JP2533703B2 - Catalyst for high temperature steam reforming reaction of hydrocarbon and method of using the same - Google Patents
Catalyst for high temperature steam reforming reaction of hydrocarbon and method of using the sameInfo
- Publication number
- JP2533703B2 JP2533703B2 JP3211854A JP21185491A JP2533703B2 JP 2533703 B2 JP2533703 B2 JP 2533703B2 JP 3211854 A JP3211854 A JP 3211854A JP 21185491 A JP21185491 A JP 21185491A JP 2533703 B2 JP2533703 B2 JP 2533703B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- high temperature
- lanthanum
- steam reforming
- alumina
- 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 - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims description 32
- 238000000034 method Methods 0.000 title claims description 16
- 238000000629 steam reforming Methods 0.000 title claims description 10
- 229930195733 hydrocarbon Natural products 0.000 title claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 title claims 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 22
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 22
- 239000002131 composite material Substances 0.000 claims description 13
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 16
- 229910052782 aluminium Inorganic materials 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000001354 calcination Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 150000003841 chloride salts Chemical class 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 150000002603 lanthanum Chemical class 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 102200118166 rs16951438 Human genes 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000012615 aggregate Substances 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- ZWOQODLNWUDJFT-UHFFFAOYSA-N aluminum lanthanum Chemical compound [Al].[La] ZWOQODLNWUDJFT-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 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
Description
【０００１】[0001]
【産業上の利用分野】本発明は、炭化水素の高温水蒸気
改質反応用触媒に係り、特に１５００℃以下の温度域に
おいて安定して使用できる耐熱性触媒およびその使用方
法に関する。本発明の触媒は、特に８００℃以上の温度
で使用するのに適する。FIELD OF THE INVENTION The present invention relates to high temperature steam of hydrocarbons.
The present invention relates to a reforming reaction catalyst, and more particularly to a heat resistant catalyst that can be stably used in a temperature range of 1500 ° C. or lower and a method of using the same. The catalysts of the invention are particularly suitable for use at temperatures above 800 ° C.
【０００２】[0002]
【発明の背景】触媒を用い高温下で反応を行わせせる方
法としては、有機溶剤或いは無臭の酸化処理，自動車排
ガス処理，高温水蒸気改質，高温脱硝などが知られてい
る。最近になって大容量のボイラーやガスタービン，航
空機用のガスタービンなどへ上記の特徴を生かした触媒
燃焼技術を応用する動きが起っている。BACKGROUND OF THE INVENTION Organic solvent or odorless oxidation treatment, automobile exhaust gas treatment, high temperature steam reforming, high temperature denitration and the like are known as methods for carrying out a reaction at a high temperature using a catalyst. Recently, there has been a movement to apply catalytic combustion technology utilizing the above characteristics to large-capacity boilers, gas turbines, gas turbines for aircraft, and the like.
【０００３】これらの処理法は、反応温度がおよそ６０
０℃以上であり、条件によっては１４００〜１５００℃
のまで達する。従って、このような高温域においても触
媒活性の低下が低なく且つ熱的安定性の高い触媒が要求
される。In these processing methods, the reaction temperature is about 60.
0 ° C. or higher, depending on conditions, 1400 to 1500 ° C.
Reach until. Therefore, even in such a high temperature range, there is a demand for a catalyst having a low catalytic activity and a high thermal stability.
【０００４】従来、高温用触媒として使用されてきた触
媒は、アルミナ，シリカ，シリカ−アルミナ等を担体と
してこれに貴金属、或いは卑金属成分を担持したもの、
あるいはジルコニア，チタン酸アルミニウム，窒化硅素
などのセラミック材料を担体としてその表面に改性アル
ミナなどをコーティングし貴金属成分を担持させたもの
などが使用されてきた。Conventionally, catalysts used as high temperature catalysts are those in which a noble metal or a base metal component is carried on alumina, silica, silica-alumina or the like as a carrier,
Alternatively, a ceramic material such as zirconia, aluminum titanate, or silicon nitride is used as a carrier, and the surface thereof is coated with modified alumina or the like to carry a noble metal component.
