JP2005320315A - Catalytic gas phase oxidation reaction - Google Patents
Catalytic gas phase oxidation reaction Download PDFInfo
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- JP2005320315A JP2005320315A JP2004306984A JP2004306984A JP2005320315A JP 2005320315 A JP2005320315 A JP 2005320315A JP 2004306984 A JP2004306984 A JP 2004306984A JP 2004306984 A JP2004306984 A JP 2004306984A JP 2005320315 A JP2005320315 A JP 2005320315A
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- Prior art keywords
- catalyst
- reaction
- phase oxidation
- gas phase
- gas
- Prior art date
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Landscapes
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
本発明は、接触気相酸化反応に関する。詳しくは、触媒を充填した固定床多管式反応器を用いた、分子状酸素または分子状酸素含有ガスによる接触気相酸化反応に関する。 The present invention relates to a catalytic gas phase oxidation reaction. More specifically, the present invention relates to a catalytic gas phase oxidation reaction with molecular oxygen or a molecular oxygen-containing gas using a fixed bed multitubular reactor filled with a catalyst.
触媒を充填した固定床多管式反応器を用いた、分子状酸素または分子状酸素含有ガスによる接触気相酸化反応において、（Ａ）プロピレン、イソブチレン、ｔ−ブチルアルコールおよびメチル−ｔ−ブチルエーテルからなる群より選ばれる少なくとも１種の化合物を原料とし、前記原料に対応する不飽和アルデヒドを製造する場合、（Ｂ）不飽和アルデヒドを原料とし、前記原料に対応する不飽和カルボン酸を製造する場合、（Ｃ）プロピレン、イソブチレン、ｔ−ブチルアルコールおよびメチル−ｔ−ブチルエーテルからなる群より選ばれる少なくとも１種の化合物を原料とし、前記原料に対応する不飽和カルボン酸を製造する場合、これら接触気相酸化反応は非常な発熱反応を伴うことから、触媒層に局所的な異常高温部（以下、「ホットスポット部」と称することがある。）が発生する。 In a catalytic gas phase oxidation reaction with molecular oxygen or molecular oxygen-containing gas using a fixed bed multitubular reactor packed with catalyst, (A) from propylene, isobutylene, t-butyl alcohol and methyl-t-butyl ether When producing an unsaturated aldehyde corresponding to the raw material using at least one compound selected from the group consisting of: (B) When producing an unsaturated carboxylic acid corresponding to the raw material using the unsaturated aldehyde as a raw material (C) When producing an unsaturated carboxylic acid corresponding to the raw material using at least one compound selected from the group consisting of propylene, isobutylene, t-butyl alcohol and methyl-t-butyl ether as a raw material, Since the phase oxidation reaction involves a very exothermic reaction, local abnormally high temperature parts (hereinafter referred to as “hot” Sometimes referred to as the spot part ".) Occurs.
ホットスポット部の温度が高いと、当該ホットスポット部では、触媒が過度の酸化反応を引き起こし、目的生成物の収率を低下させ、最悪の場合には暴走反応を引き起こす。ホットスポット部に位置する触媒は、高温に曝されるため、その物理的性質および化学的性質が変化してしまい、触媒活性や目的生成物への選択性が低下するなど、触媒の劣化が加速される。特に、モリブデン系の触媒（例えば、モリブデン−ビスマス−鉄系の触媒、モリブデン−バナジウム系の触媒など。以下においても同様である。）の場合、モリブデン成分が昇華して触媒組成および物性が変化しやすいため、触媒の劣化の度合いが大きい。
上記の問題は、ガス圧力（以下、本明細書においては、「固定床多管式反応器における各反応管のガス出口におけるガス圧」を言うとする。）を高くして反応を行う場合や、目的生成物の生産性向上を目的として、空間速度を大きくしたり、原料ガスの濃度を高くしたりして反応を行う場合に、さらに顕著となる。
When the temperature of the hot spot portion is high, the catalyst causes an excessive oxidation reaction in the hot spot portion, thereby reducing the yield of the target product, and in the worst case, causes a runaway reaction. Since the catalyst located in the hot spot is exposed to high temperatures, its physical and chemical properties change, and catalyst degradation and selectivity to the target product decrease, accelerating catalyst degradation. Is done. In particular, in the case of a molybdenum-based catalyst (for example, a molybdenum-bismuth-iron-based catalyst, a molybdenum-vanadium-based catalyst, etc.). Since it is easy, the degree of deterioration of the catalyst is large.
The above problem is caused when the reaction is carried out by increasing the gas pressure (hereinafter referred to as “the gas pressure at the gas outlet of each reaction tube in the fixed bed multitubular reactor” in the present specification). When the reaction is carried out by increasing the space velocity or increasing the concentration of the raw material gas for the purpose of improving the productivity of the target product, it becomes even more remarkable.
以上の問題について再説する。反応管に充填された触媒層全体に着目すると、ホットスポット部に位置する触媒は、過度の酸化反応を引き起こすほか、他の部分の触媒に比べて劣化が速く、特に長時間の使用においては目的生成物の収率が著しく低下し、安定的に製造を行うことが困難となり得るのである。
このような問題に対処するために、反応管に充填される触媒の大きさ（占有容積）が、原料ガス等の入口側から出口側に向けて順に小さくなるようにする方法（例えば、特許文献１、２参照。）が提案され、工業的に実施されている例もある。
また、原料ガス等の入口側に充填する触媒の活性成分担持率を低くする方法（例えば、特許文献３参照。）や、アルカリ金属を添加して活性を低下させた触媒を充填する方法（例えば、特許文献４参照。）が提案されている。
In order to cope with such a problem, a method of reducing the size (occupied volume) of the catalyst filled in the reaction tube in order from the inlet side to the outlet side of the raw material gas or the like (for example, Patent Documents) There are also examples that are proposed and industrially implemented.
Also, a method of lowering the active component loading rate of the catalyst charged on the inlet side of the raw material gas or the like (see, for example, Patent Document 3), or a method of filling a catalyst whose activity has been reduced by adding an alkali metal (for example, , See Patent Document 4).
しかしながら、このような方法であっても、目的生成物の生産性向上の点では、近年の技術進歩により要請される高い水準（高いガス圧力条件等）から見れば、ホットスポット部における蓄熱（温度上昇）を抑制することに関しては、まだ十分であるとは言えなかった。また、所定の反応帯における触媒活性をより低い範囲にするために、より大きな占有容積の触媒を用いる必要があったとしても、各反応管の管径の大きさ（長さ）には制限があるため、例えば、最大粒径が管径よりもわずかに小さな触媒を充填しようとすると、触媒が反応管内の任意の箇所でブリッジ（詰まってしまうこと）してしまう場合もあり、その場合には、すべての反応管で触媒充填量を一定にそろえることが困難になる等して、目的生成物の収率を大きく低下させたり、その品質を大きくばらつかせたりすることになる。 However, even with such a method, in terms of improving the productivity of the target product, in view of the high level (high gas pressure conditions, etc.) demanded by recent technological advances, It was not enough to suppress the rise). Even if it is necessary to use a catalyst with a larger occupied volume in order to bring the catalytic activity in a predetermined reaction zone to a lower range, there is a limit to the size (length) of each reaction tube. Therefore, for example, if a catalyst whose maximum particle size is slightly smaller than the tube diameter is filled, the catalyst may bridge (clog) at any point in the reaction tube. As a result, it becomes difficult to make the catalyst charge constant in all the reaction tubes, so that the yield of the target product is greatly reduced or the quality thereof is greatly varied.
そこで、本発明が解決しようとする課題は、触媒を充填した固定床多管式反応器を用いた、分子状酸素または分子状酸素含有ガスによる接触気相酸化反応において、より高いガス圧力や原料ガス濃度およびより大きな反応ガス空間速度の反応条件下においても、ホットスポット部における蓄熱を容易かつ低コストで十分に抑制することができ、高い収率を維持しながら長期にわたって反応を継続することができる接触気相酸化反応を提供することにある。 Therefore, the problem to be solved by the present invention is that a higher gas pressure and raw material are used in a catalytic gas phase oxidation reaction with molecular oxygen or a molecular oxygen-containing gas using a fixed bed multitubular reactor filled with a catalyst. Even under the reaction conditions of gas concentration and larger reaction gas space velocity, heat storage in the hot spot can be suppressed sufficiently easily and at low cost, and the reaction can be continued for a long time while maintaining a high yield. It is to provide a catalytic gas phase oxidation reaction that can be performed.
本発明者は、上記課題を解決するべく鋭意検討を行った。その結果、ホットスポット部の蓄熱を抑制するために、所定の反応帯（特にガス入口側）における触媒活性を調整しようとした場合、従来と同様に占有容積（大きさ）の異なる触媒を用いるようにしながら、これに不活性物質の成形体（粒子等）を混合して触媒濃度を希釈するようにすれば、従来の方法では調整不可能であった範囲の触媒活性であっても、前述の問題を生じるまでもなく、容易かつ緻密に調整できることを見出した。また、占有容積の異なる触媒を最低限必要な種類の数だけ用意しておけば、占有容積だけでは調整できない微妙な範囲の触媒活性であっても、不活性物質の成形体を併用することで、工業的にも容易にかつ低コストでしかも豊富なバリエーションで設定し調整できる。このようなハード面での優れた点を利用して、実際に不飽和アルデヒドや不飽和カルボン酸の製造を行ったところ、従来では制御が困難な面があった、より高いガス圧力やより高い原料ガス濃度およびより大きい反応ガス空間速度の条件下での反応であっても、ホットスポット部における蓄熱を十分に抑制することができ、長期間にわたって触媒の劣化を抑制し、高い収率を維持しながら反応を継続することができることが確認できた。 The present inventor has intensively studied to solve the above problems. As a result, when the catalyst activity in a predetermined reaction zone (especially on the gas inlet side) is to be adjusted in order to suppress heat storage in the hot spot part, a catalyst having a different occupied volume (size) is used as in the conventional case. However, if the catalyst concentration is diluted by mixing a compact (particles, etc.) of an inert substance with this, even if the catalyst activity is in the range that cannot be adjusted by the conventional method, It has been found that adjustments can be made easily and precisely without causing problems. In addition, if a minimum number of types of catalysts with different occupied volumes are prepared, even if the catalytic activity is in a delicate range that cannot be adjusted only with the occupied volume, it is possible to use a compact of an inert substance together. It can be set and adjusted industrially easily, at low cost, and with abundant variations. Using these excellent points in terms of hardware, actual production of unsaturated aldehydes and unsaturated carboxylic acids resulted in higher gas pressures and higher levels that were previously difficult to control. Even when the reaction is performed under conditions of the raw material gas concentration and higher reaction gas space velocity, heat storage in the hot spot can be sufficiently suppressed, deterioration of the catalyst is suppressed over a long period, and a high yield is maintained. It was confirmed that the reaction can be continued.
本発明は、以上の知見に基づき完成された。
なお、ホットスポット部での蓄熱を抑制するための別の技術として、反応管に充填した触媒を、不活性材料で希釈して、ガス出口側の方がガス入口側に比べて連続的または段階的に活性が高くなるようにする方法（例えば、特公昭５３−３０６８８号公報。）が提案されているが、本発明の接触気相酸化反応は、不活性材料での希釈によって触媒活性に勾配を設けることでホットスポット部での蓄熱を抑制するという思想に基づくものではない。詳しくは、本発明の接触気相酸化反応は、占有容積の異なる触媒粒子を段階的に充填することで触媒活性に勾配を設けるという思想を前提とするものであって、この思想に基づく技術を、さらに、前述のごときより高度な反応条件に対応させるための手段として不活性材料による希釈を採用するものであるため、不活性材料による希釈により触媒活性に勾配を設ける思想に基づくものではない。
The present invention has been completed based on the above findings.
As another technique for suppressing heat storage in the hot spot part, the catalyst filled in the reaction tube is diluted with an inert material, and the gas outlet side is continuously or stepwise compared to the gas inlet side. However, the catalytic gas phase oxidation reaction according to the present invention has a gradient in catalytic activity due to dilution with an inert material. This is not based on the idea of suppressing heat storage in the hot spot portion. Specifically, the catalytic gas phase oxidation reaction of the present invention is premised on the idea of providing a gradient in catalyst activity by stepwise filling catalyst particles having different occupied volumes. Furthermore, since dilution with an inert material is employed as a means for coping with higher reaction conditions as described above, it is not based on the idea of providing a gradient in catalyst activity by dilution with an inert material.
本発明にかかる接触気相酸化反応は、触媒を充填した固定床多管式反応器を用いた、分子状酸素または分子状酸素含有ガスによる接触気相酸化反応において、前記反応器における各反応管の触媒充填層が管軸方向に複数の反応帯に分けられていて、前記触媒の充填は、前記複数の反応帯の少なくとも２つにおいてその占有容積が異なる充填であり、かつ、前記複数の反応帯の少なくとも１つにおいて不活性物質成形体が混合されている充填であることを特徴とする。
上記において触媒の占有容積とは、触媒を各反応管の触媒充填層に充填したときの、個々の触媒粒子が占める空間の体積を意味する。
In the catalytic gas phase oxidation reaction according to the present invention, in the catalytic gas phase oxidation reaction using molecular oxygen or a molecular oxygen-containing gas using a fixed bed multitubular reactor filled with a catalyst, each reaction tube in the reactor is used. The catalyst packed bed is divided into a plurality of reaction zones in the direction of the tube axis, and the catalyst filling is a packing having a different occupied volume in at least two of the plurality of reaction zones, and the plurality of reactions It is a filling in which an inactive substance compact is mixed in at least one of the bands.
In the above, the occupied volume of the catalyst means the volume of the space occupied by individual catalyst particles when the catalyst is packed in the catalyst packed bed of each reaction tube.
