JP5130562B2 - Method for producing methacrolein and / or methacrylic acid - Google Patents

Method for producing methacrolein and / or methacrylic acid Download PDF

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JP5130562B2
JP5130562B2 JP2007288469A JP2007288469A JP5130562B2 JP 5130562 B2 JP5130562 B2 JP 5130562B2 JP 2007288469 A JP2007288469 A JP 2007288469A JP 2007288469 A JP2007288469 A JP 2007288469A JP 5130562 B2 JP5130562 B2 JP 5130562B2
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methacrylic acid
catalyst
raw material
oxidation catalyst
reaction
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JP2009114119A (en
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竜彦 倉上
渥 須藤
利丈 小島
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Nippon Kayaku Co Ltd
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Nippon Kayaku Co Ltd
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Priority to JP2007288469A priority Critical patent/JP5130562B2/en
Priority to PCT/JP2008/068846 priority patent/WO2009060704A1/en
Priority to KR1020107008636A priority patent/KR101558941B1/en
Priority to CN2008801146268A priority patent/CN101848883B/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
    • C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein

Description

本発明は、メタクロレイン及び／又はメタクリル酸の製造方法に関する。   The present invention relates to a method for producing methacrolein and / or methacrylic acid.

ターシャリーブタノール及び／またはイソブチレンを原料とし、固定床接触酸化反応により分子状酸素の存在下でメタクロレイン及び／又はメタクリル酸を製造する方法は既によく知られており、種々提案されている。   Methods for producing methacrolein and / or methacrylic acid using tertiary butanol and / or isobutylene as raw materials in the presence of molecular oxygen by a fixed bed catalytic oxidation reaction are already well known and various proposals have been made.

特許文献１（特開平４−２１７９３２）には反応管内での占有容積が、ガス流れ方向にむかって小さくなるように触媒を充填し、メタクロレイン及び／またはメタクリル酸を製造する方法が記載されている。
特許文献２（特開平６−１９２１４４）には、不活性担体に触媒活性成分を担持してなる触媒を、ガス流れ方向に沿って触媒の担持量が高くなるように充填し、メタクロレイン及び／またはメタクリル酸を製造する方法が記載されている。
特許文献３（特許第２９３４２６７号）には触媒成分のうちの、アルカリ金属およびタリウムの量を調節して触媒活性を制御し触媒を調製し、ガス流れ方向に向かって活性が高くなるように触媒を充填する方法が記載されている。
特許文献４（特開２００２−２１２１２７）には触媒層内に反応浴温度との差が５０℃を超える箇所が一つもなく、該差が１５〜５０℃となる高温域を２箇所以上設ける方法が記載されている。
特許文献５（特開２００３−２５２８２０）には触媒層内の最大ピーク温度と最小ピーク温度の差が２０℃以下になるようにする方法が記載されている。 Patent Document 1 (JP-A-4-217932) describes a method for producing methacrolein and / or methacrylic acid by filling the catalyst so that the occupied volume in the reaction tube decreases toward the gas flow direction. Yes.
In Patent Document 2 (Japanese Patent Laid-Open No. 6-192144), a catalyst obtained by supporting a catalytically active component on an inert carrier is packed so that the amount of the catalyst supported increases along the gas flow direction, and methacrolein and / or Alternatively, a method for producing methacrylic acid is described.
In Patent Document 3 (Patent No. 2934267), a catalyst is prepared by adjusting the amount of alkali metal and thallium among the catalyst components to control the catalyst activity, so that the activity increases in the gas flow direction. A method of filling is described.
Patent Document 4 (Japanese Patent Application Laid-Open No. 2002-212127) is a method in which there is no portion where the difference from the reaction bath temperature exceeds 50 ° C. in the catalyst layer, and two or more high temperature regions where the difference is 15 to 50 ° C. Is described.
Patent Document 5 (Japanese Patent Laid-Open No. 2003-252820) describes a method in which the difference between the maximum peak temperature and the minimum peak temperature in the catalyst layer is 20 ° C. or less.

