JP2733784B2 - Hydrocarbon steam reforming reactor - Google Patents
Hydrocarbon steam reforming reactorInfo
- Publication number
- JP2733784B2 JP2733784B2 JP1110496A JP11049689A JP2733784B2 JP 2733784 B2 JP2733784 B2 JP 2733784B2 JP 1110496 A JP1110496 A JP 1110496A JP 11049689 A JP11049689 A JP 11049689A JP 2733784 B2 JP2733784 B2 JP 2733784B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- catalyst layer
- steam reforming
- reaction
- hydrocarbon
- 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
- 229930195733 hydrocarbon Natural products 0.000 title claims description 30
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 30
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 18
- 238000000629 steam reforming Methods 0.000 title claims description 18
- 239000003054 catalyst Substances 0.000 claims description 78
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 12
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 11
- 229910052707 ruthenium Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 239000010948 rhodium Substances 0.000 claims description 10
- 229910052703 rhodium Inorganic materials 0.000 claims description 9
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 6
- 239000010987 cubic zirconia Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910000510 noble metal Inorganic materials 0.000 description 18
- 238000000034 method Methods 0.000 description 16
- 238000002407 reforming Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000004939 coking Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000006057 reforming reaction Methods 0.000 description 5
- 238000000975 co-precipitation Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- -1 coal liquefied oil Chemical class 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、製油所における炭化水素改質反応装置に係
り、とりわけ活性が高く、かつ炭素付着を抑制して長寿
命化を図った炭化水素類の水蒸気改質用反応装置に関す
る。Description: FIELD OF THE INVENTION The present invention relates to a hydrocarbon reforming reactor in a refinery, and particularly to a hydrocarbon having a high activity and having a long life by suppressing carbon deposition. And a steam reforming reactor.
［従来の技術］ 炭化水素の水蒸気改質（スチームリホーミング）は、
炭化水素とスチームとを触媒と接触させて、水素と酸化
炭素類よりなるガスを製造する方法であり、水素製造技
術として周知である。従来の代表的な水蒸気改質用触媒
は、アルカリ金属酸化物、アルカリ土類金属酸化物、ま
たはシリカなどを含有するアルミナ系担体にニッケル、
鉄、コバルト、白金、ロジウム、ルテニウム、パラジウ
ムなどの触媒を担持させたものがよく知られている。[Conventional technology] Steam reforming (steam reforming) of hydrocarbons
This is a method for producing a gas composed of hydrogen and carbon oxides by bringing hydrocarbons and steam into contact with a catalyst, and is well known as a hydrogen production technique. Conventional typical steam reforming catalysts include an alkali metal oxide, an alkaline earth metal oxide, or an alumina-based carrier containing silica or the like, nickel,
Those supporting a catalyst such as iron, cobalt, platinum, rhodium, ruthenium, and palladium are well known.
またニッケル、コバルトあるいはルテニウムをジルコ
ニア担体に担持してなる触媒が、炭化水素の水蒸気改質
反応において優れた性能を有することも報告されている
（特公昭43−12410号公報；五十嵐哲ほか「Rh/ZrO2上で
のｎ−ブタンの水蒸気改質反応」第58回触媒討論会
（Ａ）、４連B12、176〜177頁；ほか）。It has also been reported that a catalyst comprising nickel, cobalt or ruthenium supported on a zirconia carrier has excellent performance in the steam reforming reaction of hydrocarbons (Japanese Patent Publication No. 43-12410; Satoshi Igarashi et al. / steam reforming reaction of n- butane on ZrO 2 "58th catalytic Symposium (a), pp. quadruplicate B12,176～177; others).
更にロジウムをジルコニア単体に担持させた触媒、ま
たイットリウムを4.4重量％含有した部分安定化ジルコ
ニアを担体とするルテニウム触媒も炭化水素の水蒸気改
質反応において優れた性能を有することも報告されてい
る｛大高健ほか「第３成分を添加したRh/ZrO2触媒上で
のｎ−ブタン−スチーム反応」第62回触媒討論会、3B30
5、118〜119頁｝。Further, it has also been reported that a catalyst in which rhodium is supported on zirconia alone or a ruthenium catalyst in which partially stabilized zirconia containing 4.4% by weight of yttrium is used as a carrier have excellent performance in steam reforming of hydrocarbons. Takeshi Otaka et al., "N-Butane-Steam Reaction on Rh / ZrO 2 Catalyst Added with Third Component", 62nd Symposium on Catalysis, 3B30
5, pages 118 to 119｝.
