JP2008080219A - Temperature control method of fluidized bed reactor - Google Patents
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Abstract
Description
本発明は、気相発熱反応に用いる流動層反応器の温度制御方法に関する。 The present invention relates to a temperature control method for a fluidized bed reactor used for a gas phase exothermic reaction.
種々の合成樹脂・合成繊維の製造に有用なモノマーを、気相発熱反応により工業的に製造するに際しては、流動層反応器が広く用いられている。工業的に実施される気相発熱反応の代表例としては、部分酸化反応やアンモニア共存下のアンモ酸化反応などの逐次酸化反応があげられる。逐次酸化反応において、目的生成物である部分酸化生成物の酸化安定性は、一般的にそれ程大きなものではないため、反応の進行すなわち反応転化率の上昇に伴い、目的生成物の逐次反応が進行し、完全酸化生成物が増加することによって、目的生成物の選択率が低下する傾向にある。従って、転化率と選択率の積として得られる目的生成物の収率は、ある転化率において極大値を持つこととなる。例えば、非特許文献１には、プロピレンのアンモ酸化によるアクリロニトリル製造について、通常転化率が８５〜９５％において最高値となることが開示されている。このため、目的生成物を経済的により有利に製造するためには、反応の転化率を好ましい範囲に制御することが極めて重要である。もちろん、これは、酸化反応に限られることではなく、一般の気相発熱反応について成り立つと考えてよい。 In order to industrially produce monomers useful for the production of various synthetic resins and synthetic fibers by gas phase exothermic reaction, fluidized bed reactors are widely used. Typical examples of the gas phase exothermic reaction carried out industrially include a sequential oxidation reaction such as a partial oxidation reaction or an ammoxidation reaction in the presence of ammonia. In the sequential oxidation reaction, the oxidation stability of the partial oxidation product, which is the target product, is generally not so great, so the sequential reaction of the target product proceeds as the reaction progresses, that is, the reaction conversion rate increases. However, the increase in the complete oxidation product tends to lower the selectivity of the target product. Therefore, the yield of the target product obtained as the product of the conversion rate and the selectivity has a maximum value at a certain conversion rate. For example, Non-Patent Document 1 discloses that in the case of acrylonitrile production by propylene ammoxidation, the maximum conversion is usually obtained at 85 to 95%. For this reason, in order to produce the target product more advantageously economically, it is extremely important to control the conversion rate of the reaction within a preferable range. Of course, this is not limited to the oxidation reaction, but may be considered to hold for a general gas phase exothermic reaction.
ここで、反応の転化率は触媒の活性に依存し、触媒活性の上昇とともに転化率が上昇する。また、触媒活性は反応温度に依存し、酵素反応のような例外を除くと、一般に反応温度の上昇とともに触媒活性は上昇する。
また、例えば酸化反応の場合、部分酸化生成物と完全酸化反応物の生成エネルギーとを比較するとき、完全酸化反応物（例えばＣＯ2）の方がより安定であることは明らかであって、完全酸化反応の寄与率が上昇すれば、反応系全体の発熱量が増大することは自明である。これも一般の気相発熱反応について成り立つと考えてよい。
Here, the conversion rate of the reaction depends on the activity of the catalyst, and the conversion rate increases as the catalyst activity increases. Further, the catalytic activity depends on the reaction temperature, and the catalyst activity generally increases as the reaction temperature increases, except for exceptions such as enzyme reactions.
Also, for example, in the case of an oxidation reaction, it is clear that a complete oxidation reactant (eg, CO 2 ) is more stable when comparing the product energy of a partial oxidation product and a complete oxidation reactant. Obviously, if the contribution rate of the oxidation reaction increases, the calorific value of the entire reaction system increases. This may also be considered to hold for general gas phase exothermic reactions.
従って、気相発熱反応において、仮に、何らかの原因によって反応温度が上昇した場合、１）温度の上昇とともに触媒の活性が上昇し、２）活性の上昇とともに反応の転化率が上昇するとともに逐次反応が進行し、３）供給した原料のうち実際に反応する量が増加するとともに、逐次反応の進行に伴ってより安定な生成物の寄与が増えることで、反応系全体の単位時間当たり発熱量が増大し、４）結果としてさらに反応温度が上昇する、という循環挙動を示す傾向にある。もちろん反応温度が低下した場合も同様に、逆向きの循環挙動を示すのであって、いずれの場合にも、反応器の局所で温度が発散することで、反応器内の温度分布を生じる原因となり、さらに極端な場合には反応器全体の温度が発散し反応器の熱暴走や反応停止に繋がることとなる。従って、目的生成物を経済的により有利に製造することはもちろん、安定に反応を継続するためにも、反応温度を精緻に制御することが極めて重要である。 Therefore, in the gas phase exothermic reaction, if the reaction temperature rises for some reason, 1) the activity of the catalyst increases as the temperature increases, and 2) the conversion rate of the reaction increases as the activity increases, and successive reactions occur. 3) As the amount of the raw material that is actually reacted increases, and the contribution of more stable products increases as the successive reactions progress, the calorific value per unit time of the entire reaction system increases. 4) As a result, the reaction temperature tends to increase, and the circulation behavior tends to be exhibited. Of course, when the reaction temperature is lowered, the reverse circulation behavior is exhibited as well, and in either case, the temperature diverges locally, causing a temperature distribution in the reactor. In a more extreme case, the temperature of the entire reactor will diverge, leading to thermal runaway of the reactor and reaction stoppage. Therefore, it is extremely important to precisely control the reaction temperature in order to produce the target product more economically advantageously and to continue the reaction stably.
