JPH09239272A - Production of ammonia synthesis catalyst - Google Patents
Production of ammonia synthesis catalystInfo
- Publication number
- JPH09239272A JPH09239272A JP8047583A JP4758396A JPH09239272A JP H09239272 A JPH09239272 A JP H09239272A JP 8047583 A JP8047583 A JP 8047583A JP 4758396 A JP4758396 A JP 4758396A JP H09239272 A JPH09239272 A JP H09239272A
- Authority
- JP
- Japan
- Prior art keywords
- ruthenium
- catalyst
- hydrogen
- ammonia synthesis
- activated carbon
- 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.)
- Granted
Links
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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は窒素と水素からアン
モニアを合成するのに適した触媒に関するものである。TECHNICAL FIELD The present invention relates to a catalyst suitable for synthesizing ammonia from nitrogen and hydrogen.
【０００２】[0002]
【従来の技術】従来、アンモニアを合成するには鉄を主
成分とし、アルミナ、酸化カリウム等を助触媒として添
加した鉄触媒系が採用されているが、この触媒のアンモ
ニア合成活性は低温では発揮されず、そのために工業装
置における操業反応温度は平衡論上の不利にもかかわら
ず４００〜５００℃の高温を利用せざるを得ない。その
ため鉄系触媒を用いる現存のアンモニア製造法において
は反応器でのワンパス転化率が低く、反応ガスの再循環
比を大きくとることが必要であり、これに伴う動力、熱
伝達等の運転経費の増大は著しい。2. Description of the Related Art Conventionally, an iron catalyst system in which iron is the main component and alumina, potassium oxide, etc. are added as co-catalysts is used for synthesizing ammonia, but the ammonia synthesizing activity of this catalyst is exhibited at low temperatures. Therefore, the operating reaction temperature in the industrial equipment must use a high temperature of 400 to 500 ° C. despite the disadvantage in equilibrium theory. Therefore, in the existing ammonia production method using an iron-based catalyst, the one-pass conversion rate in the reactor is low, and it is necessary to take a large recirculation ratio of the reaction gas, which results in a reduction in operating costs such as power and heat transfer. The increase is significant.
【０００３】本発明者らは、さきに鉄、ルテニウム、オ
スミウム、およびコバルトからなる８族ないし９族遷移
金属のいずれかと、アルカリ金属とを活性炭、あるいは
多孔質炭素に担持させたアンモニア合成触媒を発明した
（特公昭５４−３７５９２号公報）。このアンモニア合
成触媒は、活性炭に担持した８族ないし９族金属触媒に
アルカリ金属を添加して調製され、２００℃のような低
温でもアンモニアを合成することができるものである。The present inventors have already proposed an ammonia synthesis catalyst in which any one of Group 8 to Group 9 transition metals consisting of iron, ruthenium, osmium, and cobalt and an alkali metal are supported on activated carbon or porous carbon. The invention was made (Japanese Patent Publication No. 54-37592). This ammonia synthesis catalyst is prepared by adding an alkali metal to a Group 8 to Group 9 metal catalyst supported on activated carbon, and is capable of synthesizing ammonia even at a low temperature such as 200 ° C.
【０００４】その後、この触媒系についてアルカリ金属
に代えてアルカリ金属塩を使用し、触媒担体として特定
の比表面積を有するグラファイト含有炭素を使用するア
ンモニア製造方法（特公昭５９−１６８１６号公報）が
報告され、また、本発明者らも塩化ルテニウムとアルカ
リ金属塩とをアルミナ担体に担持させ、一酸化炭素、水
による被毒の少ないアンモニア合成触媒（Journal of C
atalysis, 92巻, 296-304 (1985), 同 305-311 (1985)
）を報告した。After that, an ammonia production method (Japanese Patent Publication No. 59-16816) in which an alkali metal salt was used instead of an alkali metal for this catalyst system, and graphite-containing carbon having a specific surface area was used as a catalyst carrier. In addition, the inventors of the present invention also support ruthenium chloride and an alkali metal salt on an alumina carrier to form an ammonia synthesis catalyst that is less poisoned by carbon monoxide and water (Journal of C
atalysis, Volume 92, 296-304 (1985), 305-311 (1985)
) Was reported.
