JPH0251670B2 - - Google Patents
Info
- Publication number
- JPH0251670B2 JPH0251670B2 JP57018058A JP1805882A JPH0251670B2 JP H0251670 B2 JPH0251670 B2 JP H0251670B2 JP 57018058 A JP57018058 A JP 57018058A JP 1805882 A JP1805882 A JP 1805882A JP H0251670 B2 JPH0251670 B2 JP H0251670B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- carrier
- alumina
- present
- spinel
- 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 - Lifetime
Links
- 239000003054 catalyst Substances 0.000 claims description 65
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 21
- 229930195733 hydrocarbon Natural products 0.000 claims description 16
- 150000002430 hydrocarbons Chemical class 0.000 claims description 16
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 15
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 15
- 239000011029 spinel Substances 0.000 claims description 13
- 229910052596 spinel Inorganic materials 0.000 claims description 13
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000005909 Kieselgur Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000000843 powder Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000001273 butane Substances 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910020068 MgAl Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910002549 Fe–Cu Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- UAMZXLIURMNTHD-UHFFFAOYSA-N dialuminum;magnesium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mg+2].[Al+3].[Al+3] UAMZXLIURMNTHD-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- -1 iron nitrate Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 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
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、一酸化炭素を水素還元してブタンな
どの炭化水素を合成する際に使用する炭化水素合
成用触媒に関する。
従来、工業的規模で使用されている上記の炭化
水素合成用触媒としては、フイツシヤー・トロプ
ツシユ合成触媒と言われている、ニツケル、コバ
ルト、鉄などを珪藻土の担体に担持させたものが
ある。
しかしながら、かかる従来触媒においても、未
だ満足すべき活性を有する触媒とは言えない。ま
た、上記従来触媒は、担体として珪藻土を用いて
いるため、触媒の調製法が難かしく、触媒活性の
再現性が低い。即ち、珪藻土担体を用いる場合に
は、触媒調製法として鉄等の触媒成分を硝酸鉄等
の金属塩の状態の水溶液としておき、この中に珪
藻土を投入し、その後この水溶液を塩基性にな
し、珪藻土の表面に鉄等の触媒成分を沈澱させる
沈澱法を用いている。しかしながら、かかる沈澱
法による触媒の調製法は、沈澱時の条件などその
調製法が難かしく、触媒活性の再現性にバラツキ
が生じ易い。
本発明は、かかる従来の触媒の欠点を克服し
て、活性に優れ、かつ調製が容易な炭化水素合成
用触媒を開発することを目的としてなされたもの
である。
即ち、本発明はアルミナ・マグネシアスピネル
又はこのものとアルミナとからなる多孔質体を担
体とし、該担体に鉄（Fe）又は鉄と銅（Cu）と
を担持させて成り、一酸化炭素を水素還元するこ
とによりメタン、ブタン等の炭化水素を合成する
ための炭化水素合成用触媒にある。
本発明にかかる触媒は、一酸化炭素を高能率で
水素還元することができ、メタン、ブタン等C1
以上の炭化水素を収率良く生成させる。また、本
発明にかかる触媒は、担体としてアルミナ・マグ
ネシアスピネルを主体とする多孔質体を用いてい
るので、上記多孔質体に触媒成分を含浸させるの
みで触媒を調製することができ、触媒の調製法が
容易であると共に、触媒活性（転化率、選択率）
の再現性にも優れている。
また、本発明にかかる触媒は、その担体が、ア
ルミナ・マグネシア（MgAl2O4）スピネルを含
有しているため、機械的強度も高い。また、例え
高温において使用しても一般のアルミナ担体の場
合のように、アルミナの結晶構造の変化を生ぜ
ず、該変化に伴なう表面積の減少、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。
本発明において、担体としてアルミナ・マグネ
シアスピネルとアルミナとよりなる多孔質体を用
いる場合には、アルミナは担体中に20％（重量
比、以下同じ）以下において存在することが好ま
しい。この量よりも多いアルミナが存在する場合
には、前記のごとき、スピネルの存在による効果
を達成し難い。
また、上記担体としての多孔質体の平均孔径は
0.01ないし2μであることが好ましい。かかる平均
孔径の範囲を外れた場合には、優れた活性を発揮
することが困難である。
上記多孔質体に前記の触媒成分たるFe又はFe
とCuを担持させるに当つては、例えば硝酸鉄、
硝酸銅、等の触媒成分の金属塩の水溶液中に、上
記多孔質体を浸漬し、乾燥、焼成する。上記焼成
により金属塩はそれぞれ相当する触媒成分とな
る。また、この担持に当つては、多孔質体に対す
る触媒成分の全担持量は、１ないし20重量％とす
ることが好ましい。１％以下では前記触媒活性が
低くなり、また20％以上ではそれ以上担持させて
もそれに見合うだけの活性の向上が見られない。
本発明において、上記多孔質体は、マグネシア
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結体をなすこと等
により作製する。
また、平均孔径が0.01ないし2μの多孔質体を得
るには、アルミナ粉末として0.01ないし2μの平均
粒径を有するものを用いる。ここに「粒径」とは
重量平均粒径を意味する。また、上記アルミナは
α（アルフア）―アルミナの他、γ（ガンマ）―ア
ルミナ等のアルミナも使用することができる。
アルミナ粉末等と混合するマグネシア粉末は、
焼結多孔質体中においてアルミナ粉末の最適な接
合剤とも言うべきもので、その粒径は特に限定す
るものではないが、アルミナ粉末とほぼ均等に混
合し合い、アルミナとスピネルを形成すると共に
得られる担体の孔径をほぼ均一なものとするため
には、0.1ないし500μの粒径のものを用いるのが
好ましい。
また、本発明にかかる触媒は、前記従来触媒の
場合と同様に、反応温度100〜300℃、反応圧力１
〜20気圧、空間速度200〜2000H+ rにおいて使用す
ることが好ましい。
実施例 １
本発明にかかるスピネル含有多孔質担体に、
Fe及びCuを担持させてなるFe―Cu触媒を調製し
た。即ち、硝酸鉄80％（重量比以下同じ）、硝酸
銅30％を含む水溶液中に、上記担体を浸漬し、母
液を十分に除き、110℃で２時間乾燥し、その後
600℃空気中で３時間焼成した。