一方、流動層反応器が有する利点の一つとして、他の反応器形式、例えば固定床式の反応器に比べ、反応器内の熱移動が速く、反応温度の制御が比較的容易であることがあげられる。流動層反応器を用いて気相発熱反応を実施する際に、反応器の温度を制御するにあたっては、例えば特許文献１や非特許文献２において開示されているように、流動層内に垂直管群を配置し、これに冷却媒体となる流体を通じることで除熱管として用い、反応熱を回収する方法が最も一般的である。このとき、例えば特許文献２や特許文献３に開示されるように、除熱管を反応器の上部と下部とにそれぞれ配置し、別々の温度に制御する試みも行われている。
On the other hand, one of the advantages of fluidized bed reactors is that heat transfer in the reactor is faster and the reaction temperature is relatively easy to control compared to other reactor types, for example, fixed bed reactors. Can be given. When the gas phase exothermic reaction is performed using the fluidized bed reactor, the temperature of the reactor is controlled, for example, as disclosed in Patent Document 1 and Non-Patent
また、反応器内に設置された温度検出部で検出された温度に基づいて、反応器温度を制御するための方法として、例えば特許文献４は、少なくとも一つの除熱管には可変速度で冷却媒体を流し、その流量を調節することで温度を制御することのできる流動層反応器及び流動層反応器の温度調節方法を開示している。また、特許文献５では、冷却媒体として、液体とその蒸気を混合したものを供給するに際し、実質的に一定流量の蒸気中に混合する液体の流量を調節することで温度を制御する方法を開示している。
しかしながら、先に述べた、気相酸化反応における温度制御、特に安定な温度制御の重要性を鑑みると、これら先行技術による温度制御では十分ではなく、更に精緻な温度制御を可能とする方法の確立が求められていた。
Further, as a method for controlling the reactor temperature based on the temperature detected by the temperature detector installed in the reactor, for example,
However, in view of the importance of temperature control in the gas phase oxidation reaction described above, particularly stable temperature control, the temperature control according to these prior arts is not sufficient, and the establishment of a method that enables more precise temperature control. Was demanded.
本発明は気相発熱反応に用いる流動層反応器について、従来よりも改良された温度制御方法を提供することを目的とする。 It is an object of the present invention to provide a temperature control method that is improved over the prior art for a fluidized bed reactor used for a gas phase exothermic reaction.
発明者らは気相発熱反応に用いる流動層反応器について、更に精緻に反応器温度を制御しうる方法について鋭意検討を行った結果、反応器を、有効断面積が２０平方メートルを超えない面積毎に仮想的に分割し、それぞれの範囲の温度を個別に制御することにより、従来よりも改良された温度制御が可能となることを見出し、本発明を完成させるに至った。 As a result of intensive investigations on the fluidized bed reactor used in the gas phase exothermic reaction, the reactor temperature can be controlled more precisely. The present invention was completed by finding that it is possible to control the temperature in each range by controlling the temperature in each range virtually and by controlling the temperature in each range individually.
すなわち本発明は、以下のとおりである。
（１） 複数の温度検出部、及び複数系列の除熱管を有し、有効断面積が２０平方メートル以上の流動層反応器を用いて気相発熱反応を実施するにおいて、２０平方メートルを超えない有効断面積範囲毎に温度を制御することを特徴とする、流動層反応器の温度制御方法。
（２）反応を実施する温度範囲において、副反応も含めた総体としての反応熱が２５００ｋＪ／ｍｏｌ（原料）以下であり、かつ総体としての反応熱の温度に関する偏微分係数が、４０ｋＪ／ｍｏｌ（原料）・Ｋ以下であることを特徴とする前記（１）に記載の流動層反応器の温度制御方法。
That is, the present invention is as follows.
(1) When carrying out a gas phase exothermic reaction using a fluidized bed reactor having a plurality of temperature detection units and a plurality of heat removal tubes and having an effective cross-sectional area of 20 square meters or more, an effective disconnection that does not exceed 20 square meters A temperature control method for a fluidized bed reactor, wherein the temperature is controlled for each area range.
(2) In the temperature range for carrying out the reaction, the total reaction heat including side reactions is 2500 kJ / mol (raw material) or less, and the partial differential coefficient related to the temperature of the total reaction heat is 40 kJ / mol ( The temperature control method for a fluidized bed reactor according to (1) above, wherein the raw material is equal to or less than K.
（３）実施する反応がプロパンおよび／またはプロピレンを原料とする気相アンモ酸化反応であり、反応の生成物がアクリロニトリルであることを特徴とする前記（１）、（２）に記載の流動層反応器の温度制御方法。
（４）実施する反応がｎ−ブタン、１−ブテン、２−ブテン、ブタジエン、ベンゼンから選ばれる一つ以上を原料とする気相酸化反応であり、反応の生成物が無水マレイン酸であることを特徴とする前記（１）、（２）に記載の流動層反応器の温度制御方法。
(3) The fluidized bed according to (1) or (2), wherein the reaction to be performed is a gas phase ammoxidation reaction using propane and / or propylene as a raw material, and the product of the reaction is acrylonitrile. Reactor temperature control method.
(4) The reaction to be carried out is a gas phase oxidation reaction using at least one selected from n-butane, 1-butene, 2-butene, butadiene, and benzene, and the product of the reaction is maleic anhydride The temperature control method for a fluidized bed reactor according to (1) or (2) above.
（５）実施する反応がｉ−ブテンおよび／またはｉ−ブタンを原料とする気相アンモ酸化反応であり、反応の生成物がメタクリロニトリルであることを特徴とする前記（１）、（２）に記載の流動層反応器の温度制御方法。
（６）実施する反応がｏ−キシレンおよび／またはナフタレンを原料とする気相酸化反応であり、反応の生成物が無水フタル酸であることを特徴とする前記（１）、（２）に記載の流動層反応器の温度制御方法。
(5) The reaction to be carried out is a gas phase ammoxidation reaction using i-butene and / or i-butane as a raw material, and the product of the reaction is methacrylonitrile, (1), (2 ) Temperature control method for fluidized bed reactors.
(6) The reaction to be carried out is a gas phase oxidation reaction using o-xylene and / or naphthalene as a raw material, and the product of the reaction is phthalic anhydride, described in (1) and (2) above Temperature control method for a fluidized bed reactor.
（７）実施する反応がフェノールおよびメタノールを原料とする気相酸化反応であり、反応の生成物が２，６−キシレノールおよび／またはｏ−クレゾールであることを特徴とする前記（１）、（２）に記載の流動層反応器の温度制御方法。
（８）実施する反応がメタンおよび／またはメタノールを原料とする気相アンモ酸化反応であり、反応の生成物が青酸（ＨＣＮ）であることを特徴とする前記（１）、（２）に記載の流動層反応器の温度制御方法。
（９）実施する反応がエタン、エテン、エタノールから選ばれる一つ以上を原料とする気相アンモ酸化反応であり、反応の生成物がアセトニトリルであることを特徴とする前記（１）、（２）に記載の流動層反応器の温度制御方法。
(7) The reaction to be carried out is a gas phase oxidation reaction using phenol and methanol as raw materials, and the product of the reaction is 2,6-xylenol and / or o-cresol, (1), The temperature control method of the fluidized bed reactor as described in 2).
