JP2914206B2 - Nickel-supported catalyst for hydrocarbon reforming and method for producing the same - Google Patents
Nickel-supported catalyst for hydrocarbon reforming and method for producing the sameInfo
- Publication number
- JP2914206B2 JP2914206B2 JP7037436A JP3743695A JP2914206B2 JP 2914206 B2 JP2914206 B2 JP 2914206B2 JP 7037436 A JP7037436 A JP 7037436A JP 3743695 A JP3743695 A JP 3743695A JP 2914206 B2 JP2914206 B2 JP 2914206B2
- Authority
- JP
- Japan
- Prior art keywords
- nickel
- catalyst
- producing
- supported catalyst
- metal salt
- 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
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0081—Preparation by melting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/072—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
-
- 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
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S502/00—Catalyst, solid sorbent, or support therefor: product or process of making
- Y10S502/514—Process applicable either to preparing or to regenerating or to rehabilitating catalyst or sorbent
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Hydrogen, Water And Hydrids (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は、炭化水素改質用ニッケ
ル担持触媒およびその製造方法に関する。詳しくは、二
酸化炭素、水蒸気または酸素を酸化剤として使用する炭
化水素改質反応用の、ケイ素および(または)アルミニ
ウム含有担体に担持されたニッケル触媒およびその製造
方法に関する。The present invention relates to a nickel-supported catalyst for hydrocarbon reforming and a method for producing the same. More specifically, the present invention relates to a nickel catalyst supported on a silicon and / or aluminum-containing carrier for a hydrocarbon reforming reaction using carbon dioxide, steam or oxygen as an oxidizing agent, and a method for producing the same.
【0002】ニッケル担持触媒は、ニッケル金属の高活
性のため、改質反応、水素化反応、メタン化反応等の還
元反応に広く利用される触媒として、工業的に非常に重
要である。 ニッケル担持触媒はとくに、天然ガス、オ
イル、ナフサ等のスチームリフォーミング工程の触媒と
して化学工業のC1化学の主要な出発物質の製造に使用
されている。 これらの触媒はまた、メタノール、アン
モニア、含酸素化合物等の製造原料である合成ガスの生
産にも使用されている。A nickel-supported catalyst is industrially very important as a catalyst widely used for a reduction reaction such as a reforming reaction, a hydrogenation reaction and a methanation reaction because of the high activity of nickel metal. Nickel-supported catalysts are used in particular in the production of the main starting material of C1 chemistry in the chemical industry as catalysts in steam reforming processes for natural gas, oil, naphtha and the like. These catalysts are also used for producing synthesis gas, which is a raw material for producing methanol, ammonia, oxygen-containing compounds, and the like.
【0003】[0003]
【従来の技術】ニッケル担持触媒の製造方法としては、
現在まで共沈法、含浸法、イオン交換法、析出−沈積
法、ゾル−ゲル法、エアロゲル法等、多様な方法が提示
されていて、担体の種類および形態によって製造方法が
異なる。 そしてニッケル触媒の製造および処理の方法
によって、触媒の特性が大きく変化する。2. Description of the Related Art As a method for producing a nickel-supported catalyst,
Various methods such as a coprecipitation method, an impregnation method, an ion exchange method, a precipitation-sedimentation method, a sol-gel method, and an aerogel method have been proposed so far, and the production method differs depending on the type and form of the carrier. The method of producing and treating the nickel catalyst greatly changes the characteristics of the catalyst.
【0004】たとえばドイツ特許公開第2,255,9
09号は、共沈法により触媒の前駆体であるNi6Al2
(OH)16CO3・4H2Oを製造し、これを焼成してN
i−Al系触媒を製造し、これをナフサのスチームリフ
ォーミング反応の触媒として使用することを開示してい
る。 別のドイツ特許公開第2,024,282号で
は、15.3%のNi(NO3)26H2Oと7.6%の
Al(NO3)29H2Oとを含有する水溶液にNa2CO
3を添加して共沈させ、メタンのスチームリフォーミン
グ触媒であるニッケル担持触媒を製造している。 日本
特許公開第57−156,303号は、天然ゼオライト
に含浸法によりニッケル金属成分を担持させる方法を提
示した。 すなわち、1モル濃度のNi(NO3)2水溶
液に天然ゼオライトを添加して100℃で1時間含浸し
たのち、400℃で1時間焼成して製造した。 それか
ら天然ガスのスチームリフォーミング反応に適用したと
ころ、アルミニウムに担持された一般的なニッケル触媒
にくらべ、より高い活性が得られた。[0004] For example, German Patent Publication No. 2,255,9
No. 09 discloses Ni 6 Al 2 which is a catalyst precursor by a coprecipitation method.