これにより、Fe4％、Cu0.8％を担持してなる
本発明にかかる触媒を調製した。上記スピネル含
有多孔質担体としては、第１表に示す各種のもの
（担体No.１〜３））を用いた。これらの担体を用い
た触媒を第２表に示す。
The present invention relates to a hydrocarbon synthesis catalyst used when synthesizing hydrocarbons such as butane by reducing carbon monoxide with hydrogen. Conventionally, as the above-mentioned hydrocarbon synthesis catalysts used on an industrial scale, there is a catalyst called a Fischer-Tropsch synthesis catalyst in which nickel, cobalt, iron, etc. are supported on a diatomaceous earth carrier. However, even such conventional catalysts cannot be said to have satisfactory activity. Furthermore, since the above-mentioned conventional catalyst uses diatomaceous earth as a carrier, the catalyst preparation method is difficult and the reproducibility of the catalyst activity is low. That is, when using a diatomaceous earth carrier, the catalyst preparation method is to prepare a catalyst component such as iron as an aqueous solution in the form of a metal salt such as iron nitrate, add diatomaceous earth into this solution, and then make this aqueous solution basic. A precipitation method is used to precipitate catalyst components such as iron on the surface of diatomaceous earth. However, in the method of preparing a catalyst by such a precipitation method, the preparation method such as the conditions during precipitation is difficult, and the reproducibility of the catalyst activity tends to vary. The present invention was made with the object of overcoming the drawbacks of such conventional catalysts and developing a catalyst for hydrocarbon synthesis that has excellent activity and is easy to prepare. That is, the present invention uses alumina/magnesia spinel or a porous body made of this and alumina as a carrier, and supports iron (Fe) or iron and copper (Cu) on the carrier, and converts carbon monoxide into hydrogen. It is a hydrocarbon synthesis catalyst for synthesizing hydrocarbons such as methane and butane by reduction. The catalyst according to the present invention can reduce carbon monoxide with hydrogen with high efficiency, and can reduce carbon monoxide with hydrogen such as methane, butane, etc.
The above hydrocarbons are produced in good yield. Furthermore, since the catalyst according to the present invention uses a porous body mainly composed of alumina/magnesia spinel as a carrier, the catalyst can be prepared by simply impregnating the porous body with catalyst components, and the catalyst can be prepared by simply impregnating the porous body with the catalyst component. The preparation method is easy, and the catalyst activity (conversion rate, selectivity) is high.
It also has excellent reproducibility. Further, the catalyst according to the present invention has high mechanical strength because its carrier contains alumina magnesia (MgAl 2 O 4 ) spinel. In addition, even when used at high temperatures, the crystal structure of alumina does not change as in the case of general alumina supports, and there is no decrease in surface area or strength due to such changes, and the catalytic activity at high temperatures does not change. Demonstrates excellent durability and effectiveness. In the present invention, when a porous body composed of alumina/magnesia spinel and alumina is used as a carrier, it is preferable that alumina is present in the carrier in an amount of 20% or less (weight ratio, the same applies hereinafter). If more alumina is present than this amount, it will be difficult to achieve the effects of the presence of spinel as described above. Furthermore, the average pore diameter of the porous material used as the carrier is
It is preferably 0.01 to 2μ. If the average pore size falls outside of this range, it is difficult to exhibit excellent activity. Fe or Fe, which is the catalyst component, is added to the porous body.