(8) The reaction to be carried out is a gas phase ammoxidation reaction using methane and / or methanol as a raw material, and the product of the reaction is hydrocyanic acid (HCN), as described in (1) and (2) above Temperature control method for a fluidized bed reactor.
(9) The reaction to be carried out is a gas phase ammoxidation reaction using at least one selected from ethane, ethene, and ethanol as a raw material, and the product of the reaction is acetonitrile, ) Temperature control method for fluidized bed reactors.
本発明により、気相発熱反応に用いる流動層反応器について、従来よりも精緻な温度制御が可能となる。 The present invention makes it possible to control the temperature of the fluidized bed reactor used for the gas phase exothermic reaction more finely than before.
本発明について、更に詳細に説明するに、気相発熱反応を実施する流動層の温度制御を精緻に行うためには、できるだけ発生する熱量が安定に保たれていること、および流動層内の熱移動が速やかに行われることが望ましい。発生熱量を安定に保つためには、原料の供給速度や、反応圧力などの反応条件をできるだけ一定に保ち、反応が安定に行われるようにすることが望ましい。また、流動層内の熱移動を速やかに行うためには、流動層の流動状態を良好に保つことが必要である。一般に、流動層の流動状態は、ガス流速（空塔速度）や触媒の粒径などに支配されることが知られている。本発明の実施においては、ガス流速は流動層の流動状態を良好に保ちうるガス流速の範囲であれば特に制限はない。また、本発明の実施にあたって使用する触媒は、通常の流動層反応器に用いられる触媒であればそのまま使用可能であるが、重量平均の粒子径は２０〜１００μｍ、好ましくは３０〜８０μｍ、更に好ましくは４０〜６０μｍ、粒子径４４μｍ以下の微粉（いわゆるグッドフラクション）の含有量は１０〜７０重量％、かつＧｅｌｄａｒｔ粉体分類マップにおいてＡ粒子に分類されるものがよい。 The present invention will be described in more detail. In order to precisely control the temperature of the fluidized bed in which the gas phase exothermic reaction is performed, the amount of generated heat is kept as stable as possible and the heat in the fluidized bed is maintained. It is desirable that the movement be made promptly. In order to keep the amount of generated heat stable, it is desirable to keep the reaction conditions such as the feed rate of the raw material and the reaction pressure as constant as possible so that the reaction can be performed stably. In addition, in order to quickly move the heat in the fluidized bed, it is necessary to keep the fluidized state of the fluidized bed good. In general, it is known that the fluidized state of the fluidized bed is governed by gas flow rate (superficial velocity), catalyst particle size, and the like. In the practice of the present invention, the gas flow rate is not particularly limited as long as it is within the range of the gas flow rate that can keep the fluidized state of the fluidized bed good. Further, the catalyst used in the practice of the present invention can be used as it is as long as it is a catalyst used in a normal fluidized bed reactor, but the weight average particle diameter is 20 to 100 μm, preferably 30 to 80 μm, and more preferably. The content of fine powder (so-called good fraction) having a particle size of 40 to 60 μm and a particle size of 44 μm or less is preferably 10 to 70% by weight, and is classified as A particles in the Geldart powder classification map.
本発明に用いられる流動層反応器は、気相発熱反応、例えばプロパンおよび／またはプロピレンを原料とする気相アンモ酸化反応によるアクリロニトリルの製造、ｎ−ブタン、１−ブテン、２−ブテン、ブタジエン、ベンゼンから選ばれる一つ以上を原料とする気相酸化反応による無水マレイン酸の製造、ｉ−ブテンおよび／またはｉ−ブタンを原料とする気相アンモ酸化反応によるメタクリロニトリルの製造、ｏ−キシレンおよび／またはナフタレンを原料とする気相酸化反応による無水フタル酸の製造、フェノールおよびメタノールを原料とする気相酸化反応による２，６−キシレノールおよび／またはｏ−クレゾールの製造、メタンおよび／またはメタノールを原料とする気相アンモ酸化反応による青酸（ＨＣＮ）の製造、エタン、エテン、エタノールから選ばれる一つ以上を原料とする気相アンモ酸化反応によるアセトニトリルの製造などを工業的規模で行う際に多く用いられているものである。このような流動層反応器では、反応器下部から導入されるガスの上昇流によって、触媒粒子が流動化状態を保持されていることが一般的であるが、本発明は上昇流形式だけに限られるものではなく、下降流形式、あるいは他の方式であっても構わない。 The fluidized bed reactor used in the present invention has a gas phase exothermic reaction, for example, production of acrylonitrile by a gas phase ammoxidation reaction using propane and / or propylene as a raw material, n-butane, 1-butene, 2-butene, butadiene, Production of maleic anhydride by gas phase oxidation reaction using one or more selected from benzene as raw material, Production of methacrylonitrile by gas phase ammoxidation reaction using i-butene and / or i-butane as raw material, o-xylene And / or production of phthalic anhydride by gas phase oxidation reaction using naphthalene as raw material, production of 2,6-xylenol and / or o-cresol by gas phase oxidation reaction using phenol and methanol as raw materials, methane and / or methanol Of hydrocyanic acid (HCN) by gas phase ammoxidation reaction using ethane, ethane, Emissions are those widely used in making an industrial scale such as the manufacture of acetonitrile by vapor phase ammoxidation reaction of a raw material is one or ethanol. In such a fluidized bed reactor, the catalyst particles are generally kept fluidized by the upward flow of gas introduced from the lower part of the reactor, but the present invention is limited to the upward flow type. It may be a downflow type or another method.