【０００５】また、本発明者らはルテニウムカルボニ
ル、ルテニウムアセチルアセトナート等の塩素を含まな
いルテニウム化合物を出発原料とするルテニウム触媒の
調製方法（特開平２−２５８０６６号公報）を提案し
た。さらに、本発明者らはルテニウムをアルミナ担体に
担持し、促進剤として希土類元素を添加した触媒（Jour
nal of Catalysis, 136巻, 118-125 (1992) ）、および
ルテニウムを希土類酸化物上に担持した触媒（特開平６
−７９１７７）を提案した。しかしながら、ルテニウム
触媒を工業的なアンモニア合成触媒として使用するため
には、さらなる活性の向上が望まれる。本発明は担持ル
テニウム触媒の改良に関するものである。The present inventors also proposed a method for preparing a ruthenium catalyst starting from a chlorine-free ruthenium compound such as ruthenium carbonyl or ruthenium acetylacetonate (JP-A-2-258066). Furthermore, the inventors of the present invention supported ruthenium on an alumina carrier and added a rare earth element as a promoter (Jour.
nal of Catalysis, Vol. 136, 118-125 (1992)), and a catalyst in which ruthenium is supported on a rare earth oxide (Japanese Patent Laid-Open Publication No. HEI-6 (1999)).
-79177). However, in order to use the ruthenium catalyst as an industrial ammonia synthesis catalyst, further improvement in activity is desired. The present invention relates to improvements in supported ruthenium catalysts.
【０００６】[0006]
【発明が解決しようとする課題】本発明は活性炭担持ル
テニウム触媒を用いてアンモニアを合成する方法におい
て、高活性な触媒を提供することを課題とする。An object of the present invention is to provide a highly active catalyst in a method for synthesizing ammonia using a ruthenium catalyst supported on activated carbon.
【０００７】[0007]
【課題を解決するための手段】本発明は、ルテニウムお
よびアルカリ土類金属元素を活性炭に担持してなるアン
モニア合成触媒を製造するに当たり、ルテニウムの原料
としてルテニウムと一般式（１）Means for Solving the Problems In producing an ammonia synthesis catalyst comprising ruthenium and an alkaline earth metal element supported on activated carbon, the present invention uses ruthenium as a raw material for ruthenium and the general formula (1).
【０００８】[0008]
【化２】 Ｒ1−ＣＯ−ＣＨ2−ＣＯ−Ｒ2 （１） （式中、Ｒ1 およびＲ2 は炭素数１〜２０のアルキル基
を表し、同一でも異なっていてもよい。）で表される化
合物Ｘとの錯体RuX3を使用することを特徴とするアンモ
ニア合成触媒の製造法である。Embedded image R 1 —CO—CH 2 —CO—R 2 (1) (wherein, R 1 and R 2 represent an alkyl group having 1 to 20 carbon atoms and may be the same or different). A method for producing an ammonia synthesis catalyst, characterized in that a complex RuX 3 with the compound X shown is used.
【０００９】[0009]
【発明の実施の形態】本発明の触媒はルテニウムおよび
アルカリ土類金属元素を活性炭に担持したものである。
本発明において、活性炭は木材、石炭、ヤシ殻等を原料
とする通常のものが使用できる。また、形状も粉末、粒
状等、特に制限はない。活性炭の比表面積は少なくとも
６００m2/g以上、好ましくは８００m2/g以上、特に好ま
しくは１０００m2/g以上のものが良い。比表面積が小さ
いと充分なアンモニア合成速度が得られない。BEST MODE FOR CARRYING OUT THE INVENTION The catalyst of the present invention comprises ruthenium and an alkaline earth metal element supported on activated carbon.
In the present invention, as the activated carbon, usual ones made of wood, coal, coconut shell, etc. can be used. Further, the shape is not particularly limited, such as powder and granules. The specific surface area of the activated carbon is at least 600 m 2 / g or more, preferably 800 m 2 / g or more, and particularly preferably 1000 m 2 / g or more. If the specific surface area is small, a sufficient ammonia synthesis rate cannot be obtained.