［発明が解決しようとする課題］ しかしながら、アルミナにニッケルその他を担持して
なる従来の触媒は、水蒸気／炭素（原料ガス中の炭素）
モル比（S/C）が小さい場合には、通常ガス状のパラフ
ィン類のスチームリホーミングに使用すると成功する
が、原料ガスとしてオレフィン類や重質炭化水素などの
比較的分子量の大きい原料を使用する場合に、炭素付着
（コーキング）が発生し不適当となる。コーキングが発
生すると触媒層の差圧が増大すると共に反応効率が低下
し、ついには触媒層が閉塞してしまうという問題が生じ
る。そのため水蒸気／炭素比を高くしてコーキングの発
生を抑えることになるが、反応に余分の水蒸気を必要と
し、経済的に不利である。[Problems to be Solved by the Invention] However, a conventional catalyst in which nickel or the like is supported on alumina is steam / carbon (carbon in the raw material gas).
When the molar ratio (S / C) is small, it is usually successful to use it for steam reforming of gaseous paraffins, but a relatively high molecular weight raw material such as olefins and heavy hydrocarbons is used as the raw material gas. In this case, carbon adhesion (caulking) occurs and becomes unsuitable. When coking occurs, there arises a problem that the differential pressure of the catalyst layer increases, the reaction efficiency decreases, and finally the catalyst layer is clogged. Therefore, the generation of coking is suppressed by increasing the steam / carbon ratio, but extra steam is required for the reaction, which is economically disadvantageous.
更に、触媒層の差圧の増大は系の負荷を高め、触媒が
閉塞すれば、触媒を交換、又は再生しなければならず、
またそのために反応を一旦停止するか、又反応を停止せ
ずに触媒を交換、再生するためには複雑な装置が必要に
なるという不都合がある。Furthermore, an increase in the differential pressure of the catalyst layer increases the load on the system, and if the catalyst becomes blocked, the catalyst must be replaced or regenerated,
In addition, there is a disadvantage that a complicated apparatus is required to temporarily stop the reaction or to exchange and regenerate the catalyst without stopping the reaction.
本発明は、炭化水素改質反応装置における触媒管中の
触媒層がコーキングを発生することがなく、炭化水素改
質活性の優れた触媒層である炭化水素改質反応装置の提
供を課題とする。It is an object of the present invention to provide a hydrocarbon reforming reactor in which a catalyst layer in a catalyst tube in a hydrocarbon reforming reactor does not generate caulking and has excellent hydrocarbon reforming activity. .
［課題を解決するための手段］ そのため、本発明の炭化水素水蒸気改質反応装置は、
その触媒管における触媒層が、アルミナ系担体にニッケ
ル、鉄、コバルト、ロジウム、ルテニウム、パラジウ
ム、白金又はこれらの混合物を担持した触媒層（以下、
単にニッケル触媒という）上に、イットリアを含有する
正方晶系又は立方晶系ジルコニア担体にロジウム、ルテ
ニウム、パラジウム、白金又はこれらの混合物を担持し
た触媒層（以下、単に貴金属触媒という）が積層される
ことにより形成され、反応原料が貴金属触媒層側から導
入されるように配置されたことを特徴とする。[Means for Solving the Problems] Therefore, the hydrocarbon steam reforming reactor of the present invention comprises:
The catalyst layer in the catalyst tube is a catalyst layer in which nickel, iron, cobalt, rhodium, ruthenium, palladium, platinum or a mixture thereof is supported on an alumina-based carrier (hereinafter, referred to as a catalyst layer).
A catalyst layer in which rhodium, ruthenium, palladium, platinum or a mixture thereof is supported on a tetragonal or cubic zirconia support containing yttria is laminated on a nickel catalyst). And the reaction raw material is arranged so as to be introduced from the noble metal catalyst layer side.