本発明によれば、触媒を充填した固定床多管式反応器を用いた、分子状酸素または分子状酸素含有ガスによる接触気相酸化反応において、より高いガス圧力やより高い原料ガス濃度およびより大きな反応ガス空間速度の反応条件下においても、ホットスポット部における蓄熱を容易かつ低コストで十分に抑制することができ、高い収率を維持しながら長期にわたって反応を継続することができる接触気相酸化反応を提供することができる。
また、本発明にかかる接触気相酸化反応は、各種条件下の不飽和アルデヒドおよび／または不飽和カルボン酸の製造方法に利用することができ、より高いガス圧力やより高い原料ガス濃度およびより大きな反応ガス空間速度の反応条件下以外の反応条件下であっても、不飽和アルデヒドおよび／または不飽和カルボン酸の、長期間にわたる収率の安定や、収率の改善、触媒寿命の維持を達成することができる。
According to the present invention, in a catalytic gas phase oxidation reaction with molecular oxygen or a molecular oxygen-containing gas using a fixed bed multitubular reactor filled with a catalyst, higher gas pressure, higher raw material gas concentration and more Catalytic gas phase that can sufficiently suppress heat storage in the hot spot part easily and at low cost, and can continue the reaction over a long period of time while maintaining a high yield even under reaction conditions with a large reaction gas space velocity. An oxidation reaction can be provided.
In addition, the catalytic gas phase oxidation reaction according to the present invention can be used in a method for producing an unsaturated aldehyde and / or an unsaturated carboxylic acid under various conditions, with a higher gas pressure, a higher raw material gas concentration and a higher concentration. Achieves long-term yield stability improvement, yield improvement, and maintenance of catalyst life of unsaturated aldehydes and / or unsaturated carboxylic acids, even under reaction conditions other than those under the reaction gas space velocity can do.
以下、本発明にかかる接触気相酸化反応（以下、本発明の接触気相酸化反応と称することがある。）について詳しく説明するが、本発明の範囲はこれらの説明に拘束されることはなく、以下の例示以外についても、本発明の趣旨を損なわない範囲で適宜変更実施し得る。
本発明の接触気相酸化反応は、触媒を充填した固定床多管式反応器を用いた、分子状酸素または分子状酸素含有ガスによる接触気相酸化反応において、前述したような技術的特長を有することが重要である。
本発明の接触気相酸化反応は、具体的には、（Ａ）プロピレン、イソブチレン、ｔ−ブチルアルコールおよびメチル−ｔ−ブチルエーテルからなる群より選ばれる少なくとも１種の化合物を原料とし、前記原料に対応する不飽和アルデヒド（好ましくは、アクロレイン）を製造する接触気相酸化反応、（Ｂ）不飽和アルデヒドを原料とし、前記原料に対応する不飽和カルボン酸を製造する接触気相酸化反応（好ましくは、アクロレインを原料とし、アクリル酸を製造する接触気相酸化反応）、（Ｃ）プロピレン、イソブチレン、ｔ−ブチルアルコールおよびメチル−ｔ−ブチルエーテルからなる群より選ばれる少なくとも１種の化合物を原料とし、前記原料に対応する不飽和カルボン酸（好ましくは、アクリル酸）を製造する接触気相酸化反応、が好ましい。
Hereinafter, the catalytic gas phase oxidation reaction according to the present invention (hereinafter sometimes referred to as the catalytic gas phase oxidation reaction of the present invention) will be described in detail, but the scope of the present invention is not limited to these descriptions. Other than the following examples, modifications can be made as appropriate without departing from the spirit of the present invention.
The catalytic gas phase oxidation reaction of the present invention has the technical features as described above in the catalytic gas phase oxidation reaction with molecular oxygen or a molecular oxygen-containing gas using a fixed bed multitubular reactor filled with a catalyst. It is important to have.
Specifically, the catalytic gas phase oxidation reaction of the present invention comprises (A) at least one compound selected from the group consisting of propylene, isobutylene, t-butyl alcohol and methyl-t-butyl ether as a raw material. Catalytic gas phase oxidation reaction for producing a corresponding unsaturated aldehyde (preferably acrolein), (B) Catalytic gas phase oxidation reaction for producing an unsaturated carboxylic acid corresponding to the raw material using unsaturated aldehyde as a raw material (preferably Acrolein as a raw material, a catalytic gas phase oxidation reaction for producing acrylic acid), (C) at least one compound selected from the group consisting of propylene, isobutylene, t-butyl alcohol and methyl-t-butyl ether as a raw material, Catalytic gas phase oxidation reaction for producing an unsaturated carboxylic acid (preferably acrylic acid) corresponding to the raw material. , It is preferable.
本発明で用い得る触媒は、触媒成分のみを一定の形状に成形した成形型触媒であってもよいし、触媒成分を一定の形状を有する任意の不活性担体に担持させた担持型触媒であってもよいし、あるいは、これら成形型触媒と担持型触媒との組み合わせであってもよく、限定はされない。
本発明で用い得る触媒に使用する上記触媒成分としては、以下に示される酸化物および／または複合酸化物が好適に用いられる。
プロピレン、イソブチレン、ｔ−ブチルアルコールおよびメチル−ｔ−ブチルエーテルからなる群より選ばれる少なくとも１種の化合物を原料とし、前記原料に対応する不飽和アルデヒドおよび／または不飽和カルボン酸を製造する場合、プロピレン、イソブチレン、ｔ−ブチルアルコールおよびメチル−ｔ−ブチルエーテルからなる群より選ばれる少なくとも１種の化合物を原料とし、接触気相酸化反応により、この原料に対応する不飽和アルデヒドおよび／または不飽和カルボン酸を製造し得る触媒成分であればいずれも使用できるが、例えば、下記一般式（１）で表される酸化物および／または複合酸化物が好適に用いられる。
The catalyst that can be used in the present invention may be a molded catalyst in which only the catalyst component is molded into a certain shape, or a supported catalyst in which the catalyst component is supported on an arbitrary inert carrier having a certain shape. Alternatively, it may be a combination of these molding catalyst and supported catalyst, and is not limited.
As the catalyst component used in the catalyst that can be used in the present invention, the following oxides and / or composite oxides are preferably used.
When producing an unsaturated aldehyde and / or unsaturated carboxylic acid corresponding to the raw material using at least one compound selected from the group consisting of propylene, isobutylene, t-butyl alcohol and methyl-t-butyl ether as a raw material, An unsaturated aldehyde and / or an unsaturated carboxylic acid corresponding to this raw material by catalytic gas phase oxidation reaction using at least one compound selected from the group consisting of isobutylene, t-butyl alcohol and methyl-t-butyl ether Any catalyst component can be used as long as it is capable of producing an oxide, and for example, an oxide and / or a composite oxide represented by the following general formula (1) is preferably used.
ＭｏａＷｂＢｉｃＦｅｄＡｅＢｆＣｇＤｈＯｘ （１）
（ここで、Ｍｏはモリブデン、Ｗはタングステン、Ｂｉはビスマス、Ｆｅは鉄、Ａはコバルトおよびニッケルから選ばれる少なくとも１種の元素、Ｂはホウ素、リン、クロム、亜鉛、ニオブ、スズ、アンチモン、セリウムおよび鉛から選ばれる少なくとも１種の元素、Ｃはアルカリ金属から選ばれる少なくとも１種の元素、Ｄはシリコン、アルミニウム、チタニウムおよびジルコニウムから選ばれる少なくとも１種の元素、そしてＯは酸素であり、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ、ｈおよびｘはそれぞれＭｏ、Ｗ、Ｂｉ、Ｆｅ、Ａ、Ｂ、Ｃ、ＤおよびＯの原子比を表し、ａ＝１２のとき、０≦ｂ≦５、０．１≦ｃ≦１０、０．１≦ｄ≦１０、１≦ｅ≦２０、０≦ｆ≦５、０．００１≦ｇ≦３、０≦ｈ≦１００であり、ｘはそれぞれの元素の酸化状態によって定まる数値である。）
不飽和アルデヒドを原料とし、前記原料に対応する不飽和カルボン酸を製造する場合、不飽和アルデヒドを原料とし、接触気相酸化反応により、この原料に対応する不飽和カルボン酸を製造し得る触媒成分であればいずれも使用できるが、例えば、下記一般式（２）で表される酸化物および／または複合酸化物が好適に用いられる。
Mo a W b Bi c Fe d A e B f C g D h O x (1)
(Where Mo is molybdenum, W is tungsten, Bi is bismuth, Fe is iron, A is at least one element selected from cobalt and nickel, B is boron, phosphorus, chromium, zinc, niobium, tin, antimony, At least one element selected from cerium and lead, C is at least one element selected from alkali metals, D is at least one element selected from silicon, aluminum, titanium and zirconium, and O is oxygen; a, b, c, d, e, f, g, h, and x represent atomic ratios of Mo, W, Bi, Fe, A, B, C, D, and O, respectively, and when a = 12, 0 ≦ b ≦ 5, 0.1 ≦ c ≦ 10, 0.1 ≦ d ≦ 10, 1 ≦ e ≦ 20, 0 ≦ f ≦ 5, 0.001 ≦ g ≦ 3, 0 ≦ h ≦ 100, and x is Oxidation of each element Is a numerical value determined by the state.)
When an unsaturated aldehyde is used as a raw material and an unsaturated carboxylic acid corresponding to the raw material is produced, a catalyst component that can produce an unsaturated carboxylic acid corresponding to the raw material by a catalytic gas phase oxidation reaction using the unsaturated aldehyde as a raw material Any of these can be used, but for example, oxides and / or composite oxides represented by the following general formula (2) are preferably used.
ＭｏａＶｂＷｃＡｄＢｅＣｆＤｇＥｈＯｘ （２）
（一般式（２）中、Ｍｏはモリブデン、Ｖはバナジウム、Ｗはタングステン、Ａはアンチモンおよびスズから選ばれる少なくとも１種の元素、Ｂは銅および鉄から選ばれる少なくとも１種の元素、Ｃはマグネシウム、カルシウム、ストロンチウムおよびバリウムから選ばれる少なくとも１種の元素、Ｄはチタン、ジルコニウムおよびセリウムから選ばれる少なくとも１種の元素、Ｅはアルカリ金属から選ばれる少なくとも１種の元素、Ｏは酸素を表し、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ、ｈおよびｘはそれぞれＭｏ、Ｖ、Ｗ、Ａ、Ｂ、Ｃ、Ｄ、ＥおよびＯの原子比を表し、ａ＝１２のとき、ｂ＝２〜１４、ｃ＝０〜１２、ｄ＝０〜５、ｅ＝０〜６、ｆ＝０〜３、ｇ＝０〜１０、ｈ＝０〜５、ｘはそれぞれの元素の酸化状態によって定まる数値である。）
上記一般式（１）、（２）で表される酸化物および／または複合酸化物は、従来公知の方法によって調製することができる。
Mo a V b W c Ad Be C f D g E h O x (2)
(In general formula (2), Mo is molybdenum, V is vanadium, W is tungsten, A is at least one element selected from antimony and tin, B is at least one element selected from copper and iron, and C is At least one element selected from magnesium, calcium, strontium and barium, D represents at least one element selected from titanium, zirconium and cerium, E represents at least one element selected from alkali metals, and O represents oxygen. , A, b, c, d, e, f, g, h, and x represent the atomic ratio of Mo, V, W, A, B, C, D, E, and O, respectively, and when a = 12, = 2 to 14, c = 0 to 12, d = 0 to 5, e = 0 to 6, f = 0 to 3, g = 0 to 10, h = 0 to 5, x depends on the oxidation state of each element It is a fixed number .)
The oxides and / or composite oxides represented by the general formulas (1) and (2) can be prepared by a conventionally known method.
上記触媒成分を得るための出発原料としては、限定はされず、一般にこの種の触媒に使用される金属元素のアンモニウム塩、硝酸塩、炭酸塩、塩化物、硫酸塩、水酸化物、有機酸塩、酸化物またはこれらの混合物を組み合わせて用いればよいが、アンモニウム塩および硝酸塩が好適に用いられる。
出発原料の混合液（出発原料混合液）は、この種の触媒に一般に用いられている方法により調製すればよく、例えば、上記出発原料を順次水に混合して水溶液または水性スラリーとなるようにするが、出発原料の種類に応じて複数の水溶液または水性スラリーを調製した場合には、これらを順次混合すればよい。出発原料の混合条件（混合順序、温度、圧力、ｐＨ等）については、限定はされない。
The starting material for obtaining the above catalyst component is not limited and is generally an ammonium salt, nitrate, carbonate, chloride, sulfate, hydroxide, organic acid salt of a metal element used in this type of catalyst. An oxide or a mixture thereof may be used in combination, but ammonium salts and nitrates are preferably used.
The mixture of starting materials (starting material mixture) may be prepared by a method generally used for this type of catalyst. For example, the starting materials are sequentially mixed with water to form an aqueous solution or an aqueous slurry. However, when a plurality of aqueous solutions or aqueous slurries are prepared according to the type of starting material, these may be mixed sequentially. There are no limitations on the starting material mixing conditions (mixing order, temperature, pressure, pH, etc.).
調製された出発原料の混合液は、各種方法により乾燥させて乾燥物（触媒前駆体とも言う。以下においても同様である。）とする。例えば、加熱により乾燥させる方法や、減圧により乾燥させる方法が挙げられる。なかでも、乾燥物を得るための加熱方法および乾燥物の形態については、例えば、スプレードライヤー、ドラムドライヤー等を用いて粉末状の乾燥物を得るようにしてもよいし、箱型乾燥機、トンネル型乾燥機等を用いて気流中で加熱してブロック状またはフレーク状の乾燥物を得るようにしてもよい。また、乾燥物を得るための加熱方法には、出発原料の混合液を蒸発乾固（濃縮乾固）してケーキ状の固形物を得て、この固形物をさらに上記加熱処理する場合もある。一方、減圧により乾燥させる方法および乾燥物の形態については、例えば、真空乾燥機等を用いてブロック状または粉末状の乾燥物を得るようにしてよい。 The prepared mixture of starting materials is dried by various methods to obtain a dried product (also referred to as a catalyst precursor; the same applies hereinafter). For example, the method of drying by heating and the method of drying by decompression are mentioned. Among them, as for the heating method for obtaining a dried product and the form of the dried product, for example, a powdered dried product may be obtained using a spray dryer, a drum dryer, etc., a box-type dryer, a tunnel You may make it obtain a block-shaped or flake-shaped dried material by heating in airflow using a type | mold dryer etc. FIG. In addition, as a heating method for obtaining a dried product, a mixed liquid of starting materials is evaporated to dryness (concentrated to dryness) to obtain a cake-like solid, and this solid may be further subjected to the above heat treatment. . On the other hand, regarding the method of drying under reduced pressure and the form of the dried product, for example, a block or powdered dried product may be obtained using a vacuum dryer or the like.