【００１０】活性炭にルテニウムを担持する前に活性炭
を７００℃以上の温度で水素と接触させることは、高活
性触媒を得るための有効な方法である。この水素処理は
オートクレーブのような密閉容器に活性炭と水素含有ガ
スを充填して行っても良く、あるいは水素含有ガスを流
通しながら行っても良い。水素処理温度は７００℃以
上、望ましくは８００〜１０００℃である。水素処理温
度が低過ぎると触媒活性の向上が認められない。また、
必要以上に高い温度で水素処理を行っても効果は一定
で、エネルギーの損失を招くばかりでそれに見合う触媒
活性の向上が見られない。水素処理圧力は減圧、常圧、
加圧のいずれでも良いが、通常は常圧付近で水素処理を
行う。水素処理時間は１〜５０ｈｒの範囲で選択され
る。１ｈｒ以下では水素処理の効果が現れず、５０ｈｒ
以上の処理を行っても水素処理の効果は一定である。Contacting the activated carbon with hydrogen at a temperature of 700 ° C. or higher before supporting ruthenium on the activated carbon is an effective method for obtaining a highly active catalyst. This hydrogen treatment may be performed by filling a closed container such as an autoclave with activated carbon and a hydrogen-containing gas, or may be performed while circulating the hydrogen-containing gas. The hydrogen treatment temperature is 700 ° C or higher, preferably 800 to 1000 ° C. If the hydrogen treatment temperature is too low, no improvement in catalytic activity is observed. Also,
Even if the hydrogen treatment is carried out at a temperature higher than necessary, the effect is constant, only energy loss is caused, and no corresponding improvement in catalytic activity is observed. Hydrogen treatment pressure is reduced pressure, normal pressure,
Although any pressure may be applied, hydrogen treatment is usually carried out near atmospheric pressure. The hydrogen treatment time is selected within the range of 1 to 50 hours. Below 1 hr, the effect of hydrogen treatment does not appear, and 50 hr
Even if the above treatment is performed, the effect of hydrogen treatment is constant.
【００１１】本発明において、アルカリ土類金属元素と
してはマグネシウム、カルシウム、バリウム、およびス
トロンチウムが使用されるが、特にバリウムを用いた場
合に活性化の効果が顕著である。アルカリ土類金属元素
の添加は、アルカリ土類金属化合物の水溶液に担体を浸
漬し、引き続いて乾燥することによって行われる。この
操作は担体へのルテニウムの担持に先立って、あるいは
担持後に行うことができる。アルカリ土類金属元素の添
加量はルテニウムに対する原子比として０．１〜２０の
範囲で選ぶことができる。アルカリ土類金属元素の添加
量が前記の範囲より少ないとアンモニア合成活性の向上
が認められず、前記の範囲を越えると逆にアンモニア合
成活性が低下する。In the present invention, magnesium, calcium, barium and strontium are used as the alkaline earth metal element, and the activation effect is particularly remarkable when barium is used. The alkaline earth metal element is added by immersing the carrier in an aqueous solution of an alkaline earth metal compound and subsequently drying. This operation can be performed before or after the ruthenium is loaded on the carrier. The addition amount of the alkaline earth metal element can be selected in the range of 0.1 to 20 as an atomic ratio with respect to ruthenium. If the amount of the alkaline earth metal element added is less than the above range, no improvement in the ammonia synthesis activity is observed, and if it exceeds the above range, the ammonia synthesis activity decreases conversely.
【００１２】本発明ではルテニウムの原料として錯体Ru
X3を用いる。ここに、Ｘは一般式（１） （式中、Ｒ1
およびＲ2 は炭素数１〜２０のアルキル基を表し、同一
でも異なっていてもよい。）で表される化合物である。
錯体RuX3を出発原料としてアンモニア合成触媒を調製す
ることにより、大幅にアンモニア合成活性が向上する。
本発明の触媒を工業的規模で製造する場合、入手の容易
さと価格が低いことから、化合物Ｘとしてアセチルアセ
トンを使用することが望ましい。In the present invention, the complex Ru is used as a raw material for ruthenium.
Use X 3 . Where X is the general formula (1) (wherein R 1
And R 2 represent an alkyl group having 1 to 20 carbon atoms and may be the same or different. ).