特開平４−２１７９３２号公報JP-A-4-217932 特開平６−１９２１４４号公報JP-A-6-192144 特許第２９３４２６７号Patent No. 2934267 特開２００２−２１２１２７号公報JP 2002-212127 A 特開２００３−２５２８２０号公報JP 2003-252820 A

これらの発明は原料の酸化による発熱を抑制することによって、触媒寿命、反応収率などを改善するというものであり、触媒層内の最高温度に着目し、それを低減することで触媒寿命、反応収率を改善しようとしている。たしかに、ある程度の効果は得られるものの、同様の触媒によるプロピレンからのアクロレインおよび／またはアクリル酸の製造の収率に比べると、さらなる収率の改良が求められている。   These inventions improve catalyst life, reaction yield, etc. by suppressing heat generation due to oxidation of raw materials. Focusing on the maximum temperature in the catalyst layer and reducing it, it reduces catalyst life, reaction. Trying to improve the yield. Certainly, although a certain degree of effect can be obtained, there is a demand for further improvement in yield compared to the yield of production of acrolein and / or acrylic acid from propylene by the same catalyst.

本発明者らは、こうした実状のもと鋭意研究した結果、発熱ピークの間の温度の極小値を制御することで収率が著しく改良され、かつその収率が長期にわたって安定して得られることを見いだし、本発明を完成させるに至った。   As a result of intensive studies under these circumstances, the present inventors have found that the yield is remarkably improved by controlling the minimum value of the temperature between the exothermic peaks, and that the yield can be obtained stably over a long period of time. As a result, the present invention has been completed.

すなわち本発明は、
（１）ターシャリーブタノール及び／またはイソブチレンを原料とし、これを反応管ガス流れ方向に二つの発熱ピークを有するように酸化触媒を充填した反応管に供給し分子状酸素の存在下で原料を部分酸化することでメタクロレイン及び／またはメタクリル酸を製造する方法において、二つの酸化触媒層の発熱ピークの間の温度の極小値をＴｍ、反応浴温度をＴｂとしたとき、Ｔｍ−Ｔｂ≧１５℃とすることを特徴とするメタクロレイン及び／またはメタクリル酸の製造方法である。
（２）原料ガス入り口側の触媒層を不活性物質で希釈することにより二つの発熱ピークが得られるようにすることを特徴とするメタクロレイン及び／またはメタクリル酸の製造方法である。 That is, the present invention
(1) Tertiary butanol and / or isobutylene is used as a raw material, which is supplied to a reaction tube filled with an oxidation catalyst so as to have two exothermic peaks in the reaction tube gas flow direction, and the raw material is partially obtained in the presence of molecular oxygen. In the method of producing methacrolein and / or methacrylic acid by oxidation, Tm−Tb ≧ 15 ° C., where Tm is the minimum temperature between the exothermic peaks of the two oxidation catalyst layers and Tb is the reaction bath temperature. A process for producing methacrolein and / or methacrylic acid.
(2) A method for producing methacrolein and / or methacrylic acid, characterized in that two exothermic peaks are obtained by diluting the catalyst layer on the raw material gas inlet side with an inert substance.

本発明によればメタクロレイン及び／又はメタクリル酸が長期間にわたって高収率で得られる。   According to the present invention, methacrolein and / or methacrylic acid can be obtained in a high yield over a long period of time.

本発明で使用する酸化触媒は、ターシャリーブタノールやイソブチレンを気相接触酸化してメタクロレイン及び／又はメタクリル酸を得るために使用される触媒であればそれ自身公知の触媒が使用できる。
好ましい触媒としては下記一般式
ＭｏａＢｉｂＦｅｃＣｏｄＸｅＹｆＯｈ
（式中Ｍｏ、Ｂｉ、Ｆｅ及びＣｏはモリブデン、ビスマス、鉄及びコバルトをそれぞれ表す。Ｘはアルカリ金属またはＴｌから選ばれる一種以上の元素、ＹはＮｉ、Ｓｎ、Ｚｎ、Ｗ、Ｃｒ、Ｍｎ、Ｍｇ、Ｓｂ、ＣｅまたはＴｉから選ばれる一種以上の元素を表す。また、元素記号右下の添字は各元素の原子比であり、ａ＝１３とした時、ｂ＝０．１−１０、ｃ＝０．１−１０、ｄ＝１−１０、ｅ＝０．０１−２、ｆ＝０−２、ｈは各々の元素の酸化状態によって定まる数値である。）で表される複合酸化物を触媒活性成分とする触媒が挙げられる。
ここでアルカリ金属としてはＣｓが特に好ましい。
この酸化触媒の調製方法及び原料については、特に制限はなく、この種の触媒の調製に一般的に使用されている方法及び原料を用いて調製することができる。必要に応じ、粉砕、焼成などの工程が含まれる。 As the oxidation catalyst used in the present invention, a catalyst known per se can be used as long as it is a catalyst used for vapor-phase catalytic oxidation of tertiary butanol or isobutylene to obtain methacrolein and / or methacrylic acid.
The following formula is preferred catalysts Mo a Bi b Fe c Co d X e Y f O h
(Wherein Mo, Bi, Fe and Co represent molybdenum, bismuth, iron and cobalt, respectively, X is one or more elements selected from alkali metals or Tl, Y is Ni, Sn, Zn, W, Cr, Mn, It represents one or more elements selected from Mg, Sb, Ce or Ti, and the subscript at the lower right of the element symbol is the atomic ratio of each element, and when a = 13, b = 0.1-10, c = 0.1-10, d = 1-10, e = 0.01-2, f = 0-2, h is a numerical value determined by the oxidation state of each element). Examples of the catalyst include a catalyst active component.
Here, Cs is particularly preferable as the alkali metal.
There is no restriction | limiting in particular about the preparation method and raw material of this oxidation catalyst, It can prepare using the method and raw material generally used for preparation of this kind of catalyst. Steps such as pulverization and firing are included as necessary.