本発明は、気相発熱反応を実施する流動層反応器に適用される。その反応熱は反応により様々であり、例えばプロピレンとアンモニアからアクリロニトリルを生成する反応熱は５２０ｋＪ／ｍｏｌ（プロピレン）、プロパンとアンモニアからアクリロニトリルを生成する反応熱は６３７ｋＪ／ｍｏｌ（プロパン）である。しかし、実際の反応は併発・逐次反応であり、ＣＯ2、ＣＯやその他の副生成物が発生する。副反応までを含めた総体としての反応熱は、それぞれ併発する反応の寄与率（各生成物の収率）を考慮して求めることができる。例えば、プロパンが燃焼してＣＯ２と水、あるいはＣＯと水を生成する反応の反応熱は、プロパン１ｍｏｌあたりそれぞれ２０４３ｋＪ／ｍｏｌ（プロパン）と、１１９４ｋＪ／ｍｏｌ（プロパン）であるから、ある条件でプロパン１００ｍｏｌをアンモニア及び酸素と反応させたときに、８０ｍｏｌのプロパンが反応し（反応率８０％）、５０ｍｏｌのアクリロニトリル（収率５０％）、６０ｍｏｌのＣＯ２（収率２０％）、３０ｍｏｌのＣＯ（収率１０％）が生成したとすると、この条件での総体としての反応熱は、６３７×０．５＋２０４３×０．２＋１１９４×０．１＝８４６．５（ｋＪ／ｍｏｌ）として求めることができる。算出過程から明らかなように、総体としての反応熱は原料の反応率や各併発反応の寄与率（生成物の分布）等により変化するので、反応条件に依存する。総体としての反応熱に特に制限はないが、過大となれば除熱すべき熱量が増加し制御が困難となり、反応器内の温度分布を生じる原因、さらに極端な場合には反応器の熱暴走にもつながることとなるので、この点からは反応条件を選ぶにあたって、総体としての反応熱が出来るだけ小さくなるようにするのが好ましい。具体的には、フィードする原料１ｍｏｌ当たり、２５００ｋＪ／ｍｏｌ（原料）以下、好ましくは２０００ｋＪ／ｍｏｌ（原料）以下となるように反応条件を選ぶのが良い。
The present invention is applied to a fluidized bed reactor that performs a gas phase exothermic reaction. The reaction heat varies depending on the reaction. For example, the reaction heat for producing acrylonitrile from propylene and ammonia is 520 kJ / mol (propylene), and the reaction heat for producing acrylonitrile from propane and ammonia is 637 kJ / mol (propane). However, the actual reaction is a simultaneous and sequential reaction, and CO 2 , CO, and other by-products are generated. The total reaction heat including up to the side reaction can be determined in consideration of the contribution rate of each reaction (the yield of each product). For example, the reaction heat of propane combustion to produce CO 2 and water or CO and water is 2043 kJ / mol (propane) and 1194 kJ / mol (propane) per 1 mol of propane, respectively. When 100 mol of propane was reacted with ammonia and oxygen, 80 mol of propane reacted (reaction rate 80%), 50 mol acrylonitrile (yield 50%), 60 mol CO 2 (yield 20%), 30
一方、気相発熱反応において、目的とする生成物の安定性は、それ程大きなものではないため、反応の進行すなわち反応転化率の上昇に伴い、目的生成物の逐次反応が進行することによって、目的生成物の選択率が低下する傾向にある。ここで、反応転化率は触媒の活性に依存し、活性の上昇とともに転化率は上昇する。また、触媒の活性は反応温度に依存し、一般に反応温度の上昇とともに活性は上昇するので、仮に、何らかの原因によって反応温度が上昇した場合には、反応量が増加すること、及び逐次反応が進むことから、総体としての反応熱が増加する。例えば、前項の条件から他の条件を全く変えずに、温度だけが５℃上昇した場合に、供給したプロパン１００ｍｏｌのうち、８２．５ｍｏｌのプロパンが反応し（反応率８２．５％）、５０．３ｍｏｌのアクリロニトリル（収率５０．３％）、６４．５ｍｏｌのＣＯ２（収率２１．５％）、３２．１ｍｏｌのＣＯ（収率１０．７％）が生成するよう変化したとすると、この条件での総体としての反応熱は、６３７×０．５０３＋２０４３×０．２１５＋１１９４×０．１０７＝８８７．４（ｋＪ／ｍｏｌ）となる。総体としての反応熱の変化率は、総体としての反応熱の温度に関する偏微分係数として表すことができて、この場合この温度の廻りで直線近似することにより、（８８７．４−８４６．５）÷５＝８．２（ｋＪ／ｍｏｌ・Ｋ）として求められる。算出過程から判るとおり、総体としての反応熱の温度に関する偏微分係数は、反応温度、原料の反応率、各併発反応の寄与率（各生成物の収率）等により変化するので、反応条件に依存する。総体としての反応熱の変化率が過大となる場合には、熱バランス上、反応温度の制御が不安定となり、反応器内の温度分布を生じる原因、さらに極端な場合には反応器の熱暴走にもつながることとなるので、この点からは反応条件を選ぶにあたって、総体としての反応熱の変化率が出来るだけ小さくなるようにするのが好ましい。具体的には、総体としての反応熱の温度に関する偏微分係数が、４０ｋＪ／ｍｏｌ（原料）・Ｋ以下、好ましくは３０ｋＪ／ｍｏｌ（原料）・Ｋ以下となるように反応条件を選ぶのが良い。 On the other hand, in the gas phase exothermic reaction, the stability of the target product is not so great, so that the sequential reaction of the target product proceeds as the reaction proceeds, that is, the reaction conversion rate increases. Product selectivity tends to decrease. Here, the reaction conversion rate depends on the activity of the catalyst, and the conversion rate increases as the activity increases. In addition, the activity of the catalyst depends on the reaction temperature, and generally the activity increases as the reaction temperature rises. Therefore, if the reaction temperature rises for some reason, the reaction amount increases and successive reactions proceed. Therefore, the heat of reaction as a whole increases. For example, when only the temperature rises by 5 ° C. without changing other conditions from the conditions of the previous paragraph, 82.5 mol of propane reacts (reaction rate 82.5%) out of 100 mol of supplied propane, and 50 .3 mol of acrylonitrile (yield 50.3%), 64.5 mol of CO 2 (yield 21.5%), 32.1 mol of CO (yield 10.7%) The total reaction heat under these conditions is 637 × 0.503 + 2043 × 0.215 + 1194 × 0.107 = 887.4 (kJ / mol). The rate of change of the reaction heat as a whole can be expressed as a partial differential coefficient with respect to the temperature of the reaction heat as a whole. In this case, by linear approximation around this temperature, (887.4-846.5) ÷ 5 = 8.2 (kJ / mol · K). As can be seen from the calculation process, the partial differential coefficient related to the temperature of the reaction heat as a whole changes depending on the reaction temperature, the reaction rate of the raw materials, the contribution rate of each concurrent reaction (the yield of each product), etc. Dependent. If the overall rate of change in the heat of reaction is excessive, the control of the reaction temperature becomes unstable due to heat balance, causing the temperature distribution in the reactor, and in extreme cases, the thermal runaway of the reactor From this point, it is preferable that the rate of change in reaction heat as a whole is as small as possible when selecting reaction conditions. Specifically, the reaction conditions should be selected so that the partial differential coefficient related to the temperature of the reaction heat as a whole is 40 kJ / mol (raw material) · K or less, preferably 30 kJ / mol (raw material) · K or less. .