得られた乾燥物は、必要に応じて適当な粒度の粉体を得るための粉砕工程や分級工程を経て、続く成形工程に送られる。また、成形工程に送られる前に、得られた乾燥物を焼成してもよい。
触媒の成形方法は、所望の形状を有する粒状触媒（担持型触媒を含む）を形成できる方法であれば特に限定されず、従来公知の方法を採用できる。例えば、転動造粒法、押出成形法（押出し成形機）、打錠成形法、マルメライザー法、含浸法、蒸発乾固法およびスプレー法などが挙げられる。
成形工程においては、触媒成分の前駆体となる乾燥物を成形する（乾燥物の担体への担持を含む）にあたり液状バインダー等を用いることができる。
The obtained dried product is sent to a subsequent molding step through a pulverization step and a classification step for obtaining a powder having an appropriate particle size as required. Moreover, you may bake the obtained dried material before sending to a shaping | molding process.
The method for forming the catalyst is not particularly limited as long as it is a method capable of forming a granular catalyst (including a supported catalyst) having a desired shape, and a conventionally known method can be adopted. Examples thereof include a rolling granulation method, an extrusion molding method (extrusion molding machine), a tableting molding method, a malmerizer method, an impregnation method, an evaporation to dryness method, and a spray method.
In the molding step, a liquid binder or the like can be used for molding a dried product that is a precursor of the catalyst component (including supporting the dried product on a carrier).
なお、本発明で用いる触媒を得るにあたっては、前述した製法のほかに、出発原料混合液を乾燥させずに液のまま用い、所望の担体に該液を吸収させたり、塗布したりして、触媒成分を担体に担持させる方法（例えば、蒸発乾固法、スプレー法など）も採用できる。よって、担体に触媒成分を担持させる方法としては、前述した乾燥物を担持させる方法のほかに、出発原料混合液そのものを担持させる方法も挙げることができる。
上記液状バインダーとしては、特に限定はされないが、一般にこの種の触媒の成形や担持に用いられるバインダーを使用できる。具体的には、水のほか、エチレングリコール、グリセリン、プロピオン酸、ベンジルアルコール、プロピルアルコール、ポリビニルアルコール、フェノールなどの有機化合物や、硝酸、シリカゾルなどが使用できる。また、これらは１種のみ用いても、２種以上を併用してもよい。
In obtaining the catalyst used in the present invention, in addition to the production method described above, the starting raw material mixture is used as it is without being dried, and the desired carrier is absorbed or coated, A method of supporting the catalyst component on a carrier (for example, evaporation to dryness, spraying, etc.) can also be employed. Therefore, as a method of supporting the catalyst component on the carrier, in addition to the method of supporting the dried product described above, a method of supporting the starting raw material mixture itself can also be mentioned.
Although it does not specifically limit as said liquid binder, Generally the binder used for shaping | molding and carrying | support of this kind of catalyst can be used. Specifically, in addition to water, organic compounds such as ethylene glycol, glycerin, propionic acid, benzyl alcohol, propyl alcohol, polyvinyl alcohol, and phenol, nitric acid, silica sol, and the like can be used. These may be used alone or in combination of two or more.
本発明で用い得る触媒を得る場合には、成形性を向上させ得る成形助剤や、触媒の強度を向上させる補強剤、触媒に適度な細孔を形成させる気孔形成剤など、一般に触媒の製造においてこれらの効果を目的として使用されている各種物質を用いることができる。これら各種物質としては、例えば、ステアリン酸、マレイン酸、硝酸アンモニウム、炭酸アンモニウム、グラファイト、でんぷん、セルロース、シリカ、アルミナ、ガラス繊維、炭化珪素、窒化珪素などが挙げられ、添加によって触媒性能（例えば、活性、目的生成物の選択性等）に悪影響を及ぼさないものが好ましい。これら各種物質は、例えば、上記液状バインダーや、出発原料混合液、出発原料混合液の乾燥物などに添加・混合して用いることができる。これら物質は、添加量が過剰な場合、触媒の機械強度を著しく低下させる場合があるので、工業触媒として実用不可能な程度まで触媒の機械強度が低下しない程度の量を添加することが好ましい。 In the case of obtaining a catalyst that can be used in the present invention, it is generally possible to produce a catalyst such as a molding aid that can improve moldability, a reinforcing agent that improves the strength of the catalyst, or a pore-forming agent that forms appropriate pores in the catalyst. Various substances used for the purpose of these effects can be used. Examples of these various substances include stearic acid, maleic acid, ammonium nitrate, ammonium carbonate, graphite, starch, cellulose, silica, alumina, glass fiber, silicon carbide, silicon nitride, and the like. Those which do not adversely affect the selectivity of the target product) are preferred. These various substances can be used, for example, by adding to and mixing with the above-mentioned liquid binder, starting material mixture, dried starting material mixture, and the like. When these substances are added in an excessive amount, the mechanical strength of the catalyst may be significantly reduced. Therefore, it is preferable to add such an amount that the mechanical strength of the catalyst does not decrease to the extent that it cannot be used as an industrial catalyst.
本発明で用い得る触媒の形状については、限定はされず、例えば、球状および円柱状（ペレット状）など、いずれでもよいが、なかでも球状、円柱状が好ましい。上記触媒の形状は、さらに孔部をも有する形状であってもよく、限定はされない。さらに孔部をも有する形状の場合、孔部は貫通形（リング状）であってもよく、底付きの凹部形であってもよいが、好ましくは貫通した孔部である。もちろん、例えば球状の場合、真球である必要はなく、実質的に球状であればよい。この点は、円柱状の場合もその断面形状等において同様である。なお、球状の場合、真球であれば当該球体の直径を、真球でないときには最長外径と最短外径の平均値を、当該球状触媒の直径Ｄとして扱う。円柱状の場合、軸心（円軸）に対し垂直方向の断面が真円形状であれば当該真円の直径を、真円形状でないときには最長外径と最短外径の平均値を、当該円柱状触媒の断面の直径Ｄとして扱う。 The shape of the catalyst that can be used in the present invention is not limited, and may be any of, for example, a spherical shape and a cylindrical shape (pellet shape). Among them, a spherical shape and a cylindrical shape are preferable. The shape of the catalyst may be a shape having holes, and is not limited. Further, in the case of a shape having a hole portion, the hole portion may be a through shape (ring shape) or a concave shape with a bottom, but is preferably a through hole portion. Of course, for example, in the case of a spherical shape, it is not necessary to be a true sphere, and it may be substantially spherical. This is the same in the cross-sectional shape of the cylindrical shape. In the case of a spherical shape, the diameter of the spherical body is treated as the diameter D of the spherical catalyst, and the average value of the longest outer diameter and the shortest outer diameter is treated as the diameter D of the spherical catalyst. In the case of a cylindrical shape, if the cross section perpendicular to the axis (circular axis) is a perfect circle, the diameter of the true circle is calculated. If not, the average value of the longest outer diameter and the shortest outer diameter is calculated. Treated as the diameter D of the cross section of the columnar catalyst.
なお、本発明の接触気相酸化反応においては、１つの反応帯には、基本的に、同一形状かつ同一サイズとなり得る設定条件下で調製して得られた実質的に均一な触媒を充填するようにする。触媒の形状に関しては、各反応帯間で互いに同じであってもよいし異なっていてもよい（例えば、ガス入口側：球状触媒、ガス出口側：円柱状触媒）が、すべての反応帯において同一形状の触媒を充填するようにするのが好ましい。
本発明の接触気相酸化反応において言う触媒の「占有容積」とは、各反応管の触媒充填層（詳しくは各反応帯）に充填される触媒（触媒粒子）の１個あたりが占有する空間容積を意味する。なお、触媒（触媒粒子）の占有容積は、その形状に応じて、後述する算出式により求められるが、本発明では、所定の反応帯に充填される触媒の占有容積を算出するにあたっては、予め、その反応帯に充填される触媒から任意にサンプリングした１００個の全てについて直径Ｄや長さＬを実測しそれぞれ平均値を算出しておき、この平均直径や平均長さをその反応帯に充填する触媒の直径Ｄや長さＬとみなして、触媒の占有容積を求めることと定義する。この定義は、後述する実施例においても同様に適用される。
In the catalytic gas phase oxidation reaction of the present invention, one reaction zone is basically filled with a substantially uniform catalyst prepared under setting conditions that can be the same shape and size. Like that. The shape of the catalyst may be the same or different between the reaction zones (for example, gas inlet side: spherical catalyst, gas outlet side: cylindrical catalyst), but the same in all reaction zones It is preferable to fill the catalyst in the shape.
The “occupied volume” of the catalyst referred to in the catalytic gas phase oxidation reaction of the present invention is a space occupied by one catalyst (catalyst particle) filled in the catalyst packed bed (specifically, each reaction zone) of each reaction tube. Means volume. Note that the occupied volume of the catalyst (catalyst particles) can be obtained by a calculation formula described later according to the shape, but in the present invention, in calculating the occupied volume of the catalyst filled in a predetermined reaction zone, Measure the diameter D and length L of all 100 samples arbitrarily sampled from the catalyst packed in the reaction zone, calculate the average value, and fill the average diameter and average length into the reaction zone. The volume occupied by the catalyst is defined as the diameter D or length L of the catalyst. This definition is similarly applied to embodiments described later.
触媒の形状が球状である場合、その占有容積（Ｖ）は、下記式：
Ｖ（ｍｍ３）＝（４／３）×π×（Ｄ／２）３
（式中、Ｄ（ｍｍ）は球状触媒の直径を表す。）
により表すことができる。したがって、球状触媒の場合、その直径Ｄを変更することにより占有容積が異なる触媒を調製できる。
触媒の形状が円柱状である場合、その占有容積（Ｖ）は、下記式：
Ｖ（ｍｍ３）＝π×（Ｄ／２）２×Ｌ
（式中、Ｄ（ｍｍ）は円柱状触媒の円形断面の直径を表し、Ｌ（ｍｍ）は軸心方向の長さを表す。）
により表すことができる。したがって、円柱状触媒の場合、その直径Ｄおよび／または長さＬを変更することにより占有容積が異なる触媒を調製できる。
When the shape of the catalyst is spherical, the occupied volume (V) is represented by the following formula:
V (mm 3 ) = (4/3) × π × (D / 2) 3
(In the formula, D (mm) represents the diameter of the spherical catalyst.)
Can be represented by Therefore, in the case of a spherical catalyst, it is possible to prepare catalysts having different occupied volumes by changing the diameter D thereof.
When the shape of the catalyst is cylindrical, the occupied volume (V) is represented by the following formula:
V (mm 3 ) = π × (D / 2) 2 × L
(In the formula, D (mm) represents the diameter of the circular cross section of the cylindrical catalyst, and L (mm) represents the length in the axial direction.)
Can be represented by Therefore, in the case of a cylindrical catalyst, it is possible to prepare catalysts having different occupied volumes by changing the diameter D and / or the length L thereof.
本発明の接触気相酸化反応においては、使用する触媒の形状が、前述のさらに孔部をも有する形状の場合であっても、上記触媒の占有容積には影響を与えないものとし、孔部の大きさ（すなわち孔径、孔部の深さ、孔部容積など）は、任意に設定できる。
上記球状触媒または円柱状触媒においては、その直径Ｄおよび長さＬは、限定はされないが、いずれも３〜１５ｍｍであることが好ましく、より好ましくは４〜１０ｍｍである。直径Ｄおよび長さＬが、３ｍｍ未満の場合、触媒粒子が小さすぎてホットスポット部の温度が上昇しやすくなるおそれがあり、１５ｍｍを超えると、触媒粒子が大きすぎて各反応管への充填が困難となるおそれがある。円柱状触媒においては、特にその長さＬは、その直径Ｄの０．５〜２．０倍であることが好ましく、より好ましくは０．７〜１．５倍である。
In the catalytic gas phase oxidation reaction of the present invention, even if the shape of the catalyst to be used is a shape having holes as described above, the occupied volume of the catalyst is not affected. The size (namely, hole diameter, hole depth, hole volume, etc.) can be arbitrarily set.
In the spherical catalyst or the columnar catalyst, the diameter D and the length L are not limited, but are preferably 3 to 15 mm, more preferably 4 to 10 mm. If the diameter D and the length L are less than 3 mm, the catalyst particles may be too small and the temperature of the hot spot may be easily increased. If the diameter D exceeds 15 mm, the catalyst particles are too large to fill each reaction tube. May become difficult. In the columnar catalyst, the length L is preferably 0.5 to 2.0 times the diameter D, more preferably 0.7 to 1.5 times.
本発明の接触気相酸化反応に用いる触媒が担持型触媒の場合、担体としては、接触気相酸化反応用触媒を製造する際に通常用いることができる担体であれば、その材質等は限定はされず、いずれも使用することができる。例えば、アルミナ、シリカ、シリカ・アルミナ、チタニア、マグネシア、シリカ・マグネシア、シリカ・マグネシア・アルミナ、炭化珪素、窒化珪素、ゼオライトなどを含んでなる一定の形状を有する担体が挙げられる。触媒の形状が、前述のさらに孔部をも有する形状である場合は、孔部を有する担体を用いるようにすればよい。
担持型触媒の場合、触媒成分の担持率は、酸化反応条件、触媒の活性、および強度等を勘案して最適な活性および選択性が得られるように適宜決定されるが、好ましくは５〜９５質量％、より好ましくは２０〜９０質量％である。なお、本発明の接触気相酸化反応においては、触媒成分の担持率は、各反応帯に充填する触媒どうし互いに同じであってもよいし異なっていてもよく、限定はされない。ここで、担持率は、下記式により求められる値とする。
When the catalyst used in the catalytic gas phase oxidation reaction of the present invention is a supported catalyst, the carrier is not limited as long as it is a carrier that can be normally used in the production of a catalytic gas phase oxidation reaction catalyst. Neither can be used. Examples thereof include a carrier having a certain shape including alumina, silica, silica / alumina, titania, magnesia, silica / magnesia, silica / magnesia / alumina, silicon carbide, silicon nitride, zeolite, and the like. In the case where the shape of the catalyst is a shape having a hole portion as described above, a support having a hole portion may be used.
In the case of a supported catalyst, the loading ratio of the catalyst component is appropriately determined so as to obtain optimum activity and selectivity in consideration of oxidation reaction conditions, catalyst activity, strength, etc., preferably 5 to 95. It is 20 mass%, More preferably, it is 20-90 mass%. In the catalytic gas phase oxidation reaction of the present invention, the catalyst component loading may be the same as or different from each other, and the catalyst charged in each reaction zone is not limited. Here, the carrying rate is a value obtained by the following formula.