(OH) 16 CO 3 .4H 2 O is produced and calcined to produce N 2
It discloses that an i-Al-based catalyst is produced and used as a catalyst for a naphtha steam reforming reaction. In another German Patent Publication No. 2,024,282, 15.3% of Ni (NO 3) 2 6H 2 O and 7.6% of Al (NO 3) 2 9H 2 O and Na in an aqueous solution containing 2 CO
3 is added and coprecipitated to produce a nickel-supported catalyst that is a steam reforming catalyst for methane. Japanese Patent Publication No. 57-156,303 proposed a method of supporting a nickel metal component on a natural zeolite by an impregnation method. That is, a natural zeolite was added to a 1 molar aqueous solution of Ni (NO 3 ) 2 , impregnated at 100 ° C. for 1 hour, and then calcined at 400 ° C. for 1 hour. Then, when applied to a steam reforming reaction of natural gas, higher activity was obtained as compared with a general nickel catalyst supported on aluminum.
【0005】[0005]
【発明が解決しようとする課題】このように、一般的に
利用されているニッケル担持触媒は、その製造方法が大
部分湿式法である。 このような湿式の製造方法は乾燥
過程を必要とするだけではなく、製造方法によって酸性
および塩基性の廃水が生じるから、工業的に実施するに
は問題がある。As described above, generally used nickel-supported catalysts are mostly produced by a wet method. Such a wet production method not only requires a drying step, but also has a problem in industrial implementation since acidic and basic wastewater is generated by the production method.
【0006】本発明の目的は、乾燥過程が必要なく、廃
水問題もなく、工業的に高価な貴金属担持触媒に代えて
メタンの改質反応に対して高活性触媒であるニッケル担
持触媒を提供することにある。 本発明の目的はまた、
二酸化炭素、スチーム、酸素等の酸化剤を利用する炭化
水素の改質反応に高活性で作用し、便利で経済的に製造
することができる、ニッケルまたはニッケルとアルカリ
金属および(または)アルカリ土類金属担持触媒を提供
することにもある。An object of the present invention is to provide a nickel-supported catalyst which does not require a drying process, has no waste water problem, and is a highly active catalyst for methane reforming reaction instead of an industrially expensive noble metal-supported catalyst. It is in. The object of the present invention is also
Nickel or nickel and alkali metals and / or alkaline earths, which have a high activity on hydrocarbon reforming reactions using oxidizing agents such as carbon dioxide, steam and oxygen and can be produced conveniently and economically There is also to provide a metal supported catalyst.
【0007】[0007]
【課題を解決するための手段】本発明のこのような目的
は、100℃以下の低融点のニッケル塩と、必要に応
じ、アルカリ金属塩および(または)アルカリ土類金属
塩を、ゼオライト、シリカ、ガンマ−アルミナ、シリケ
ートおよびシリカ−アルミナからえらんだ、表面積10
0m2/g以上の担体に常温で物理的に混合する段階、上
記塩類の溶融点以上の一定の温度に加熱してすべての塩
類を溶融しながら金属塩を分解する段階、および300
〜1200℃の範囲で焼成する段階からなる、ニッケル
担持触媒の製造方法によって達成される。SUMMARY OF THE INVENTION An object of the present invention is to provide a low melting point nickel salt having a temperature of 100 ° C. or lower and, if necessary, an alkali metal salt and / or an alkaline earth metal salt, by using zeolite and silica. Surface area of 10 selected from gamma-alumina, silicate and silica-alumina
Physical mixing with a carrier of 0 m 2 / g or more at room temperature, heating to a certain temperature above the melting point of the salts to decompose metal salts while melting all the salts, and 300
This is achieved by a method for producing a nickel-supported catalyst, comprising a step of calcining at a temperature in the range of to 1200 ° C.
【0008】金属塩と担体との混合方法は、好ましくは
乳鉢またはボールミル等を利用して均一に磨砕して混合
する。[0008] The method of mixing the metal salt and the carrier is preferably uniformly ground using a mortar or a ball mill and mixed.
【0009】塩を溶融するに当っては、焼成炉で金属塩
の溶融点以上、とくに100℃ないし400℃の範囲で
溶融することが好ましい。In melting the salt, it is preferable that the salt is melted in a firing furnace at a temperature higher than the melting point of the metal salt, particularly in the range of 100 ° C. to 400 ° C.
【0010】焼成は、酸素または酸素を含有するガス気
流下に、焼成温度がとくに300℃ないし1200℃で
ある範囲で実施することが好ましい。The calcination is preferably carried out in an oxygen or gas stream containing oxygen at a calcination temperature of 300 ° C. to 1200 ° C.
【0011】担体としてゼオライトを使用する場合は、
ペンタシル型構造を有し、構造内のアルミニウム対ケイ
素の含有量が、モル比にして0〜1.0の範囲にあるも
のが好ましい。When zeolite is used as a carrier,
Preference is given to those having a pentasil type structure, wherein the content of aluminum to silicon in the structure is in the range of 0 to 1.0 in terms of molar ratio.
【0012】触媒のアルカリ金属塩は、たとえばカリウ
ム、ナトリウムまたはセシウムの塩である。The alkali metal salt of the catalyst is, for example, a potassium, sodium or cesium salt.
