JPH0245606B2 - - Google Patents
Info
- Publication number
- JPH0245606B2 JPH0245606B2 JP57158017A JP15801782A JPH0245606B2 JP H0245606 B2 JPH0245606 B2 JP H0245606B2 JP 57158017 A JP57158017 A JP 57158017A JP 15801782 A JP15801782 A JP 15801782A JP H0245606 B2 JPH0245606 B2 JP H0245606B2
- Authority
- JP
- Japan
- Prior art keywords
- ruthenium
- hydrocarbons
- catalyst
- manganese
- synthesis gas
- 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
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 32
- 239000003054 catalyst Substances 0.000 claims description 24
- 229930195733 hydrocarbon Natural products 0.000 claims description 19
- 150000002430 hydrocarbons Chemical class 0.000 claims description 19
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- 229910052707 ruthenium Inorganic materials 0.000 claims description 15
- 238000003786 synthesis reaction Methods 0.000 claims description 15
- 239000011572 manganese Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000007789 gas Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 239000003921 oil Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000003245 coal Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002309 gasification Methods 0.000 description 3
- 150000002697 manganese compounds Chemical class 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical group O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- GBDZMMXUOBAJMN-UHFFFAOYSA-K azane;ruthenium(3+);trichloride Chemical compound N.N.N.N.N.N.[Cl-].[Cl-].[Cl-].[Ru+3] GBDZMMXUOBAJMN-UHFFFAOYSA-K 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000003034 coal gas Substances 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
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- -1 nuclear power Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 238000004525 petroleum distillation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 239000001993 wax 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
Description
本発明は、一酸化炭素と水素との混合ガス（以
下、合成ガスという）から、炭素数２以上の炭化
水素を高収率で得る方法に関し、特に該方法に適
用するに適した触媒を提供せんとするものであ
る。
現在、エネルギーの中心を占めている石油をめ
ぐる環境は非常に不安定であり、1980年代後半か
ら1990年代にかけては石油不足からエネルギーの
谷間が来ることが憂慮されている。このため石油
の消費を節約をすすめるとともに、石炭、原子
力、LNGなどの石油代替エネルギーで対応する
ことが考えられている。このため、わが国では、
今後相対的に高い需要の伸びを示すと予想されて
いるガソリン、灯油、軽油、Ａ重油等の供給不足
を石油以外の炭素源、例えば石炭又は天然ガス等
から製造する新技術の開発に関心が向けられてい
る。このうち、石炭から炭化水素油を製造する方
法としては、直接法である石炭の液化、及び間接
法である合成ガスを経由する製造方法が知られて
おり、前者は未だ研究開発過程にあり、現状では
製品品質が劣るとともに経済性も劣る。一方後者
はすでに南アフリカSASOL社で石炭のガス化プ
ロセスとフイツシヤー・トロプシユプロセスを組
合せたSASOL社の実用運転がなされている。
このように石炭、天然ガス又はアスフアルト等
のガソリン、灯油、軽油への直接転化が困難な炭
素含有物もガス化によつて一酸化炭素と水素との
混合ガスに容易に転化できることは公知である。
またこの混合ガスを適当な触媒の存在下で接触さ
せることにより炭化水素混合物へ転化できること
も公知である。
例えば、フイツシヤー・トロプシユ法は、鉄、
コバルト、ニツケル、ルテニウム及びロジウムに
基づく触媒の存在下で合成ガスから炭化水素混合
物を製造することで知られているが、この方法で
は反応生成物がメタンからワツクスに至る幅広い
炭化水素混合物（パラフイン、オレフイン）と各
種の含酸素化合物（アルコール、エーテル等）で
あり、価値のある特定沸点範囲の生成物を選択的
に得ることはできない。
上記の各種金属を用いたフイツシヤー・トロプ
シユ触媒のうち、実用運転に使用されているのは
鉄系の触媒であるが、これは炭酸ガスの副生が多
く、またカーボン析出が多く劣化しやすいという
欠点がある。
また、炭酸ガスの副生が少ない触媒としてルテ
ニウム系の触媒が知られているが、従来のアルミ
ナ担体にルテニウムを担持した触媒では、比較的
低圧では殆んどメタンが主成分であり、液状の炭
化水素があまり得られないという欠点がある。
そこで本発明者らは、これらの欠点を解決する
ため、一酸化炭素を水素化する活性金属と金属化
合物との組合わせについて鋭意実験検討を重ねた
結果、マンガンの価数が３〜４の範囲にあるマン
ガンの酸化物を含有する担体にルテニウムを担持
した触媒が、合成ガスから炭素数２以上の炭化水