By preparing the ammonia synthesis catalyst using the complex RuX 3 as a starting material, the ammonia synthesis activity is significantly improved.
When producing the catalyst of the present invention on an industrial scale, it is desirable to use acetylacetone as the compound X because of its easy availability and low cost.
【００１３】ルテニウムの錯体RuX3はアセトン、テトラ
ヒドロフラン等の極性有機溶媒、または水に溶解させて
活性炭に含浸させる。ルテニウム担持量はルテニウム金
属として活性炭に対して０．１〜２０重量％、好ましく
は１〜５重量％である。担持量０．１重量％以下では触
媒活性が低く、担持量２０重量％以上では担持量を増や
してもアンモニア合成活性の向上が認められず、高価な
ルテニウムを多量に使用する意味がない。Ruthenium complex RuX 3 is dissolved in a polar organic solvent such as acetone or tetrahydrofuran, or water to impregnate activated carbon. The amount of ruthenium supported on the activated carbon as ruthenium metal is 0.1 to 20% by weight, preferably 1 to 5% by weight. When the loading amount is 0.1% by weight or less, the catalytic activity is low, and when the loading amount is 20% by weight or more, the ammonia synthesis activity is not improved even if the loading amount is increased, and it is meaningless to use a large amount of expensive ruthenium.
【００１４】ルテニウムを含浸させた後、真空排気およ
び／または水素還元処理を行う。真空排気は５０℃〜６
００℃、好ましくは１５０℃〜５５０℃で行う。真空排
気時間は０．５〜２０ｈｒである。水素還元温度は１０
０℃〜７００℃、好ましくは２００℃〜６５０℃、水素
還元時間は０．５〜２０ｈｒである。水素還元処理を真
空排気に引き続いて行う方法も、真空排気処理か水素還
元処理の一方のみを行う方法も、いずれも本発明の範囲
に含まれるが、本発明の触媒においては水素還元処理を
行うことによってそのアンモニア合成活性が飛躍的に向
上するので、水素還元処理を実施することが望ましい。After impregnating with ruthenium, vacuum evacuation and / or hydrogen reduction treatment is performed. Vacuum exhaust is 50 ℃ to 6
It is carried out at 00 ° C, preferably 150 ° C to 550 ° C. The evacuation time is 0.5 to 20 hours. Hydrogen reduction temperature is 10
The temperature is 0 ° C to 700 ° C, preferably 200 ° C to 650 ° C, and the hydrogen reduction time is 0.5 to 20 hours. Both the method of performing the hydrogen reduction treatment subsequent to the vacuum exhaust and the method of performing only one of the vacuum exhaust treatment and the hydrogen reduction treatment are included in the scope of the present invention, but the catalyst of the present invention performs the hydrogen reduction treatment. As a result, the ammonia synthesizing activity is dramatically improved, so it is desirable to carry out hydrogen reduction treatment.
【００１５】アンモニア合成反応における反応条件は、
平衡論上低温高圧が望ましいが、本発明の触媒は反応温
度１００℃〜５００℃、好ましくは１５０℃〜３５０℃
で使用される。また、反応圧力は０．５〜３００kg/cm2
である。空間速度は、通常１０００〜１００，０００／
ｈｒである。水素と窒素のモル比は１：１〜５：１の範
囲で選択されるが、化学両論比である３：１またはこれ
より窒素過剰側の条件が好ましい。本発明の触媒は、低
温活性であるためにアンモニアが高濃度で得られるの
で、液化分離が容易である。以下、本発明の効果を実施
例により説明する。The reaction conditions in the ammonia synthesis reaction are as follows:
Although low temperature and high pressure are desirable in equilibrium theory, the catalyst of the present invention has a reaction temperature of 100 ° C to 500 ° C, preferably 150 ° C to 350 ° C.
Used in. The reaction pressure is 0.5 to 300 kg / cm 2
It is. Space velocity is usually 1000-100,000 /
It is hr. The molar ratio of hydrogen to nitrogen is selected in the range of 1: 1 to 5: 1, but a stoichiometric ratio of 3: 1 or a nitrogen excess side condition is preferred. Since the catalyst of the present invention is active at a low temperature, ammonia can be obtained at a high concentration, so that liquefaction separation is easy. Hereinafter, the effects of the present invention will be described with reference to examples.