【0013】アルカリ土類金属塩は、たとえばカルシウ
ム、マグネシウム、ストロンチウムまたはバリウムの塩
である。The alkaline earth metal salt is, for example, a calcium, magnesium, strontium or barium salt.
【0014】金属塩は500℃以下の低融点を有する、
アルカリ金属、アルカリ土類金属およびニッケルの硝酸
塩、塩化物、酢酸塩、炭酸塩が好ましい。The metal salt has a low melting point of 500 ° C. or less;
Preference is given to nitrates, chlorides, acetates, carbonates of alkali metals, alkaline earth metals and nickel.
【0015】触媒のニッケル含有量はとくに1〜20重
量%が好ましく、アルカリ金属含有量はとくに10重量
%以下、アルカリ土類金属含有量はとくに20重量%以
下が好ましい。The nickel content of the catalyst is particularly preferably 1 to 20% by weight, the alkali metal content is particularly preferably 10% by weight or less, and the alkaline earth metal content is particularly preferably 20% by weight or less.
【0016】以下、本発明を実施例をあげて詳しく説明
するが、これらは本発明の範囲を限定するものではな
い。Hereinafter, the present invention will be described in detail with reference to examples, but these do not limit the scope of the present invention.
【0017】[0017]
〔実施例1〕硝酸ニッケル(融点:56.7℃)、硝酸
カルシウム(融点:39.7℃)および硝酸カリウム
(融点:370℃)を、カリウム:ニッケル:カルシウ
ム=0.08:1.0:3.2のモル比で配合し、高表
面積のペンタシル型のZSM−5構造を有する結晶性ゼ
オライトI(ケイ素/アルミニウムのモル比>500)
に、物理的によく混合した。 アルゴン気流下に、常温
から400℃まで毎分2℃の速度で昇温してすべての硝
酸塩を溶融し、次に酸素気流下に400℃に4時間加熱
して硝酸塩を分解したのち、650℃に昇温してやはり
4時間熱処理して、ゼオライトIに担持されたカルシウ
ム−ニッケル−カルシウム/ゼオライトI(溶融)触媒
を製造した。 製造された触媒の比表面積を、液体窒素
温度でBET法により窒素吸着で測定して得た結果は、
180m2/gであった。Example 1 Nickel nitrate (melting point: 56.7 ° C.), calcium nitrate (melting point: 39.7 ° C.) and potassium nitrate (melting point: 370 ° C.) were converted to potassium: nickel: calcium = 0.08: 1.0: A crystalline zeolite I having a high surface area pentasil-type ZSM-5 structure, compounded at a molar ratio of 3.2 (silicon / aluminum molar ratio> 500)
And physically mixed well. The temperature was raised from room temperature to 400 ° C. at a rate of 2 ° C. per minute under an argon stream to melt all the nitrates, and then heated to 400 ° C. for 4 hours under an oxygen stream to decompose the nitrates. And heated again for 4 hours to produce a calcium-nickel-calcium / zeolite I (melted) catalyst supported on zeolite I. The results obtained by measuring the specific surface area of the produced catalyst by nitrogen adsorption at a liquid nitrogen temperature by the BET method,
It was 180 m 2 / g.
【0018】製造された触媒の活性を測定するため、モ
デル反応として二酸化炭素を使用したメタンの改質反応
に適用した。 すなわち、上記溶融法によって製造され
たカリウム−ニッケル−カルシウム/ゼオライトI触媒
を1/4インチ石英反応器に充填し、水素で前処理した
のち、常圧、700℃、空間速度60,000/Hrの条
件で、二酸化炭素の分圧を0.25気圧、二酸化炭素/
メタンのモル比を1:1に固定して反応させた。 この
反応条件で測定した二酸化炭素およびメタンの転化率と
一酸化炭素および水素の収率は、表1に記載したとおり
である。In order to measure the activity of the produced catalyst, it was applied to a methane reforming reaction using carbon dioxide as a model reaction. That is, the potassium-nickel-calcium / zeolite I catalyst produced by the above-mentioned melting method was filled in a 1/4 inch quartz reactor, pretreated with hydrogen, and then subjected to normal pressure, 700 ° C., space velocity 60,000 / hr. Under the conditions described above, the partial pressure of carbon dioxide is 0.25 atm.
The reaction was carried out with the methane molar ratio fixed at 1: 1. The conversion rates of carbon dioxide and methane and the yields of carbon monoxide and hydrogen measured under these reaction conditions are as described in Table 1.