素を得るのに極めて有効なことを見出し、本発明
を完成するに至つた。
すなわち、本発明は、合成ガスから炭化水素を
製造する方法において、マンガンの価数が３〜４
の範囲にあるマンガンの酸化物を含有する担体に
ルテニウムを担持した触媒の存在下で、合成ガス
を圧力10〜100Kg／cm2Ｇ、温度200〜400℃の条件
で接触させ、生成炭化水素中の炭素数５以上の炭
化水素の割合が40重量％以上の炭化水素を製造す
ることを特徴とする炭化水素の製法である。
本発明でいうマンガン酸化物を含有する担体と
は、次のものをさす。
(i) 市販のマンガン酸化物を焼成処理したもの
(ii) マンガン化合物、例えば硝酸マンガンを含有
する水溶液にアンモニア水等のアルカリを加え
てゲル化したもの、又は焼成したもの、
(iii) マンガン化合物、例えば硝酸マンガンを含有
する水溶液にアルミナ等の担体を浸漬し乾燥、
焼成したもの
(iv) 上記(i)，(ii)，(iii)においてマンガン酸化物又
は
マンガン化合物以外に、周期律表，，，
，族、ａ，ａ，族の化合物を共存さ
せたもの
上記(i)〜(iv)のマンガン酸化物はMn2O3又は
MnO2である。Mn2O3，MnO2は焼成条件（温度）
によつて決定される。
次に、上記のマンガン酸化物を含有する担体に
ルテニウムを担持する方法についてであるが、塩
化ルテニウムやヘキサアンミンルテニウムトリク
ロライド等のルテニウム化合物を含有する水溶液
又はアセトン等の溶剤に溶かした非水溶液中に上
記のマンガン酸化物を含有する担体を浸漬し、含
浸担持する通常の含浸技術が利用できる。
触媒組成中のルテニウムのマンガン酸化物に対
する担持量は重要であり、ルテニウムは金属とし
て0.1〜20重量％好ましくは0.5〜10重量％であ
る。
この場合、触媒を成形する際に、シリカアルミ
ナ、これらのゾル又はゾル、その他の耐火性酸化
物、或いは天然粘土鉱物などを添加することは、
触媒の性能を損なわないかぎりの量であればさし
つかえない。
本発明の方法において原料ガスとなる合成ガス
は石炭、天然ガス、石油コークス、頁岩油、ター
ルサンド又は石油蒸留からの残渣油などの化石燃
料を公知のガス化反応、例えば部分酸化反応又は
スチームリフオーミング反応などにより任意に製
造される。又合成ガスの前駆物質である一酸化炭
素とスチームとの混合物、或いは二酸化炭素と水
素との混合物も使用することができる。更には、
生成物中の液状炭化水素留分を除去した未反応ガ
ス混合物も又原料ガスとして使用できる。合成ガ
ス中の水素と一酸化炭素との比率はガス化される
炭素源により変化するが、本転化反応のために
は、その比率は0.2〜6.0の範囲にすることが好適
である。
合成ガスは触媒と200〜400℃の温度、10〜100
Kg／cm2Ｇの圧力及び触媒体積当り１時間標準温
度、圧力で約100−10000の合成ガス体積の
GHSV（ガス基準空塔速度）で接触反応を行う。
また、本発明は固定床タイプだけではなく、流
動床、液相スラリータイプのリアクターで行うこ
とができる。
次に本発明を実施例により具体的に説明するが
本発明はその要旨を越えないかぎり限定されるも
のではない。
〔実施例 １〕
硝酸マンガンを含有する水溶液のPHが9.0にな
るまでアンモニア水を加えて水酸化マンガンのゲ
ルを作つた後、これを過洗浄し、130℃で３時
間乾燥続いて500℃で３時間焼成してマンガン酸
化物Mn2O3の微粉末を得た。
このマンガン酸化物をルテニウム含有量が２重
量％になる量の塩化ルテニウム水溶液に浸漬した
後、130℃で３時間乾燥して触媒１を得た。
同様の方法でルテニウム担持量が６，１，０重
量％になるように触媒２，３，４を各々調製し
た。
これらの触媒１，２，３，４をそれぞれ流通式
マイクロリアクター（固定床）に充填し、転化反
応に供する前に水素を用いて、常圧
GHSV1000h-1，温度350℃で１時間、さらに400
℃で３時間予め還元処理し、引き続きH2／COモ
ル比２の合成ガスを用いて、290℃の温度、40
Kg／cm2Ｇの圧力、GHSV500h-1の条件で反応さ
せ表１のような結果を得た。
The present invention relates to a method for obtaining hydrocarbons having two or more carbon atoms in high yield from a mixed gas of carbon monoxide and hydrogen (hereinafter referred to as synthesis gas), and provides a catalyst particularly suitable for application to the method. This is what I am trying to do. The environment surrounding oil, which currently occupies the center of energy, is extremely unstable, and there are concerns that there will be an energy trough due to oil shortages from the late 1980s to the 1990s. For this reason, efforts are being made to reduce oil consumption and to use alternative energy sources such as coal, nuclear power, and LNG to replace oil. For this reason, in our country,
There is interest in the development of new technology for producing gasoline, kerosene, diesel oil, A-heavy oil, etc., which are expected to show relatively high demand growth in the future, from carbon sources other than petroleum, such as coal or natural gas, to solve the shortage of supplies. It is directed towards. Among these methods, known methods for producing hydrocarbon oil from coal include a direct method of coal liquefaction and an indirect method of production via synthesis gas, and the former is still in the research and development process. At present, product quality is inferior and economical efficiency is also inferior. The latter, on the other hand, is already in practical operation at SASOL South Africa, which combines a coal gasification process with a Fitscher-Tropsch process. It is well known that carbon-containing substances such as coal, natural gas, or asphalt, which are difficult to convert directly into gasoline, kerosene, or light oil, can be easily converted into a mixed gas of carbon monoxide and hydrogen through gasification. .