本発明における貴金属触媒層について説明する。 The noble metal catalyst layer in the present invention will be described.
この触媒担体におけるイットリアの含有量は、0.5〜2
0mol％、より好ましくは1.5〜10mol％の範囲内が好まし
い。イットリアの含有量が多くなりすぎると結晶系が安
定化しない。一方イットリアの含有量が少ないとイット
リア含有の効果がなくなる。The content of yttria in this catalyst support is 0.5 to 2
0 mol%, more preferably in the range of 1.5 to 10 mol%. If the yttria content is too large, the crystal system will not be stabilized. On the other hand, if the yttria content is small, the effect of yttria content is lost.
触媒担体の製造は、所定割合のイットリアのジルコニ
アの粉末混合物を焼成することによって、あるいはジル
コニウム化合物を用いた共沈法、加水分解法、又はアル
コキシド法によって行うことができる。好ましいのは共
沈法である。特にイットリウムクロライド（YCl3）およ
びジルコニウムオキシクロライド（ZrOCl2）を用いた共
沈法が好適である。このようにして調製されることによ
りイットリアを含有するジルコニアを正方晶系又は立方
晶系ジルコニアとすることができ、安定したものとする
ことができる。The catalyst carrier can be produced by calcining a powder mixture of yttria zirconia at a predetermined ratio, or by a coprecipitation method, a hydrolysis method, or an alkoxide method using a zirconium compound. Preferred is the coprecipitation method. Particularly, a coprecipitation method using yttrium chloride (YCl 3 ) and zirconium oxychloride (ZrOCl 2 ) is suitable. By preparing in this manner, zirconia containing yttria can be made into tetragonal or cubic zirconia, and can be made stable.
この触媒担体に担持される触媒金属成分としては、ロ
ジウム、ルテニウム、パラジウム、白金、又はこれらの
混合物を用いることができるが、特にロジウム又はルテ
ニウムが好ましい。触媒担体に担持される触媒金属の量
は、特に限定されないが、触媒担体と触媒金属の合計重
量に対して0.01〜10重量％の範囲内が好ましく、より好
ましくは0.1〜３重量％である。触媒金属量が多すぎる
と不経済であり、一方金属量が少なすぎると活性が低く
炭化水素類の改質が不充分となる。Rhodium, ruthenium, palladium, platinum, or a mixture thereof can be used as the catalytic metal component supported on the catalyst carrier. Rhodium or ruthenium is particularly preferred. The amount of the catalyst metal supported on the catalyst carrier is not particularly limited, but is preferably in the range of 0.01 to 10% by weight, more preferably 0.1 to 3% by weight, based on the total weight of the catalyst carrier and the catalyst metal. If the amount of catalyst metal is too large, it is uneconomical, while if the amount of metal is too small, the activity is low and the reforming of hydrocarbons becomes insufficient.
イットリア含有ジルコニア担体に触媒金属を担持する
方法は慣用方法に従うことができるが、通常、含浸法が
採用される。The method of supporting the catalyst metal on the yttria-containing zirconia support can be in accordance with a conventional method, but usually an impregnation method is employed.
また本発明において用いる触媒担体は一般に円柱状、
リング状又は粒子状であるが、必ずしもそれに限定され
ない。繊維状あるいは三次元構造体でもよい。The catalyst carrier used in the present invention is generally cylindrical,
It has a ring shape or a particle shape, but is not necessarily limited thereto. It may be a fibrous or three-dimensional structure.
次に、貴金属触媒層が積層されるニッケル触媒層につ
いて説明する。Next, the nickel catalyst layer on which the noble metal catalyst layer is laminated will be described.