酸化触媒の形状に特に制限はなく、例えば円柱状、打錠状、球状、リング状等の形状が運転条件を考慮して適宜選択可能であるが、球状担体、特にシリカやアルミナ等の不活性担体に触媒活性成分を担持した、粒径３〜６ｍｍの担持触媒が好ましい。   The shape of the oxidation catalyst is not particularly limited, and for example, a cylindrical shape, a tablet shape, a spherical shape, a ring shape, or the like can be appropriately selected in consideration of operating conditions, but a spherical carrier, particularly an inert material such as silica or alumina. A supported catalyst having a particle diameter of 3 to 6 mm, in which a catalytically active component is supported on a carrier, is preferable.

本発明においては、異なった活性を持つ二種類の触媒を調製し、これらを混合することなく反応管内に別々に充填して、反応管ガス流れ方向に２つの酸化触媒層を形成する。これによって、反応管内の発熱ピークが、通常二つになる。一般的には原料ガス流れ方向に活性が高くなるように触媒を充填するのが好ましい。必要に応じ、原料ガス入り口側に予熱層を設置したり、ターシャリーブタノールを原料とした場合は脱水層を設置したりする。予熱層または脱水層に充填される物質は、シリカ、アルミナ、チタニア、あるいはシリカアルミナが好ましい。脱水層を設置することでターシャリーブタノールとイソブチレンの原料の差異を無視できる程度にすることができる。   In the present invention, two types of catalysts having different activities are prepared, and these are separately packed in the reaction tube without mixing, and two oxidation catalyst layers are formed in the reaction tube gas flow direction. This usually results in two exothermic peaks in the reaction tube. In general, it is preferable to fill the catalyst so as to increase the activity in the direction of flow of the raw material gas. If necessary, a preheating layer is installed on the raw material gas inlet side, or a dehydration layer is installed if tertiary butanol is used as a raw material. The material filled in the preheating layer or dehydration layer is preferably silica, alumina, titania, or silica alumina. By installing a dehydration layer, the difference between the raw materials of tertiary butanol and isobutylene can be neglected.

触媒活性の制御は、公知の方法で行うことが出来る。例えば触媒の焼成温度や、触媒組成を変更する方法、一方の触媒層（原料ガス入り口側）を、不活性物質で希釈する方法が挙げられるが、後者のほうが簡便で好ましい。なお、本発明において、不活性物質とは、酸化反応に使用する触媒の活性を１００％とした場合に０から２０％の活性を有する物質とする。   The catalyst activity can be controlled by a known method. For example, there are a method of changing the calcination temperature and catalyst composition of the catalyst, and a method of diluting one catalyst layer (raw material gas inlet side) with an inert substance. The latter is simpler and preferred. In the present invention, the inactive substance is a substance having an activity of 0 to 20% when the activity of the catalyst used for the oxidation reaction is 100%.