【０００５】しかし、これらの触媒は通常８００℃以上
になると、担体の相転移や結晶成長に伴う比表面積の減
少，活性成分の凝集に伴う表面積の減少などが生じ触媒
の活性が著しく劣化する欠点があった。上記したセラミ
ック材料を用いた触媒は、それ自体の耐熱性は高いがコ
ーティング材の耐熱性が低いために触媒成分が有効に活
用されないという欠点もある。However, these catalysts usually have a disadvantage that when the temperature is 800 ° C. or higher, the activity of the catalyst is remarkably deteriorated due to the phase transition of the carrier, the reduction of the specific surface area due to the crystal growth, and the reduction of the surface area due to the aggregation of the active ingredient. was there. The catalyst using the above-mentioned ceramic material has a disadvantage that the heat resistance of the coating material itself is high, but the catalyst component is not effectively used because the heat resistance of the coating material is low.
【０００６】[0006]
【発明の目的】本発明の目的は、上記した従来技術の欠
点を改善し、高温度の反応条件下においても活性成分の
凝集および担体の比表面積の減少を抑えることができる
耐熱性触媒及びかかる触媒の使用方法を提供することに
ある。OBJECT OF THE INVENTION The object of the present invention is to improve the above-mentioned drawbacks of the prior art and to suppress the aggregation of the active ingredient and the reduction of the specific surface area of the carrier even under the reaction conditions of high temperature, and such a heat-resistant catalyst. It is to provide a method of using the catalyst.
【０００７】[0007]
【発明の概要】γあるいはηアルミナは高比表面積を有
し、担体やコーティング材として多く使用されている
が、７００℃以上特に９００℃以上においてはαアルミ
ナへの相転移及び結晶粒子径の成長などにより比表面積
が低下し、これに伴って触媒活性成分である貴金属，卑
金属などの粒子の凝集が起こり触媒活性が低下する。SUMMARY OF THE INVENTION Gamma or η alumina has a high specific surface area and is often used as a carrier or coating material. However, at 700 ° C. or more, especially at 900 ° C. or more, phase transition to α-alumina and growth of the crystal particle diameter occur. As a result, the specific surface area decreases, and along with this, particles of the catalytically active components, such as noble metals and base metals, aggregate, and the catalytic activity decreases.
【０００８】本発明者等は、アルミナの上記の様な熱的
不安定性を改善し、担持された触媒成分の粒子が凝集す
ることを防ぐために種々検討した結果、アルミニウムに
ランタンを添加して得られるランタンβアルミナ（１１
〜１４Ａｌ2Ｏ3・Ｌａ2Ｏ3）担体に触媒活性成分である
貴金属，卑金属などを組合わせた触媒が非常に有効であ
ることを見出した。The present inventors have conducted various studies to improve the above thermal instability of alumina and prevent the particles of the supported catalyst component from aggregating. As a result, lanthanum was added to aluminum. Lanthanum β-alumina (11
~14Al 2 O 3 · La 2 O 3) a noble metal as a catalyst active component on a carrier, the catalyst was such a combined base metal is found to be very effective.
【０００９】本発明は、１１〜１４Ａｌ 2 Ｏ 3 ・Ｌａ 2 Ｏ 3
で表されるランタンβアルミナからなる複合酸化物を主
成分とする担体に触媒活性成分としてニッケルの酸化物
を担持してなる炭化水素の高温水蒸気改質反応用触媒で
ある。[0009] The present invention is, 11~14Al 2 O 3 · La 2 O 3
Is a catalyst for high temperature steam reforming reaction of hydrocarbons, which comprises nickel oxide as a catalytically active component supported on a carrier whose main component is a complex oxide composed of lanthanum β-alumina .