【0019】〔比較例〕本比較例は、上記実施例1と同
一の成分と組成の触媒を含浸法によって製造するため、
実施例1と同一の金属の硝酸塩を同一の組成で水に溶解
して水溶液をつくり、この水溶液を同じ重さの結晶性ゼ
オライトIを添加して撹拌機により撹拌したのち、電気
ヒータを利用して120℃で水を蒸発させて乾燥し、電
気炉で650℃まで昇温して4時間熱処理して製造し
た。 製造された触媒の比表面積は、上記実施例1と同
一の方法によって測定した結果、181m2/gであっ
た。上記実施例1と同一なモデル反応および同じ条件
で、触媒として含浸法によって製造したカルシウム−ニ
ッケル−カルシウム/ゼオライトI(含浸)触媒を使用
して、実施例1のように触媒活性を比較した。 その反
応の結果は、下記の表1に記載したとおりである。Comparative Example In this comparative example, a catalyst having the same components and composition as in Example 1 was produced by an impregnation method.
A nitrate of the same metal as in Example 1 was dissolved in water with the same composition to form an aqueous solution, and this aqueous solution was added with crystalline zeolite I of the same weight, stirred with a stirrer, and then used with an electric heater. The solution was dried by evaporating water at 120 ° C., heated to 650 ° C. in an electric furnace, and heat-treated for 4 hours. The specific surface area of the produced catalyst was 181 m 2 / g as measured by the same method as in Example 1 above. The catalytic activity was compared as in Example 1 using the calcium-nickel-calcium / zeolite I (impregnated) catalyst prepared by the impregnation method as the catalyst under the same model reaction and the same conditions as in Example 1 above. The results of the reaction are as described in Table 1 below.
【0020】〔実施例2〕本実施例は、実施例1の方法
で製造した触媒を二酸化炭素を使用したメタンの改質反
応に適用して、反応時間による触媒安定度を測定した結
果に関するものである。 反応温度800℃で触媒活性
を測定し、そのほかの条件は実施例1と同一であった。
反応時間による活性は、下記表2に示した。 二酸化
炭素の転化率は93%であって、この値は熱力学的平衡
値に近接したものであり、800℃の高温で140時間
以上反応させたにもかかわらず、触媒活性はほぼ一定に
維持された。 反応後、触媒の重さを測定した結果、コ
ークス形成による重量増加はなく、反応後触媒の形状を
電子顕微鏡により観察した結果、コークスの形成なく、
反応前の形状とほぼ同一であった。Example 2 The present example relates to the results obtained by applying the catalyst produced by the method of Example 1 to a methane reforming reaction using carbon dioxide and measuring the catalyst stability depending on the reaction time. It is. The catalyst activity was measured at a reaction temperature of 800 ° C., and other conditions were the same as in Example 1.
The activity according to the reaction time is shown in Table 2 below. The conversion of carbon dioxide is 93%, which is close to the thermodynamic equilibrium value, and the catalyst activity is maintained almost constant despite the reaction at a high temperature of 800 ° C. for 140 hours or more. Was done. After the reaction, as a result of measuring the weight of the catalyst, there was no weight increase due to coke formation, and as a result of observing the shape of the catalyst after the reaction with an electron microscope, no coke was formed.
The shape was almost the same as before the reaction.
【0021】〔実施例3〕ニッケルの前駆体として硝酸
ニッケルを使用し、マグネシウムの前駆体としてマグネ
シウム硝酸塩(融点:89℃)を使用し、担体として上
記実施例1で使用したものと同一の結晶性ゼオライトI
を使用して、上記実施例1と同一の方法でニッケル含有
量も上記実施例1と同じであり、ニッケルとマグネシウ
ムとがモル比にして1:2.2であるニッケル−マグネ
シウム/ゼオライトI(溶融)触媒を製造した。 上記
実施例1と同一の反応条件で触媒活性を測定し、その結
果を表1に記載した。Example 3 Nickel nitrate was used as a nickel precursor, magnesium nitrate (melting point: 89 ° C.) was used as a magnesium precursor, and the same crystal as that used in Example 1 was used as a carrier. Zeolite I
In the same manner as in Example 1 above, the nickel content was the same as in Example 1, and nickel-magnesium / zeolite I (molar ratio of nickel to magnesium: 1: 2.2) was used. A (melted) catalyst was prepared. The catalyst activity was measured under the same reaction conditions as in Example 1 above, and the results are shown in Table 1.
【0022】〔実施例4〕ニッケルの前駆体として硝酸
ニッケルを用い、担体として上記実施例1で使用したも
のと同一の結晶性ゼオライトIを使用して、上記実施例
1と同一の方法でニッケル含有量も上記実施例1と同一
の、ニッケル/ゼオライトI(溶融)触媒を製造した。
上記実施例1と同一の反応条件で触媒活性を測定し
て、その結果を表1に記載した。Example 4 Nickel nitrate was used as a nickel precursor, and the same crystalline zeolite I used in Example 1 was used as a carrier, and nickel was used in the same manner as in Example 1 above. A nickel / zeolite I (molten) catalyst having the same content as in Example 1 was produced.
The catalyst activity was measured under the same reaction conditions as in Example 1 above, and the results are shown in Table 1.