こうして得られた二種類の活性の異なる触媒を、二つの発熱ピークの間の温度の極小値をＴｍ、反応浴温度をＴｂとしたとき、Ｔｍ−Ｔｂ≧１５となるように充填する。原料ガスの濃度、組成、空間速度、反応管径、反応圧力、反応器の除熱能力など、様々な要因がＴｂ、Ｔｍに影響するため、事前にコンピューターによるシミュレーションなどによって、触媒活性や不活性物質による希釈割合、異なる触媒層同士の充填長比などを最適化する。Ｔｍ−Ｔｂは２０℃以上がより好ましい。   The two kinds of catalysts having different activities thus obtained are packed so that Tm−Tb ≧ 15, where Tm is the minimum temperature between the two exothermic peaks and Tb is the reaction bath temperature. Various factors such as source gas concentration, composition, space velocity, reaction tube diameter, reaction pressure, and reactor heat removal ability affect Tb and Tm. Optimize the dilution ratio by substance and the filling length ratio between different catalyst layers. Tm-Tb is more preferably 20 ° C. or higher.

反応管内にガス流れ方向に熱伝対を設置し、１０ｃｍ間隔程度で温度測定を行い、得られた触媒層内温度をＹ軸に、触媒充填長をＸ軸にしたプロットからＴｍを求める。１０ｃｍ以上の間隔で測定した場合、正確なデータが得られない場合があり、好ましくない。   A thermocouple is installed in the gas flow direction in the reaction tube, temperature is measured at intervals of about 10 cm, and Tm is obtained from a plot with the obtained catalyst layer temperature on the Y axis and the catalyst packing length on the X axis. When measured at intervals of 10 cm or more, accurate data may not be obtained, which is not preferable.

次に本発明を更に実施例により具体的に説明する。なお、実施例において、転化率、収率、選択率は以下の式に従って算出した。
原料転化率（％）＝（反応したターシャリーブタノールまたはイソブチレンのモル数）／（供給したターシャリーブタノールまたはイソブチレンのモル数）×１００
メタクロレイン収率（％）＝（生成したメタクロレインのモル数）／（供給したターシャリーブタノールまたはイソブチレンのモル数）×１００
メタクリル酸収率（％）＝（生成したメタクリル酸のモル数）／（供給したターシャリーブタノールまたはイソブチレンのモル数）×１００
有効選択率（％）＝（メタクロレイン収率＋メタクリル酸収率）／原料転化率×１００ Next, the present invention will be described more specifically with reference to examples. In Examples, the conversion rate, yield, and selectivity were calculated according to the following formulas.
Raw material conversion (%) = (number of moles of reacted tertiary butanol or isobutylene) / (number of moles of supplied tertiary butanol or isobutylene) × 100
Yield of methacrolein (%) = (number of moles of methacrolein produced) / (number of moles of supplied tertiary butanol or isobutylene) × 100
Methacrylic acid yield (%) = (number of moles of methacrylic acid produced) / (number of moles of supplied tertiary butanol or isobutylene) × 100
Effective selectivity (%) = (methacrolein yield + methacrylic acid yield) / raw material conversion rate × 100

実施例１
（触媒の調製）
蒸留水１２０００ｍｌを加熱攪拌しながらモリブデン酸アンモニウム３０００ｇと硝酸セシウム５５．２ｇを溶解して水溶液（Ａ）を得た。別に、硝酸コバルト２７８２ｇ、硝酸第二鉄１１４４ｇ、硝酸ニッケル４１２ｇを蒸留水２３００ｍｌに溶解して水溶液（Ｂ）を、また濃硝酸２９２ｍｌを加えて酸性にした蒸留水１２１５ｍｌに硝酸ビスマス１１６７ｇを溶解して水溶液（Ｃ）をそれぞれ調製した。上記水溶液（Ａ）に（Ｂ）、（Ｃ）を順次、水溶液（Ａ）を激しく攪拌しながら混合し、生成した懸濁液をスプレードライヤーを用いて乾燥し、得られた粉末を４６０℃で５時間焼成し予備焼成粉末（Ｄ）を得た。このときの触媒活性成分の酸素を除いた組成比は原子比でＭｏ＝１２、Ｂｉ＝１．７、Ｆｅ＝２．０、Ｃｏ＝６．７５、Ｎｉ＝１．０、Ｃｓ＝０．２０であった。
その後、予備焼成粉末（Ｄ）をシリカ−アルミナ混合物不活性担体（粒径４．０ｍｍ）に成型後の触媒に対して４５重量％を占める割合で担持した。こうして得た成型物を５２０℃で５時間焼成し酸化触媒（Ｅ）を得た。 Example 1
(Preparation of catalyst)
While heating and stirring 12,000 ml of distilled water, 3000 g of ammonium molybdate and 55.2 g of cesium nitrate were dissolved to obtain an aqueous solution (A). Separately, 2782 g of cobalt nitrate, 1144 g of ferric nitrate and 412 g of nickel nitrate were dissolved in 2300 ml of distilled water to dissolve the aqueous solution (B). Aqueous solutions (C) were prepared respectively. (B) and (C) were sequentially mixed with the aqueous solution (A) while vigorously stirring the aqueous solution (A), the resulting suspension was dried using a spray dryer, and the resulting powder was dried at 460 ° C. Firing for 5 hours gave a pre-fired powder (D). At this time, the composition ratio of the catalytically active component excluding oxygen is Mo = 12, Bi = 1.7, Fe = 2.0, Co = 6.75, Ni = 1.0, Cs = 0.20 in atomic ratio. Met.
Thereafter, the pre-fired powder (D) was supported on a silica-alumina mixture inert carrier (particle size: 4.0 mm) in a proportion of 45% by weight based on the molded catalyst. The molded product thus obtained was calcined at 520 ° C. for 5 hours to obtain an oxidation catalyst (E).