【００１０】更に、担体はアルミニウムとランタンの複
合酸化物のみからなることが最も望ましいが、他の担体
成分を含んでもかまわない。Further, the carrier is most preferably composed only of a complex oxide of aluminum and lanthanum, but other carrier components may be contained.
【００１１】ランタンβアルミナは、１１〜１４Ａｌ2
Ｏ3・Ｌａ2Ｏ3よりなる化合物である。この複合酸化物
は、それらの水酸化物あるいは酸化物あるいは熱処理す
ることにより酸化物を与える化合物を原料として、それ
らの混合物を少なくとも８００℃以上の温度で焼成する
ことによって生成する。Lanthanum β-alumina is 11-14 Al 2
It is a compound consisting of O 3 · La 2 O 3 . This composite oxide is produced by firing a mixture of these hydroxides or oxides or a compound that gives an oxide by heat treatment at a temperature of at least 800 ° C. or higher.
【００１２】アルミニウムとランタンの複合酸化物より
なる担体に触媒活性成分を担持した触媒は、１０００℃
以上の高温で使用しても触媒活性成分の熱による凝集が
起り難く安定した触媒性能を維持することができる。そ
の理由としては、アルミニウムとランタンとの複合酸化
物と触媒活性成分とが強い相互作用を示すことが挙げら
れる。A catalyst in which a catalytically active component is supported on a carrier composed of a composite oxide of aluminum and lanthanum is 1000 ° C.
Even when used at the above-mentioned high temperature, aggregation of the catalytically active component due to heat hardly occurs, and stable catalytic performance can be maintained. The reason is that the composite oxide of aluminum and lanthanum and the catalytically active component exhibit strong interaction.
【００１３】ランタンβアルミナはそれ自体が耐熱性が
良く、比表面積も大きいが、そのほかにこの化合物は活
性アルミナからαアルミナへの相転移及び結晶成長を抑
制する効果があることが詳細なＸ線回折，電子顕微鏡観
察の結果より明らかになった。従って、ランタンβアル
ミナのみならず、この複合酸化物を主成分として含むア
ルミナ担体も高温で用いる触媒用担体として優れてい
る。Although lanthanum β-alumina itself has good heat resistance and a large specific surface area, in addition to that, this compound has the effect of suppressing the phase transition from activated alumina to α-alumina and the crystal growth, which is detailed in detail. It became clear from the results of diffraction and electron microscopy. Therefore, not only lanthanum β-alumina, but also an alumina carrier containing this complex oxide as a main component is excellent as a catalyst carrier used at a high temperature.
【００１４】アルミニウムとランタンの複合酸化物より
なる担体は、高温条件下での比表面積の低下も少ないこ
とがＮ2 吸着実験により明らかとなった。更に上記複合
酸化物に担持された触媒成分であるパラジウムの分散状
態を電子顕微鏡及び一酸化炭素の化学吸着法で調べたと
ころ、１２００℃で焼成しても高分散状態にあることが
わかった。It was revealed from the N 2 adsorption experiment that the carrier made of a composite oxide of aluminum and lanthanum showed a small decrease in the specific surface area under high temperature conditions. Further, the dispersion state of palladium as a catalyst component supported on the composite oxide was examined by an electron microscope and a carbon monoxide chemisorption method. As a result, it was found that the dispersion state was high even after firing at 1200 ° C.
【００１５】アルミニウムとランタンの複合酸化物を他
のセラミックスにコーティング或いは複合してもよい。
例えばαアルミナ，チタニア，ジルコニア，マグネシ
ア，コージェライト，ムライト，アルミニウムチタネー
トなどの耐熱性酸化物に加えて使用することもできる。
またシリコンカーバイドや窒化硅素のような酸化物以外
のものにコーティングあるいは混合しても良い。複合す
る場合、アルミニウムとランタンの複合酸化物の量は、
担体全重量の５０％以上を有するようにすることが望ま
しい。The composite oxide of aluminum and lanthanum may be coated or combined with other ceramics.