【００１６】[0016]
実施例１ 和光純薬製、粒状活性炭を石英製の反応管に充填し、３
０ml/minの水素を流通させながら、常圧、８００℃で２
４ｈｒ、引き続いて９１５℃で２４ｈｒ水素処理した。
０．０８０ｇのルテニウムアセチルアセトナートRu(aca
c)3 を約３０mlのテトラヒドロフラン（ＴＨＦ）に溶解
し、その中に１．０ｇの水素処理活性炭を加えた。一晩
放置後、溶媒をロータリーエバポレーターで除去し、ル
テニウムアセチルアセトナートを担体上に担持した。得
られたRu(acac)3/水素処理活性炭を４００℃に至るまで
２ｈｒで昇温しながら真空排気処理し、錯体を分解し
た。得られた Ru/水素処理活性炭触媒中のルテニウム担
持量は活性炭に対して２重量％であった。硝酸バリウム
Ba(NO3)2 ０．５１７ｇを１５mlの純水に溶解し、その
中に前記Ru/水素処理活性炭を投入して攪拌し、一晩放
置した。水浴上で水を蒸発させ、次いで空気中で１２０
℃、１hr乾燥してRu/Ba(NO3)2/水素処理活性炭触媒を調
製した。触媒中の Ba/Ru原子比は１０であった。得られ
た触媒を流通式反応器に充填し、水素５０ml/min流通下
５ｈｒ水素還元を行った。水素還元温度は３１５〜６０
０℃の範囲で変化させた。引き続いて反応温度３１５
℃、反応圧力１kg/cm2、反応原料のフィード量は水素４
５ml/min、窒素１５ml/minでアンモニア合成反応を行っ
た。反応成績は触媒１ｇ、１ｈｒ当たりのアンモニア生
成モル数で表現した。反応の結果を表１に示す。Example 1 A Wako Pure Chemical Industries, Ltd. granular activated carbon was filled in a quartz reaction tube, and 3
While circulating 0 ml / min of hydrogen, 2 at normal pressure and 800 ° C
It was treated with hydrogen for 4 hours and subsequently at 915 ° C. for 24 hours.
0.080 g of ruthenium acetylacetonate Ru (aca
c) 3 was dissolved in about 30 ml of tetrahydrofuran (THF), into which 1.0 g of hydrotreated activated carbon was added. After standing overnight, the solvent was removed by a rotary evaporator, and ruthenium acetylacetonate was loaded on the carrier. The obtained Ru (acac) 3 / hydrogen-treated activated carbon was vacuum-exhausted while heating up to 400 ° C. for 2 hours to decompose the complex. The amount of ruthenium supported on the obtained Ru / hydrogen-treated activated carbon catalyst was 2% by weight based on the activated carbon. Barium nitrate
0.517 g of Ba (NO 3 ) 2 was dissolved in 15 ml of pure water, and the Ru / hydrogen-treated activated carbon was charged therein, stirred, and left overnight. Evaporate the water on a water bath and then 120 in air.
Ru / Ba (NO 3 ) 2 / hydrogen-treated activated carbon catalyst was prepared by drying at ℃ for 1 hr. The Ba / Ru atomic ratio in the catalyst was 10. The obtained catalyst was filled in a flow reactor and hydrogen reduction was carried out for 5 hours under a flow of hydrogen of 50 ml / min. Hydrogen reduction temperature is 315-60
It was changed in the range of 0 ° C. Then reaction temperature 315
° C, reaction pressure 1 kg / cm 2 , feed amount of reaction raw material is 4
Ammonia synthesis reaction was performed at 5 ml / min and 15 ml / min of nitrogen. The reaction results were expressed by the number of moles of ammonia produced per 1 g of catalyst and 1 hr. The results of the reaction are shown in Table 1.