担持率（質量％）＝〔（得られた触媒の質量（ｇ）−用いた担体の質量（ｇ））／得られた触媒の質量（ｇ）〕×１００
触媒調製時の熱処理条件（いわゆる焼成条件）についても、限定はされず、この種の触媒製造において一般的に採用されている焼成条件を適用できる。熱処理温度としては、プロピレン、イソブチレン、ｔ−ブチルアルコールおよびメチル−ｔ−ブチルエーテルからなる群より選ばれる少なくとも１種の化合物を原料とし、前記原料に対応する不飽和アルデヒドおよび／または不飽和カルボン酸を製造する場合に用いる触媒の場合、好ましくは３５０〜６５０℃、より好ましくは４００〜６００℃であり、不飽和アルデヒドを原料とし、前記原料に対応する不飽和カルボン酸を製造する場合、好ましくは３００〜５００℃、より好ましくは３５０〜４５０℃である。熱処理時間としては、好ましくは１〜２４時間、より好ましくは３〜１２時間である。なお、本発明の接触気相酸化反応においては、上記焼成条件は、各反応帯に充填する触媒どうし互いに同じであってもよいし異なっていてもよく、限定はされない。
Loading rate (mass%) = [(mass of the obtained catalyst (g) −mass of the used carrier (g)) / mass of the obtained catalyst (g)] × 100
The heat treatment conditions (so-called calcination conditions) at the time of catalyst preparation are also not limited, and calcination conditions generally employed in this type of catalyst production can be applied. As the heat treatment temperature, at least one compound selected from the group consisting of propylene, isobutylene, t-butyl alcohol and methyl-t-butyl ether is used as a raw material, and an unsaturated aldehyde and / or unsaturated carboxylic acid corresponding to the raw material is used. In the case of a catalyst used for production, it is preferably 350 to 650 ° C., more preferably 400 to 600 ° C., and when an unsaturated aldehyde is produced from an unsaturated aldehyde as a raw material, preferably 300 It is -500 degreeC, More preferably, it is 350-450 degreeC. The heat treatment time is preferably 1 to 24 hours, more preferably 3 to 12 hours. In the catalytic gas phase oxidation reaction of the present invention, the calcination conditions may be the same or different from each other in the catalysts filled in each reaction zone, and are not limited.
本発明の接触気相酸化反応においては、反応に使用する固定床多管式反応器における各反応管の触媒充填層が管軸方向に複数の反応帯に分けられていて、この複数の反応帯の少なくとも２つにおいて前述した占有容積が異なるように各反応帯のそれぞれに触媒が充填され、かつ、上記複数の反応帯の少なくとも１つにおいて不活性物質成形体が混合されていることが重要である。
触媒充填層における反応帯の数は、限定されないが、工業的には２または３程度にすることが好ましく、目的とする効果を十分に得ることができる。また、触媒充填層の分割比（各反応帯の触媒充填層長の比）については、酸化反応条件や各層に充填された触媒の組成、形状、サイズなどによって最適値が左右されるため一概に特定できず、全体としての最適な活性および選択率が得られるように適宜選択すればよい。
In the catalytic gas phase oxidation reaction of the present invention, the catalyst packed bed of each reaction tube in the fixed-bed multitubular reactor used for the reaction is divided into a plurality of reaction zones in the tube axis direction. It is important that at least two of the reaction zones are filled with a catalyst so that the above-mentioned occupied volumes are different, and that an inert material compact is mixed in at least one of the plurality of reaction zones. is there.
The number of reaction zones in the catalyst packed bed is not limited, but is preferably about 2 or 3 industrially, and the desired effect can be sufficiently obtained. In addition, the optimum ratio of the catalyst packed bed split ratio (ratio of catalyst packed bed length in each reaction zone) depends on the oxidation reaction conditions and the composition, shape, size, etc. of the catalyst packed in each layer. What is necessary is just to select suitably so that the optimal activity and selectivity as a whole cannot be obtained.
本発明の接触気相酸化反応において、触媒の占有容積に関する具体的な触媒充填態様については、前述したように複数の反応帯の少なくとも２つ（隣り合っていても離れていてもよい）において異なる態様であればよく、限定はされないが、好ましくは、最もガス入口側の反応帯より最もガス出口側の反応帯の方が充填された触媒の占有容積が小さくなる態様であり、より好ましくは、最もガス入口側の反応帯より最もガス出口側の反応帯の方が充填された触媒の占有容積が小さく、かつ、任意の隣り合う２つの反応帯においてそのガス入口側の反応帯よりそのガス出口側の反応帯の方が充填された触媒の占有容積が大きくなることはない（すなわち、小さいか又は同一）態様であり、さらに好ましくは、最もガス入口側の反応帯から最もガス出口側の反応帯に向けて充填された触媒の占有容積が順に小さくなる態様である。より具体的には、例えば、反応帯を３つ設け、ガス入口側からガス出口側に向けて第１反応帯、第２反応帯、第３反応帯とした場合においては、触媒の占有容積が、第１反応帯から第３反応帯へ順に小さくなる態様でもよいし、第１反応帯より第２反応帯の方が小さく第２反応帯と第３反応帯とでは同じである態様でもよいし、第１反応帯と第２反応帯とは同じであり第２反応帯より第３反応帯の方が小さくなる態様でもよいし、第１反応帯より第２反応帯の方が大きく第２反応帯より第３反応帯の方が小さくなり、かつ、第１反応帯より第３反応帯の方が小さくなる態様でもよいし、第１反応帯より第２反応帯の方が小さく第２反応帯より第３反応帯の方が大きくなり、かつ、第１反応帯より第３反応帯の方が小さくなる態様でもよく、これらに限定はされない。 In the catalytic gas phase oxidation reaction of the present invention, the specific catalyst filling mode relating to the occupied volume of the catalyst is different in at least two of the reaction zones (which may be adjacent or separated) as described above. Although the embodiment is not limited, it is preferable that the occupied volume of the catalyst filled in the reaction zone closest to the gas outlet is smaller than the reaction zone closest to the gas inlet, and more preferably, The occupied volume of the catalyst filled in the reaction zone on the gas outlet side is smaller than the reaction zone on the gas inlet side, and the gas outlet is smaller than the reaction zone on the gas inlet side in any two adjacent reaction zones. The side reaction zone has a mode in which the occupied volume of the packed catalyst does not increase (that is, it is small or the same), and more preferably, the most gas from the reaction zone on the most gas inlet side. Occupied volume of the filled catalyst toward the reaction zone on the outlet side is smaller aspect in order. More specifically, for example, in the case where three reaction zones are provided and the first reaction zone, the second reaction zone, and the third reaction zone are provided from the gas inlet side to the gas outlet side, the occupied volume of the catalyst is Alternatively, the first reaction zone may decrease in order from the third reaction zone, or the second reaction zone may be smaller than the first reaction zone, and the second reaction zone and the third reaction zone may be the same. The first reaction zone and the second reaction zone may be the same, and the third reaction zone may be smaller than the second reaction zone, or the second reaction zone may be larger than the first reaction zone. The third reaction zone may be smaller than the first reaction zone, and the third reaction zone may be smaller than the first reaction zone, or the second reaction zone may be smaller than the first reaction zone. The third reaction zone may be larger and the third reaction zone may be smaller than the first reaction zone. Luo but are not limited to.
本発明において、各反応帯は、反応に使用する固定床多管式反応器における各反応管の管軸方向に整列した形態、すなわち、各反応帯の境界が反応管の断面と平行の状態で配置された形態が好ましいが、この形態に限定はされず、例えば、各反応帯の境界が反応管の断面とある角度を有した状態（傾斜した状態）で配置された形態でもよい。また、各反応帯の境界の一部が反応管の断面と平行の状態であって残りの部分が反応管の断面とある角度を有した状態（傾斜した状態）で配置された形態でもよい。
上記触媒の占有容積に関する触媒充填態様については、特に好ましくは、隣接する２つに反応帯における触媒の占有容積の比が、特定範囲にあるように調整することであり、ホットスポット部での蓄熱の抑制の点で非常に優れた効果が得られる。具体的には、２つの隣接する反応帯において、そのガス入口側の反応帯での占有容積をＶ１とし、ガス出口側の反応帯での占有容積をＶ２としたとき、例えば、Ｖ１／Ｖ２が１．２／１〜６４／１となるようにするのが好ましく、より好ましくはＶ１／Ｖ２＝１．３／１〜２７／１である。上記占有容積の比（Ｖ１／Ｖ２）が、１．２／１より小さい場合は、ホットスポット部での蓄熱の抑制効果が十分に得られず、反応帯を複数設けることの意義がなくなるおそれがあり、６４／１より大きい場合は、占有容積の小さいほうの反応帯におけるホットスポット部での蓄熱を抑制するために低い生産性に甘んじる必要が生じ、また反応帯での圧力損失が大きくなるおそれがある。
In the present invention, each reaction zone is aligned in the axial direction of each reaction tube in the fixed bed multitubular reactor used for the reaction, that is, the boundary of each reaction zone is parallel to the cross section of the reaction tube. However, the present invention is not limited to this configuration. For example, a configuration in which the boundary of each reaction zone has an angle with the cross section of the reaction tube (an inclined state) may be used. Moreover, the form arrange | positioned in the state (inclined state) in which the part of the boundary of each reaction zone was in the state parallel to the cross section of the reaction tube, and the remaining part had an angle with the cross section of the reaction tube may be sufficient.
Regarding the catalyst filling aspect related to the occupied volume of the catalyst, particularly preferably, the ratio of the occupied volume of the catalyst in the reaction zone to the adjacent two is adjusted so as to be in a specific range, and heat storage in the hot spot portion is performed. A very excellent effect is obtained in terms of suppression of the above. Specifically, in two adjacent reaction zones, when the occupied volume in the reaction zone of the gas inlet side is V 1, the occupied volume of the reaction zone of the gas outlet side was set to V 2, for example, V 1 / V 2 is preferably 1.2 / 1 to 64/1, more preferably V 1 / V 2 = 1.3 / 1 to 27/1. When the ratio of the occupied volume (V 1 / V 2 ) is smaller than 1.2 / 1, the effect of suppressing heat storage at the hot spot is not sufficiently obtained, and it is not meaningful to provide a plurality of reaction zones. If it is larger than 64/1, it is necessary to be satisfied with low productivity in order to suppress the heat storage in the hot spot in the reaction zone with the smaller occupied volume, and the pressure loss in the reaction zone is large. There is a risk.
本発明の接触気相酸化反応において、不活性物質成形体の混合に関する具体的な充填態様については、前述のごとく複数の反応帯の少なくとも１つにおいて触媒とともに不活性物質成形体をも混合して、触媒活性を低下させる（希釈させる）ようにすればよく、限定はされないが、例えば、最もガス入口側の反応帯において不活性物質成形体を混合する態様や、すべての反応帯において不活性物質成形体を混合する態様が挙げられるが、好ましくは、最もガス入口側の反応帯において不活性物質成形体を混合する態様である。より具体的には、例えば、前述のごとく、反応帯を３つ設け、ガス入口側からガス出口側に向けて第１反応帯、第２反応帯、第３反応帯とした場合においては、不活性物質成形体を混合する反応帯は、第１反応帯のみでもよいし、第１反応帯および第２反応帯のみでもよいし、第１〜第３反応帯のすべてでもよく、限定はされないが、好ましくは、第１反応帯のみに不活性物質成形体を混合する態様、または、第１反応帯および第２反応帯に不活性物質成形体を混合する態様である。 In the catalytic gas phase oxidation reaction of the present invention, the specific filling mode relating to the mixing of the inert substance molded body is as described above, in which at least one of the plurality of reaction zones is mixed with the inert substance molded body together with the catalyst. The catalyst activity may be reduced (diluted), and is not limited. For example, an embodiment in which an inert substance molded body is mixed in the reaction zone closest to the gas inlet, or an inert substance in all reaction zones. Although the aspect which mixes a molded object is mentioned, Preferably, it is an aspect which mixes an inert substance molded object in the reaction zone of the most gas inlet side. More specifically, for example, as described above, when three reaction zones are provided and the first reaction zone, the second reaction zone, and the third reaction zone are set from the gas inlet side toward the gas outlet side, the The reaction zone for mixing the active substance molded body may be only the first reaction zone, only the first reaction zone and the second reaction zone, or all of the first to third reaction zones, and is not limited. Preferably, it is an embodiment in which the inert substance molded body is mixed only in the first reaction zone, or an inert substance molded body is mixed in the first reaction zone and the second reaction zone.
本発明で使用する不活性物質成形体としては、反応ガスに実質的に不活性な物質であればいずれも使用することができる。例えば、一般に不活性担体として用いられている、アルミナ、シリカ、シリカ・アルミナ、ジルコニア、チタニア、マグネシア、シリカ・マグネシア、シリカ・マグネシア・アルミナ、炭化珪素、窒化珪素、ゼオライトから選ばれる少なくとも１種の成分を含んでなる、一定形状を有する成形体が挙げられる。
不活性物質成形体の形状については、特に制限はなく、球状、円柱状（ペレット状）、あるいはリング状など、いずれでも良い。
本発明で使用する不活性物質成形体は、以下に示す（Ａ）であっても（Ｂ）であっても良い。
As the inert substance molded body used in the present invention, any substance that is substantially inert to the reaction gas can be used. For example, at least one selected from alumina, silica, silica / alumina, zirconia, titania, magnesia, silica / magnesia, silica / magnesia / alumina, silicon carbide, silicon nitride, and zeolite, which is generally used as an inert carrier The molded object which has a fixed shape which contains a component is mentioned.
There is no restriction | limiting in particular about the shape of an inert substance molded object, Any may be spherical, cylindrical shape (pellet shape), or ring shape.
The inactive substance molded body used in the present invention may be (A) or (B) shown below.