For example, it can be used in addition to heat-resistant oxides such as α-alumina, titania, zirconia, magnesia, cordierite, mullite, and aluminum titanate.
It may be coated or mixed with a material other than oxides such as silicon carbide and silicon nitride. When composited, the amount of aluminum and lanthanum composite oxide is
It is desirable to have 50% or more of the total weight of the carrier.
【００１６】アルミニウムとランタンの複合酸化物を形
成するための焼成温度は８００℃以上、好ましくは９０
０℃以上１５００℃以下である。焼成温度が８００℃以
下ではランタンβアルミナが生成せず、１５００℃を超
えると焼結が進行するため好ましくない。The firing temperature for forming the composite oxide of aluminum and lanthanum is 800 ° C. or higher, preferably 90.
It is 0 ° C or higher and 1500 ° C or lower. When the firing temperature is 800 ° C. or lower, lanthanum β-alumina is not formed, and when it exceeds 1500 ° C., sintering proceeds, which is not preferable.
【００１７】上記複合酸化物を含む粉体は種々の形状、
例えば球状，円柱状，リング状，ハニカム状などに成形
して使用することができる。また、種々の形状に成形さ
れた無機質耐熱性担体、例えばムライト，コージライ
ト，αアルミナ，ジルコン，チタン酸アルミニウム，シ
リコンカーバイド，窒化硅素等のセラミックスに上記複
合酸化物を含む粉体のスラリーをコーティングして使用
することもできる。無機質耐熱性担体に担持する上記複
合酸化物の量は担体全重量の５％以上、好ましくは５〜
３０重量％である。Powders containing the above complex oxide have various shapes,
For example, it can be used after being formed into a spherical shape, a cylindrical shape, a ring shape, a honeycomb shape, or the like. Further, inorganic heat-resistant carriers formed into various shapes, for example, ceramics such as mullite, cordierite, α-alumina, zircon, aluminum titanate, silicon carbide and silicon nitride are coated with a slurry of powder containing the above complex oxide. It can also be used. The amount of the composite oxide supported on the inorganic heat-resistant carrier is 5% or more of the total weight of the carrier, preferably 5 to 5%.
It is 30% by weight.
【００１８】上記のアルミニウムとランタンの複合酸化
物を製造する方法としては、通常の沈殿法，沈着法，混
練法，含浸法などを適用することができ、特に限定され
ない。一例としてアルミニウム塩とランタン塩の混合水
溶液にアルカリを添加して緊密な共沈物を生成させ、こ
れを加熱焼成する方法，アルミナおよび／またはアルミ
ナゾルと酸化ランタンおよび／または水酸化ランタンを
緊密に混合し、これを加熱焼成する方法，アルミナにラ
ンタン塩の溶液を含浸し、これを加熱焼成する方法など
が挙げられる。As a method for producing the above-mentioned aluminum-lanthanum composite oxide, a usual precipitation method, a deposition method, a kneading method, an impregnation method or the like can be applied and is not particularly limited. As an example, a method of adding an alkali to a mixed aqueous solution of an aluminum salt and a lanthanum salt to form an intimate coprecipitate, and heating and calcining this, intimately mixing alumina and / or alumina sol with lanthanum oxide and / or lanthanum hydroxide. Then, a method of heating and calcining this, a method of impregnating alumina with a solution of a lanthanum salt, and heating and calcining this are mentioned.
【００１９】なお、アルミナとランタンを含む水溶液に
アリカリを加えて両者の緊密な混合物を共沈させてから
焼成すると、比較的低い焼成温度でもアルミニウムとラ
ンタンの複合酸化物が得られるので好ましい方法であ
る。If alikari is added to an aqueous solution containing alumina and lanthanum to coprecipitate an intimate mixture of both, and then calcination is carried out, a composite oxide of aluminum and lanthanum can be obtained even at a relatively low calcination temperature. is there.