【0023】〔実施例5〕ニッケルの前駆体として硝酸
ニッケルを用い、担体としてペンタシル型ZSM−5構
造を有する結晶性ゼオライトII(シリコン/アルミニウ
ムのモル比=50)を使用して、上記実施例1と同一の
方法でニッケル含有量も上記実施例1と同じ、ニッケル
/ゼオライトII(溶融)触媒を製造した。 上記実施例
1と同一の反応条件で触媒活性を測定して、その結果を
表1に記載した。Example 5 The above-mentioned Example was carried out using nickel nitrate as a nickel precursor and crystalline zeolite II having a pentasil-type ZSM-5 structure (silicon / aluminum molar ratio = 50) as a carrier. In the same manner as in Example 1, a nickel / zeolite II (melted) catalyst having the same nickel content as in Example 1 was produced. The catalyst activity was measured under the same reaction conditions as in Example 1 above, and the results are shown in Table 1.
【0024】〔実施例6〕ニッケルの前駆体として硝酸
ニッケルを使用し、担体としてペンタシル型ZSM−5
構造を有する結晶性ゼオライトIII(シリコン/アルミ
ニウムのモル比=30)を使用して、上記実施例1と同
一の方法で、ニッケル含有量も上記実施例1と同じであ
る、ニッケル/ゼオライトIII(溶融)触媒を製造した。
上記実施例1と同一の反応条件で触媒活性を測定し
て、その結果を表1に記載した。Example 6 Nickel nitrate was used as a nickel precursor and pentasil type ZSM-5 was used as a carrier.
Using crystalline zeolite III having a structure (silicon / aluminum molar ratio = 30), nickel / zeolite III (nickel content is the same as in Example 1) in the same manner as in Example 1 above. A (melted) catalyst was prepared.
The catalyst activity was measured under the same reaction conditions as in Example 1 above, and the results are shown in Table 1.
【0025】〔実施例7〕ニッケルの前駆体として硝酸
ニッケルを使用し、担体としてシリカを使用して、上記
実施例1と同一の方法でニッケル含有量も上記実施例1
と同一であるニッケル/シリカ(溶融)触媒を製造し
た。 上記実施例1と同一の反応条件で触媒活性を測定
して、その結果を表1に記載した。[Example 7] Using nickel nitrate as a nickel precursor and silica as a carrier, the nickel content was also adjusted in the same manner as in Example 1 above.
A nickel / silica (fused) catalyst identical to was prepared. The catalyst activity was measured under the same reaction conditions as in Example 1 above, and the results are shown in Table 1.
【0026】〔実施例8〕ニッケルの前駆体として硝酸
ニッケルを使用し、担体としてガンマ−アルミナを使用
して、上記実施例1と同一の方法で、ニッケル含有量も
上記実施例1と同一であるニッケル/ガンマ−アルミナ
(溶融)触媒を製造した。 上記実施例1と同一の反応
条件で触媒活性を測定して、その結果を表1に記載し
た。Example 8 Nickel nitrate was used as a nickel precursor, and gamma-alumina was used as a carrier. The nickel content was the same as in Example 1 using the same method as in Example 1. A nickel / gamma-alumina (molten) catalyst was produced. The catalyst activity was measured under the same reaction conditions as in Example 1 above, and the results are shown in Table 1.
【0027】〔実施例9〕上記実施例1で使用したもの
と同一の触媒から、同一の反応条件下で、ただし反応剤
としてメタンと二酸化炭素のほかスチームをスチーム/
メタンの比1/10で添加した場合の反応活性を調査し
た。 その結果、メタンと二酸化炭素転化率がそれぞれ
76%および79%で、一酸化炭素と水素の収率はそれ
ぞれ74%および82%であった。 上記実施例1と比
較すると、二酸化炭素の転化率と水素の収率はそれぞれ
1%と3%の増加をみ、反面、メタンの転化率と一酸化
炭素の収率はそれぞれ3%ずつ減少した。 合成ガス比
(水素/一酸化炭素の比)は1.11であって、上記実
施例1に比較して12%増加した。Example 9 From the same catalyst as used in Example 1 above, under the same reaction conditions, but using methane and carbon dioxide as the reactants and steam /
The reaction activity when methane was added at a ratio of 1/10 was investigated. As a result, the conversion rates of methane and carbon dioxide were 76% and 79%, respectively, and the yields of carbon monoxide and hydrogen were 74% and 82%, respectively. Compared with Example 1, the conversion of carbon dioxide and the yield of hydrogen increased by 1% and 3%, respectively, while the conversion of methane and the yield of carbon monoxide decreased by 3%, respectively. . The synthesis gas ratio (ratio of hydrogen / carbon monoxide) was 1.11, which was 12% higher than that in Example 1 above.
