JPH0938490A - Method for producing ethylene - Google Patents
Method for producing ethyleneInfo
- Publication number
- JPH0938490A JPH0938490A JP7190185A JP19018595A JPH0938490A JP H0938490 A JPH0938490 A JP H0938490A JP 7190185 A JP7190185 A JP 7190185A JP 19018595 A JP19018595 A JP 19018595A JP H0938490 A JPH0938490 A JP H0938490A
- Authority
- JP
- Japan
- Prior art keywords
- ethane
- ethylene
- catalyst
- reaction
- oxide
- 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
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
(57)【要約】
【課題】反応ガス中のエタン濃度を１０％以上とし且つ
エタン転化率を１％以上としても、エチレンの選択率が
６０％を上回る新たなエチレンの製造技術を提供するこ
とを主な目的とする。
【解決手段】（１）ＳｎとＷとを含む酸化物を触媒活性
成分とすることを特徴とする、エタンの酸化によるエチ
レン製造用触媒。
（２）ＳｎとＷとを含む酸化物触媒の存在下にエタンと
酸素とを反応させることを特徴とするエチレンの製造方
法。(57) Abstract: To provide a new ethylene production technology in which the selectivity of ethylene exceeds 60% even when the ethane concentration in the reaction gas is 10% or more and the ethane conversion rate is 1% or more. Is the main purpose. SOLUTION: (1) A catalyst for ethylene production by oxidizing ethane, which comprises an oxide containing Sn and W as a catalytically active component. (2) A method for producing ethylene, which comprises reacting ethane with oxygen in the presence of an oxide catalyst containing Sn and W.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、エタンと酸素とを
反応させてエチレンを製造する方法に関する。TECHNICAL FIELD The present invention relates to a method for producing ethylene by reacting ethane with oxygen.
【０００２】[0002]
【従来の技術】エチレンは、有機化学製品の約４割の原
料となる基幹化学原料である。飽和炭化水素であるエタ
ンを化学原料として利用するためには、まずエチレンに
転換する必要がある。この場合、エタンを酸素と反応さ
せて直接エチレンを製造することができれば、簡便で望
ましい。しかしながら、エタンと酸素との反応において
は、通常燃焼反応が優先して起こり、ＣＯ2（炭酸ガ
ス）およびＣＯ（一酸化炭素）が形成される。2. Description of the Related Art Ethylene is a basic chemical raw material which is a raw material for about 40% of organic chemical products. In order to use ethane, which is a saturated hydrocarbon, as a chemical raw material, it is necessary to first convert it into ethylene. In this case, it is convenient and desirable if ethylene can be directly produced by reacting ethane with oxygen. However, in the reaction between ethane and oxygen, the combustion reaction usually takes precedence and CO 2 (carbon dioxide gas) and CO (carbon monoxide) are formed.
【０００３】これまでにも、Ｖを含む複合酸化物が、エ
タンからエチレンを直接製造する触媒として報告されて
いる（小安、PETROTECH、1994）。しかしながら、この
方法では、反応ガス中のエタン濃度を１０％以上とし、
エタン転化率を１％以上にすれば、エチレンの選択率が
６０％以下となってしまうため、実用化には適していな
い。So far, a complex oxide containing V has been reported as a catalyst for directly producing ethylene from ethane (Oyasu, PETROTECH, 1994). However, in this method, the ethane concentration in the reaction gas is set to 10% or more,
If the ethane conversion is 1% or more, the ethylene selectivity is 60% or less, which is not suitable for practical use.
【０００４】[0004]
【発明が解決しようとする課題】従って、本発明は、反
応ガス中のエタン濃度を１０％以上とし且つエタン転化
率を１％以上としても、エチレンの選択率が６０％を上
回る新たなエチレンの製造技術を提供することを主な目
的とする。Therefore, according to the present invention, even if the ethane concentration in the reaction gas is 10% or more and the ethane conversion rate is 1% or more, a new ethylene having ethylene selectivity of more than 60% is obtained. Its main purpose is to provide manufacturing technology.