For supporting Cu, for example, iron nitrate,
The porous body is immersed in an aqueous solution of a metal salt of a catalyst component such as copper nitrate, dried, and fired. By the above-mentioned calcination, each metal salt becomes a corresponding catalyst component. In this case, the total amount of catalyst components supported on the porous body is preferably 1 to 20% by weight. If it is less than 1%, the catalytic activity will be low, and if it is more than 20%, even if it is supported more than that, no commensurate improvement in activity will be observed. In the present invention, the porous body is produced by mixing magnesia powder and alumina powder, molding the mixture into a desired shape, and heating the mixture to form a porous sintered body. Furthermore, in order to obtain a porous body with an average pore size of 0.01 to 2μ, an alumina powder having an average particle size of 0.01 to 2μ is used. The term "particle size" used herein means the weight average particle size. In addition to α (alpha)-alumina, alumina such as γ (gamma)-alumina can also be used as the alumina. Magnesia powder mixed with alumina powder etc.
It can be said to be the optimal bonding agent for alumina powder in the sintered porous body, and its particle size is not particularly limited, but it mixes almost evenly with the alumina powder, forming alumina and spinel, and is a good binder for alumina powder. In order to make the pore size of the carrier substantially uniform, it is preferable to use particles with a particle size of 0.1 to 500μ. Further, the catalyst according to the present invention has a reaction temperature of 100 to 300°C and a reaction pressure of 1, as in the case of the conventional catalyst.
Preferably used at ~20 atmospheres and a space velocity of 200-2000 H + r . Example 1 Spinel-containing porous carrier according to the present invention,
An Fe--Cu catalyst was prepared by supporting Fe and Cu. That is, the above carrier was immersed in an aqueous solution containing 80% iron nitrate (the same weight ratio below) and 30% copper nitrate, the mother liquor was thoroughly removed, and it was dried at 110°C for 2 hours.
It was fired at 600°C in air for 3 hours. In this way, a catalyst according to the present invention was prepared which supported 4% Fe and 0.8% Cu. As the spinel-containing porous carrier, various types shown in Table 1 (Carrier Nos. 1 to 3) were used. Catalysts using these carriers are shown in Table 2.
【表】
また、比較のため、Al2O3を多量に含有するス
ピネル含有多孔質体（担体No.S1）を用い、他は上
記と同様にして調整した触媒（触媒NOS1）も作
製した（第１、２表参照）。更に比較触媒として、
珪藻土（担体No.S2）を担体とするFe―Cu触媒を
調製した。即ち、まず、水500c.c.に、硝酸鉄200
ｇ、硝酸銅２ｇを加え溶解煮沸させた。また担体
としての粉末状の珪藻土30ｇを水200c.c.に加え、
煮沸し、次いでこれに上記の硝酸鉄等を含む煮沸
液を加えた。次に、水500ｇに炭酸カリウム150ｇ
を溶かした液を、激しく撹はんした上記の硝酸
鉄、珪藻土等を含む液に徐々に加えた。約２分間
撹はんしながら煮沸した後、この溶液を渦し、
残をイオン交換水により、カリウムイオンがな
くなるまで洗浄した。次に、この残を110℃で
20時間乾燥し、直径３mmφの球状体に成形し
Fe49％―Cul％を珪藻土に担持させた比較触媒
（触媒No.S2）を調製した。
次いで、上記各種の触媒について、その触媒活
性の評価を行なつた。
触媒活性の評価は、直径20mmφの石英反応管に
上記の触媒20mlを充填し、350℃で３時間水素還
元し、その後、反応温度250℃、反応圧力10Kg／
cm2（ゲージ）、空間速度600H- rで、水素（H2）／
一酸化炭素（CO）モル比３の混合ガスを上記反
応管に送入し、一酸化炭素の転化率と反応生成物
中の炭化水素量とを測定することによつて行なつ
た。ここに一酸化炭素転化率とは一酸化炭素が他
の物質に転化した割合（％）を示す。また、反応
生成物中の炭化水素は、炭化水素１分子中の炭素
量で示されるC1，C2，C3，C4，C5等について、
ガスクロマトグラムにより、CO，CO2の量と共
に測定した。上記C1はメタン、C2はエタン、エ
チレン、C3はプロパン、プロピレン、C4はブタ
ン、ブチレン、C5はペンタン等を意味する。な
お、C5以上の炭化水素は、一括して測定した。
これらの測定結果を第２表に示す。同表には、
上記C1〜C4、及びC5以上の炭化水素についての
生成割合（選択率％）を示した。
第２表より知られるごとく、本発明にかかる触
媒はCOの転化率に関しては、珪藻土担体を用い
た比較触媒S2の約1.3〜1.6倍の値を示しているこ
とが分る。また、C1〜C5以上の選択率は、両者
の触媒ともほぼ同様の効果を有している。このよ
うに、本発明の触媒は、上記従来の触媒よりも優
れた活性を発揮し、優れた触媒であることが分
る。また、上記よりも知られるごとく、本発明に
かかる触媒は、担体として珪藻土を用いた場合に