本発明に用いられる流動層反応器には、有効断面積２０平方メートル毎に、少なくとも一つ以上の温度検出部を設置する。好ましくは有効断面積１５平方メートル毎に、より好ましくは１０平方メートル毎に少なくとも一つ以上の温度検出部を設置する。なお、有効断面積とは、流動層反応器における内挿物部分等を除いた、内容物が実際に流動可能な断面積のことをいう。温度検出部を単位面積あたり複数個設置した場合においては、そのうち一つの検出部を使うよう選択して用いても良いし、二つ以上の検出部を選択して複数の温度出力を平均するなどの演算を行った後に用いても良い。安定的に反応器の温度を測定できる場所であれば、設置する位置には特に制限はなく、目的に応じて触媒濃厚層・希薄層・ガス出口などに設置することができる。設置する温度検出器の形式には特に制限はなく、通常用いられる形式の検出器、例えば熱電対、測温抵抗体などを用いることができる。 In the fluidized bed reactor used in the present invention, at least one temperature detector is installed for every 20 square meters of effective area. Preferably, at least one temperature detection unit is installed every 15 square meters, more preferably every 10 square meters. In addition, an effective cross-sectional area means a cross-sectional area in which the contents can actually flow, excluding the interpolated portion in the fluidized bed reactor. When multiple temperature detectors are installed per unit area, you may choose to use one of them, or select two or more detectors and average multiple temperature outputs. It may be used after performing the above calculation. As long as the temperature of the reactor can be stably measured, the installation position is not particularly limited, and it can be installed in a catalyst rich layer, a dilute layer, a gas outlet, or the like according to the purpose. The type of the temperature detector to be installed is not particularly limited, and a commonly used type of detector such as a thermocouple or a resistance temperature detector can be used.
本発明に用いられる流動層反応器には、反応熱を除去して反応温度を制御するとともにエネルギーを回収する目的で、有効断面積２０平方メートル毎に、少なくとも一つの除熱管を設置する。好ましくは有効断面積１５平方メートル毎に、より好ましくは１０平方メートル毎に少なくとも一つ以上の除熱管を設置する。設置する除熱管の形状は、反応器内に適切に設置できるものであれば、特に制限はないが、材料の入手の容易さや加工の容易さから、通常配管に用いられる材料、すなわち鋼管と鋼管継ぎ手を組み合わせ、いくつか連なったＵ字型に施工されるのが一般的である。除熱管の材質にも特に制限はなく、使用される条件、すなわち冷却媒体や反応ガスといった接触する流体の温度、圧力、腐食性の有無等に応じて、通常用いられる配管材料、例えばＪＩＳ Ｇ−３４５４、Ｇ−３４５８、Ｇ−３４５９等に規定される一般的な配管材料、及びＪＩＳ Ｂ−２３１１等に規定される通常用いられる鋼管継ぎ手等から自由に選択して用いることができる。 In the fluidized bed reactor used in the present invention, at least one heat removal pipe is installed for every 20 square meters of effective sectional area for the purpose of removing reaction heat to control reaction temperature and recover energy. Preferably, at least one heat removal tube is installed every 15 square meters, more preferably every 10 square meters. The shape of the heat removal pipe to be installed is not particularly limited as long as it can be properly installed in the reactor. However, from the viewpoint of the availability of materials and the ease of processing, materials used for normal piping, that is, steel pipes and steel pipes. It is common to construct several U-shaped joints by combining joints. There are no particular restrictions on the material of the heat removal pipe, and pipe materials that are usually used, such as JIS G-, depending on the conditions used, that is, the temperature, pressure, presence or absence of corrosiveness of the fluid such as the cooling medium and reaction gas. It can be freely selected from general piping materials defined in 3454, G-3458, G-3459, etc., and commonly used steel pipe joints defined in JIS B-2311.
除熱管は、原料の供給速度に応じて、あるいは汚れ等による除熱管の能力低下に応じて、除熱能力を調整して用いる。従って、能力の総計を概略調整できるように、必要な除熱量に対して一定の余裕を持った能力のものを、複数の系列に分割して設置するのが好ましく、一般的である。ここで、系列とは、各個に冷却媒体の流れを開閉できる弁を有しており、使用／不使用を個別に設定できるものを言う。除熱管の除熱能力は、流動層の濃厚層部分と接触する面積、流動層の希薄層と接触する面積、触媒層の温度、通ずる冷却媒体の種類・物理形態・供給する温度・供給する速度など様々な要因に支配される。定常除熱管の能力総計は、発生する反応熱量等から定まる除熱すべき熱量（必要能力）以上であれば、特に制限はないが、好ましくは必要能力の１３０％以上、より好ましくは１５０％以上、最も好ましくは１８０％以上の能力を有するのが良い。また、好ましくは５系列以上、より好ましくは８系列以上、最も好ましくは１０系列以上を設置するのが良い。これら複数の系列について、適宜、使用／不使用を切り替えることで、除熱能力の総計を概略調整して用いる。 The heat removal tube is used by adjusting the heat removal capability in accordance with the feed rate of the raw material or in accordance with a decrease in the capacity of the heat removal tube due to dirt or the like. Therefore, it is preferable to divide and install those having a certain margin with respect to the required heat removal amount into a plurality of series so that the total capacity can be roughly adjusted. Here, the series means a valve that has a valve capable of opening and closing the flow of the cooling medium in each unit, and that can be used / not used individually. The heat removal capacity of the heat removal pipe is determined by the area in contact with the dense part of the fluidized bed, the area in contact with the diluted layer of the fluidized bed, the temperature of the catalyst layer, the type of cooling medium to be communicated, the physical form, the supply temperature, and the supply speed. It is controlled by various factors. The total capacity of the steady heat removal pipe is not particularly limited as long as it is equal to or greater than the amount of heat to be removed (required capacity) determined from the amount of reaction heat generated, but preferably 130% or more of the necessary capacity, more preferably 150% or more. Most preferably, it has a capacity of 180% or more. Moreover, it is preferable to install 5 lines or more, more preferably 8 lines or more, and most preferably 10 lines or more. About these several series, the total of heat removal capability is roughly adjusted and used by switching use / nonuse suitably.