【0028】〔実施例10〕上記実施例1で使用したも
のと同一の触媒から、同一の反応条件下で、ただし反応
剤としてメタンと二酸化炭素のほかに酸素を、酸素/メ
タンの比1/10で添加した場合の反応活性を調査し
た。 その結果は、メタンと二酸化炭素の転化率がそれ
ぞれ80%および66%であり、一酸化炭素と水素の収
率はそれぞれ74%と80%であった。 上記実施例1
と比較すると、メタンの転化率と水素の収率はそれぞれ
れ1%および2%増加し、反面、二酸化炭素の転化率と
一酸化炭素の収率は、それぞれ13%および5%減少し
た。 合成ガス比(水素/一酸化炭素の比)は1.08
であって、上記実施例1に比較して9%増加した。Example 10 From the same catalyst as used in Example 1 above, under the same reaction conditions, except that methane and carbon dioxide were used as the reactants and oxygen / methane ratio 1 / When 10 was added, the reaction activity was investigated. The results showed that the conversions of methane and carbon dioxide were 80% and 66%, respectively, and the yields of carbon monoxide and hydrogen were 74% and 80%, respectively. Example 1 above
Compared to, the conversion of methane and the yield of hydrogen increased by 1% and 2%, respectively, while the conversion of carbon dioxide and the yield of carbon monoxide decreased by 13% and 5%, respectively. The synthesis gas ratio (ratio of hydrogen / carbon monoxide) is 1.08
And increased by 9% as compared with Example 1 described above.
【0029】表1に示したように、常圧、反応温度70
0℃、空間速度60,000/Hrの条件で二酸化炭素を
利用したメタンの改質反応に関して触媒活性を比較する
と、溶融法によってニッケル、カリウム、カルシウムを
ゼオライトI担体に担持したカリウム−ニッケル−カル
シウム/ゼオライトI(溶融)触媒の場合、含浸法によ
って製造したカリウム−ニッケル−カルシウム/ゼオラ
イトI(含浸)触媒に比べて、約20%以上の転化率お
よび収率の向上が観察された。 そして助触媒を添加し
ない溶融法によって製造された種々のニッケル担持触媒
でも、熱力学的平衡値に近接する70〜80%の高いメ
タンおよび二酸化炭素転化率と、水素および一酸化炭素
収率が得られた。 図1に示したように、カリウム−ニ
ッケル−カルシウム/ゼオライトI(溶融)触媒では、
反応温度800℃の高温で140時間以上反応させた場
合にも、コークス生成と触媒活性の低下なく高活性が維
持される結果を得られた。As shown in Table 1, at normal pressure and at a reaction temperature of 70
A comparison of the catalytic activity for the methane reforming reaction using carbon dioxide at 0 ° C. and a space velocity of 60,000 / Hr shows that potassium-nickel-calcium in which nickel, potassium, and calcium are supported on a zeolite I carrier by a melting method. In the case of the / Zeolite I (melted) catalyst, an improvement in conversion and yield of about 20% or more was observed as compared with the potassium-nickel-calcium / Zeolite I (impregnated) catalyst produced by the impregnation method. Also, various nickel-supported catalysts produced by a melting method without the addition of a cocatalyst can obtain high methane and carbon dioxide conversions of 70 to 80% close to the thermodynamic equilibrium value and hydrogen and carbon monoxide yields. Was done. As shown in FIG. 1, for the potassium-nickel-calcium / zeolite I (molten) catalyst,
Even when the reaction was carried out at a high reaction temperature of 800 ° C. for 140 hours or more, a result was obtained in which high activity was maintained without reducing coke generation and catalytic activity.
【0030】 表 1 転化率(%) 収率(%) 区分 触 媒 二酸化 メタン 一酸化 水素 炭 素 炭 素 実施例1 カリウム-ニッケル-カルシウム 79 78 79 78 /ゼオライトI(溶融) 比較例1 カリウム-ニッケル-カルシウム 58 59 59 59 /ゼオライトI(含浸) 実施例3 ニッケル−マグネシウム 69 83 75 76 /ゼオライトI(溶融) 実施例4 ニッケル/ゼオライトI (溶融) 78 78 77 77 実施例5 ニッケル/ゼオライトII (溶融) 77 79 78 78 実施例6 ニッケル/ゼオライトIII(溶融) 68 72 70 71 実施例7 ニッケル/シリカ(溶融) 75 77 76 76 実施例8 ニッケル/ガンマ-アルミナ(溶融) 78 78 72 78
注)一酸化炭素の収率は、反応前装入した二酸化炭素お
よびメタン分圧の和に対して反応により生成した一酸化
炭素の分圧の百分率(%)で示し、水素の収率は、反応
前2倍のメタン分圧に対して生成した水素分圧の百分率
(%)で示した。Table 1 Conversion (%) Yield (%) Category Catalyst Dioxide Methane Hydrogen monoxide Carbon Carbon Example 1 Potassium-nickel-calcium 79 78 79 78 / Zeolite I (melted) Comparative Example 1 Potassium- Nickel-Calcium 58 59 59 59 / Zeolite I (impregnated) Example 3 Nickel-Magnesium 69 83 75 76 / Zeolite I (melted) Example 4 Nickel / Zeolite I (melted) 78 78 77 77 Example 5 Nickel / Zeolite II (Fused) 77 79 78 78 Example 6 Nickel / zeolite III (fused) 68 72 70 71 Example 7 Nickel / silica (fused) 75 77 76 76 Example 8 Nickel / gamma-alumina (fused) 78 78 72 78
Note) The yield of carbon monoxide is shown as a percentage (%) of the partial pressure of carbon monoxide generated by the reaction with respect to the sum of the partial pressures of carbon dioxide and methane charged before the reaction. It is shown as a percentage (%) of the hydrogen partial pressure generated with respect to twice the methane partial pressure before the reaction.