【０００５】[0005]
【課題を解決するための手段】本発明者は、上記のよう
な課題を解決するために研究を進めた結果、（イ）Ｓｎ
がエタンの酸化反応において、低温域（300〜400℃）か
ら反応活性を示すこと、（ロ）しかしながら、Ｓｎを用
いたエタンの酸化反応では、二酸化炭素が主生成物とな
ること、（ハ）これに対し、Ｗを用いたエタンの酸化反
応では、エチレンが主生成物となること、（ニ）低温域
で反応活性を示すＳｎとエチレン選択性の高いＷとを組
み合わせた触媒が、エタンの酸化反応において比較的穏
和な条件下でも高い活性を示し、エチレンの選択性も高
く、且つ高い活性を長時間維持することなどを見出し
た。The present inventor has conducted research to solve the above-mentioned problems, and as a result, (a) Sn
Shows reaction activity in a low temperature range (300 to 400 ° C.) in the ethane oxidation reaction, (b) However, carbon dioxide becomes a main product in the ethane oxidation reaction using Sn, (c) On the other hand, in the ethane oxidation reaction using W, ethylene is the main product, and (d) a catalyst that combines Sn exhibiting reaction activity in a low temperature range and W having high ethylene selectivity It was found that the oxidation reaction shows a high activity even under relatively mild conditions, the selectivity of ethylene is high, and the high activity is maintained for a long time.
【０００６】本発明は、上記のような新たな知見に基づ
いて完成されたものであり、下記のエチレン製造用触媒
及びエチレン製造方法を提供するものである； １．ＳｎとＷとを含む酸化物を触媒活性成分とすること
を特徴とする、エタンの酸化によるエチレン製造用触
媒。The present invention has been completed based on the above new findings, and provides the following ethylene production catalyst and ethylene production method; A catalyst for ethylene production by oxidation of ethane, which comprises an oxide containing Sn and W as a catalytically active component.
【０００７】２．触媒活性成分が、ＳｎとＷとをＳｎ：
Ｗ＝１〜９９：９９〜１（原子比）の割合で含む上記項
１に記載のエタンの酸化によるエチレン製造用触媒。[0007] 2. The catalytically active component converts Sn and W into Sn:
The catalyst for ethylene production by the oxidation of ethane described in the above item 1, which comprises W = 1 to 99:99 to 1 (atomic ratio).
【０００８】３．ＳｎとＷとを含む酸化物触媒の存在下
にエタンと酸素とを反応させることを特徴とするエチレ
ンの製造方法。[0008] 3. A process for producing ethylene, which comprises reacting ethane with oxygen in the presence of an oxide catalyst containing Sn and W.
【０００９】４．アルミナ、シリカ、チタニア、マグネ
シア、ジルコニアおよびゼオライトの少なくとも１種か
らなる担体にＳｎとＷとを含む酸化物からなる触媒活性
成分を担持させて使用する上記項３に記載のエチレンの
製造方法。4. Item 4. The method for producing ethylene according to Item 3, wherein a carrier comprising at least one of alumina, silica, titania, magnesia, zirconia, and zeolite is loaded with a catalytically active component made of an oxide containing Sn and W, and used.
【００１０】本発明におけるエチレンの生成反応は次式
で示される。The reaction for producing ethylene in the present invention is represented by the following formula.
【００１１】Ｃ2Ｈ6＋1/2Ｏ2→Ｃ2Ｈ4＋Ｈ2Ｏ ＳｎおよびＷは、それぞれ各種の触媒における助触媒と
して用いられた例はあるが、両者が触媒活性成分として
併用された例は知られていないし、併用した場合にどの
ような効果が達成されるかも、全く予想し得ないところ
である。C 2 H 6 + 1 / 2O 2 → C 2 H 4 + H 2 O Sn and W have been used as cocatalysts in various catalysts, but they are used as catalytically active components. Is unknown, and it is completely unpredictable what kind of effect will be achieved when used together.
【００１２】[0012]
【発明の実施の形態】Ｉ．触媒の調製方法 本発明で用いるＳｎ−Ｗ触媒は、例えば、ＷＯ3粉末に
エチルヘキサンスズ、硫酸スズ、塩化スズ、酢酸スズな
どのスズ源となる材料の溶液を含浸させ、乾燥した後、
焼成することにより、調製することができる。或いは、
逆にＳｎＯ2粉末にタングステン酸アンモニウム、燐タ
ングステン酸などのタングステン源となる材料の溶液を
含浸させ、乾燥した後、焼成して調製してもよい。BEST MODE FOR CARRYING OUT THE INVENTION I. Method for Preparing Catalyst The Sn—W catalyst used in the present invention is, for example, WO 3 powder impregnated with a solution of a material serving as a tin source such as ethylhexanetin, tin sulfate, tin chloride, tin acetate, and after drying,
It can be prepared by firing. Alternatively,
Conversely, SnO 2 powder may be impregnated with a solution of a material serving as a tungsten source, such as ammonium tungstate or phosphotungstic acid, dried, and then calcined.