除熱管に通ずる冷却媒体は、必要な除熱能力を満たすことができるものであれば特に制限はないが、好ましくは反応器の運転温度において蒸発することで蒸発潜熱による除熱を利用できる液体を、より好ましくは水を、更に好ましくは０．５〜５ＭＰａ（ゲージ圧力）に加圧された水を用いるのが良い。これは、蒸発潜熱を利用することで当該除熱管の総括伝熱係数を比較的高くすることができるため、除熱管の単位表面積当たりの除熱量を大きくすることができ、除熱管の必要本数を減じることができること、及び得られた冷却媒体蒸気の可用性による。また、より好ましくは定常除熱管として、冷却媒体に液体を用いるものだけでなく、冷却媒体として気体を用いるものを併設すること、更に好ましくは冷却媒体に液体を用い冷却媒体の一部を蒸発させ液体−蒸気の気液混相流として回収する定常除熱管に加え、ここで発生した蒸気をさらに冷却媒体として用いて、過熱蒸気として回収する定常除熱管を併設することが望ましい。 The cooling medium leading to the heat removal pipe is not particularly limited as long as it can satisfy the necessary heat removal capability, but preferably a liquid that can be used for heat removal by latent heat of vaporization by evaporating at the operating temperature of the reactor. More preferably, water is used, and more preferably water pressurized to 0.5 to 5 MPa (gauge pressure) is used. This is because the overall heat transfer coefficient of the heat removal tube can be made relatively high by using the latent heat of vaporization, so the amount of heat removal per unit surface area of the heat removal tube can be increased, and the required number of heat removal tubes can be reduced. Due to the ability to be reduced and the availability of the resulting coolant vapor. More preferably, the stationary heat removal tube is not only one that uses a liquid as a cooling medium but also one that uses a gas as a cooling medium, and more preferably a liquid is used as a cooling medium to evaporate a part of the cooling medium. In addition to the steady heat removal pipe recovered as a gas-liquid mixed phase flow of liquid-vapor, it is desirable to additionally provide a steady heat removal pipe that collects the generated steam as a cooling medium and collects it as superheated steam.
有効断面積２０平方メートル毎、好ましくは有効断面積１５平方メートル毎、より好ましくは１０平方メートル毎を単位として、温度検出部で検出された温度と目標温度との差に応じて、除熱管の能力を調整し、温度を調節する。除熱管の能力調整は、調節計を用いて自動で行っても良いし、適宜判断して手動で行っても良い。 The capacity of the heat removal pipe is adjusted according to the difference between the temperature detected by the temperature detection unit and the target temperature, with an effective area of every 20 square meters, preferably every 15 square meters, more preferably every 10 square meters. And adjust the temperature. The capacity adjustment of the heat removal tube may be performed automatically using a controller, or may be performed manually with appropriate judgment.
本発明の好ましい一態様を図面に基づいて更に詳細に説明する。図１は本発明にかかる流動層反応器の一例である。流動層反応器（１）の直径が６ｍであるとすると、その断面積は約２８平方メートルであるので、２０平方メートルを超えないように、例えば南北の線で仮想的に２分割する（図２中、ａゾーン及びｂゾーン）。流動層反応器（１）内部には触媒による触媒流動層（２）が形成されている。反応器下部に設けられた酸素導入管（３）からは酸素を含むガス（通常は空気）が、原料供給管（４）からは原料を含むガスが供給される。反応生成物を含むガスは抜き出し管（５）を経て流動層反応器（１）外へと抜き出される。 A preferred embodiment of the present invention will be described in more detail based on the drawings. FIG. 1 is an example of a fluidized bed reactor according to the present invention. If the diameter of the fluidized bed reactor (1) is 6 m, its cross-sectional area is about 28 square meters, so it is virtually divided into two, for example, the north and south lines so as not to exceed 20 square meters (in FIG. 2). , A zone and b zone). A catalyst fluidized bed (2) is formed in the fluidized bed reactor (1). A gas containing oxygen (usually air) is supplied from an oxygen introduction pipe (3) provided at the lower part of the reactor, and a gas containing a raw material is supplied from a raw material supply pipe (4). The gas containing the reaction product is extracted out of the fluidized bed reactor (1) through the extraction pipe (5).
流動層反応器（１）の内部には、触媒流動層（２）内に位置して液体を冷却媒体に用いる除熱管（６ａ、６ｂ）、及び気体を冷却媒体に用いる除熱管（７ａ、７ｂ）が設置されている。なお、図ではそれぞれの除熱管は各１系列しか示されていないが、通常はそれぞれの複数系列が設置されている。 Inside the fluidized bed reactor (1), there are a heat removal pipe (6a, 6b) which is located in the catalyst fluidized bed (2) and uses a liquid as a cooling medium, and a heat removal pipe (7a, 7b) which uses a gas as a cooling medium. ) Is installed. In the figure, each of the heat removal tubes is shown as only one series, but usually a plurality of series is provided.