ニッケル触媒層は、前述した従来のニッケル触媒を使
用することができるものであり、例えばナフサ用として
市販されている円柱状、リング状又は粒子状、繊維状あ
るいは三次元構造体の形状のものなどを使用するとよ
い。これらの触媒は、６〜30重量％のNiとAl2O3、MgO、
CaO、BaO、SrO、SiO2、K2O等を含有する担体成分で構成
されるものである。The nickel catalyst layer can use the conventional nickel catalyst described above, and is, for example, a columnar, ring-shaped or particle-shaped, fibrous or three-dimensionally structured one that is commercially available for naphtha. It is better to use These catalysts, 6-30 wt% of Ni and Al 2 O 3, MgO,
It is composed of a carrier component containing CaO, BaO, SrO, SiO 2 , K 2 O and the like.
本発明の炭化水素改質反応装置においては、貴金属触
媒層とニッケル触媒層を積層することを特徴とするが、
その充填量比は特に限定はないが、経済性の観点から貴
金属触媒層は全体の５容量部〜70容量部とするとよい。The hydrocarbon reforming reactor of the present invention is characterized in that a noble metal catalyst layer and a nickel catalyst layer are stacked,
The filling ratio is not particularly limited, but from the viewpoint of economy, the noble metal catalyst layer is preferably 5 to 70 parts by volume in total.
本発明における水蒸気改質反応とは、次の反応式で示
されるものである。The steam reforming reaction in the present invention is represented by the following reaction formula.
CH4＋H2OCO＋3H2 CO＋H2OCO2＋H2 但し、ｍ＝１〜20程度 ｎ＝４〜42程度 反応温度は一般に300〜1000℃であるが、700℃以下で
も本発明の貴金属触媒はコーキングしにくいので、水蒸
気改質触媒として好適である。 CH 4 + H 2 OCO + 3H 2 CO + H 2 OCO 2 + H 2 However, m is about 1 to 20 and n is about 4 to 42. The reaction temperature is generally 300 to 1000 ° C., but even at 700 ° C. or less, the noble metal catalyst of the present invention is difficult to coke, and thus is suitable as a steam reforming catalyst.
反応圧力は、約0.01kg/cm2 Ｇ〜50kg/cm2G、 特に好ましくは約0.1kg/cm2 Ｇ〜30kg/cm2Gである。The reaction pressure is from about 0.01kg / cm 2 G~50kg / cm 2 G, particularly preferably about 0.1kg / cm 2 G~30kg / cm 2 G.
S/Cは小さい方が好ましいが、コーキングの問題を回
避するには、1.2以上とするのが好ましい。It is preferable that the S / C is small, but it is preferable to set the S / C to 1.2 or more to avoid the problem of coking.
本発明の反応装置による水蒸気改質反応に使用される
原料は、例えば、LNGやLPGなどの軽質炭化水素含有ガ
ス、ナフサや灯油などの石油留分や、石炭液化油など主
として炭化水素、特に分子量のあまり大きくない炭化水
素（C1〜C20程度）等を使用しうる。原料ガスは好まし
くは炭化水素のみからなるが、微量の異成分を含んでい
てもよい。異成分としてのイオウ化合物は原料がナフサ
の場合0.5ppm以下が望ましく、原料が灯油の場合は50pp
m以下とするのが望ましい。原料から異成分を除去する
には水素化脱硫などの精製手段が採用される。Raw materials used in the steam reforming reaction by the reactor of the present invention include, for example, light hydrocarbon-containing gases such as LNG and LPG, petroleum fractions such as naphtha and kerosene, and mainly hydrocarbons such as coal liquefied oil, and especially molecular weight. Not so large hydrocarbons (about C 1 to C 20 ) and the like. The source gas is preferably composed of only hydrocarbons, but may contain a trace amount of a different component. The sulfur compound as a foreign component is preferably 0.5 ppm or less when the raw material is naphtha, and 50 pp when the raw material is kerosene.
m or less is desirable. Purification means such as hydrodesulfurization are employed to remove foreign components from the raw material.
更に原料である炭化水素類の比重は、0.80以下、好ま
しくは0.75以下で、C/H重量比は65以下、好ましくは6.0
以下の炭化水素類が用いられる。Further, the specific gravity of hydrocarbons as raw materials is 0.80 or less, preferably 0.75 or less, C / H weight ratio is 65 or less, preferably 6.0.