（Ａ）不活性物質の粉砕物。具体的には、不活性物質を粉砕後、所定の粒子径になるように篩にかけたものや、所定の形状（球状等）になるように調整したもの。
（Ｂ）不活性物質の微粒子や粉砕物に糊剤や添加剤を混ぜ、担体形状（球状、円盤状、円柱状、ペレット状等）に成形したもの。
本発明で使用できる不活性物質については、その製造方法、形状は特に限定されない。本発明で使用する不活性物質成形体としては、形状がそろっており、必要な大きさ、形状のものを得やすく、反応管の条件を調整しやすい充填が可能になる点で、上記（Ｂ）の場合が好ましい。
(A) Inactive substance pulverized product. Specifically, an inert substance is crushed and then sieved to a predetermined particle size, or adjusted to have a predetermined shape (spherical shape, etc.).
(B) A paste or additive mixed with fine particles of an inert substance or pulverized product, and formed into a carrier shape (spherical, disc-shaped, cylindrical, pellet-shaped, etc.).
About the inert substance which can be used by this invention, the manufacturing method and shape are not specifically limited. The inactive substance molded body used in the present invention has a uniform shape, it is easy to obtain a necessary size and shape, and the above-mentioned (B ) Is preferred.
上記球状の不活性物質成形体や円柱状の不活性物質成形体においては、その直径Ｄおよび長さＬは、限定はされないが、いずれも３〜１５ｍｍであることが好ましく、より好ましくは４〜１０ｍｍである。直径Ｄおよび長さＬが、３ｍｍ未満の場合、不活性物質成形体が小さすぎてホットスポット部の温度が上昇しやすくなるおそれがあり、１５ｍｍを超えると、不活性物質成形体が大きすぎて各反応管への充填が困難となるおそれがある。円柱状の不活性物質成形体においては、特にその長さＬは、その直径Ｄの０．５〜２．０倍であることが好ましく、より好ましくは０．７〜１．５倍である。
本発明で使用する不活性物質成形体の占有容積は、任意に設定することができるが、好ましくは混合する触媒の占有容積の２０〜２００容量％、より好ましくは３０〜１５０容量％である。
In the spherical inert substance molded body and the cylindrical inert substance molded body, the diameter D and the length L are not limited, but both are preferably 3 to 15 mm, more preferably 4 to 10 mm. If the diameter D and the length L are less than 3 mm, the inert substance molded body may be too small and the temperature of the hot spot part may be easily increased. If it exceeds 15 mm, the inert substance molded body is too large. There is a possibility that filling each reaction tube may be difficult. In the columnar inert substance molded body, the length L is preferably 0.5 to 2.0 times the diameter D, more preferably 0.7 to 1.5 times.
The occupied volume of the inactive substance molded body used in the present invention can be arbitrarily set, but is preferably 20 to 200% by volume, more preferably 30 to 150% by volume of the occupied volume of the catalyst to be mixed.
本発明で使用する不活性物質成形体の形状、大きさは、前述した本発明で用い得る担体の形状、大きさであってもよい。
上記不活性物質成形体の混合に関する充填態様については、不活性物質成形体の混合率は、８０容積％以下であることが好ましく、より好ましくは５〜６０容積％、さらに好ましくは１０〜５０容積％である。上記混合率が８０容積％を超えると、活性が著しく低下して反応効率が悪化するばかりか、反応管中の触媒成分の絶対量が少なくなり過ぎて触媒寿命が短縮されてしまうおそれがある。不活性物質成形体の混合率の定義については、後述する実施例において説明する。
The shape and size of the molded body of the inert material used in the present invention may be the shape and size of the carrier that can be used in the present invention described above.
About the filling aspect regarding the mixing of the above-mentioned inert substance molded body, the mixing ratio of the inert substance molded body is preferably 80% by volume or less, more preferably 5 to 60% by volume, still more preferably 10 to 50% by volume. %. When the mixing ratio exceeds 80% by volume, not only the activity is remarkably lowered and the reaction efficiency is deteriorated, but also the absolute amount of the catalyst component in the reaction tube becomes too small, and the catalyst life may be shortened. The definition of the mixing ratio of the inactive substance compact will be described in the examples described later.
なお、本発明の接触気相酸化反応においては、上記混合率は、不活性物質成形体が混合された各反応帯どうしで互いに同じであってもよいし異なっていてもよく、限定はされない。
本発明の接触気相酸化反応においては、触媒の充填態様として、前述した以外にも、さらに前記複数の反応帯に充填される触媒の活性が異なるようにすることが好ましい。当該活性の異なる触媒の調製方法は、限定されず、従来公知の調製方法を用いればよいが、例えば、アルカリ金属から選ばれる少なくとも１種の元素（本発明で用いることができる触媒成分（１）におけるＣ成分や触媒成分（２）におけるＥ成分のアルカリ金属（Ｌｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓなど））の種類および／または量を変える方法、担持率を変える方法、焼成温度を変える方法、および、これらの組み合わせによる方法などが挙げられる。なかでも、上記組み合わせによる方法が、触媒寿命や収率面で好ましい。このように活性の異なる複数の触媒を配列することによって、ホットスポット部における蓄熱を抑制し、また、長期間安定して高選択率で目的生成物を得ることができる。
In the contact gas phase oxidation reaction of the present invention, the mixing ratio may be the same or different between the reaction zones mixed with the inert substance molded body, and is not limited.
In the catalytic gas phase oxidation reaction of the present invention, it is preferable that the activity of the catalyst filled in the plurality of reaction zones is different from that described above as the catalyst filling mode. The method for preparing the catalyst having different activities is not limited, and a conventionally known preparation method may be used. For example, at least one element selected from alkali metals (catalyst component (1) that can be used in the present invention) A method of changing the type and / or amount of the alkali metal (Li, Na, K, Rb, Cs, etc.) of the E component in the C component or the catalyst component (2), a method of changing the loading rate, a method of changing the firing temperature, And the method by these combination etc. are mentioned. Especially, the method by the said combination is preferable in terms of catalyst life and a yield. By arranging a plurality of catalysts having different activities in this way, heat storage in the hot spot portion can be suppressed, and the target product can be obtained stably for a long period of time with high selectivity.
上記複数の反応帯に充填される触媒の活性が異なる場合の触媒の充填態様については、限定はされないが、例えば、ガス入口側の反応帯からガス出口側の反応帯に向かって活性が順に高くなるように充填する態様や、ガス入口側の反応帯からガス出口側の反応帯に向かって活性が一旦下がった後に高くなるように充填する態様などが挙げられ、好ましくは、前者の態様である。また、後者の態様においては、高活性触媒が充填されたガス入口側の反応帯の充填層長は、触媒充填層の全長の５０％以下が好ましく、より好ましくは２０％以下、さらに好ましくは１０％以下である。
本発明の接触気相酸化反応を実施するにあたっては、触媒の充填態様として前述した態様を採ること以外は、限定はされず、一般に用いられている装置、方法および条件を適宜採用して行うことができる。以下に、一般的接触気相酸化反応や接触気相酸化反応条件等について説明する。
The catalyst filling mode when the activities of the catalyst filled in the plurality of reaction zones are different is not limited. For example, the activity increases in order from the reaction zone on the gas inlet side to the reaction zone on the gas outlet side. And a mode in which the activity is once lowered from the reaction zone on the gas inlet side to the reaction zone on the gas outlet side, and the like, and the like is preferable. The former mode is preferable. . In the latter embodiment, the packed bed length of the reaction zone on the gas inlet side filled with the highly active catalyst is preferably 50% or less, more preferably 20% or less, and even more preferably 10% of the total length of the catalyst packed bed. % Or less.
In carrying out the catalytic gas phase oxidation reaction of the present invention, there is no limitation except that the above-described embodiment of the catalyst filling mode is adopted, and a generally used apparatus, method and conditions are appropriately adopted. Can do. Hereinafter, general contact gas phase oxidation reaction, contact gas phase oxidation reaction conditions, and the like will be described.
本発明の接触気相酸化反応は、通常の単流通法あるいはリサイクル法で行うことができる。
本発明の接触気相酸化反応の反応条件としては、プロピレン、イソブチレン、ｔ−ブチルアルコールおよびメチル−ｔ−ブチルエーテルからなる群より選ばれる少なくとも１種の化合物を原料とし、前記原料に対応する不飽和アルデヒドおよび／または不飽和カルボン酸を製造する場合、例えば、１〜１０容量％の原料ガスとしてのプロピレン、イソブチレン、ｔ−ブチルアルコールおよびメチル−ｔ−ブチルエーテルからなる群より選ばれる少なくとも１種の化合物、３〜２０容量％の酸素（分子状酸素）、０〜６０容量％の水蒸気、および、２０〜８０容量％の希釈剤としての不活性ガス（例えば、窒素および炭酸ガス等）などからなる混合ガス（反応ガス）を、２５０〜４５０℃の温度範囲で、３００〜５０００ｈｒ−１（ＳＴＰ）の空間速度で、各反応管に導入し、触媒と接触させて反応させること、などが挙げられる。不飽和アルデヒドを原料とし、前記原料に対応する不飽和カルボン酸を製造する場合、例えば、１〜１０容量％の原料ガスとしての不飽和アルデヒド（好ましくはアクロレイン）、０．５〜２０容量％の酸素（分子状酸素）、０〜６０容量％の水蒸気、および、２０〜８０容量％の希釈剤としての不活性ガス（例えば、窒素および炭酸ガス等）などからなる混合ガス（反応ガス）を、２００〜４００℃の温度範囲で、３００〜５０００ｈｒ−１（ＳＴＰ）の空間速度で、各反応管に導入し、触媒と接触させて反応させること、などが挙げられる。
The catalytic gas phase oxidation reaction of the present invention can be carried out by an ordinary single flow method or a recycling method.
As the reaction conditions for the catalytic gas phase oxidation reaction of the present invention, at least one compound selected from the group consisting of propylene, isobutylene, t-butyl alcohol and methyl-t-butyl ether is used as a raw material, and the unsaturated corresponding to the raw material When producing an aldehyde and / or an unsaturated carboxylic acid, for example, at least one compound selected from the group consisting of propylene, isobutylene, t-butyl alcohol, and methyl-t-butyl ether as a raw material gas of 1 to 10% by volume 3-20% by volume of oxygen (molecular oxygen), 0-60% by volume of water vapor, and 20-80% by volume of inert gas as a diluent (for example, nitrogen and carbon dioxide). gas (reaction gas), in the temperature range of 250~450 ℃, 300~5000hr -1 (STP) At a space velocity, it was introduced into each reaction tube, to react in contact with the catalyst, and the like. When an unsaturated aldehyde is used as a raw material and an unsaturated carboxylic acid corresponding to the raw material is produced, for example, an unsaturated aldehyde (preferably acrolein) as a raw material gas of 1 to 10% by volume, 0.5 to 20% by volume A mixed gas (reactive gas) composed of oxygen (molecular oxygen), 0 to 60% by volume of water vapor, and 20 to 80% by volume of an inert gas (for example, nitrogen and carbon dioxide) as a diluent, In the temperature range of 200 to 400 ° C., it is introduced into each reaction tube at a space velocity of 300 to 5000 hr −1 (STP), and brought into contact with a catalyst to cause a reaction.
本発明の接触気相酸化反応において、プロピレン、イソブチレン、ｔ−ブチルアルコールおよびメチル−ｔ−ブチルエーテルからなる群より選ばれる少なくとも１種の化合物を原料とし、前記原料に対応する不飽和カルボン酸を製造する場合、プロピレン、イソブチレン、ｔ−ブチルアルコールおよびメチル−ｔ−ブチルエーテルからなる群より選ばれる少なくとも１種の化合物から不飽和アルデヒドへの第１段反応と、不飽和アルデヒドから不飽和カルボン酸への第２段反応に関して、後述の実施例で示すように、第１段反応と第２段反応を別々の反応管を用いて行っても良いし、第１段反応を行う触媒充填層と第２段反応を行う触媒充填層とを一つの反応管に順番に配置して第１段反応と第２段反応を行っても良い。 In the catalytic gas phase oxidation reaction of the present invention, an unsaturated carboxylic acid corresponding to the raw material is produced using at least one compound selected from the group consisting of propylene, isobutylene, t-butyl alcohol and methyl-t-butyl ether as a raw material. A first stage reaction from at least one compound selected from the group consisting of propylene, isobutylene, t-butyl alcohol and methyl-t-butyl ether to an unsaturated aldehyde, and from an unsaturated aldehyde to an unsaturated carboxylic acid. Regarding the second stage reaction, the first stage reaction and the second stage reaction may be performed using separate reaction tubes, as shown in the examples described later, or the catalyst packed bed and the second stage for performing the first stage reaction. The first stage reaction and the second stage reaction may be performed by sequentially arranging the catalyst packed bed for performing the stage reaction in one reaction tube.
不飽和アルデヒドを原料とし、前記原料に対応する不飽和カルボン酸を製造する場合、原料ガスとしては、不飽和アルデヒド（好ましくはアクロレイン）の他に、例えば、モリブデン−ビスマス−鉄系の触媒を用いたプロピレンの接触気相酸化反応によって得られるアクロレイン含有ガスなど、別途の反応によって得られる不飽和アルデヒド含有ガス（好ましくはアクロレイン含有ガス）を用いることもできる。この場合、例えば、プロピレンの接触気相酸化反応によって得られるアクロレイン含有ガスに含まれるアクロレイン以外の成分、具体的には、アセトアルデヒド、酢酸、酸化炭素などの副生成物、未反応のプロピレン、プロパンなどの存在は、本発明に対して何ら影響を与えるものではない。 When an unsaturated aldehyde is used as a raw material and an unsaturated carboxylic acid corresponding to the raw material is produced, as a raw material gas, for example, a molybdenum-bismuth-iron-based catalyst is used in addition to the unsaturated aldehyde (preferably acrolein). An unsaturated aldehyde-containing gas (preferably an acrolein-containing gas) obtained by a separate reaction, such as an acrolein-containing gas obtained by a catalytic gas phase oxidation reaction of propylene, can also be used. In this case, for example, components other than acrolein contained in the acrolein-containing gas obtained by the catalytic gas phase oxidation reaction of propylene, specifically, by-products such as acetaldehyde, acetic acid, carbon oxide, unreacted propylene, propane, etc. The presence of has no effect on the present invention.