【００１３】さらにまた、本発明においては、Ｓｎ−Ｗ
触媒をアルミナ、シリカ、チタニア、マグネシア、ジル
コニアおよびゼオライトの少なくとも１種からなる担体
に担持させた状態で使用することもできる。この場合に
は、触媒担体にスズを含む溶液を含浸させ、乾燥した後
焼成し、次いでタングステンを含む溶液を含浸させ、乾
燥した後焼成することにより、調製することが出来る。
或いは、触媒担体にタングステンを含む溶液を含浸さ
せ、乾燥した後焼成し、次いでスズを含む溶液を含浸さ
せ、乾燥した後焼成して、調製してもよい。本発明によ
る触媒中のＳｎ：Ｗの原子比は、通常Ｓｎ：Ｗ＝１：９
９〜９９：１である。Furthermore, in the present invention, Sn-W
The catalyst can also be used in a state of being supported on a carrier composed of at least one of alumina, silica, titania, magnesia, zirconia and zeolite. In this case, it can be prepared by impregnating a catalyst carrier with a solution containing tin, drying and firing, then impregnating a solution containing tungsten, drying and firing.
Alternatively, the catalyst carrier may be impregnated with a solution containing tungsten, dried and then calcined, then impregnated with a solution containing tin, dried, and calcined. The atomic ratio Sn: W in the catalyst according to the invention is usually Sn: W = 1: 9.
9-99: 1.
【００１４】ＩＩ．反応操作 本発明においては、エタンと酸素とを気相で触媒に接触
させることにより、エチレンを製造することができる。
反応方式については、特に限定はなく、例えば、触媒を
充填した反応装置に原料ガス（エタンおよび酸素）を導
入して、エチレンを製造する固定床流通方式でもよい。
反応は、窒素、Ｈｅ、Ａｒなどの不活性ガスの存在下に
行うことが好ましい。反応原料を希釈することにより、
反応温度の抑制、万一の場合の爆発防止などの効果が達
成される。特に、局所的な反応温度の上昇を抑制するこ
とにより、副反応の増加によるエチレン選択率の低下が
防止され、また触媒の急速な劣化も抑制される。不活性
ガスとしては、コストなどの点で、窒素がより好まし
い。 II. Reaction Operation In the present invention, ethylene can be produced by bringing ethane and oxygen into contact with the catalyst in the gas phase.
The reaction system is not particularly limited, and may be, for example, a fixed bed flow system in which a raw material gas (ethane and oxygen) is introduced into a reactor filled with a catalyst to produce ethylene.
The reaction is preferably carried out in the presence of an inert gas such as nitrogen, He or Ar. By diluting the reaction raw materials,
Effects such as suppression of reaction temperature and prevention of explosion in case of emergency are achieved. In particular, by suppressing the local increase in the reaction temperature, a decrease in ethylene selectivity due to an increase in side reactions is prevented, and rapid deterioration of the catalyst is also suppressed. Nitrogen is more preferable as the inert gas in terms of cost and the like.
【００１５】また、反応条件についても特に限定はない
が、一般に、反応温度200℃〜800℃程度、より好ましく
は350℃〜700℃程度、特に好ましくは400℃〜600℃程度
とし、反応圧力は常圧付近とするのがよい。また、固定
床流通方式でエチレンを製造する場合の原料ガスの流通
速度は、特に限定されないが、反応装置への触媒の充填
密度を考慮した空間速度（SV）で1000〜100000ml/g・ca
t/hr程度、より好ましくは5000〜50000ml/g・cat/hr程
度とするのがよい。なお、一般に空間速度を高くしすぎ
ると、エタンの転化率が低下する傾向があるので、留意
する必要がある。The reaction conditions are not particularly limited, but generally the reaction temperature is about 200 ° C to 800 ° C, more preferably about 350 ° C to 700 ° C, particularly preferably about 400 ° C to 600 ° C, and the reaction pressure is It is recommended that the pressure be around normal pressure. In addition, the flow rate of the raw material gas in the case of producing ethylene by the fixed bed flow method is not particularly limited, but the space velocity (SV) considering the packing density of the catalyst in the reactor is 1000 to 100000 ml / g · ca.