The following hydrocarbons are used:
また本発明の改質反応装置は改質（転換）効率が高
く、かつ炭素付着（コーキング）を抑制する効果に優れ
ているので、炭化水素を原料とする燃料電池用水蒸気改
質反応装置として使用してもよい。In addition, the reforming reactor of the present invention has a high reforming (conversion) efficiency and an excellent effect of suppressing carbon deposition (coking), so that it is used as a steam reforming reactor for fuel cells using hydrocarbons as a raw material. May be.
例えば溶融炭酸塩型燃料電池においては、電解質の溶
融炭酸塩が飛散して触媒表面に付着し、触媒成分の溶出
による活性低下が指摘されているが、本発明で使用する
触媒は炭酸塩に対して安定であることが確認されてお
り、この型の燃料電池への適用にも有用である。燃料電
池内における触媒層として本発明の反応装置を配置する
方法としては、セルのアノード側燃料ガス流路中に、配
置する直接的内部改質方法と、積層セル間に触媒層を配
置する間接式内部改質方法がある。For example, in a molten carbonate fuel cell, it has been pointed out that the molten carbonate of the electrolyte is scattered and adheres to the catalyst surface, resulting in a decrease in the activity due to elution of the catalyst component. Has been confirmed to be stable, and is useful for application to this type of fuel cell. The method of arranging the reactor of the present invention as a catalyst layer in a fuel cell includes a direct internal reforming method of arranging the catalyst layer in a fuel gas flow path on the anode side of the cell and an indirect method of arranging the catalyst layer between stacked cells. There is a formula internal reforming method.
イットリアを少量含有する正方晶系又は立方晶系ジル
コニアは部分安定化ジルコニアとして知られ、この部分
安定化ジルコニアを担体として貴金属触媒を担持させた
触媒は、高い反応活性と炭素付着（コーキング）抑制効
果を有している。本発明の炭化水素改質反応装置は、そ
の触媒管における触媒層として、ニッケル触媒層と貴金
属触媒層を積層して形成し、貴金属触媒層側から原料ガ
スを導入させる構造とすることにより、S/C比が小さく
てもコーキングを生じにくくすることができ、また貴金
属触媒層単独、またニッケル触媒層単独の場合に比較し
て、予期しえないことであるがより炭化水素改質活性が
改善された触媒層とすることができることを見出したも
のであり、優れた炭化水素改質反応装置となしえるもの
である。Tetragonal or cubic zirconia containing a small amount of yttria is known as partially stabilized zirconia. A catalyst loaded with a noble metal catalyst using this partially stabilized zirconia as a carrier has a high reaction activity and an effect of suppressing carbon adhesion (coking). have. The hydrocarbon reforming reaction device of the present invention has a structure in which a nickel catalyst layer and a noble metal catalyst layer are stacked and formed as a catalyst layer in the catalyst tube, and a raw material gas is introduced from the noble metal catalyst layer side, so that S Even if the / C ratio is small, caulking is less likely to occur, and unexpectedly improved hydrocarbon reforming activity compared to the case of using noble metal catalyst layer alone or nickel catalyst layer alone It has been found that the resulting catalyst layer can be an excellent hydrocarbon reforming reactor.
以下、実施例により具体的に説明する。 Hereinafter, specific examples will be described.
（実施例１） 、貴金属触媒の調製 共沈法によって得た３モル％のイットリアを含有する
正方晶系ジルコニア粉末を加圧成形し、円柱（5mmΦ×5
mm）とし、これを1000℃、３時間焼成した。次に、この
触媒担体を塩化ルテニウム水溶液に浸漬し、乾燥後、50
0℃、１時間焼成して、0.5wt％のルテニウムを含有する
触媒を得た。Example 1 Preparation of Noble Metal Catalyst A tetragonal zirconia powder containing 3 mol% of yttria obtained by a coprecipitation method was subjected to pressure molding to form a cylinder (5 mmΦ × 5 mm).
mm) and fired at 1000 ° C. for 3 hours. Next, the catalyst support was immersed in an aqueous ruthenium chloride solution, dried, and then dried.
Calcination was performed at 0 ° C. for 1 hour to obtain a catalyst containing 0.5 wt% of ruthenium.