本発明の接触気相酸化反応によれば、生産性を上げることを目的とした高負荷反応条件下、例えば、より高いガス圧力、より高い原料ガス濃度、より大きい空間速度の反応条件下において、従来法に比べて著しい好結果が得られる。特にガス圧力については、プロピレン、イソブチレン、ｔ−ブチルアルコールおよびメチル−ｔ−ブチルエーテルからなる群より選ばれる少なくとも１種の化合物を原料とし、前記原料に対応する不飽和アルデヒドを製造する場合、固定床多管式反応器における各反応管のガス出口におけるガス圧（すなわち「反応管における触媒充填層のガス出口におけるガス圧」や「反応管のガス出口におけるガス圧」を示す。）が、絶対圧で、０．１５ＭＰａ以上の場合において好ましく適用でき、より厳しくは０．１７ＭＰａ以上、さらに厳しくは０．１９ＭＰａ以上であっても好ましく適用できる。また、原料ガス濃度については、好ましくは５容量％以上、より好ましくは７容量％以上、さらに好ましくは９容量％以上であっても、本発明の目的が十分達成できる。また、不飽和アルデヒドを原料とし、前記原料に対応する不飽和カルボン酸を製造する場合、あるいは、プロピレン、イソブチレン、ｔ−ブチルアルコールおよびメチル−ｔ−ブチルエーテルからなる群より選ばれる少なくとも１種の化合物を原料とし、前記原料に対応する不飽和カルボン酸を製造する場合、固定床多管式反応器における各反応管のガス出口におけるガス圧（すなわち「反応管における触媒充填層のガス出口におけるガス圧」や「反応管のガス出口におけるガス圧」を示す。）が、絶対圧で、０．１３ＭＰａ以上の場合において好ましく適用でき、より厳しくは０．１５ＭＰａ以上、さらに厳しくは０．１７ＭＰａ以上、特に厳しくは０．１９ＭＰａ以上であっても好ましく適用できる。また、原料ガス濃度については、好ましくは５容量％以上、より好ましくは７容量％以上、さらに好ましくは９容量％以上であっても、本発明の目的が十分達成できる。 According to the catalytic gas phase oxidation reaction of the present invention, under high load reaction conditions aimed at increasing productivity, for example, under higher gas pressure, higher raw material gas concentration, higher space velocity reaction conditions, Compared with the conventional method, remarkable results are obtained. In particular, with respect to the gas pressure, when an unsaturated aldehyde corresponding to the raw material is produced using at least one compound selected from the group consisting of propylene, isobutylene, t-butyl alcohol and methyl-t-butyl ether as a fixed bed, The gas pressure at the gas outlet of each reaction tube in the multi-tube reactor (that is, “the gas pressure at the gas outlet of the catalyst packed bed in the reaction tube” or “the gas pressure at the gas outlet of the reaction tube”) is an absolute pressure. Therefore, it can be preferably applied in the case of 0.15 MPa or more, more strictly 0.17 MPa or more, and even more strictly 0.19 MPa or more. Further, even if the raw material gas concentration is preferably 5% by volume or more, more preferably 7% by volume or more, and further preferably 9% by volume or more, the object of the present invention can be sufficiently achieved. In addition, when an unsaturated aldehyde is used as a raw material to produce an unsaturated carboxylic acid corresponding to the raw material, or at least one compound selected from the group consisting of propylene, isobutylene, t-butyl alcohol, and methyl-t-butyl ether And producing an unsaturated carboxylic acid corresponding to the raw material, the gas pressure at the gas outlet of each reaction tube in the fixed-bed multitubular reactor (ie, “the gas pressure at the gas outlet of the catalyst packed bed in the reaction tube”) Or “gas pressure at the gas outlet of the reaction tube”) is preferably applied when the absolute pressure is 0.13 MPa or more, more strictly 0.15 MPa or more, and even more strictly 0.17 MPa or more. Strictly, even if it is 0.19 MPa or more, it can be preferably applied. Further, even if the raw material gas concentration is preferably 5% by volume or more, more preferably 7% by volume or more, and further preferably 9% by volume or more, the object of the present invention can be sufficiently achieved.
以下に、実施例および比較例によって本発明をより具体的に説明するが、本発明はこれらに限定されるものではない。以下では、便宜上、「質量部」を単に「部」と記すことがある。
実施例および比較例における、測定方法および評価方法を以下に示す。
＜転化率、選択率および収率＞
転化率（モル％）＝（反応した原料化合物のモル数／供給した原料化合物のモル数）×１００
選択率（モル％）＝（生成した目的物のモル数／反応した原料化合物のモル数）×１００
収率（モル％）＝（生成した目的物のモル数／供給した原料化合物のモル数）×１００
＜不活性物質成形体の混合率＞
（１）実際の接触気相酸化反応に用いる反応管（実際の反応管と同じ内径）と触媒を用意し、実際の反応管に充填する際の充填速度で、該触媒のみを充填する。
Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these. Hereinafter, for convenience, “parts by mass” may be simply referred to as “parts”.
Measurement methods and evaluation methods in Examples and Comparative Examples are shown below.
<Conversion rate, selectivity and yield>
Conversion rate (mol%) = (number of moles of reacted raw material compound / number of moles of supplied raw material compound) × 100
Selectivity (mol%) = (number of moles of target product produced / number of moles of reacted raw material compound) × 100
Yield (mol%) = (number of moles of target product produced / number of moles of supplied raw material compound) × 100
<Mixing ratio of inactive material compact>
(1) Prepare a reaction tube (the same inner diameter as that of an actual reaction tube) and a catalyst to be used for an actual catalytic gas phase oxidation reaction, and fill only the catalyst at a filling speed when filling the actual reaction tube.
（２）触媒の充填層長と充填された触媒の質量から、下記式により触媒のみを充填したときの充填密度を求める。
触媒のみの充填密度＝（充填された触媒の質量）／（反応管の断面積×充填層長）
（３）上記触媒のみを充填したときと同様にして、実際に用いる不活性物質成形体のみを充填して、下記式により不活性物質成形体のみの充填密度を求める。
不活性物質成形体のみの充填密度＝
（充填された不活性物質成形体の質量）／（反応管の断面積×充填層長）
（４）上で求めた触媒のみの充填密度、および、不活性物質成形体の充填密度とから、不活性物質成形体の混合率を下記式により求める。
(2) From the catalyst packed bed length and the mass of the packed catalyst, the packing density when only the catalyst is packed is obtained by the following formula.
Packing density of catalyst of packed catalyst) / (cross-sectional area of reaction tube x packed bed length)
(3) In the same manner as when only the catalyst is filled, only the inert substance molded body actually used is filled, and the packing density of only the inert substance molded body is obtained by the following formula.
Packing density of inert material compact > (Mass of filled inactive material compact) / (Cross sectional area of reaction tube × packed layer length)
(4) From the packing density of only the catalyst determined above and the packing density of the inert material molded body, the mixing ratio of the inert material molded body is determined by the following equation.
不活性物質成形体の混合率（容積％）＝
〔（不活性物質成形体の質量）／（不活性物質成形体のみの充填密度）〕／〔（不活性物質成形体の質量）／（不活性物質成形体のみの充填密度）＋（触媒の質量）／（触媒のみの充填密度）〕×１００
〔製造例１〕
イオン交換水１０００部に、硝酸コバルト６８７部、硝酸ニッケル４１２部および硝酸第二鉄１９１部を溶解させ、溶液（１）を得た。別途、濃硝酸５０部とイオン交換水２００部とからなる硝酸水溶液に、硝酸ビスマス２２９部を溶解させ、溶液（２）を得た。
Mixing ratio of inert material compact (volume%) =
[(Mass of inert material molded body) / (Packing density of inert material molded body only)] / [(Mass of inert material molded body) / (Packing density of inert material molded body only) + (Catalyst density Mass) / (packing density of catalyst only)] × 100
[Production Example 1]
In 1000 parts of ion exchange water, 687 parts of cobalt nitrate, 412 parts of nickel nitrate and 191 parts of ferric nitrate were dissolved to obtain a solution (1). Separately, 229 parts of bismuth nitrate was dissolved in an aqueous nitric acid solution consisting of 50 parts of concentrated nitric acid and 200 parts of ion-exchanged water to obtain a solution (2).
加熱したイオン交換水３０００部に、パラモリブテン酸アンモニウム１０００部およびパラタングステン酸アンモニウム６４部を溶解させた溶液に、溶液（１）および溶液（２）を攪拌しながら順次滴下混合し、さらに、硝酸カリウム４．８部をイオン交換水５０部に溶解させた水溶液を添加して、スラリーを得た。
こうして得られたスラリーを攪拌しながら加熱を続けて乾燥物を得た。次いで、この乾燥物を粉砕し、得られた粉体に、バインダーとしてイオン交換水を加え、１時間混練した後、外径６ｍｍ、内径２ｍｍ、長さ６ｍｍのリング状に押出し成形し、空気流通下４８０℃で８時間焼成して、触媒（１）を得た。この触媒の金属元素組成（酸素を除く原子比、以下同じ）は次の通りであった。
Solution (1) and solution (2) were sequentially added dropwise to a solution prepared by dissolving 1000 parts of ammonium paramolybdate and 64 parts of ammonium paratungstate in 3000 parts of heated ion-exchanged water. An aqueous solution in which 4.8 parts were dissolved in 50 parts of ion-exchanged water was added to obtain a slurry.
The slurry thus obtained was continuously heated with stirring to obtain a dried product. Next, the dried product is pulverized, and ion-exchanged water is added as a binder to the obtained powder, and the mixture is kneaded for 1 hour. The catalyst (1) was obtained by calcination at 480 ° C. for 8 hours. The metal element composition (atomic ratio excluding oxygen, hereinafter the same) of this catalyst was as follows.
触媒（１）： Ｍｏ１２Ｗ０．５Ｂｉ１Ｆｅ１Ｃｏ５Ｎｉ３Ｋ０．１
〔製造例２〕
製造例１の触媒（１）の製造方法において、外径８ｍｍ、内径２ｍｍ、長さ８ｍｍのリング状に押出し成形した以外は、製造例１と同様にして、触媒（２）を得た。
触媒（１）および触媒（２）の触媒組成、形状、触媒サイズおよび占有容積を表１に示した。
〔実施例１〕
溶融硝酸塩で加熱した内径２５ｍｍのステンレス鋼製反応管に、ガス入口側からガス出口側に向けて、順に、触媒（２）と不活性物質成形体としての平均直径７ｍｍのアルミナボール（占有容積：１８０ｍｍ３）とを混合率２０容積％で混合した触媒希釈物（充填層長：１０００ｍｍ）、および、触媒（１）（充填層長：２０００ｍｍ）を充填した。すなわち、反応管における触媒充填層を２つの反応帯に分け、ガス入口側の反応帯には触媒（２）の希釈物を、ガス出口側の反応帯には触媒（１）のみを、充填した。
Catalyst (1): Mo 12 W 0.5 Bi 1 Fe 1 Co 5 Ni 3 K 0.1
[Production Example 2]
A catalyst (2) was obtained in the same manner as in Production Example 1 except that the catalyst (1) in Production Example 1 was extruded into a ring shape having an outer diameter of 8 mm, an inner diameter of 2 mm, and a length of 8 mm.
Table 1 shows the catalyst composition, shape, catalyst size, and occupied volume of the catalyst (1) and catalyst (2).
[Example 1]
From a gas inlet side to a gas outlet side, a catalyst (2) and an alumina ball having an average diameter of 7 mm as an inert material compact (occupied volume: in order) from a gas inlet side to a gas outlet side in a stainless steel reaction tube heated with molten nitrate. 180 mm 3 ) and a catalyst dilution (packed layer length: 1000 mm) mixed with a mixing ratio of 20% by volume, and catalyst (1) (packed layer length: 2000 mm) were packed. That is, the catalyst packed bed in the reaction tube is divided into two reaction zones, and the reaction zone on the gas inlet side is filled with the diluted catalyst (2), and the reaction zone on the gas outlet side is filled with only the catalyst (1). .
下記組成の反応ガスを、接触時間が２．３秒となるように反応管に導入し、プロピレンの接触気相酸化反応を行った。なお、反応管のガス出口でのガス圧力が０．１２ＭＰａ（絶対圧）となるように調節した。反応は８０００時間継続して行い、反応開始から５０時間および８０００時間経過時点での測定結果を表２に示した。
＜反応ガスの組成＞
プロピレン ８容量％
酸素 １４容量％
水蒸気 １０容量％
窒素等の不活性ガス ６８容量％
ここで、触媒（２）の希釈に用いた平均直径７ｍｍのアルミナボールのみを、反応管に（充填層長：３０００ｍｍ）充填し、上記と同様のプロピレンの接触気相酸化反応を行ったところ、プロピレン転化率は０．３モル％であり、上記アルミナボールはプロピレンに対して実質的に不活性であることが確認された。以下の実施例および比較例においても、不活性物質成形体としてこのアルミナボールを使用した。
A reaction gas having the following composition was introduced into the reaction tube so that the contact time was 2.3 seconds, and propylene contact gas phase oxidation reaction was performed. The gas pressure at the gas outlet of the reaction tube was adjusted to be 0.12 MPa (absolute pressure). The reaction was continued for 8000 hours, and the measurement results after 50 hours and 8000 hours from the start of the reaction are shown in Table 2.
<Reaction gas composition>
8% by volume of propylene
14% oxygen by volume
Water vapor 10%
68% by volume of inert gas such as nitrogen
Here, only the alumina balls having an average diameter of 7 mm used for diluting the catalyst (2) were filled in the reaction tube (packed layer length: 3000 mm), and the same propylene catalytic gas phase oxidation reaction as described above was performed. The propylene conversion was 0.3 mol%, and it was confirmed that the alumina balls were substantially inert to propylene. In the following examples and comparative examples, this alumina ball was used as an inert material molded body.
〔比較例１〕
実施例１において、平均直径７ｍｍのアルミナボールと触媒（２）とを混合した触媒希釈物の代わりに、触媒（２）のみを充填した以外は、実施例１と同様にして、プロピレンの接触気相酸化反応を行った。反応開始から５０時間および８０００時間経過時点での測定結果を表２に示した。
〔比較例２〕
実施例１において、平均直径７ｍｍのアルミナボールと触媒（２）とを混合した触媒希釈物の代わりに、上記アルミナボールと触媒（１）とを混合率４０容積％で混合した触媒希釈物を充填した以外は、実施例１と同様にして、プロピレンの接触気相酸化反応を行った。反応開始から５０時間および８０００時間経過時点での測定結果を表２に示した。
[Comparative Example 1]
In Example 1, except that only catalyst (2) was filled in place of the catalyst dilution obtained by mixing alumina balls having an average diameter of 7 mm and catalyst (2), a propylene contact gas was obtained in the same manner as in Example 1. A phase oxidation reaction was performed. Table 2 shows the measurement results after 50 hours and 8000 hours from the start of the reaction.