【００２０】アルミニウム原料としては、硝酸塩，硫酸
塩，塩化物などの可溶性塩，アルコキシドなどの有機
塩，水酸化物，酸化物などが使用できる。一方、ランタ
ン原料としては、硝酸塩，塩化物，シュウ酸塩などの可
溶性塩，水酸化物，酸化物などが使用できる。ランタン
を含有している混合希土も使用できる。As the aluminum material, soluble salts such as nitrates, sulfates and chlorides, organic salts such as alkoxides, hydroxides and oxides can be used. On the other hand, as the lanthanum raw material, soluble salts such as nitrates, chlorides and oxalates, hydroxides and oxides can be used. Mixed rare earths containing lanthanum can also be used.
【００２１】触媒活性成分は、最終的に金属又は酸化物
の形で担持される。The catalytically active components are finally supported in the form of metals or oxides.
【００２２】触媒活性成分の担持方法としては、含浸法
或いは混練法などの通常行われている方法を適用するこ
とができる。触媒活性成分の原料としては、無機塩や錯
塩などを使用できる。As a method for supporting the catalytically active component, a commonly used method such as an impregnation method or a kneading method can be applied. As a raw material of the catalytically active component, an inorganic salt or a complex salt can be used.
【００２３】本発明の触媒は炭化水素の水蒸気改質に使
用される。この場合には、触媒活性成分としてニッケル
の酸化物を用い、４００〜１５００℃の温度範囲で反応
を行わせて水素及び一酸化炭素からなるガスを製造す
る。The catalyst of the present invention is used for steam reforming of hydrocarbons . In this case, nickel is used as the catalytically active component.
Using the oxide of 1) , the reaction is carried out in the temperature range of 400 to 1500 ° C. to produce a gas composed of hydrogen and carbon monoxide.
【００２４】[0024]
【発明の実施例】以下に実施例により本発明の内容をよ
り具体的に説明するが、本発明はこれらの実施例に何等
限定されるものではない。The present invention will be described in more detail with reference to the following Examples, which by no means limit the present invention.
【００２５】実施例１ 硝酸アルミニウム３７５.１ｇ と硝酸ランタン２２８ｇ
を蒸留水１リットルに溶解する（Ａｌ／Ｌａ＝９５／５
原子比）。この溶液を撹拌しながら３Ｎアンモニア水を
滴下しｐＨ７.５ まで中和する。得られたアルミニウム
とランタンの共沈物を充分水洗し乾燥した後粉砕して１
０００℃で５時間焼成する。得られた粉体をプレス成型
機で直径３mm，長さ３mmの円柱状にし担体とした。Example 1 375.1 g of aluminum nitrate and 228 g of lanthanum nitrate
In 1 liter of distilled water (Al / La = 95/5)
Atomic ratio). While stirring this solution, 3N aqueous ammonia was added dropwise to neutralize the solution to pH 7.5. The obtained coprecipitate of aluminum and lanthanum is sufficiently washed with water, dried and pulverized to obtain 1
Bake at 000 ° C for 5 hours. The obtained powder was formed into a columnar shape having a diameter of 3 mm and a length of 3 mm by a press molding machine to obtain a carrier.
【００２６】Ｎ 2 ガス吸着によるＢ.Ｅ.Ｔ法で担体の比
表面積を測定した結果、６０.９ｍ 2 ／ｇであった。担体
の結晶構造は、Ｘ線回折(Ｃｕ−Ｋα，出力４０ｋＶ,１
００ｍＡ）によりランタンβアルミナ（１１〜１４Ａｌ
2 Ｏ 3 ・Ｌａ 2 Ｏ 3 ）であることを確認した。 The ratio of carriers by the BET method by N 2 gas adsorption
As a result of measuring the surface area, it was 60.9 m 2 / g. Carrier
X-ray diffraction (Cu-Kα, output 40 kV, 1
Lanthanum β-alumina (11-14Al
2 O 3 · La 2 O 3 ) was confirmed.
【００２７】この担体１００ｇに硝酸ニッケル水溶液を
含浸し、１２０℃で乾燥後、９００℃で２時間焼成し
た。このようにして得た触媒はニッケルをＮｉＯに換算
して１５重量％含有していた。100 g of this carrier was impregnated with an aqueous solution of nickel nitrate, dried at 120 ° C., and calcined at 900 ° C. for 2 hours. The catalyst thus obtained contained 15% by weight of nickel in terms of NiO.