、ニッケル触媒 ナフサ用として市販されている水蒸気改質触媒X,Yの
円柱品を使用する。Nickel catalysts Steam reforming catalysts X and Y which are commercially available for naphtha are used.
その組成（重量％）は Ｘ Ｙ Ni 8.5 10.1 Al2O3 62.9 68.9 MgO 15.1 0 CaO 3.8 20.4 Others 9.7 0.6 、触媒管への充填方法。Its composition (% by weight) is XY Ni 8.5 10.1 Al 2 O 3 62.9 68.9 MgO 15.1 0 CaO 3.8 20.4 Others 9.7 0.6, and the method of filling the catalyst tube.
第１図に示すように、触媒管１にまず上記の円柱状の
ニッケル触媒３を充填し、次いで円柱状の貴金属触媒２
をそのニッケル触媒層３上に、その容量比がそれぞれ50
対50となるように積層し充填した。As shown in FIG. 1, a catalyst tube 1 is first filled with the above-mentioned columnar nickel catalyst 3, and then a columnar noble metal catalyst 2
Is placed on the nickel catalyst layer 3 with a capacity ratio of 50
The layers were stacked and filled so as to be 50 pairs.
、改質反応 炭化水素原料として、脱硫処理された軽質ナフサ（比
重0.69、C/H重量比5.38、イオウ分60ppb）を用い、800
℃（反応管出口）、4kg/cm2Gで、スチーム／カーボン
（S/C）モル比を3.0、及び原料供給空間速度（GHSV）を
2500h-1として反応を行った。, Reforming reaction Using desulfurized light naphtha (specific gravity 0.69, C / H weight ratio 5.38, sulfur content 60ppb) as a hydrocarbon raw material, 800
C (reaction tube outlet), 4 kg / cm 2 G, steam / carbon (S / C) molar ratio of 3.0, and feed space velocity (GHSV)
The reaction was performed at 2500 h −1 .
これらの反応における改質活性を、メタン生成量から
計算される化学平衡へのアプローチ温度により求めた。
尚、メタン生成量から計算される化学平衡へのアプロー
チ温度については、John.R.Anderson＆Michael Boudart
著「CATALYSIS」Vol.5.第６頁（1984）に詳細に説明さ
れているが、この種類の炭化水素の改質反応における生
成ガス組成についての推定方法として公知の手法であ
る。ここではアプローチ温度（ΔＴ）を、生成ガス組成
から計算して得られる平衡定数に対応する温度Ｔ（QR）
と、触媒層出口温度との差とし、じしきのように示され
る。The reforming activity in these reactions was determined by the approach temperature to chemical equilibrium calculated from the amount of methane produced.
For the approach temperature to chemical equilibrium calculated from the amount of methane generated, see John R. Anderson & Michael Boudart
This is described in detail in "CATALYSIS" Vol.5, page 6 (1984), and is a known method as a method for estimating the composition of a product gas in a reforming reaction of this kind of hydrocarbon. Here, the approach temperature (ΔT) is a temperature T (Q R ) corresponding to an equilibrium constant obtained by calculation from the product gas composition.
, And the difference from the catalyst layer outlet temperature, which is shown like a dash.
ΔＴ＝Ｔ（QR）−Ｔ（触媒温度） この温度差が小さい程、反応活性が高いことを示して
いる。ΔT = T (Q R ) −T (catalyst temperature) The smaller this temperature difference, the higher the reaction activity.
この反応結果について下記に示す。 The results of this reaction are shown below.
尚、下記においては、ニッケル触媒Ｘ、Ｙのみを充填
した場合、また貴金属触媒のみを充填した場合につい
て、それぞれ比較例として示す。 触媒 アプローチ温度（ΔＴ）℃ 貴金属触媒/X 11 貴金属触媒/Y 12 貴金属触媒のみ 19 Ｘのみ （コーキングによりデータ採取不能） Ｙのみ （コーキングによりデータ採取不能） この結果からわかるように、本発明の炭化水素改質反
応装置は、貴金属触媒層単独、またニッケル触媒層単独
の場合に比較して、コーキングを生じることがなく、ま
た反応活性も高いことがわかる。In the following, a case where only the nickel catalysts X and Y are charged and a case where only the noble metal catalyst is charged are shown as comparative examples. Catalyst Approach temperature (ΔT) ° C Noble metal catalyst / X 11 Noble metal catalyst / Y 12 Noble metal catalyst only 19 X only (data cannot be collected due to caulking) Y only (data cannot be collected due to caulking) It can be seen that the hydrogen reforming reactor does not cause coking and has a higher reaction activity than the case of using the noble metal catalyst layer alone or the nickel catalyst layer alone.
