydrocarbon and method for producing the same | |
| US5134109A (en) | Catalyst for reforming hydrocarbon with steam | |
| US3957691A (en) | Catalyst for treating exhaust gas from engine vehicles | |
| JP3329839B2 (en) | Catalyst for steam reforming of hydrocarbons | |
| AU5191998A (en) | Alumina-supported ruthenium catalyst | |
| JPH0510133B2 (en) | ||
| JP2000000469A (en) | Nickel based catalyst for reforming and production of synthetic gas using the same | |
| JPH06182201A (en) | Catalyst stable at high temperature, its preparation, and method for effecting chemical reaction using this catalyst | |
| JPS592537B2 (en) | Carbon monoxide conversion catalyst and method for producing the catalyst | |
| KR100892033B1 (en) | High surface area spinel structured nano crystalline sized ymgo (1-y) al2o3-supported nano-sized nickel reforming catalysts and their use for producing synthesis gas from combined steam and carbon dioxide reforming of natural gas | |
| JP3260411B2 (en) | Hydrocarbon steam reforming catalyst and method for producing the same | |
| JPS6138627A (en) | Catalyst stable at high temperature, process for preparing the catalyst, and process for carrying out chemical reaction using the catalyst | |
| JPS6035176B2 (en) | Steam reforming catalyst and its manufacturing method | |
| KR20010101612A (en) | Catalyst Carrier Carrying Nickel Ruthenium and Lanthanum | |
| JPS60222145A (en) | Method for using heat resistant catalyst | |
| JP4715999B2 (en) | Catalyst for water gas shift reaction and process for producing the same | |
| JP4262798B2 (en) | Cobalt catalyst for reforming and synthesis gas production method using the same | |
| JPS6114861B2 (en) | ||
| JPH0435220B2 (en) | ||
| JPS63248444A (en) | Steam reforming and/or partial oxidation catalyst for hydrocarbon | |
| JPS60238146A (en) | Heat resistant carrier composition | |
| JP2533703B2 (en) | Catalyst for high temperature steam reforming reaction of hydrocarbon and method of using the same | |
| JPH0620559B2 (en) | Catalyst for catalytic combustion reaction and method for producing the same |