（酸化反応試験）
熱媒体として溶融塩を循環させるためのジャケット及び触媒層温度を測定するための熱電対を管軸に設置した、内径２３ｍｍのステンレス製反応器の原料ガス入り口側からターシャリーブタノールの脱水層として直径５ｍｍのシリカ―アルミナ球を２０ｃｍ、酸化触媒層第一層（原料ガス入り口側）として酸化触媒（Ｅ）とシリカ−アルミナ混合物不活性担体を重量比４：１で混合した希釈触媒９０ｃｍ、酸化触媒第二層（ガス出口側）として酸化触媒（Ｅ）を２２５ｃｍの順で充填し、反応浴温度Ｔｂを３４５℃にした。ここに原料モル比がイソブチレン：酸素：窒素：水＝１：２：１０：１．６となるようにターシャリーブタノール、空気、窒素、水の供給量を設定したガスを空間速度１０００ｈ−１で酸化反応器内へ導入し、反応を行った結果、反応開始後２００時間経過したときの原料転化率９９．６％、メタクロレイン収率８１．０７％、メタクリル酸収率３．５９％、有効選択率８５．０２％であった。また、触媒層内の温度は、酸化触媒層第一層目の発熱ピーク温度が４１０℃、酸化触媒層第二層目の発熱ピーク温度が３８９℃、二つの発熱ピークの間の極小値Ｔｍが３７７℃、Ｔｍ−Ｔｂ＝３２℃であった。 (Oxidation reaction test)
A diameter of a dehydrated layer of tertiary butanol from a raw material gas inlet side of a stainless steel reactor having an inner diameter of 23 mm, in which a jacket for circulating molten salt as a heat medium and a thermocouple for measuring the catalyst layer temperature are installed on the tube axis Diluted catalyst 90 cm, oxidation catalyst comprising 20 mm of 5 mm silica-alumina sphere, mixing oxidation catalyst (E) and silica-alumina mixture inert carrier at a weight ratio of 4: 1 as oxidation catalyst layer first layer (source gas inlet side) As the second layer (gas outlet side), the oxidation catalyst (E) was filled in the order of 225 cm, and the reaction bath temperature Tb was set to 345 ° C. A gas in which the supply amounts of tertiary butanol, air, nitrogen, and water are set so that the raw material molar ratio is isobutylene: oxygen: nitrogen: water = 1: 2: 10: 1.6 at a space velocity of 1000 h −1 . As a result of introducing into the oxidation reactor and carrying out the reaction, the raw material conversion was 99.6%, methacrolein yield 81.07%, methacrylic acid yield 3.59% when 200 hours passed after the start of the reaction, effective The selectivity was 85.02%. The temperature within the catalyst layer is 410 ° C. for the first exothermic peak temperature of the oxidation catalyst layer, 389 ° C. for the second exothermic peak temperature of the oxidation catalyst layer, and a minimum value Tm between the two exothermic peaks. They were 377 degreeC and Tm-Tb = 32 degreeC.