本発明の炭化水素改質反応装置は、その改質触媒層を
原料導入側に貴金属触媒、次いでニッケル触媒を積層し
て形成することにより、コーキングを生じることがな
く、また高い反応活性を奏するものである。The hydrocarbon reforming reaction apparatus of the present invention has a high catalytic activity without coking by forming the reforming catalyst layer by laminating a noble metal catalyst and then a nickel catalyst on the raw material introduction side. It is.
第１図は本発明の炭化水素改質反応装置の概略構成を示
す図である。 図中１は触媒管、２は貴金属触媒層、３はニッケル触媒
層、４は原料導入管、５は反応ガス導出管を示す。FIG. 1 is a diagram showing a schematic configuration of a hydrocarbon reforming reaction device of the present invention. In the figure, 1 is a catalyst tube, 2 is a noble metal catalyst layer, 3 is a nickel catalyst layer, 4 is a raw material introduction tube, and 5 is a reaction gas outlet tube.
Claims (1)
において、その触媒管における触媒層が、アルミナ系担
体にニッケル、鉄、コバルト、ロジウム、ルテニウム、
パラジウム、白金又はこれらの混合物を担持した触媒層
上に、イットリアを含有する正方晶系又は立方晶系ジル
コニア担体にロジウム、ルテニウム、パラジウム、白金
又はこれらの混合物を担持した触媒層が積層されること
により形成され、反応原料がイットリアを含有する正方
晶系又は立方晶系ジルコニア担体にロジウム、ルテニウ
ム、パラジウム、白金又はこれらの混合物を担持した触
媒層側から導入されるように配置されたことを特徴とす
る炭化水素の水蒸気改質反応装置。In a steam reforming reactor using a hydrocarbon as a raw material, a catalyst layer in a catalyst tube is provided on an alumina-based carrier with nickel, iron, cobalt, rhodium, ruthenium,
A catalyst layer supporting rhodium, ruthenium, palladium, platinum or a mixture thereof on a tetragonal or cubic zirconia support containing yttria is stacked on a catalyst layer supporting palladium, platinum or a mixture thereof. And the reaction raw material is arranged so as to be introduced from the catalyst layer side supporting rhodium, ruthenium, palladium, platinum or a mixture thereof on a tetragonal or cubic zirconia support containing yttria. Hydrocarbon steam reforming reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1110496A JP2733784B2 (en) | 1989-04-28 | 1989-04-28 | Hydrocarbon steam reforming reactor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1110496A JP2733784B2 (en) | 1989-04-28 | 1989-04-28 | Hydrocarbon steam reforming reactor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02286787A JPH02286787A (en) | 1990-11-26 |
| JP2733784B2 true JP2733784B2 (en) | 1998-03-30 |
Family
ID=14537232
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1110496A Expired - Fee Related JP2733784B2 (en) | 1989-04-28 | 1989-04-28 | Hydrocarbon steam reforming reactor |
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| Country | Link |
|---|---|
| JP (1) | JP2733784B2 (en) |
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|---|---|---|---|---|
| JP4783240B2 (en) * | 2006-08-29 | 2011-09-28 | Ｊｘ日鉱日石エネルギー株式会社 | Steam reforming catalyst, hydrogen production apparatus and fuel cell system |
| EP3800162A1 (en) * | 2009-12-18 | 2021-04-07 | Indian Oil Corporation Limited | Production of a mixture of hydrogen and natural gas |
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1989
- 1989-04-28 JP JP1110496A patent/JP2733784B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02286787A (en) | 1990-11-26 |
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