It is preferably about t / hr, more preferably about 5000 to 50000 ml / g · cat / hr. It should be noted that generally, if the space velocity is too high, the conversion rate of ethane tends to decrease.
【００１６】原料として使用するエタンと酸素との使用
割合は、特に限定されないが、両者の合計を100容量部
として、通常エタン：酸素＝50〜95：50〜5程度、より
好ましくは70〜85：30〜15程度、特に好ましくは80：20
程度とするのがよい。不活性ガスを使用する場合には、
エタンと酸素の合計容量と同容量程度を添加することが
好ましい。The use ratio of ethane and oxygen used as raw materials is not particularly limited, but the total amount of both is 100 parts by volume, and usually ethane: oxygen = 50-95: 50-5, more preferably 70-85. : About 30 to 15, particularly preferably 80:20
It is good to set the degree. When using an inert gas,
It is preferable to add about the same volume as the total volume of ethane and oxygen.
【００１７】本発明において、エタンからエチレンを製
造する触媒は、ＳｎとＷとを活性成分とする酸化物であ
る。Ｓｎは、エタンの酸化反応において、低温域（300
〜400℃程度）から反応活性を発揮するが、二酸化炭素
が主生成物となるのに対し、Ｗはエタンの酸化反応にお
いて600℃以上の高温域でしか活性を発揮しないが、エ
チレンが主生成物となる。しかるに、この様な低温域で
活性のあるＳｎとエチレン選択性の高いＷとを組み合わ
せる場合には、両成分が互いに他の成分の特性を阻害す
ることなく、それぞれの特性を高度に発揮して、エタン
の酸化反応に際し、比較的穏和な条件下でも高い活性を
示し、エチレンの選択性をも高める。また、長時間反応
を行った場合にも、触媒表面上に炭素の析出がなく、構
造が安定しているため、高い触媒活性を長時間にわたり
維持し続ける。In the present invention, the catalyst for producing ethylene from ethane is an oxide containing Sn and W as active components. Sn is a low temperature region (300
Approximately 400 ℃), but the main product is carbon dioxide, while W is active only in the high temperature range of 600 ℃ or higher in the oxidation reaction of ethane, but ethylene is the main product. It becomes a thing. However, when combining Sn that is active in such a low temperature range and W that has a high ethylene selectivity, both components exhibit their respective properties to a high degree without interfering with the properties of the other components. In the oxidation reaction of ethane, it exhibits high activity even under relatively mild conditions, and also enhances the selectivity of ethylene. Further, even when the reaction is carried out for a long time, no carbon is deposited on the catalyst surface and the structure is stable, so that high catalytic activity is continuously maintained for a long time.
【００１８】[0018]
【発明の効果】本発明による触媒の存在下にエタンの酸
化を行う場合には、比較的穏和な条件下で且つ高速反応
条件下でも高い転化率を示し、且つ長時間高い触媒活性
を維持できるので、本発明によれば、エタンから効率よ
くエチレンを製造することがでWhen ethane is oxidized in the presence of the catalyst according to the present invention, it exhibits a high conversion rate under a relatively mild condition and a fast reaction condition, and can maintain a high catalytic activity for a long time. Therefore, according to the present invention, ethylene can be efficiently produced from ethane.
【００１９】きる。[OK]
実施例１ 本発明によるＳｎ−Ｗ系酸化物触媒（Ｓｎ:Ｗ＝4.6:95.
4）を調製した。すなわち、ＷＯ3粉末110.6グラムに0.5
mol/l酢酸スズ水溶液46mlを含浸させ、エバポレーター
で乾燥した後、700℃で3時間焼成して、Ｓｎ−Ｗ系酸化
物触媒を調製した。Example 1 Sn-W based oxide catalyst according to the present invention (Sn: W = 4.6: 95.
4) was prepared. That is, 0.5 to 110.6 grams of WO 3 powder
46 ml of a mol / l tin acetate aqueous solution was impregnated, dried with an evaporator, and then calcined at 700 ° C. for 3 hours to prepare a Sn—W oxide catalyst.