実施例２
実施例１の反応を原料転化率９９．５％になるように反応浴温度Ｔｂを調節しながら６０００ｈ継続したところ、メタクロレイン収率８０．７３％、メタクリル酸収率３．７４％、有効選択率８４．８２％であった。また、触媒層内の温度は、Ｔｂが３４８℃、酸化触媒層第一層目の発熱ピーク温度が３９９℃、酸化触媒層第二層目の発熱ピーク温度が３７７℃、二つの発熱ピークの間の極小値Ｔｍが３７０℃、Ｔｍ−Ｔｂ＝２２℃であった。 Example 2
When the reaction of Example 1 was continued for 6000 hours while adjusting the reaction bath temperature Tb so that the raw material conversion was 99.5%, methacrolein yield 80.3%, methacrylic acid yield 3.74%, effective selection The rate was 84.82%. The temperature in the catalyst layer is Tb of 348 ° C., the exothermic peak temperature of the first oxidation catalyst layer is 399 ° C., the exothermic peak temperature of the second oxidation catalyst layer is 377 ° C., and it is between the two exothermic peaks. The minimum value Tm was 370 ° C. and Tm−Tb = 22 ° C.

実施例３
実施例１の反応を原料転化率９９．５％になるように反応浴温度Ｔｂを調節しながら１２０００ｈ継続したところ、メタクロレイン収率８０．１８％、メタクリル酸収率４．０４％、有効選択率８４．７０％であった。また、触媒層内の温度は、Ｔｂが３５５℃、酸化触媒層第一層目の発熱ピーク温度が４０８℃、酸化触媒層第二層目の発熱ピーク温度が３８４℃、二つの発熱ピークの間の極小値Ｔｍが３８０℃で、Ｔｍ−Ｔｂ＝２５℃であった。 Example 3
When the reaction of Example 1 was continued for 12000 h while adjusting the reaction bath temperature Tb so that the raw material conversion was 99.5%, methacrolein yield 80.18%, methacrylic acid yield 4.04%, effective selection The rate was 84.70%. The temperature in the catalyst layer is Tb of 355 ° C., the exothermic peak temperature of the first oxidation catalyst layer is 408 ° C., the exothermic peak temperature of the second oxidation catalyst layer is 384 ° C., and between the two exothermic peaks. The minimum value Tm of 380 ° C. was Tm−Tb = 25 ° C.

実施例４
実施例１において触媒を充填する反応管の内径を２１ｍｍとし、空間速度を１２００ｈ−１としたこと以外は実施例１と同様に反応を行った。反応開始後３００時間における、原料転化率は９９．５％、メタクロレイン収率８０．２％、メタクリル酸収率３．７７％、有効選択率８４．４％であった。また、触媒層内の温度は、Ｔｂが３５２℃、酸化触媒層第一層目の発熱ピーク温度が４０３℃、酸化触媒層第二層目の発熱ピーク温度が３７５℃、二つの発熱ピークの間の極小値Ｔｍが３７０℃、Ｔｍ−Ｔｂ＝１８℃であった。 Example 4
In Example 1, the reaction was carried out in the same manner as in Example 1 except that the inner diameter of the reaction tube filled with the catalyst was 21 mm and the space velocity was 1200 h- 1 . 300 hours after the start of the reaction, the raw material conversion rate was 99.5%, methacrolein yield 80.2%, methacrylic acid yield 3.77%, and effective selectivity 84.4%. The temperature in the catalyst layer is Tb of 352 ° C., the exothermic peak temperature of the first oxidation catalyst layer is 403 ° C., the exothermic peak temperature of the second oxidation catalyst layer is 375 ° C., and between the two exothermic peaks. The minimum value Tm was 370 ° C. and Tm−Tb = 18 ° C.