【0031】[0031]
【発明の効果】本発明の溶融法によって製造されたカリ
ウム−ニッケル−カルシウム/ペンタシル型ゼオライト
触媒が、溶融法および含浸法によって製造されたニッケ
ル/ペンタシル型ゼオライト触媒、および含浸法によっ
て製造されたカリウム−ニッケル−カルシウム/ペンタ
シル型ゼオライト触媒にくらべてより高い活性を示した
理由は、溶融工程によって、カリウム、ニッケル、カル
シウム間の相互作用および金属成分の担体中のケイ素と
の相互作用が高まり、また助触媒として使用したアルカ
リ金属およびアルカリ土類金属の助触媒が二酸化炭素の
親和度を高めるからであると推定される。The potassium-nickel-calcium / pentasil-type zeolite catalyst produced by the melting method of the present invention is a nickel / pentasil-type zeolite catalyst produced by the melting method and the impregnation method, and the potassium produced by the impregnation method. The higher activity compared to the nickel-calcium / pentasil type zeolite catalysts is due to the increased interaction between potassium, nickel and calcium and the interaction of the metal component with silicon in the support due to the melting process; It is presumed that the alkali metal and alkaline earth metal promoters used as promoters increase the affinity of carbon dioxide.
【図1】 本発明のデータであって、実施例10の触媒
を反応に使用したときの、反応時間と二酸化炭素の転化
率との関係を示すグラフ。FIG. 1 is a graph showing the relationship between the reaction time and the conversion of carbon dioxide when the catalyst of Example 10 is used in the reaction, which is data of the present invention.
Claims (11)
要ならアルカリ金属塩および(または)アルカリ土類金
属塩を、ゼオライト、シリカ、ガンマ−アルミナ、シリ
ケートおよびシリカ−アルミナからえらんだ、表面積1
00m2/g以上の担体に常温で物理的に混合する段階、
上記塩類の溶融点以上の一定の温度に加熱してすべての
塩類を溶融しながら金属塩を分解する段階、および30
0〜1200℃の温度範囲で焼成する段階からなる、二
酸化炭素、水蒸気、酸素等を酸化剤として利用する炭化
水素改質反応のニッケル担持触媒を製造する方法。1. The method according to claim 1, wherein the nickel salt having a low melting point of 100 ° C. or less and the alkali metal salt and / or the alkaline earth metal salt are selected from zeolite, silica, gamma-alumina, silicate and silica-alumina.
Physically mixing at room temperature with a carrier of at least 00 m 2 / g,
Heating to a certain temperature above the melting point of the salts to decompose the metal salts while melting all the salts;
A method for producing a nickel-supported catalyst for a hydrocarbon reforming reaction using carbon dioxide, water vapor, oxygen or the like as an oxidizing agent, comprising a step of firing at a temperature range of 0 to 1200 ° C.
ールミル等を利用して均一に磨砕することにより行なう
ことを特徴とする請求項1に記載のニッケル担持触媒の
製造方法。2. The method for producing a nickel-supported catalyst according to claim 1, wherein the mixing of the metal salt and the carrier is performed by uniformly grinding using a mortar or a ball mill.
属塩の溶融点以上、とくに100℃ないし400℃の範
囲で実施することを特徴とする請求項1に記載のニッケ
ル担持触媒の製造方法。3. The method for producing a nickel-supported catalyst according to claim 1, wherein the step of melting and decomposing the metal salt is carried out at a temperature higher than the melting point of the metal salt, particularly in the range of 100 ° C. to 400 ° C. .
し、構造内のアルミニウム対ケイ素の含有量がモル比に
して0〜1.0であることを特徴とする請求項1に記載
のニッケル担持触媒の製造方法。4. The nickel-supported catalyst according to claim 1, wherein the zeolite support has a pentasil-type structure, and the content of aluminum to silicon in the structure is 0 to 1.0 in a molar ratio. Manufacturing method.
ナトリウムまたはセシウムであることを特徴とする請求
項1に記載のニッケル担持触媒の製造方法。5. The catalyst according to claim 1, wherein the alkali metal component of the catalyst is potassium,
The method for producing a nickel-supported catalyst according to claim 1, wherein the catalyst is sodium or cesium.
ム、マグネシウム、ストロンチウムまたはバリウムであ
ることを特徴とする請求項1に記載のニッケル担持触媒
の製造方法。6. The method for producing a nickel-supported catalyst according to claim 1, wherein the alkaline earth metal salt of the catalyst is calcium, magnesium, strontium or barium.