【００２０】一方、触媒のＳｎ／Ｗの原子比を考慮しつ
つ、同様の手法により、ＳｎＯ2粉末にタングステン酸
アンモニウム水溶液を含浸させ、乾燥し、焼成して、Ｗ
−Ｓｎ系酸化物触媒を調製した。On the other hand, in consideration of the Sn / W atomic ratio of the catalyst, SnO 2 powder is impregnated with an ammonium tungstate aqueous solution by the same method, dried and baked to obtain W.
A -Sn-based oxide catalyst was prepared.
【００２１】調製した触媒0.2グラムを内径8mmの石英ガ
ラス製反応管に充填し、流通反応装置にセットした。原
料ガス（Ｃ2Ｈ6：Ｏ2：Ｎ2＝40：10：50）を常圧下、SV
=15000ml/g・cat/hrで供給した場合のエタンの反応結果
を表１に示す。生成物の分析はオンラインガスクロマト
グラフにより行った。酸化物触媒組成の（）内の数値
は、酸化物中のＳｎおよびＷの原子％を示す。0.2 g of the prepared catalyst was filled in a quartz glass reaction tube having an inner diameter of 8 mm and set in a flow reactor. SV of raw material gas (C 2 H 6 : O 2 : N 2 = 40: 10: 50) under normal pressure
Table 1 shows the reaction results of ethane when supplied at = 15000 ml / g · cat / hr. The analysis of the product was performed by an online gas chromatograph. The values in parentheses in the oxide catalyst composition indicate atomic% of Sn and W in the oxide.
【００２２】実施例２ 反応時のSVを3000ml/g・cat/hrとする以外は実施例１と
同様にしてエタンの酸化によるエチレンの製造を行っ
た。結果を表１に併せて示す。Example 2 Ethylene was produced by oxidizing ethane in the same manner as in Example 1 except that the SV during the reaction was 3000 ml / g.cat / hr. The results are shown in Table 1.
【００２３】[0023]
【表１】 [Table 1]
【００２４】通常、炭化水素の酸化的脱水素反応におい
ては、反応温度が上昇すると、燃焼反応が優先して起こ
り、所望の生成物の選択率が低下する傾向が顕著とな
る。しかしながら、表１に示す実施例１についての結果
から明かな様に、本発明によれば、反応温度が高くなっ
て転化率が上昇しても、エチレン選択率は余り変化しな
いという特異な現象が認められる。Usually, in the oxidative dehydrogenation reaction of hydrocarbons, when the reaction temperature rises, the combustion reaction occurs preferentially, and the selectivity of the desired product tends to decrease. However, as is clear from the results of Example 1 shown in Table 1, according to the present invention, there is a peculiar phenomenon that the ethylene selectivity does not change much even when the reaction temperature rises and the conversion rate increases. Is recognized.
【００２５】また、同一組成の触媒（Ｗ：Ｓｎ＝２２：
７８）を使用する実施例１と実施例２の結果を対比すれ
ば、触媒との接触時間が長くても、エチレン選択率には
あまり影響がないことが明かである。Further, a catalyst having the same composition (W: Sn = 22:
By comparing the results of Example 1 and Example 2 in which 78) is used, it is clear that a long contact time with the catalyst does not significantly affect the ethylene selectivity.
【００２６】実施例２ 本発明によるＳｎ−Ｗ系触媒をシリカに担持した場合の
活性を表２に示す。Example 2 Table 2 shows the activity of the Sn-W catalyst according to the present invention supported on silica.
【００２７】これらの触媒は、触媒のＳｎ／Ｗの原子比
を考慮しつつ、ＳｉＯ2粉末に所定量比の酢酸スズ水溶
液とタングステン酸アンモニウム水溶液とを含浸させ、
エバポレーターで乾燥した後、700℃で3時間焼成して調
製した。次いでSV=6000ml/g・cat/hｒとする以外は実施
例１と同じ条件下にエタンの酸化反応を行った。結果を
表２に示す。酸化物触媒組成の（）内の数値は、酸化物
中のＳｎ、ＷおよびＳｉの原子％を示す。In these catalysts, SiO 2 powder is impregnated with a tin acetate aqueous solution and an ammonium tungstate aqueous solution at a predetermined ratio while taking into consideration the Sn / W atomic ratio of the catalyst,
After drying with an evaporator, it was calcined at 700 ° C. for 3 hours to prepare. Then, the ethane oxidation reaction was carried out under the same conditions as in Example 1 except that SV = 6000 ml / g.cat / hr. Table 2 shows the results. The values in parentheses in the oxide catalyst composition indicate atomic% of Sn, W and Si in the oxide.