It is also known that this gas mixture can be converted into a hydrocarbon mixture by contacting it in the presence of a suitable catalyst. For example, the Fitscher-Tropsch method uses iron,
Known for the production of hydrocarbon mixtures from synthesis gas in the presence of catalysts based on cobalt, nickel, ruthenium and rhodium, this method produces a wide range of hydrocarbon mixtures ranging from methane to waxes (paraffins, olefins) and various oxygenated compounds (alcohols, ethers, etc.), and it is not possible to selectively obtain valuable products with specific boiling point ranges. Among the above-mentioned Fitscher-Tropschew catalysts using various metals, the one used in practical operation is an iron-based catalyst, but it is said that it produces a lot of carbon dioxide gas as a by-product and is prone to deterioration due to a large amount of carbon deposits. There are drawbacks. In addition, ruthenium-based catalysts are known as catalysts that produce less carbon dioxide as a by-product, but with conventional catalysts in which ruthenium is supported on an alumina carrier, methane is the main component at relatively low pressures, and liquid The disadvantage is that very few hydrocarbons are obtained. Therefore, in order to solve these drawbacks, the present inventors conducted intensive experimental studies on combinations of active metals and metal compounds that hydrogenate carbon monoxide, and found that the valence of manganese is in the range of 3 to 4. The present inventors have discovered that a catalyst in which ruthenium is supported on a manganese oxide-containing carrier is extremely effective in obtaining hydrocarbons having two or more carbon atoms from synthesis gas, leading to the completion of the present invention. That is, the present invention provides a method for producing hydrocarbons from synthesis gas in which the valence of manganese is 3 to 4.
In the presence of a catalyst in which ruthenium is supported on a support containing a manganese oxide in the range of This is a process for producing hydrocarbons characterized by producing hydrocarbons in which the proportion of hydrocarbons having a carbon number of 5 or more is 40% by weight or more. The carrier containing manganese oxide as used in the present invention refers to the following. (i) A commercially available manganese oxide that has been calcined; (ii) A manganese compound, for example, an aqueous solution containing manganese nitrate that has been gelled or calcined by adding an alkali such as aqueous ammonia; (iii) A manganese compound. , for example, by immersing a support such as alumina in an aqueous solution containing manganese nitrate and drying it.
Calcined products (iv) In addition to manganese oxides or manganese compounds in (i), (ii), and (iii) above, the periodic table,...