る、アルカリ金属、アルカリ土類金属およびニッケル
の、硝酸塩、塩化物、酢酸塩および炭酸塩からえらんだ
ものであることを特徴とする請求項1に記載のニッケル
担持触媒の製造方法。7. The method according to claim 1, wherein the metal salt is selected from nitrates, chlorides, acetates and carbonates of alkali metals, alkaline earth metals and nickel having a low melting point of 500 ° C. or lower. Item 4. A method for producing a nickel-supported catalyst according to Item 1.
であることを特徴とする請求項1に記載のニッケル担持
触媒の製造方法。8. The catalyst has a nickel content of 1 to 20% by weight.
The method for producing a nickel-supported catalyst according to claim 1, wherein:
量%であることを特徴とする請求項1に記載のニッケル
担持触媒の製造方法。9. The method according to claim 1, wherein the alkali metal content of the catalyst is 0 to 10% by weight.
20重量%であることを特徴とする請求項1に記載のニ
ッケル担持触媒の製造方法。10. An alkaline earth metal content of the catalyst of 0 to 10.
The method for producing a nickel-supported catalyst according to claim 1, wherein the amount is 20% by weight.
必要ならアルカリ金属塩および(または)アルカリ土類
金属塩を、ゼオライト、シリカ、ガンマ−アルミナ、シ
リケートおよびシリカ−アルミナからえらんだ、表面積
100m2/g以上の担体と常温で物理的に混合し、混合
物を上記塩類の溶融点以上の一定の温度に加熱してすべ
ての塩類を溶融しながら金属塩を分解し、ついでおよび
300〜1200℃の温度範囲で焼成して製造された、
二酸化炭素、水蒸気、酸素等を酸化剤として利用する炭
化水素改質反応用のニッケル担持触媒。11. A low melting point nickel salt of less than 100 ° C. and, if necessary, an alkali metal salt and / or an alkaline earth metal salt, selected from zeolite, silica, gamma-alumina, silicate and silica-alumina, having a surface area of 100 m 2. 2 / g or more of the carrier is physically mixed at room temperature, and the mixture is heated to a certain temperature above the melting point of the above salts to decompose the metal salts while melting all the salts, and then at 300 to 1200 ° C. Manufactured by firing in the temperature range of
Nickel-supported catalyst for hydrocarbon reforming reactions using carbon dioxide, steam, oxygen, etc. as oxidants.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1994-3644 | 1994-02-26 | ||
KR1019940003644A KR0132012B1 (en) | 1994-02-26 | 1994-02-26 | Preparation of hydrocarbon reforming catalyst |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH07275711A JPH07275711A (en) | 1995-10-24 |
JP2914206B2 true JP2914206B2 (en) | 1999-06-28 |
Family
ID=19377919
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP7037436A Expired - Lifetime JP2914206B2 (en) | 1994-02-26 | 1995-02-24 | Nickel-supported catalyst for hydrocarbon reforming and method for producing the same |
Country Status (2)
Country | Link |
---|---|
JP (1) | JP2914206B2 (en) |
KR (1) | KR0132012B1 (en) |
Families Citing this family (7)
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---|---|---|---|---|
KR100406363B1 (en) * | 1998-12-11 | 2004-01-24 | 주식회사 포스코 | A method for preparation of nickel-alumina catalyst, a nickel-alumina catalyst prepared thereby and a method for refor ming carbon dioxide with methan by using the same |
KR20040017491A (en) * | 2002-08-21 | 2004-02-27 | 에스케이 주식회사 | Method for preparing synthesis gas from dimethyl ether |
KR100711349B1 (en) * | 2005-06-17 | 2007-04-27 | 한국가스공사 | Manufacturing method for syngas using tri-reforming reaction |
KR100963778B1 (en) * | 2008-07-25 | 2010-06-14 | 현대제철 주식회사 | Manufacture method of catalyst for the carbon dioxide reforming of methane, and its reforming reaction |
KR101317723B1 (en) * | 2011-07-28 | 2013-10-15 | 한국에너지기술연구원 | Manufacturing method for metal or metal oxide catalyst support using melt-infiltration process of metal hydrate salt and metal or metal oxide catalyst support thereof |
KR102408100B1 (en) * | 2021-05-31 | 2022-06-15 | 충북대학교 산학협력단 | Synthesis method of 2-dimensional Nickel silicate molecular sieve catalyst for dry reforming of methane and 2-dimensional Nickel silicate molecular sieve catalyst for dry reforming of methane made thereby |
CN115282975B (en) * | 2022-07-29 | 2024-02-20 | 东南大学 | Catalyst suitable for wet reforming of methane, preparation method, reduction method and application method |
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-
1994
- 1994-02-26 KR KR1019940003644A patent/KR0132012B1/en not_active IP Right Cessation
-
1995
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KR0132012B1 (en) | 1998-04-08 |
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