【００２８】[0028]
【表２】 [Table 2]
【００２９】表２に示す結果からも、実施例１と同様
に、反応温度が高くなって転化率が上昇しても、エチレ
ン選択率は余り変化しないという特異な現象が認められ
る。From the results shown in Table 2, as in Example 1, a peculiar phenomenon that the ethylene selectivity does not change much even when the reaction temperature rises and the conversion rate increases is recognized.
【００３０】実施例３ 実施例１と同様にして調製したＳｎ−Ｗ系酸化物触媒
（Ｓｎ：Ｗ＝22：78）の耐久性を調べるために、原料ガ
ス（Ｃ2Ｈ6：Ｏ2：Ｎ2＝40：10：50）を常圧下、温度55
0℃、SV=15000ml/g・cat/hrで酸化反応に供し、所定時
間経過後の転化率およびエチレン選択率を測定した。そ
の結果を表３に示す。Example 3 In order to examine the durability of the Sn-W type oxide catalyst (Sn: W = 22: 78) prepared in the same manner as in Example 1, a raw material gas (C 2 H 6 : O 2 :) was used. N 2 = 40: 10: 50) under normal pressure, temperature 55
It was subjected to an oxidation reaction at 0 ° C. and SV = 15000 ml / g · cat / hr, and the conversion and ethylene selectivity were measured after a lapse of a predetermined time. Table 3 shows the results.
【００３１】[0031]
【表３】 [Table 3]
【００３２】表３に示す結果から、本発明によるＳｎ−
Ｗ系酸化物触媒が耐久性に優れていることが明かであ
る。From the results shown in Table 3, Sn-according to the present invention was obtained.
It is clear that the W-based oxide catalyst has excellent durability.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成８年１月１１日[Submission date] January 11, 1996
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１８[Correction target item name] 0018
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１８】[0018]
【発明の効果】本発明による触媒の存在下にエタンの酸
化を行う場合には、比較的穏和な条件下で且つ高速反応
条件下でも高い転化率を示し、且つ長時間高い触媒活性
を維持できるので、本発明によれば、エタンから効率よ
くエチレンを製造することができる。 When ethane is oxidized in the presence of the catalyst according to the present invention, it exhibits a high conversion rate under a relatively mild condition and a fast reaction condition, and can maintain a high catalytic activity for a long time. since, according to the present invention, as possible out to produce efficiently ethylene from ethane.
【手続補正２】[Procedure amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１９[Correction target item name] 0019
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１９】 [0019]
【 実施例】 実施例１ 本発明によるＳｎ−Ｗ系酸化物触媒（Ｓｎ:Ｗ＝4.6:95.
4）を調製した。すなわち、ＷＯ3粉末110.6グラムに0.5
mol/l酢酸スズ水溶液46mlを含浸させ、エバポレーター
で乾燥した後、700℃で3時間焼成して、Ｓｎ−Ｗ系酸化
物触媒を調製した。 EXAMPLES Sn-W-based oxide catalyst according to Example 1 the invention (Sn: W = 4.6: 95 .
4) was prepared. That is, 0.5 to 110.6 grams of WO 3 powder
46 ml of a mol / l tin acetate aqueous solution was impregnated, dried with an evaporator, and then calcined at 700 ° C. for 3 hours to prepare a Sn—W oxide catalyst.
【手続補正３】[Procedure 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２０[Correction target item name] 0020
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００２０】一方、触媒のＳｎ／Ｗの原子比を考慮しつ
つ、同様の手法により、ＳｎＯ2粉末にタングステン酸
アンモニウム水溶液を含浸させ、乾燥し、焼成して、Ｗ
−Ｓｎ系酸化物触媒を調製した。On the other hand, in consideration of the Sn / W atomic ratio of the catalyst, SnO 2 powder is impregnated with an ammonium tungstate aqueous solution by the same method, dried and baked to obtain W.
The -Sn based oxides catalysts were prepared.
【手続補正４】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２６[Correction target item name] 0026
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００２６】実施例３ 本発明によるＳｎ−Ｗ系触媒をシリカに担持した場合の
活性を表２に示す。Example 3 Table 2 shows the activity of the Sn-W catalyst according to the present invention supported on silica.