[Comparative Example 2]
In Example 1, instead of the catalyst dilution obtained by mixing the alumina balls having an average diameter of 7 mm and the catalyst (2), the catalyst dilution obtained by mixing the alumina balls and the catalyst (1) at a mixing ratio of 40% by volume is filled. A propylene catalytic gas phase oxidation reaction was carried out in the same manner as in Example 1 except that. Table 2 shows the measurement results after 50 hours and 8000 hours from the start of the reaction.
〔実施例２〕
実施例１において、反応管のガス出口でのガス圧力を０．１６ＭＰａ（絶対圧）に変更した以外は、実施例１と同様にして、プロピレンの接触気相酸化反応を行った。反応開始から５０時間および８０００時間経過時点での測定結果を表３に示した。
〔比較例３〜４〕
比較例１および２において、反応管のガス出口でのガス圧力を０．１６ＭＰａ（絶対圧）に変更した以外は、比較例１および２と同様にして、それぞれプロピレンの接触気相酸化反応を行った。反応開始から５０時間および８０００時間経過時点での測定結果を表３に示した。
[Example 2]
In Example 1, the catalytic gas phase oxidation reaction of propylene was performed in the same manner as in Example 1 except that the gas pressure at the gas outlet of the reaction tube was changed to 0.16 MPa (absolute pressure). Table 3 shows the measurement results after 50 hours and 8000 hours from the start of the reaction.
[Comparative Examples 3 to 4]
In Comparative Examples 1 and 2, the catalytic gas phase oxidation reaction of propylene was performed in the same manner as in Comparative Examples 1 and 2, except that the gas pressure at the gas outlet of the reaction tube was changed to 0.16 MPa (absolute pressure). It was. Table 3 shows the measurement results after 50 hours and 8000 hours from the start of the reaction.
〔実施例３〕
実施例２において、触媒（１）の代わりに、平均直径７ｍｍのアルミナボールと触媒（１）とを混合率５容積％で混合した触媒希釈物を充填した以外は、実施例２と同様にして、プロピレンの接触気相酸化反応を行った。反応開始から５０時間および８０００時間経過時点での測定結果を表３に示した。
〔実施例４〕
実施例１において、反応管のガス出口でのガス圧力を０．２０ＭＰａ（絶対圧）に変更した以外は、実施例１と同様にして、プロピレンの接触気相酸化反応を行った。反応開始から５０時間および８０００時間経過時点での測定結果を表４に示した。
Example 3
In Example 2, instead of the catalyst (1), the same procedure as in Example 2 was performed, except that a catalyst dilution in which an alumina ball having an average diameter of 7 mm and the catalyst (1) were mixed at a mixing ratio of 5% by volume was filled. Then, propylene contact gas phase oxidation reaction was carried out. Table 3 shows the measurement results after 50 hours and 8000 hours from the start of the reaction.
Example 4
In Example 1, the catalytic gas phase oxidation reaction of propylene was performed in the same manner as in Example 1 except that the gas pressure at the gas outlet of the reaction tube was changed to 0.20 MPa (absolute pressure). Table 4 shows the measurement results after 50 hours and 8000 hours from the start of the reaction.
〔比較例５〜６〕
比較例１および２において、反応管のガス出口でのガス圧力を０．２０ＭＰａ（絶対圧）に変更した以外は、比較例１および２と同様にして、それぞれプロピレンの接触気相酸化反応を行った。反応開始から５０時間および８０００時間経過時点での測定結果を表４に示した。
〔実施例５〕
実施例１と同様の反応管に、ガス入口側からガス出口側に向けて、順に、触媒（２）と平均直径７ｍｍのアルミナボール（占有容積：１８０ｍｍ３）とを混合率２０容積％で混合した触媒希釈物（充填層長：８００ｍｍ）、触媒（１）と上記アルミナボールとを混合率３５容積％で混合した触媒希釈物（充填層長：１１００ｍｍ）、および、触媒（１）（充填層長：１１００ｍｍ）を充填した。すなわち、反応管における触媒充填層を３つの反応帯に分け、最も入口側の反応帯（第１反応帯）には触媒（２）の希釈物を、最も出口側の反応帯（第３反応帯）には触媒（１）のみを、これらの間の反応帯（第２反応帯）には触媒（１）の希釈物を、充填した。
[Comparative Examples 5-6]
In Comparative Examples 1 and 2, the catalytic gas phase oxidation reaction of propylene was performed in the same manner as in Comparative Examples 1 and 2, except that the gas pressure at the gas outlet of the reaction tube was changed to 0.20 MPa (absolute pressure). It was. Table 4 shows the measurement results after 50 hours and 8000 hours from the start of the reaction.
Example 5
In the same reaction tube as in Example 1, the catalyst (2) and alumina balls with an average diameter of 7 mm (occupied volume: 180 mm 3 ) were mixed in order from the gas inlet side to the gas outlet side at a mixing ratio of 20% by volume. Catalyst dilution (packed bed length: 800 mm), catalyst diluent (packed bed length: 1100 mm) in which catalyst (1) and the above-mentioned alumina balls were mixed at a mixing rate of 35% by volume, and catalyst (1) (packed bed) Length: 1100 mm). That is, the catalyst packed bed in the reaction tube is divided into three reaction zones, and the dilution of the catalyst (2) is added to the reaction zone on the most inlet side (first reaction zone), and the reaction zone on the most outlet side (third reaction zone). ) Was charged with only the catalyst (1), and the reaction zone (second reaction zone) between them was charged with a dilution of the catalyst (1).
実施例１と同様の組成の反応ガスを、接触時間が２．３秒となるように反応管に導入し、プロピレンの接触気相酸化反応を行った。なお、反応管のガス出口でのガス圧力は０．２０ＭＰａ（絶対圧）となるように調節した。反応は８０００時間継続して行い、反応開始から５０時間および８０００時間経過時点での測定結果を表４に示した。
〔実施例６〕
実施例４において、ガス入口側からガス出口側に向けて、順に、触媒（２）と平均直径１０ｍｍのアルミナボール（占有容積：５２４ｍｍ３）とを混合率３０容積％で混合した触媒希釈物（充填層長：７００ｍｍ）、触媒（１）と平均直径７ｍｍのアルミナボール（占有容積：１８０ｍｍ３）とを混合率３０容積％で混合した触媒希釈物（充填層長：１１００ｍｍ）、および、触媒（１）（充填層長：１２００ｍｍ）を充填した以外は、実施例４と同様にして、プロピレンの接触気相酸化反応を行った。反応は８０００時間継続して行い、反応開始から５０時間および８０００時間経過時点での測定結果を表４に示した。
A reaction gas having the same composition as in Example 1 was introduced into the reaction tube so that the contact time was 2.3 seconds, and propylene contact gas phase oxidation reaction was performed. The gas pressure at the gas outlet of the reaction tube was adjusted to 0.20 MPa (absolute pressure). The reaction was continued for 8000 hours, and the measurement results after 50 hours and 8000 hours from the start of the reaction are shown in Table 4.
Example 6
In Example 4, from the gas inlet side toward the gas outlet side, a catalyst dilution (a mixture of catalyst (2) and alumina balls having an average diameter of 10 mm (occupied volume: 524 mm 3 ) in a mixing ratio of 30% by volume ( Packed bed length: 700 mm), catalyst dilution (packed bed length: 1100 mm) in which the catalyst (1) and alumina balls having an average diameter of 7 mm (occupied volume: 180 mm 3 ) were mixed at a mixing ratio of 30% by volume, and catalyst ( 1) A catalytic gas phase oxidation reaction of propylene was performed in the same manner as in Example 4 except that (packed layer length: 1200 mm) was filled. The reaction was continued for 8000 hours, and the measurement results after 50 hours and 8000 hours from the start of the reaction are shown in Table 4.
なお、触媒（２）の希釈に用いた平均直径１０ｍｍのアルミナボールのみを、内径２５ｍｍのステンレス鋼製反応管に層長３０００ｍｍで充填し、実施例１と同様のプロピレンの接触気相酸化反応（反応継続時間５０時間）を行ったところ、プロピレン転化率は０．２モル％であり、上記アルミナボールはプロピレンに対して実質的に不活性であることが確認された。 In addition, only the alumina balls having an average diameter of 10 mm used for diluting the catalyst (2) were filled in a stainless steel reaction tube having an inner diameter of 25 mm with a layer length of 3000 mm, and the same propylene catalytic gas phase oxidation reaction as in Example 1 ( When the reaction duration was 50 hours, the propylene conversion was 0.2 mol%, and it was confirmed that the alumina balls were substantially inactive with respect to propylene.
〔製造例３〕
イオン交換水４０００部を加熱攪拌しながら、この中に、パラモリブテン酸アンモニウム６００部、メタバナジン酸アンモニウム１６６部、およびパラタングステン酸アンモニウム１２２部を溶解した。
別に、イオン交換水５００部を加熱攪拌しながら、この中に、硝酸第二銅１７８部および三酸化アンチモン４部を添加した。
得られた二つの液を混合した後、湯浴上の磁製蒸発器に入れ、これに平均直径５ｍｍのシリカ−アルミナからなる担体２０００部を加え、攪拌しながら蒸発乾固して担体に付着させた後、４００℃で６時間焼成し、触媒（３）を得た。
[Production Example 3]
While heating and stirring 4000 parts of ion-exchanged water, 600 parts of ammonium paramolybdate, 166 parts of ammonium metavanadate, and 122 parts of ammonium paratungstate were dissolved therein.
Separately, 178 parts of cupric nitrate and 4 parts of antimony trioxide were added to 500 parts of ion-exchanged water while heating and stirring.
After mixing the two liquids obtained, put them in a magnetic evaporator on a hot water bath, add 2000 parts of a carrier made of silica-alumina with an average diameter of 5 mm, and evaporate to dryness with stirring to adhere to the carrier. Then, it was calcined at 400 ° C. for 6 hours to obtain a catalyst (3).
触媒（３）の金属元素組成（酸素を除く原子比、以下同じ）は次の通りであった。
触媒（３）： Ｍｏ１２Ｖ５Ｗ１．６Ｃｕ２．６Ｓｂ０．１
〔製造例４〕
製造例３の触媒（３）の製造方法において、平均直径５ｍｍのシリカ−アルミナからなる担体の代わりに平均直径１０ｍｍのシリカ−アルミナからなる担体を使用した以外は、製造例３と同様にして触媒（４）を得た。
触媒（３）および触媒（４）の触媒組成、形状、触媒成分担持率、触媒サイズおよび占有容積を表５に示した。
The metal element composition of the catalyst (3) (atomic ratio excluding oxygen, hereinafter the same) was as follows.
The catalyst (3): Mo 12 V 5 W 1.6 Cu 2.6 Sb 0.1
[Production Example 4]
In the production method of the catalyst (3) of Production Example 3, a catalyst was prepared in the same manner as in Production Example 3 except that a carrier made of silica-alumina having an average diameter of 10 mm was used instead of a carrier made of silica-alumina having an average diameter of 5 mm. (4) was obtained.
Table 5 shows the catalyst composition, shape, catalyst component loading, catalyst size, and occupied volume of the catalyst (3) and catalyst (4).
〔比較例７〕
溶融硝酸塩にて加熱した内径２５ｍｍのステンレス鋼製反応管に、反応ガス入口側から反応ガス出口側に向けて、順に、触媒（４）を層長１０００ｍｍ、触媒（３）を層長２０００ｍｍとなるように充填した。
下記組成の反応ガスを、接触時間が２．３秒となるように反応管に導入し、アクロレインの接触気相酸化反応を行った。なお、反応管のガス出口でのガス圧力が０．１１ＭＰａ（絶対圧）となるように調節した。反応は８０００時間継続して行い、反応開始から５０時間および８０００時間経過時点での測定結果を表６に示した。
[Comparative Example 7]
From a reaction gas inlet side to a reaction gas outlet side, a catalyst (4) has a layer length of 1000 mm and a catalyst (3) has a layer length of 2000 mm in a stainless steel reaction tube heated with molten nitrate and having an inner diameter of 25 mm. Filled.
A reaction gas having the following composition was introduced into the reaction tube so that the contact time was 2.3 seconds, and a contact gas phase oxidation reaction of acrolein was performed. The gas pressure at the gas outlet of the reaction tube was adjusted to 0.11 MPa (absolute pressure). The reaction was continued for 8000 hours, and the measurement results after 50 hours and 8000 hours from the start of the reaction are shown in Table 6.
＜反応ガスの組成＞
アクロレイン ６容量％
酸素 １０容量％
水蒸気 １０容量％
窒素等の不活性ガス ７４容量％
〔比較例８〕
比較例７において、触媒（４）の代わりに、不活性物質成形体としての平均直径７ｍｍのアルミナボール（占有容積１８０ｍｍ３）と触媒（３）とを混合率４０容積％で混合した触媒希釈物を充填（すなわち、反応ガス入口側に触媒（３）の希釈物、反応ガス出口側に触媒（３）のみを充填）した以外は比較例７と同様にして、アクロレインの接触気相酸化反応を行った。反応開始から５０時間および８０００時間経過時点での測定結果を表６に示した。
<Reaction gas composition>
Acrolein 6% by volume
Oxygen 10% by volume
Water vapor 10%
74% by volume of inert gas such as nitrogen
[Comparative Example 8]
In Comparative Example 7, instead of the catalyst (4), a catalyst dilution obtained by mixing an alumina ball having an average diameter of 7 mm (occupied volume 180 mm 3 ) and a catalyst (3) as an inert substance molded body at a mixing ratio of 40% by volume. Was carried out in the same manner as in Comparative Example 7 except that the reaction gas inlet side was filled with the diluted catalyst (3) and the reaction gas outlet side was filled with only the catalyst (3). went. Table 6 shows the measurement results after 50 hours and 8000 hours from the start of the reaction.