【００１７】比較例１ 実施例１と同じ条件で水素処理活性炭を製造した。０．
０２９ｇのルテニウムカルボニルRu3(CO)12 を約３０ml
のＴＨＦに溶解し、その中に０．６６９ｇの水素処理活
性炭を加えた。一晩放置後、溶媒をロータリーエバポレ
ーターで除去し、ルテニウムカルボニルを担体上に担持
した。得られたRu3(CO)12/水素処理活性炭を４５０℃に
至るまで２ｈｒで昇温しながら真空排気処理し、カルボ
ニルを分解してCOを除去した。得られた Ru/水素処理活
性炭触媒中のルテニウム担持量は活性炭に対して２重量
％であった。得られた Ru/水素処理活性炭触媒に対して
実施例１と同じ条件で硝酸バリウムBa(NO3)2を添加し、
Ru/Ba(NO3)2/水素処理活性炭触媒を調製した。触媒中の
Ba/Ru原子比は１０であった。得られた触媒を流通式反
応器に充填し、実施例１と同じ条件でアンモニア合成反
応を行った。結果を表１に示す。Comparative Example 1 A hydrogenated activated carbon was produced under the same conditions as in Example 1. 0.
About 30 ml of ruthenium carbonyl Ru 3 (CO) 12 of 029 g
Of THF and 0.669 g of hydrotreated activated carbon was added thereto. After standing overnight, the solvent was removed by a rotary evaporator, and ruthenium carbonyl was loaded on the carrier. The obtained Ru 3 (CO) 12 / hydrogen-treated activated carbon was vacuum-exhausted while heating up to 450 ° C. for 2 hours to decompose carbonyl and remove CO. The amount of ruthenium supported on the obtained Ru / hydrogen-treated activated carbon catalyst was 2% by weight based on the activated carbon. Barium nitrate Ba (NO 3 ) 2 was added to the obtained Ru / hydrogen-treated activated carbon catalyst under the same conditions as in Example 1,
Ru / Ba (NO 3 ) 2 / hydrogen-treated activated carbon catalyst was prepared. In the catalyst
The Ba / Ru atomic ratio was 10. The obtained catalyst was packed in a flow reactor, and an ammonia synthesis reaction was carried out under the same conditions as in Example 1. The results are shown in Table 1.
【００１８】[0018]
【表１】 表１ ──────────────────────────────────── Ｒｕ原料 Ｂａ／Ｒｕ 触媒 反応温度 活性 原子比 還元温度 ［℃］ ［℃］ (*1) ──────────────────────────────────── 実施例１ Ru(acac)3 １０ ３１５ ３１５ １０３ ４００ 〃 ３１８ ５００ 〃 ８３８ ６００ 〃 １２２１ ──────────────────────────────────── 比較例１ Ru3(CO)12 １０ ３１５ ３１５ ６０ ４００ 〃 １４９ ５００ 〃 ３１８ ６００ 〃 ４４３ ──────────────────────────────────── 注 （*１）単位：μmol/(g・hr)[Table 1] Table 1 ──────────────────────────────────── Ru raw material Ba / Ru Catalyst reaction temperature Active atomic ratio Reduction temperature [℃] [℃] (* 1) ──────────────────────────────────── --Example 1 Ru (acac) 3 10 315 315 103 400 〃 318 500 〃 838 600 〃 1221 ──────────────────────────── Comparative Example 1 Ru 3 (CO) 12 10 315 315 60 60 400 〃 149 500 〃 318 600 〃 443 ──────────────────── ──────────────── Note (* 1) Unit: μmol / (g ・ hr)
【００１９】[0019]
【発明の効果】本発明の触媒は、従来の担持ルテニウム
触媒に比べてアンモニア合成活性が高い。The catalyst of the present invention has a higher ammonia synthesis activity than the conventional supported ruthenium catalyst.
Claims (4)
を活性炭に担持してなるアンモニア合成触媒を製造する
に当たり、ルテニウムの原料としてルテニウムと一般式
（１） 【化１】 Ｒ1−ＣＯ−ＣＨ2−ＣＯ−Ｒ2 （１） （式中、Ｒ1 およびＲ2 は炭素数１〜２０のアルキル基
を表し、同一でも異なっていてもよい。）で表される化
合物Ｘとの錯体RuX3を使用することを特徴とするアンモ
ニア合成触媒の製造法。1. When producing an ammonia synthesis catalyst comprising ruthenium and an alkaline earth metal element supported on activated carbon, ruthenium and a compound represented by the general formula (1): R 1 —CO—CH 2 — CO—R 2 (1) (In the formula, R 1 and R 2 represent an alkyl group having 1 to 20 carbon atoms and may be the same or different.) The complex RuX 3 with the compound X is used. A method for producing an ammonia synthesis catalyst, which comprises:
セチルアセトンである請求項１記載のアンモニア合成触
媒の製造法。2. The method for producing an ammonia synthesis catalyst according to claim 1, wherein the compound X represented by the general formula (1) is acetylacetone.