The manganese oxides of (i) to (iv) above are Mn 2 O 3 or
It is MnO2 . Mn 2 O 3 and MnO 2 are firing conditions (temperature)
determined by. Next, regarding the method of supporting ruthenium on the above-mentioned manganese oxide-containing carrier, in an aqueous solution containing a ruthenium compound such as ruthenium chloride or hexaammineruthenium trichloride, or a non-aqueous solution dissolved in a solvent such as acetone. A conventional impregnation technique can be used in which a carrier containing the manganese oxide is immersed in the manganese oxide to impregnate and support the manganese oxide. The amount of ruthenium supported relative to manganese oxide in the catalyst composition is important, and the amount of ruthenium as a metal is 0.1 to 20% by weight, preferably 0.5 to 10% by weight. In this case, adding silica alumina, their sols or sols, other refractory oxides, or natural clay minerals when forming the catalyst is
Any amount may be used as long as it does not impair the performance of the catalyst. Synthesis gas, which serves as the raw material gas in the method of the present invention, is obtained by converting fossil fuels such as coal, natural gas, petroleum coke, shale oil, tar sands or residual oil from petroleum distillation into known gasification reactions, such as partial oxidation reactions or steam reflux reactions. Manufactured arbitrarily by Ohming reaction, etc. It is also possible to use a mixture of carbon monoxide and steam, or a mixture of carbon dioxide and hydrogen, which are precursors to synthesis gas. Furthermore,
The unreacted gas mixture from which the liquid hydrocarbon fraction in the product has been removed can also be used as feed gas. The ratio of hydrogen to carbon monoxide in the synthesis gas varies depending on the carbon source to be gasified, but for the main conversion reaction, the ratio is preferably in the range of 0.2 to 6.0. Synthesis gas has a catalyst and a temperature of 200-400℃, 10-100℃
About 100-10000 synthesis gas volumes at standard temperature and pressure of Kg/cm 2 G and catalyst volume per hour.
Catalytic reaction is carried out at GHSV (gas standard superficial velocity). Furthermore, the present invention can be carried out not only in a fixed bed type reactor but also in a fluidized bed or liquid phase slurry type reactor. Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to the extent that it does not go beyond the gist thereof. [Example 1] Aqueous ammonia was added to an aqueous solution containing manganese nitrate until the pH reached 9.0 to create a manganese hydroxide gel, which was then overwashed, dried at 130°C for 3 hours, and then dried at 500°C. After firing for 3 hours, a fine powder of manganese oxide Mn 2 O 3 was obtained. This manganese oxide was immersed in an aqueous ruthenium chloride solution having a ruthenium content of 2% by weight, and then dried at 130° C. for 3 hours to obtain catalyst 1. Catalysts 2, 3, and 4 were prepared in the same manner so that the amount of ruthenium supported was 6, 1, and 0% by weight, respectively. These catalysts 1, 2, 3, and 4 were each packed into a flow-type microreactor (fixed bed), and heated to normal pressure using hydrogen before being subjected to the conversion reaction.
GHSV1000h -1 , 1 hour at 350℃, then 400℃
℃ for 3 hours, followed by synthesis gas at a H 2 /CO molar ratio of 2 at a temperature of 290℃ and 40℃.
The reaction was carried out under the conditions of a pressure of Kg/cm 2 G and a GHSV of 500 h -1 , and the results shown in Table 1 were obtained.