比して、その調製が簡易であることが分る。
また、本発明にかかる触媒は、アルミナ含有量
の多い担体を用いた比較触媒S1に比して、C5以
上の選択率が高いという優れた活性を有している
ことが分る。[Table] For comparison, a catalyst (catalyst NOS 1 ) prepared using a spinel-containing porous material containing a large amount of Al 2 O 3 (Support No. S 1 ) but in the same manner as above was also prepared. (See Tables 1 and 2). Furthermore, as a comparative catalyst,
An Fe-Cu catalyst using diatomaceous earth (carrier No. S 2 ) as a carrier was prepared. That is, first, add 200 c.c. of water to 200 c.c. of iron nitrate.
g, and 2 g of copper nitrate were added and dissolved and boiled. Also, add 30 g of powdered diatomaceous earth as a carrier to 200 c.c. of water,
The mixture was boiled, and then the above-mentioned boiling liquid containing iron nitrate, etc. was added thereto. Next, add 150g of potassium carbonate to 500g of water.
The solution was gradually added to the vigorously stirred solution containing iron nitrate, diatomaceous earth, etc. After boiling with stirring for about 2 minutes, swirl the solution,
The residue was washed with ion-exchanged water until potassium ions disappeared. Next, heat this residue at 110℃
Dry for 20 hours and form into a sphere with a diameter of 3 mmφ.
A comparative catalyst (Catalyst No. S 2 ) in which Fe49%-Cul% was supported on diatomaceous earth was prepared. Next, the various catalysts mentioned above were evaluated for their catalytic activity. To evaluate the catalytic activity, 20 ml of the above catalyst was filled into a quartz reaction tube with a diameter of 20 mmφ, hydrogen reduction was performed at 350°C for 3 hours, and then the reaction temperature was 250°C and the reaction pressure was 10 kg/kg.
cm 2 (gauge), space velocity 600H - r , hydrogen (H 2 )/
This was carried out by introducing a mixed gas of carbon monoxide (CO) at a molar ratio of 3 into the reaction tube, and measuring the conversion rate of carbon monoxide and the amount of hydrocarbons in the reaction product. The carbon monoxide conversion rate here indicates the rate (%) of carbon monoxide converted into other substances. In addition, regarding the hydrocarbons in the reaction product, C 1 , C 2 , C 3 , C 4 , C 5 etc. indicated by the amount of carbon in one molecule of hydrocarbon,
It was measured along with the amount of CO and CO 2 by gas chromatogram. The above C1 means methane, C2 means ethane or ethylene, C3 means propane or propylene, C4 means butane or butylene, C5 means pentane, etc. Note that hydrocarbons of C5 or higher were measured all at once. The results of these measurements are shown in Table 2. In the same table,
The production ratios (selectivity %) of the above C 1 to C 4 and C 5 or higher hydrocarbons are shown. As can be seen from Table 2, the catalyst according to the present invention exhibits a conversion rate of CO that is about 1.3 to 1.6 times higher than that of the comparative catalyst S 2 using a diatomaceous earth carrier. In addition, both catalysts have almost the same effect on the selectivity of C 1 to C 5 or more. As described above, it can be seen that the catalyst of the present invention exhibits superior activity to the above-mentioned conventional catalyst and is an excellent catalyst. Further, as is known from the above, the catalyst according to the present invention is easier to prepare than when diatomaceous earth is used as a carrier. Furthermore, it can be seen that the catalyst according to the present invention has excellent activity in that the selectivity for C 5 or more is higher than that of the comparative catalyst S 1 using a carrier with a high alumina content.