液体を用いる定常除熱管（６）には、気液分離容器（８）から冷却媒体輸送ポンプ（９）により冷却媒体が供給される。触媒流動層（２）と除熱管（６）との熱交換により冷却媒体の一部は蒸発し、気液二相流として気液分離容器（８）に戻り気液が分離される。蒸発により液体の冷却媒体が減少する分は、冷却媒体追加管（１０）を通じて追加供給される。 The cooling medium is supplied from the gas-liquid separation container (8) to the steady heat removal pipe (6) using the liquid by the cooling medium transport pump (9). A part of the cooling medium evaporates by heat exchange between the catalyst fluidized bed (2) and the heat removal pipe (6), and returns to the gas-liquid separation container (8) as a gas-liquid two-phase flow to separate the gas and liquid. The amount of the liquid cooling medium reduced by evaporation is additionally supplied through the cooling medium additional pipe (10).
定常除熱管（６）で発生した冷却媒体蒸気の一部は、除熱管（７）に供給される。触媒流動層（２）と除熱管（７）との熱交換により冷却媒体蒸気は過熱蒸気となり、過熱蒸気抜き出し管（１１）を通じて系外に供給される。 A part of the cooling medium vapor generated in the steady heat removal pipe (6) is supplied to the heat removal pipe (7). Due to the heat exchange between the catalyst fluidized bed (2) and the heat removal pipe (7), the cooling medium vapor becomes superheated steam and is supplied outside the system through the superheated steam extraction pipe (11).
また、触媒流動層（２）中には、温度検出部（１２ａ、１２ｂ）が設置されている。図中には各１つずつの温度検出部しか示していないが、複数を設置することも行われる。複数の検出部を設置した場合には、適当な検出部を選び、平均するなどの適当な演算を行った後、流動層の温度として用いる。温度検出部（１２）で検出された温度情報は、温度指示計（１３ａ、１３ｂ）に伝えられ、流動層の温度として検出される。 In the catalyst fluidized bed (2), temperature detectors (12a, 12b) are installed. Although only one temperature detection unit is shown in the figure, a plurality of temperature detection units may be installed. When a plurality of detection units are provided, an appropriate detection unit is selected and subjected to an appropriate calculation such as averaging, and then used as the temperature of the fluidized bed. The temperature information detected by the temperature detector (12) is transmitted to the temperature indicator (13a, 13b) and detected as the temperature of the fluidized bed.
検出された流動層の温度と、設定温度との差に基づいて冷却媒体の流量調節弁（１４ａ、１４ｂ）を操作し、除熱管（７）に通じる冷却媒体の流量を調整することで、除熱管（７）の能力を調整する。 By operating the cooling medium flow rate control valves (14a, 14b) based on the difference between the detected fluidized bed temperature and the set temperature, the flow rate of the cooling medium leading to the heat removal pipe (7) is adjusted. Adjust the capacity of the heat pipe (7).
除熱管（６）で発生した冷却媒体蒸気のうち、除熱管（７）で用いなかった余剰分は、飽和蒸気抜き出し管（１５）を通じて系外に供給される。 Of the cooling medium vapor generated in the heat removal pipe (6), the surplus not used in the heat removal pipe (7) is supplied outside the system through the saturated vapor extraction pipe (15).
以下、実施例を用いて本発明を更に詳細に説明するが、本発明は以下の実施例に限定されるものではない。
［実施例１］
図１に示したような形式の、直径６．８２ｍの流動層反応器（１）に、モリブデン、バナジウム、アンチモン、ニオブからなる平均粒子径５０μｍ、粒子径４４μｍ以下の微粉を１２％含有する複合酸化物触媒８０トンを充填した。酸素供給管（３）から空気４５０００Ｎｍ3／Ｈｒを、原料供給管（４）からプロパン３０００Ｎｍ3／Ｈｒとアンモニア２７００Ｎｍ3／Ｈｒを混合したガスを供給し、主としてアクリロニトリルを製造した。
EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example, this invention is not limited to a following example.
[Example 1]
A composite containing 12% fine powder of molybdenum, vanadium, antimony and niobium with an average particle size of 50 μm and a particle size of 44 μm or less in a fluidized bed reactor (1) of the type shown in FIG. 80 tons of oxide catalyst was charged. Oxygen supply tube (3) from the air 45000Nm 3 / Hr, the raw material supply pipe (4) by supplying propane 3000 Nm 3 / Hr and ammonia 2700 nm 3 / Hr were mixed gas from was mainly producing acrylonitrile.
内挿物部分を除いた有効な断面積は、おおよそ３６平方メートルであったので、それぞれが２０平方メートルを超えないように図２に示すように仮想的に２分割し、ａゾーン、及びｂゾーンとした。 Since the effective cross-sectional area excluding the interpolated portion was approximately 36 square meters, each was virtually divided into two so as not to exceed 20 square meters as shown in FIG. did.
触媒流動層（２）には、ＪＩＳ Ｇ−３４５８に規定される外径１１４．３ｍｍの鋼管と、ＪＩＳ Ｂ−２３１１に規定される対応する径の突合せ溶接式１８０°ショートエルボ管を用いて製作した除熱管（６）をａゾーンに１５系列、ｂゾーンに１５系列（直管部の総合計は１２５０ｍ）を設置した。これら除熱管（６）には、気液分離容器（８）から２３５℃の水８００トン／Ｈｒを供給し、その一部を蒸発させ、温度２３６℃、圧力３ＭＰａ（ゲージ圧力）の気液２相流として回収した。定常条件での蒸発率は５．８％であった。
The catalyst fluidized bed (2) is manufactured using a steel pipe with an outer diameter of 114.3 mm specified in JIS G-3458 and a butt-welded 180 ° short elbow pipe with a corresponding diameter specified in JIS B-2311. The removed heat removal pipe (6) was installed in 15 series in the a zone and 15 series in the b zone (the total sum of the straight pipe sections was 1250 m). These heat removal tubes (6) are supplied with 800 ton / Hr of water at 235 ° C. from the gas-liquid separation vessel (8), and part of the water is evaporated to form gas-
また、除熱管（６）と同じ材料を用いて製作した除熱管（７）をａゾーンに８系列、ｂゾーンに８系列（直管部の総合計は４５０ｍ）を設置した。これら除熱管（７）には、除熱管（６）で発生した気液二相流から気液分離容器（８）にて分離された温度２３６℃、圧力３ＭＰａ（ゲージ圧力）の飽和水蒸気１７トン／Ｈｒを供給し、温度３７０〜３７２℃の過熱蒸気として回収した。 In addition, 8 series of heat removal pipes (7) manufactured using the same material as the heat removal pipe (6) were installed in the a zone and 8 series in the b zone (total length of the straight pipe section was 450 m). These heat removal tubes (7) include 17 tons of saturated water vapor at a temperature of 236 ° C. and a pressure of 3 MPa (gauge pressure) separated from the gas-liquid two-phase flow generated in the heat removal tube (6) in the gas-liquid separation vessel (8). / Hr was supplied and recovered as superheated steam at a temperature of 370 to 372 ° C.