市販の酸化マンガン（MnO2）粉末とアルミナ
ゾルとを混合した後焼成し、MnO2：Al2O3＝
１：１（重量比）の混合物を得た。
この混合物にルテニウム含有量が１重量％にな
る量の塩化ルテニウム水溶液に浸漬した後、130
℃で３時間乾燥して触媒５を得た。
実施例１で得たマンガン酸化物の微粉末と酸化
マグネシウムの微粉末とを１対１の重量比で混合
し、乳鉢ですりつぶして両者の均一混合組成物を
得た。
この混合物にルテニウム含有量が１重量％にな
る量の塩化ルテニウム水溶液に浸漬した後、130
℃で３時間乾燥して触媒６を得た。
また、比較例として、アルミニ担体にルテニウ
ム含有量が１重量％になる量の塩化ルテニウム水
溶液に浸漬した後、130℃で乾燥して比較触媒を
得た。
これらの触媒を流通式マイクロリアクターで実
施例１と同じ方法、条件により合成ガスの転化反
応を行わせたところ、表２のような結果が得られ
た。
Commercially available manganese oxide (MnO 2 ) powder and alumina sol are mixed and fired to form MnO 2 :Al 2 O 3 =
A 1:1 (weight ratio) mixture was obtained. After immersing this mixture in an aqueous ruthenium chloride solution with a ruthenium content of 1% by weight,
Catalyst 5 was obtained by drying at ℃ for 3 hours. The manganese oxide fine powder obtained in Example 1 and the magnesium oxide fine powder were mixed at a weight ratio of 1:1 and ground in a mortar to obtain a uniform mixed composition of the two. After immersing this mixture in an aqueous ruthenium chloride solution with a ruthenium content of 1% by weight,
Catalyst 6 was obtained by drying at ℃ for 3 hours. Further, as a comparative example, an aluminum carrier was immersed in an aqueous ruthenium chloride solution having a ruthenium content of 1% by weight, and then dried at 130°C to obtain a comparative catalyst. When these catalysts were subjected to a synthesis gas conversion reaction in a flow microreactor using the same method and conditions as in Example 1, the results shown in Table 2 were obtained.
【表】
以上実施例で示したごとく、本発明におけるマ
ンガンの価数が３〜４の範囲にあるマンガン酸化
物を含有する担体にルテニウムを担持した触媒を
用いることにより、合成ガスから炭素数５以上の
炭化水素の割合が40重量％以上の炭化水素が高収
率で得られる。[Table] As shown in the examples above, by using a catalyst in which ruthenium is supported on a carrier containing a manganese oxide having a valence of manganese in the range of 3 to 4, synthesis gas can be Hydrocarbons containing the above hydrocarbons in a proportion of 40% by weight or more can be obtained in high yield.
Claims (1)
て、マンガンの価数が３〜４の範囲にあるマンガ
ンの酸化物を含有する担体にルテニウム担持した
触媒の存在下で、合成ガスを圧力10〜100Kg／cm2
Ｇ、温度200〜400℃の条件で接触させ、生成炭化
水素中の炭素数５以上の炭化水素の割合が40重量
％以上の炭化水素を製造することを特徴とする炭
化水素の製法。1. In a method for producing hydrocarbons from synthesis gas, synthesis gas is heated at a pressure of 10 to 100 kg/kg in the presence of a catalyst in which ruthenium is supported on a carrier containing a manganese oxide with a manganese valence in the range of 3 to 4. cm2
G. A method for producing hydrocarbons, which comprises contacting at a temperature of 200 to 400°C to produce hydrocarbons in which the proportion of hydrocarbons having 5 or more carbon atoms in the produced hydrocarbons is 40% by weight or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57158017A JPS5948424A (en) | 1982-09-13 | 1982-09-13 | Preparation of hydrocarbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57158017A JPS5948424A (en) | 1982-09-13 | 1982-09-13 | Preparation of hydrocarbon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5948424A JPS5948424A (en) | 1984-03-19 |
| JPH0245606B2 true JPH0245606B2 (en) | 1990-10-11 |
Family
ID=15662446
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57158017A Granted JPS5948424A (en) | 1982-09-13 | 1982-09-13 | Preparation of hydrocarbon |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5948424A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4914612A (en) * | 1988-03-31 | 1990-04-03 | International Business Machines Corporation | Massively distributed simulation engine |
| AU2002313208B2 (en) | 2001-06-18 | 2007-07-26 | Cosmo Oil Co., Ltd. | Method for producing hydrocarbons by fischer-tropsch process |
| JP4660039B2 (en) * | 2001-09-28 | 2011-03-30 | 独立行政法人石油天然ガス・金属鉱物資源機構 | Process for producing hydrocarbons by Fischer-Tropsch process in the presence of carbon dioxide |
| JP4660021B2 (en) * | 2001-06-18 | 2011-03-30 | 独立行政法人石油天然ガス・金属鉱物資源機構 | Process for producing hydrocarbons by the Fischer-Tropsch process |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US420613A (en) * | 1890-02-04 | Ashes from steamboats or other vessels |
-
1982
- 1982-09-13 JP JP57158017A patent/JPS5948424A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US420613A (en) * | 1890-02-04 | Ashes from steamboats or other vessels |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5948424A (en) | 1984-03-19 |
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