比較例１
実施例１において酸化触媒層第一層として酸化触媒（Ｅ）とシリカ−アルミナ混合物不活性担体を重量比２：１で混合した希釈触媒を充填したこと以外は実施例１と同様に反応を行った。反応開始後３００時間における、原料転化率は９９．５％、メタクロレイン収率７９．４％、メタクリル酸収率３．６６％、有効選択率８３．５％であった。また、触媒層内の温度は、Ｔｂが３５１℃、酸化触媒層第一層目の発熱ピーク温度が３７０℃、酸化触媒層第二層目の発熱ピーク温度が３８５℃、二つの発熱ピークの間の極小値Ｔｍが３６５℃、Ｔｍ−Ｔｂ＝１４℃であった。 Comparative Example 1
The reaction was conducted in the same manner as in Example 1 except that the oxidation catalyst (E) and the silica-alumina mixture inert carrier mixed at a weight ratio of 2: 1 were filled as the first oxidation catalyst layer in Example 1. It was. 300 hours after the start of the reaction, the raw material conversion rate was 99.5%, methacrolein yield 79.4%, methacrylic acid yield 3.66%, and effective selectivity 83.5%. The temperature in the catalyst layer is as follows: Tb is 351 ° C., the exothermic peak temperature of the first oxidation catalyst layer is 370 ° C., the exothermic peak temperature of the second oxidation catalyst layer is 385 ° C., and between the two exothermic peaks. The minimum value Tm was 365 ° C. and Tm−Tb = 14 ° C.

以上のように、反応浴温度Ｔｂや、発熱ピーク温度を公知の範囲にした場合より、Ｔｍ−Ｔｂ≧１５℃となるようにした場合のほうが、長期間にわたって高い収率、有効選択率を維持できることが分る。   As described above, when the reaction bath temperature Tb and the exothermic peak temperature are within a known range, the case where Tm−Tb ≧ 15 ° C. maintains a higher yield and effective selectivity over a long period of time. I know I can

Claims (2)

ターシャリーブタノール及び／またはイソブチレンを原料とし、これを反応管ガス流れ方向に二つの発熱ピークを有するように酸化触媒を充填した反応管に供給し、分子状酸素の存在下で原料を部分酸化しメタクロレイン及び／またはメタクリル酸を製造する方法において、前記酸化触媒がＭｏ ａ Ｂｉ ｂ Ｆｅ ｃ Ｃｏ ｄ Ｘ ｅ Ｙ ｆ Ｏ ｈ （式中Ｍｏ、Ｂｉ、Ｆｅ及びＣｏはモリブデン、ビスマス、鉄及びコバルトをそれぞれ表し、Ｘはアルカリ金属またはＴｌから選ばれる一種以上の元素、ＹはＮｉ、Ｓｎ、Ｚｎ、Ｗ、Ｃｒ、Ｍｎ、Ｍｇ、Ｓｂ、ＣｅまたはＴｉから選ばれる一種以上の元素を表し、元素記号右下の添字は各元素の原子比であり、ａ＝１３とした時、ｂ＝０．１−１０、ｃ＝０．１−１０、ｄ＝１−１０、ｅ＝０．０１−２、ｆ＝０−２、ｈは各々の元素の酸化状態によって定まる数値である。）で表され、二つの酸化触媒層の発熱ピークの間の温度の極小値をＴｍ、反応浴温度をＴｂとしたとき、Ｔｍ−Ｔｂ≧１５℃とすることを特徴とするメタクロレイン及び／またはメタクリル酸の製造方法。 Tertiary butanol and / or isobutylene is used as a raw material, and this is supplied to a reaction tube filled with an oxidation catalyst so as to have two exothermic peaks in the reaction tube gas flow direction, and the raw material is partially oxidized in the presence of molecular oxygen. a method for producing methacrolein and / or methacrylic acid, wherein the oxidation catalyst is Mo a Bi b Fe c Co d X e Y f O h ( wherein Mo, Bi, Fe and Co are molybdenum, bismuth, iron and cobalt X represents one or more elements selected from alkali metals or Tl, Y represents one or more elements selected from Ni, Sn, Zn, W, Cr, Mn, Mg, Sb, Ce or Ti The subscript at the lower right is an atomic ratio of each element. When a = 13, b = 0.1-10, c = 0.1-10, d = 1-10, e = 0.01- , F = 0-2, h is represented by a numerical value determined by the oxidation state of each element.), And the minimum value of temperature during the exothermic peak of the two oxidation catalyst layer Tm, the reaction bath temperature Tb A process for producing methacrolein and / or methacrylic acid, wherein Tm−Tb ≧ 15 ° C. 原料ガス入り口側の触媒層を不活性物質で希釈することにより二つの発熱ピークが得られるようにすることを特徴とする請求項１記載のメタクロレイン及び／またはメタクリル酸の製造方法。   2. The method for producing methacrolein and / or methacrylic acid according to claim 1, wherein two exothermic peaks are obtained by diluting the catalyst layer on the raw material gas inlet side with an inert substance.
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