【００２８】上記方法で調製した触媒を反応管に充填
し、Ｈ2 気流中、６００℃で２時間還元した。反応は触
媒層入口温度を５８０〜６００℃，触媒層出口温度を８
５０〜９００℃に保ち、圧力１５Kg／cm2 でｎ−ブタン
の水蒸気改質反応を行った。水蒸気／カーボン（モル
比）＝３０，空間速度３０００ｈ-1で行った。１００時
間の連続試験の結果、ｎ−ブタンの反応率は９９.９％
以上を維持し、反応後、触媒層での炭素析出もほとんど
認められなかった。反応生成ガスはＨ2 ，ＣＯ，ＣＯ2
及びＣＨ4 であり、これらの生成は触媒層出口の温度条
件下における平衡組成にほぼ等しい割合で存在してい
た。The catalyst prepared by the above method was filled in a reaction tube and reduced in a H 2 stream at 600 ° C. for 2 hours. In the reaction, the catalyst layer inlet temperature is 580 to 600 ° C., and the catalyst layer outlet temperature is 8
A steam reforming reaction of n-butane was carried out at a pressure of 15 kg / cm 2 while maintaining the temperature at 50 to 900 ° C. Water vapor / carbon (molar ratio) = 30, and space velocity was 3000 h −1 . As a result of a 100-hour continuous test, the reaction rate of n-butane was 99.9%.
After maintaining the above, after the reaction, almost no carbon deposition was observed in the catalyst layer. The reaction product gas is H 2 , CO, CO 2
And CH 4 , and these generations were present at a ratio approximately equal to the equilibrium composition under the temperature condition at the catalyst layer outlet.
【００２９】本実施例の結果からも明らかなように本発
明になる耐熱性触媒によれば、高温水蒸気改質反応に対
しも優れた性能を示す。As is clear from the results of this example, the heat-resistant catalyst according to the present invention exhibits excellent performance in high temperature steam reforming reaction.
【００３０】[0030]
【発明の効果】以上述べたように本発明によれば、１５
００℃以下の高範囲の温度ですぐれた活性を有する耐熱
性触媒を得ることができる。As described above, according to the present invention, 15
It is possible to obtain a heat-resistant catalyst having excellent activity in a high temperature range of 00 ° C. or lower.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ１０Ｇ 11/04 9279−4Ｈ Ｃ１０Ｇ 11/04 11/20 9279−4Ｈ 11/20 Ｂ０１Ｊ 23/74 ３２１Ｍ (72)発明者 水本 守 茨城県日立市幸町３丁目１番１号 株式 会社 日立製作所 日立研究所内 (72)発明者 松田 臣平 茨城県日立市幸町３丁目１番１号 株式 会社 日立製作所 日立研究所内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location C10G 11/04 9279-4H C10G 11/04 11/20 9279-4H 11/20 B01J 23/74 321M (72) Inventor Mamoru Mizumoto 3-1-1 Sachimachi, Hitachi, Ibaraki Prefecture Hitachi Ltd. Hitachi Research Laboratory (72) Inventor Shinpei Matsuda 3-1-1, Sachimachi, Hitachi, Ibaraki Hitachi Factory Hitachi Research Laboratory
Claims (4)
ランタンβアルミナからなる複合酸化物を主成分とする
担体に、ニッケルの酸化物よりなる触媒活性成分を担持
したことを特徴とする炭化水素の高温水蒸気改質反応用
触媒。The method according to claim 1] 11~14Al 2 O 3 · La 2 O made of lanthanum β-alumina represented by 3 composite oxide support mainly, that carrying a catalytically active component consisting of oxides of nickel Characteristic hydrocarbon for high temperature steam reforming reaction
Catalyst .