【手続補正５】[Procedure Amendment 5]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００３０[Correction target item name] 0030
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００３０】実施例４ 実施例１と同様にして調製したＳｎ−Ｗ系酸化物触媒
（Ｓｎ：Ｗ＝22：78）の耐久性を調べるために、原料ガ
ス（Ｃ2Ｈ6：Ｏ2：Ｎ2＝40：10：50）を常圧下、温度55
0℃、SV=15000ml/g・cat/hrで酸化反応に供し、所定時
間経過後の転化率およびエチレン選択率を測定した。そ
の結果を表３に示す。Example 4 In order to investigate the durability of the Sn-W type oxide catalyst (Sn: W = 22: 78) prepared in the same manner as in Example 1, a raw material gas (C 2 H 6 : O 2 :) was used. N 2 = 40: 10: 50) under normal pressure, temperature 55
It was subjected to an oxidation reaction at 0 ° C. and SV = 15000 ml / g · cat / hr, and the conversion and ethylene selectivity were measured after a lapse of a predetermined time. Table 3 shows the results.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 春田 正毅 大阪府池田市緑丘１丁目８番31号 工業技 術院大阪工業技術研究所内 (72)発明者 中原 佳子 京都府相楽郡木津町木津川台９丁目２番地 財団法人地球環境産業技術研究機構内 (72)発明者 安藤 尚功 京都府相楽郡木津町木津川台９丁目２番地 財団法人地球環境産業技術研究機構内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Masatake Haruta, 8-83 Midorigaoka, Ikeda, Osaka Prefecture, Osaka Institute of Industrial Technology (72) Inventor, Keiko Nakahara, Kizugawadai, Kizu-cho, Soraku-gun, Kyoto Prefecture 2-chome, Institute for Global Environmental Technology (72) Inventor Naoko Ando 9-2, Kizugawadai, Kizu-cho, Soraku-gun, Kyoto Prefectural Institute for Global Environmental Technology
Claims (4)
することを特徴とする、エタンの酸化によるエチレン製
造用触媒。1. A catalyst for ethylene production by oxidation of ethane, which comprises an oxide containing Sn and W as a catalytically active component.
１〜９９：９９〜１（原子比）の割合で含む請求項１に
記載のエタンの酸化によるエチレン製造用触媒。2. The catalytically active component comprises Sn and W as Sn: W =
The catalyst for ethylene production by oxidation of ethane according to claim 1, wherein the catalyst is contained in a ratio of 1 to 99:99 to 1 (atomic ratio).
タンと酸素とを反応させることを特徴とするエチレンの
製造方法。3. A method for producing ethylene, which comprises reacting ethane with oxygen in the presence of an oxide catalyst containing Sn and W.
ア、ジルコニアおよびゼオライトの少なくとも１種から
なる担体にＳｎとＷとを含む酸化物からなる触媒活性成
分を担持させて使用する請求項３に記載のエチレンの製
造方法。4. The ethylene according to claim 3, wherein the carrier comprising at least one selected from the group consisting of alumina, silica, titania, magnesia, zirconia, and zeolite is used to carry a catalytically active component consisting of an oxide containing Sn and W. Manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7190185A JP2903073B2 (en) | 1995-07-26 | 1995-07-26 | Method for producing ethylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7190185A JP2903073B2 (en) | 1995-07-26 | 1995-07-26 | Method for producing ethylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0938490A true JPH0938490A (en) | 1997-02-10 |
| JP2903073B2 JP2903073B2 (en) | 1999-06-07 |
Family
ID=16253873
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7190185A Expired - Lifetime JP2903073B2 (en) | 1995-07-26 | 1995-07-26 | Method for producing ethylene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2903073B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109833903A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of low-carbon alkanes anaerobic dehydrogenation alkene catalyst and its preparation and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04257528A (en) * | 1990-10-11 | 1992-09-11 | Bp Chem Internatl Ltd | Method and catalyst for producing ethyl- ene and acetic acid |
-
1995
- 1995-07-26 JP JP7190185A patent/JP2903073B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04257528A (en) * | 1990-10-11 | 1992-09-11 | Bp Chem Internatl Ltd | Method and catalyst for producing ethyl- ene and acetic acid |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109833903A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of low-carbon alkanes anaerobic dehydrogenation alkene catalyst and its preparation and application |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2903073B2 (en) | 1999-06-07 |
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