【表】
実施例 ２
担体としてMgAl2O4スピネルとアルミナとよ
りなる多孔質体を用いた本発明にかかるFe触媒
を調製し、触媒活性を測定した。
即ち、上記スピネル担体は、前記実施例１の担
体No.２のものを用い、これに対して実施例１と同
様にして４％のFeを担持させた触媒を調製した。
また、比較のために、担体としては、第３表に
示す種類のアルミナ・シリカ、α―アルミナ、γ
―アルミナ、δ―アルミナを用い、他は上記触媒
を同様にして調製したFe4％担持の触媒を作成し
た。また、担体として珪藻土（担体No.S2）を用
い、実施例１と同様にしてFe49％を担持させた
触媒（触媒No.S7）も調製した。
しかして、上記した触媒について、水素中で
350℃、３時間の還元処理を行ない、その後触媒
活性の測定を行なつた。[Table] Example 2 An Fe catalyst according to the present invention was prepared using a porous body made of MgAl 2 O 4 spinel and alumina as a carrier, and the catalytic activity was measured. That is, as the spinel carrier, carrier No. 2 of Example 1 was used, and in the same manner as in Example 1, a catalyst was prepared in which 4% Fe was supported. For comparison, the types of carriers shown in Table 3 were alumina/silica, α-alumina, and γ.
A catalyst with 4% Fe supported was prepared using -alumina and δ-alumina, but in the same manner as above. Further, a catalyst (catalyst No. S 7 ) on which 49% of Fe was supported was also prepared in the same manner as in Example 1 using diatomaceous earth (carrier No. S 2 ) as a carrier. However, regarding the above catalyst, in hydrogen
Reduction treatment was performed at 350°C for 3 hours, and then the catalytic activity was measured.
【表】
触媒活性の測定は、触媒層温度が230℃である
他は、実施例１と同様の条件にて行なつた。な
お、反応圧力は０，５，10Kg／cm3Ｇの３種につい
て行なつた。
測定の結果を第４表に、CO転化率については
各反応圧力毎に、選択率については10Kg／cm2の場
合について示す。
同表より知られるごとく、本発明にかかる触媒
は、CO転化率はいずれの反応圧力の場合にも、
比較触媒S3〜S7より優れていることが分る。ま
た、選択率についても本発明の触媒は比較触媒S3
〜S6よりも、炭素数の多い炭化水素を多く生成
し、優れた触媒であることが分る。[Table] The catalyst activity was measured under the same conditions as in Example 1, except that the catalyst layer temperature was 230°C. The reaction pressures were 0, 5, and 10 Kg/cm 3 G. The measurement results are shown in Table 4, showing the CO conversion rate for each reaction pressure and the selectivity for the case of 10 Kg/cm 2 . As can be seen from the same table, the catalyst according to the present invention has a CO conversion rate of
It can be seen that it is superior to the comparative catalysts S 3 to S 7 . In addition, regarding the selectivity, the catalyst of the present invention is better than the comparative catalyst S 3
It can be seen that it produces more hydrocarbons with a larger number of carbon atoms than S 6 and is an excellent catalyst.
Claims (1)
のとアルミナとよりなる多孔質体を担体とし、該
担体に鉄又は鉄および銅を担持させて成り、一酸
化炭素を水素還元することにより炭化水素を合成
するための炭化水素合成用触媒。 ２ 担体中におけるアルミナの量は、20重量％以
下であることを特徴とする特許請求の範囲第１項
に記載の炭化水素合成用触媒。[Claims] 1 A porous body made of alumina/magnesia spinel or spinel and alumina is used as a carrier, iron or iron and copper are supported on the carrier, and carbon monoxide is reduced by hydrogen. Hydrocarbon synthesis catalyst for synthesizing hydrocarbons. 2. The catalyst for hydrocarbon synthesis according to claim 1, wherein the amount of alumina in the carrier is 20% by weight or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57018058A JPS58137444A (en) | 1982-02-05 | 1982-02-05 | Catalyst for synthesizing hydrocarbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57018058A JPS58137444A (en) | 1982-02-05 | 1982-02-05 | Catalyst for synthesizing hydrocarbon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58137444A JPS58137444A (en) | 1983-08-15 |
| JPH0251670B2 true JPH0251670B2 (en) | 1990-11-08 |
Family
ID=11961088
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57018058A Granted JPS58137444A (en) | 1982-02-05 | 1982-02-05 | Catalyst for synthesizing hydrocarbon |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58137444A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2006325209B2 (en) * | 2005-12-16 | 2010-11-04 | Shell Internationale Research Maatschappij B.V. | Process for preparing a hydrocarbon synthesis catalyst |
-
1982
- 1982-02-05 JP JP57018058A patent/JPS58137444A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58137444A (en) | 1983-08-15 |
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