ａゾーン、ｂゾーンのほぼ中心位置の流動層部分に、温度検出部（１２ａ、１２ｂ）としてＫタイプの熱電対を各１つ設置し、温度指示計（１３ａ、１３ｂ）で熱起電力を温度信号に変換し検出した。 One K-type thermocouple is installed as a temperature detector (12a, 12b) in the fluidized bed part at the center of the a zone and b zone, and the thermoelectromotive force is measured by the temperature indicator (13a, 13b). Converted to signal and detected.
温度指示計（１３ａ）により検出される温度が４４５℃となるように、流量調節弁（１４ａ）の開度を調整して除熱管（７ａ）の能力を調整し、ａゾーンの温度調節を行った。同様に、温度指示計（１３ｂ）により検出される温度が４４５℃となるように、流量調節弁（１４ｂ）の開度を調整して除熱管（７ｂ）の能力を調整し、ｂゾーンの温度調節を行った。このとき、流動層内の各所１０点の温度を測定したところ、最も低い箇所は４４３℃、最も高い箇所は４４６．５℃であって、温度差は３．５℃であり、良好であった。 Adjust the opening of the flow control valve (14a) to adjust the capacity of the heat removal pipe (7a) so that the temperature detected by the temperature indicator (13a) is 445 ° C, and adjust the temperature of the a zone. It was. Similarly, the capacity of the heat removal pipe (7b) is adjusted by adjusting the opening of the flow control valve (14b) so that the temperature detected by the temperature indicator (13b) is 445 ° C. Adjustments were made. At this time, when the temperature at 10 points in the fluidized bed was measured, the lowest point was 443 ° C., the highest point was 446.5 ° C., and the temperature difference was 3.5 ° C., which was good. .
［比較例１］
実施例１において、仮想的に２分割することを止め、温度検出部の設置位置を以下のように変更した。すなわち、流動層の中心部に温度検出部（１２）としてＫタイプの熱電対を１つ設置し、温度指示計（１３）で熱起電力を温度信号に変換し検出した。
[Comparative Example 1]
In Example 1, the virtual division into two was stopped, and the installation position of the temperature detection unit was changed as follows. That is, one K-type thermocouple was installed as a temperature detector (12) in the center of the fluidized bed, and the thermoelectromotive force was converted into a temperature signal and detected by the temperature indicator (13).
温度指示計（１３）により検出される温度が４４５℃となるように、流量調節弁（１４）の開度を調整して除熱管（７）の能力を調整し、反応器全体の温度調節を行った。このとき、流動層内の各所１０点の温度を測定したところ、最も低い箇所は４４０℃、最も高い箇所は４５１℃であって、温度差は１１℃であり、良好ではなかった。 The temperature of the entire reactor is adjusted by adjusting the opening of the flow control valve (14) and adjusting the capacity of the heat removal pipe (7) so that the temperature detected by the temperature indicator (13) is 445 ° C. went. At this time, when the temperature at 10 points in the fluidized bed was measured, the lowest point was 440 ° C., the highest point was 451 ° C., and the temperature difference was 11 ° C., which was not good.
本発明によれば、種々の合成樹脂・合成繊維の製造に有用なモノマーを、工業的に製造する際に広く用いられている流動層反応器の温度を精細に制御することが可能となり、触媒が最高収率となる温度領域で、長期間安定に運転することができる。 According to the present invention, it is possible to finely control the temperature of a fluidized bed reactor widely used in industrial production of monomers useful for the production of various synthetic resins and synthetic fibers. Can be stably operated for a long period of time in a temperature range where the maximum yield is obtained.
１ 流動層反応器
２ 触媒流動層
３ 酸素供給管
４ 原料供給管
５ 反応生成ガス抜き出し管
６ 液体の冷却媒体を用いる除熱管
７ 気体の冷却媒体を用いる除熱管
８ 気液分離容器
９ 冷却媒体輸送ポンプ
１０ 冷却媒体追加管
１１ 過熱蒸気抜き出し管
１２ 温度検出部
１３ 温度指示計
１４ 流量調節弁（能力調整用）
１５ 飽和蒸気抜き出し管
DESCRIPTION OF SYMBOLS 1
15 Saturated steam extraction pipe
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| JP2009286758A (en) * | 2008-05-30 | 2009-12-10 | Asahi Kasei Chemicals Corp | Fluidized bed reaction apparatus and gas-phase exothermic reaction method using the same |
| JP2010095451A (en) * | 2008-10-14 | 2010-04-30 | Asahi Kasei Chemicals Corp | Gas-phase exothermic reaction method |
| JP2011521884A (en) * | 2008-06-06 | 2011-07-28 | エボニック レーム ゲゼルシャフト ミット ベシュレンクテル ハフツング | Method for producing hydrogen cyanide using a particulate heat transfer material guided cyclically as a moving fluidized bed |
| WO2012035881A1 (en) * | 2010-09-14 | 2012-03-22 | 旭化成ケミカルズ株式会社 | Gaseous phase exothermic reaction method and gaseous phase exothermic reaction device |
| JP2015174063A (en) * | 2014-03-17 | 2015-10-05 | 旭化成株式会社 | Design method of fluidized-bed reactor, and fluidized-bed reactor designed thereby |
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| JP2017511326A (en) * | 2014-03-31 | 2017-04-20 | イネオス ユーロープ アクチェンゲゼルシャフト | Cooling coil design for oxidation or ammoxidation reactors |
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