請求項１または２記載のアンモニア合成触媒の製造法。3. The method for producing an ammonia synthesis catalyst according to claim 1, wherein the alkaline earth metal element is barium.
て、活性炭を７００℃以上の温度で水素と接触させるこ
とを特徴とする請求項１〜３のいずれかに記載のアンモ
ニア合成触媒の製造法。4. The production of the ammonia synthesis catalyst according to claim 1, wherein the activated carbon is brought into contact with hydrogen at a temperature of 700 ° C. or higher before supporting the complex RuX 3 on the activated carbon. Law.
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| JP04758396A JP3773293B2 (en) | 1996-03-05 | 1996-03-05 | Method for producing ammonia synthesis catalyst |
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|---|---|---|---|
| JP04758396A JP3773293B2 (en) | 1996-03-05 | 1996-03-05 | Method for producing ammonia synthesis catalyst |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100421788C (en) * | 2006-03-03 | 2008-10-01 | 厦门大学 | Mixed ruthenium base amino synthetic catalyst and its preparing method |
| WO2012077658A1 (en) | 2010-12-07 | 2012-06-14 | 国立大学法人東京工業大学 | Ammonia synthesis catalyst and ammonia synthesis method |
| US10131545B2 (en) | 2013-01-22 | 2018-11-20 | Nippon Shokubai Co., Ltd. | Ammonia synthesis method and catalyst for ammonia synthesis |
| CN110280268A (en) * | 2019-07-03 | 2019-09-27 | 北京氦舶科技有限责任公司 | A kind of synthetic ammonia catalyst and preparation method thereof |
| US10695751B2 (en) | 2015-09-15 | 2020-06-30 | Japan Science And Technology Agency | Laves phase intermetallic compound, catalyst using intermetallic compound, and method for producing ammonia |
| US10759668B2 (en) | 2015-11-10 | 2020-09-01 | Japan Science And Technology Agency | Supported metal material, supported metal catalyst, and ammonia synthesis method using the same |
| US10792645B2 (en) | 2015-12-25 | 2020-10-06 | Japan Science And Technology Agency | Transition-metal-supporting intermetallic compound, supported metallic catalyst, and ammonia producing method |
-
1996
- 1996-03-05 JP JP04758396A patent/JP3773293B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100421788C (en) * | 2006-03-03 | 2008-10-01 | 厦门大学 | Mixed ruthenium base amino synthetic catalyst and its preparing method |
| WO2012077658A1 (en) | 2010-12-07 | 2012-06-14 | 国立大学法人東京工業大学 | Ammonia synthesis catalyst and ammonia synthesis method |
| US9150423B2 (en) | 2010-12-07 | 2015-10-06 | Tokyo Institute Of Technology | Ammonia synthesis catalyst and ammonia synthesis method |
| US10131545B2 (en) | 2013-01-22 | 2018-11-20 | Nippon Shokubai Co., Ltd. | Ammonia synthesis method and catalyst for ammonia synthesis |
| US10695751B2 (en) | 2015-09-15 | 2020-06-30 | Japan Science And Technology Agency | Laves phase intermetallic compound, catalyst using intermetallic compound, and method for producing ammonia |
| US10759668B2 (en) | 2015-11-10 | 2020-09-01 | Japan Science And Technology Agency | Supported metal material, supported metal catalyst, and ammonia synthesis method using the same |
| US10792645B2 (en) | 2015-12-25 | 2020-10-06 | Japan Science And Technology Agency | Transition-metal-supporting intermetallic compound, supported metallic catalyst, and ammonia producing method |
| CN110280268A (en) * | 2019-07-03 | 2019-09-27 | 北京氦舶科技有限责任公司 | A kind of synthetic ammonia catalyst and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| JP3773293B2 (en) | 2006-05-10 |
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