なお、触媒（３）の希釈に用いた平均直径７ｍｍのアルミナボールのみを、内径２５ｍｍのステンレス鋼製反応管に層長３０００ｍｍで充填し、比較例７と同様のアクロレインの接触気相酸化反応（反応継続時間５０時間）を行ったところ、アクロレイン転化率は０．３モル％であり、上記アルミナボールはアクロレインに対して実質的に不活性であることが確認された。以下の実施例および比較例においても、不活性物質成形体としてこのアルミナボールを使用した。
〔実施例７〕
比較例７において、触媒（４）の代わりに、平均直径７ｍｍのアルミナボールと触媒（４）とを混合率２０容積％で混合した触媒希釈物を充填（すなわち、反応ガス入口側に触媒（４）の希釈物、反応ガス出口側に触媒（３）のみを充填）した以外は比較例７と同様にして、アクロレインの接触気相酸化反応を行った。反応開始から５０時間および８０００時間経過時点での測定結果を表６に示した。
It should be noted that only the alumina balls having an average diameter of 7 mm used for diluting the catalyst (3) were packed in a stainless steel reaction tube having an inner diameter of 25 mm with a layer length of 3000 mm, and the acrolein catalytic vapor phase oxidation reaction similar to Comparative Example 7 ( When the reaction duration was 50 hours), the acrolein conversion was 0.3 mol%, and it was confirmed that the alumina balls were substantially inactive with respect to acrolein. In the following examples and comparative examples, this alumina ball was used as an inert material molded body.
Example 7
In Comparative Example 7, instead of the catalyst (4), an alumina ball having an average diameter of 7 mm and a catalyst (4) mixed with a mixing ratio of 20% by volume were filled (that is, the catalyst (4 on the reaction gas inlet side). ), And a catalytic gas phase oxidation reaction of acrolein was carried out in the same manner as in Comparative Example 7 except that the catalyst (3) alone was filled on the reaction gas outlet side. Table 6 shows the measurement results after 50 hours and 8000 hours from the start of the reaction.
〔比較例９〜１０〕
比較例７〜８において、反応管のガス出口でのガス圧力を０．１４ＭＰａ（絶対圧）に変更した以外は比較例７〜８と同様にして、それぞれアクロレインの接触気相酸化反応を行った。反応開始から５０時間および８０００時間経過時点での測定結果を表７に示した。
〔実施例８〕
実施例７において、反応管のガス出口でのガス圧力を０．１４ＭＰａ（絶対圧）に変更した以外は実施例７と同様にして、アクロレインの接触気相酸化反応を行った。反応開始から５０時間および８０００時間経過時点での測定結果を表７に示した。
[Comparative Examples 9 to 10]
In Comparative Examples 7-8, the catalytic gas phase oxidation reaction of acrolein was performed in the same manner as Comparative Examples 7-8, except that the gas pressure at the gas outlet of the reaction tube was changed to 0.14 MPa (absolute pressure). . Table 7 shows the measurement results after 50 hours and 8000 hours from the start of the reaction.
Example 8
In Example 7, the catalytic gas phase oxidation reaction of acrolein was performed in the same manner as in Example 7 except that the gas pressure at the gas outlet of the reaction tube was changed to 0.14 MPa (absolute pressure). Table 7 shows the measurement results after 50 hours and 8000 hours from the start of the reaction.
〔実施例９〕
実施例８において、触媒（３）の代わりに、平均直径７ｍｍのアルミナボールと触媒（３）とを混合率５容積％で混合した触媒希釈物を充填（すなわち、反応ガス入口側に触媒（４）の希釈物、反応ガス出口側に触媒（３）の希釈物を充填）した以外は実施例８と同様にして、アクロレインの接触気相酸化反応を行った。反応開始から５０時間および８０００時間経過時点での測定結果を表７に示した。
〔比較例１１〜１２〕
比較例７〜８において、反応管のガス出口でのガス圧力を０．１８ＭＰａ（絶対圧）に変更した以外は比較例７〜８と同様にして、それぞれアクロレインの接触気相酸化反応を行った。反応開始から５０時間および８０００時間経過時点での測定結果を表８に示した。
Example 9
In Example 8, instead of the catalyst (3), a catalyst diluent in which an alumina ball having an average diameter of 7 mm and the catalyst (3) were mixed at a mixing ratio of 5% by volume was filled (that is, the catalyst (4 on the reaction gas inlet side). The acrolein catalytic gas phase oxidation reaction was carried out in the same manner as in Example 8 except that the reaction gas outlet side was filled with the catalyst (3) dilution). Table 7 shows the measurement results after 50 hours and 8000 hours from the start of the reaction.
[Comparative Examples 11-12]
In Comparative Examples 7-8, the catalytic gas phase oxidation reaction of acrolein was carried out in the same manner as Comparative Examples 7-8, except that the gas pressure at the gas outlet of the reaction tube was changed to 0.18 MPa (absolute pressure). . Table 8 shows the measurement results after 50 hours and 8000 hours from the start of the reaction.
〔実施例１０〕
実施例７において、反応管のガス出口でのガス圧力を０．１８ＭＰａ（絶対圧）に変更した以外は実施例７と同様にして、アクロレインの接触気相酸化反応を行った。反応開始から５０時間および８０００時間経過時点での測定結果を表８に示した。
〔実施例１１〕
実施例１０において、反応ガス入口側から反応ガス出口側に向けて、順に、触媒（４）と平均直径７ｍｍのアルミナボールとを混合率２０容積％で混合した触媒希釈物（充填層長：８００ｍｍ）、触媒（３）と上記アルミナボールとを混合率３５容積％で混合した触媒希釈物（充填層長：１１００ｍｍ）、および、触媒（３）（充填層長：１１００ｍｍ）を充填した以外は実施例１０と同様にして、アクロレインの接触気相酸化反応を行った。すなわち、反応管における触媒充填層を３つの反応帯に分け、最も入口側の反応帯（第１反応帯）には触媒（４）の希釈物を、最も出口側の反応帯（第３反応帯）には触媒（３）のみを、これらの間の反応帯（第２反応帯）には触媒（３）の希釈物を、充填した。
Example 10
In Example 7, an acrolein catalytic gas phase oxidation reaction was carried out in the same manner as in Example 7 except that the gas pressure at the gas outlet of the reaction tube was changed to 0.18 MPa (absolute pressure). Table 8 shows the measurement results after 50 hours and 8000 hours from the start of the reaction.
Example 11
In Example 10, from the reaction gas inlet side to the reaction gas outlet side, a catalyst dilution (packed layer length: 800 mm) in which the catalyst (4) and alumina balls having an average diameter of 7 mm were mixed in order at a mixing rate of 20% by volume. ), A catalyst diluent (packed layer length: 1100 mm) in which the catalyst (3) and the above-mentioned alumina balls were mixed at a mixing rate of 35% by volume, and catalyst (3) (packed layer length: 1100 mm) were charged. In the same manner as in Example 10, a catalytic vapor phase oxidation reaction of acrolein was performed. That is, the catalyst packed bed in the reaction tube is divided into three reaction zones, and the dilution of the catalyst (4) is added to the reaction zone on the most inlet side (first reaction zone), and the reaction zone on the most outlet side (third reaction zone). ) Was charged with catalyst (3) only, and the reaction zone (second reaction zone) between them was charged with a dilution of catalyst (3).
反応開始から５０時間および８０００時間経過時点での測定結果を表８に示した。
〔実施例１２〕
実施例１０において、反応ガス入口側から反応ガス出口側に向けて、順に、触媒（４）と平均直径１０ｍｍのアルミナボールとを混合率３０容積％で混合した触媒希釈物（充填層長：７００ｍｍ）、触媒（３）と平均直径７ｍｍのアルミナボールとを混合率３０容積％で混合した触媒希釈物（充填層長：１１００ｍｍ）、および、触媒（３）（充填層長：１２００ｍｍ）を充填した以外は実施例１０と同様にして、アクロレインの接触気相酸化反応を行った。すなわち、反応管における触媒充填層を３つの反応帯に分け、最も入口側の反応帯（第１反応帯）には触媒（４）の希釈物を、最も出口側の反応帯（第３反応帯）には触媒（３）のみを、これらの間の反応帯（第２反応帯）には触媒（３）の希釈物を、充填した。
Table 8 shows the measurement results after 50 hours and 8000 hours from the start of the reaction.
Example 12
In Example 10, from the reaction gas inlet side to the reaction gas outlet side, a catalyst dilution (packed layer length: 700 mm) in which the catalyst (4) and alumina balls having an average diameter of 10 mm were mixed in order at a mixing rate of 30% by volume. ), Catalyst dilution (mixing layer length: 1100 mm) in which catalyst (3) and alumina balls having an average diameter of 7 mm were mixed at a mixing rate of 30% by volume, and catalyst (3) (packing layer length: 1200 mm) were packed. Acrolein was subjected to a catalytic gas phase oxidation reaction in the same manner as in Example 10 except that. That is, the catalyst packed bed in the reaction tube is divided into three reaction zones, and the dilution of the catalyst (4) is added to the reaction zone on the most inlet side (first reaction zone), and the reaction zone on the most outlet side (third reaction zone). ) Was charged with catalyst (3) only, and the reaction zone (second reaction zone) between them was charged with a dilution of catalyst (3).
反応開始から５０時間および８０００時間経過時点での測定結果を表８に示した。
なお、触媒（４）の希釈に用いた平均直径１０ｍｍのアルミナボールのみを、内径２５ｍｍのステンレス鋼製反応管に層長３０００ｍｍで充填し、比較例７と同様のアクロレインの接触気相酸化反応（反応継続時間５０時間）を行ったところ、アクロレイン転化率０．４モル％であり、上記アルミナボールはアクロレインに対して実質的に不活性であることが確認された。
〔実施例１３〕
溶融硝酸塩で加熱した内径２５ｍｍのステンレス鋼製反応管に、反応ガス入口側から反応ガス出口側に向けて、順に、触媒（２）と不活性物質成形体としての平均直径７ｍｍのアルミナボール（占有容積：１８０ｍｍ３）とを混合率３０容積％で混合した触媒希釈物（充填層長：７００ｍｍ）、触媒（２）（充填層長：１１００ｍｍ）、および、触媒（１）（充填層長：１２００ｍｍ）を充填した。
Table 8 shows the measurement results after 50 hours and 8000 hours from the start of the reaction.
In addition, only the alumina balls having an average diameter of 10 mm used for diluting the catalyst (4) were filled in a stainless steel reaction tube having an inner diameter of 25 mm with a layer length of 3000 mm, and the acrolein catalytic vapor phase oxidation reaction (comparative example 7) ( When the reaction duration was 50 hours), the acrolein conversion was 0.4 mol%, and it was confirmed that the alumina balls were substantially inert to acrolein.
Example 13
From a reaction gas inlet side to a reaction gas outlet side, a catalyst (2) and an alumina ball with an average diameter of 7 mm as an inert substance compact (occupied sequentially) from a reaction gas inlet side to a reaction gas outlet side heated in molten nitrate 25 mm volume: 180 mm 3) and a catalyst dilution obtained by mixing in a mixing ratio of 30 volume% (packed bed length: 700 mm), the catalyst (2) (packed bed length: 1100 mm), and the catalyst (1) (packed bed length: 1200 mm ).
下記組成の反応ガスを、接触時間が２．３秒となるように反応管に導入し、プロピレンの接触気相酸化反応を行った。
＜反応ガスの組成＞
プロピレン ８容量％
酸素 １５容量％
水蒸気 １０容量％
窒素等の不活性ガス ６７容量％
得られた反応ガスを、反応ガス入口側から反応ガス出口側に向けて、順に、触媒（４）と不活性物質成形体としての平均直径７ｍｍのアルミナボール（占有容積：１８０ｍｍ３）とを混合率２５容積％で混合した触媒希釈物（充填層長：７００ｍｍ）、触媒（４）（充填層長：１１００ｍｍ）、および、触媒（３）（充填層長：１２００ｍｍ）を充填した、溶融硝酸塩で加熱した内径２５ｍｍのステンレス鋼製反応管に導入した。
A reaction gas having the following composition was introduced into the reaction tube so that the contact time was 2.3 seconds, and propylene contact gas phase oxidation reaction was performed.
<Reaction gas composition>
8% by volume of propylene
15% oxygen by volume
Water vapor 10%
Inert gas such as nitrogen 67% by volume
From the reaction gas inlet side toward the reaction gas outlet side, the obtained reaction gas was mixed with the catalyst (4) and alumina balls having an average diameter of 7 mm (occupied volume: 180 mm 3 ) as an inactive substance compact. With molten nitrate filled with catalyst dilution (packed bed length: 700 mm), catalyst (4) (packed bed length: 1100 mm), and catalyst (3) (packed bed length: 1200 mm) mixed at a rate of 25% by volume The sample was introduced into a heated stainless steel reaction tube having an inner diameter of 25 mm.
なお、反応管のガス出口でのガス圧力が０．２０ＭＰａ（絶対圧）となるように調節した。反応は８０００時間継続して行い、反応開始から５０時間および８０００時間経過時点での測定結果を表９に示した。 The gas pressure at the gas outlet of the reaction tube was adjusted to 0.20 MPa (absolute pressure). The reaction was continued for 8000 hours, and the measurement results after 50 hours and 8000 hours from the start of the reaction are shown in Table 9.
本発明の接触気相酸化反応は、触媒を充填した固定床多管式反応器を用いた、分子状酸素または分子状酸素含有ガスによる接触気相酸化反応を行う場合に、好適である。 The catalytic gas phase oxidation reaction of the present invention is suitable when a catalytic gas phase oxidation reaction using molecular oxygen or a molecular oxygen-containing gas is performed using a fixed bed multitubular reactor filled with a catalyst.
Claims (9)
前記反応器における各反応管の触媒充填層が管軸方向に複数の反応帯に分けられていて、
前記触媒の充填は、前記複数の反応帯の少なくとも２つにおいてその占有容積が異なる充填であり、かつ、前記複数の反応帯の少なくとも１つにおいて不活性物質成形体が混合されている充填である、
ことを特徴とする、接触気相酸化反応。 In a catalytic gas phase oxidation reaction with molecular oxygen or a molecular oxygen-containing gas using a fixed bed multitubular reactor packed with catalyst,
The catalyst packed bed of each reaction tube in the reactor is divided into a plurality of reaction zones in the tube axis direction,
The filling of the catalyst is filling in which the occupied volume is different in at least two of the plurality of reaction zones, and is a filling in which an inert substance compact is mixed in at least one of the plurality of reaction zones. ,
A catalytic gas phase oxidation reaction.
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