が実質的に前記複合酸化物のみからなることを特徴とす
る炭化水素の高温水蒸気改質反応用触媒。2. A catalyst for high temperature steam reforming reaction of hydrocarbon according to claim 1, wherein the carrier is substantially composed of the complex oxide.
酸化物がセラミックスの表面にコーティングされている
ことを特徴とする炭化水素の高温水蒸気改質反応用触
媒。3. The catalyst for high temperature steam reforming reaction of hydrocarbons according to claim 1, wherein the surface of ceramics is coated with the complex oxide.
Medium .
ランタンβアルミナからなる複合酸化物を主成分とする
担体に触媒活性成分としてニッケルの酸化物を担持した
触媒に、炭化水素類と水蒸気を４００〜１５００℃の温
度で接触させて水素及び一酸化炭素からなるガスを製造
することを特徴とする炭化水素の水蒸気改質方法。 4. A 11~14Al 2 O 3 · La 2 O 3 with a catalyst composite oxide carrying an oxide of nickel as catalytically active component on a carrier composed mainly made of lanthanum β-alumina represented carbide A steam reforming method for hydrocarbons, which comprises contacting hydrogen with steam at a temperature of 400 to 1500 ° C to produce a gas composed of hydrogen and carbon monoxide .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3211854A JP2533703B2 (en) | 1983-07-01 | 1991-08-23 | Catalyst for high temperature steam reforming reaction of hydrocarbon and method of using the same |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58118207A JPH0824843B2 (en) | 1983-07-01 | 1983-07-01 | Heat resistant catalyst and method of using the same |
| JP3211854A JP2533703B2 (en) | 1983-07-01 | 1991-08-23 | Catalyst for high temperature steam reforming reaction of hydrocarbon and method of using the same |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58118207A Division JPH0824843B2 (en) | 1983-07-01 | 1983-07-01 | Heat resistant catalyst and method of using the same |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7082220A Division JP2570647B2 (en) | 1995-04-07 | 1995-04-07 | Nitrogen oxide reduction catalyst and nitrogen oxide reduction method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06134305A JPH06134305A (en) | 1994-05-17 |
| JP2533703B2 true JP2533703B2 (en) | 1996-09-11 |
Family
ID=26456181
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3211854A Expired - Fee Related JP2533703B2 (en) | 1983-07-01 | 1991-08-23 | Catalyst for high temperature steam reforming reaction of hydrocarbon and method of using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2533703B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06182201A (en) * | 1984-07-31 | 1994-07-05 | Hitachi Ltd | Catalyst stable at high temperature, its preparation, and method for effecting chemical reaction using this catalyst |
| JP3664182B2 (en) * | 1994-12-19 | 2005-06-22 | トヨタ自動車株式会社 | High heat-resistant exhaust gas purification catalyst and production method thereof |
| JP4781642B2 (en) * | 2004-06-07 | 2011-09-28 | 花王株式会社 | Method for producing aldehyde |
| JP5691098B2 (en) * | 2009-04-24 | 2015-04-01 | 国立大学法人山梨大学 | Selective methanation catalyst for carbon monoxide, process for producing the same, and apparatus using the same |
| WO2018021192A1 (en) | 2016-07-29 | 2018-02-01 | 住友化学株式会社 | Alumina and method for producing automotive catalyst using same |
| CN113736508A (en) * | 2021-08-11 | 2021-12-03 | 润和科华催化剂(上海)有限公司 | Inorganic dechlorinating agent, preparation method and application |
-
1991
- 1991-08-23 JP JP3211854A patent/JP2533703B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06134305A (en) | 1994-05-17 |
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