JP5045124B2 - Reaction control method - Google Patents
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Description
本発明は反応の制御方法に関する。詳しくは多段で反応する際に、容易に迅速に転化率を求め、反応を制御する方法に関する。 The present invention relates to a reaction control method. Specifically, the present invention relates to a method for easily and quickly obtaining a conversion rate and controlling the reaction when reacting in multiple stages.
反応の制御は、一般的に、反応器出口の反応物組成を定期的に分析して転化率を求め、反応条件を変更することによって行なわれている。しかしながら、この方法は、作業量が多くなると共に、少なからず時間遅れが生じ、規格外の製品を生産することによるロス(loss)や精製プロセスの運転条件の不安定化などを生じさせる恐れがある。 In general, the reaction is controlled by periodically analyzing the composition of the reactant at the outlet of the reactor to obtain the conversion rate and changing the reaction conditions. However, this method increases the amount of work and causes a considerable time delay, which may cause loss due to production of non-standard products and unstable operating conditions of the purification process. .
この問題を解決するために、反応器出口の反応物を、近赤外線スペクトルで組成分析する方法（特開平８−３０１７９３号公報）、中赤外線スペクトルで組成分析する方法（特開２００３−３４０２７０号公報）が知られている。
しかしながら、これらの近赤外線スペクトル、中赤外線スペクトルを用いる方法は、反応物の組成、不純物、ノイズなどによって必ずしも精度良く定量できない反応系も多く存在する。
However, these methods using the near-infrared spectrum and the mid-infrared spectrum have many reaction systems that cannot always be accurately quantified due to the composition of the reaction product, impurities, noise, and the like.
本発明の目的は、多段で反応する際に、容易に迅速に転化率を求め、反応を制御する方法を提供することにある。 It is an object of the present invention to provide a method for controlling the reaction by obtaining the conversion rate easily and quickly when reacting in multiple stages.
本発明は以下の発明を提供する。
（１）多段の反応器を有する発熱反応プロセスであって、直列に連続する二段の反応器のうちの前段反応器が気液接触による反応を行う反応器であり、後段反応器が前段反応器で蒸発した未反応原料ガスについての気相反応を完全に行う反応器であって相変化を伴わない断熱反応を行う反応器である発熱反応プロセスにおいて、
後段反応器における発熱量と前段反応器における転化率との関係を予め求めておき、実際の反応を行う際に、後段反応器における発熱量を求め、求めた発熱量と前記関係とから前段反応器における転化率を求め、求めた転化率をもとに前段反応器の反応を制御する反応制御方法。
（２）前段反応器における転化率が８０％〜９９．９％である前記（１）記載の反応制御方法。
（３）第一反応器でニトロベンゼンと水素を気液接触により反応させ、第一反応器で蒸発
した未反応ニトロベンゼンについての気相反応を第二反応器で行う前記（１）または（２）記載の反応制御方法。
（４）ニトロベンゼンの水素還元反応によりアニリンを製造する方法であって、該反応を
前記（３）記載の方法により制御するアニリンの製造方法。
The present invention provides the following inventions.
(1) an exothermic reaction process having a multi-stage reactor, a reactor preceding reactor of the reactor of a two-stage continuous in series carry out the reaction by gas-liquid contact, subsequent reactor primary reaction In an exothermic reaction process that is a reactor that completely performs a gas phase reaction on an unreacted raw material gas evaporated in a reactor and that performs an adiabatic reaction without phase change,
The relationship between the calorific value in the post-reactor and the conversion rate in the pre-reactor is obtained in advance, and when performing the actual reaction, the calorific value in the post-reactor is obtained, and the pre-reaction is determined from the obtained calorific value and the relationship. The reaction control method which calculates | requires the conversion rate in a reactor and controls reaction of a prestage reactor based on the calculated | required conversion rate.
(2) The reaction control method according to the above (1), wherein the conversion rate in the pre-reactor is 80% to 99.9% .
(3) The above (1) or (2), wherein nitrobenzene and hydrogen are reacted in a first reactor by gas-liquid contact, and a gas phase reaction of unreacted nitrobenzene evaporated in the first reactor is performed in the second reactor. Reaction control method.
(4) A method for producing aniline by a hydrogen reduction reaction of nitrobenzene, wherein the reaction is controlled by the method described in (3) above.
本発明の方法によって、多段で反応する際に、容易に迅速に前段反応器における転化率を求めることができ、従って、容易に前段反応器における反応を制御することが可能になる。また、少ない作業量で、規格外の製品を生産することによるロスや精製プロセスの運転条件の不安定化を低減したアニリンの製造方法が提供される。 According to the method of the present invention, when the reaction is carried out in multiple stages, the conversion rate in the pre-stage reactor can be determined easily and quickly, and therefore the reaction in the pre-stage reactor can be easily controlled. In addition, a method for producing aniline is provided that reduces loss due to production of non-standard products and instability in the operating conditions of the purification process with a small amount of work.
本発明の多段の反応器を有する発熱反応プロセスとしては、ニトロベンゼンの水素還元反応によるアニリンの製造プロセス、ベンゼンの水素還元反応によるシクロヘキサンの製造プロセスなどが挙げられるが、これらに限定されるものではない。多段反応としては、通常、２〜３段の反応である。なお、ここでいう多段の反応器とは、別個に制御されている複数の反応帯域を持つ反応器であり、一つの反応器中で触媒の充填方法や温度制御条件などが別個に制御されている反応器や、それらが別個に制御されている複数の反応器が挙げられる。
以下、ニトロベンゼンの水素還元反応によるアニリンの製造プロセスを例に、本発明を詳細に説明する。
Examples of the exothermic reaction process having a multi-stage reactor of the present invention include, but are not limited to, an aniline production process by nitrobenzene hydrogen reduction reaction, a cyclohexane production process by benzene hydrogen reduction reaction, and the like. . The multistage reaction is usually a 2-3 stage reaction. The multi-stage reactor referred to here is a reactor having a plurality of reaction zones that are separately controlled, and the charging method of the catalyst, temperature control conditions, and the like are separately controlled in one reactor. Or a plurality of reactors in which they are controlled separately.
Hereinafter, the present invention will be described in detail by taking as an example a process for producing aniline by hydrogen reduction of nitrobenzene.
ニトロベンゼンの水素還元反応によるアニリンの製造は、通常、２段反応で行なわれる。第一反応器にニトロベンゼンおよび水素ガスを供給し、気液接触による反応を行う。反応は、通常、溶媒の存在下に行い、一般的には反応生成物であるアニリンを溶媒とし、触媒を分散させて行う。
触媒としては、パラジウム触媒、パラジウム−白金系担持触媒、ニッケル系触媒、コバルト系触媒などを使用する。
反応は約１５０℃〜２５０℃で行なう。
The production of aniline by the hydrogen reduction reaction of nitrobenzene is usually performed in a two-stage reaction. Nitrobenzene and hydrogen gas are supplied to the first reactor, and the reaction is carried out by gas-liquid contact. The reaction is usually carried out in the presence of a solvent, and in general, the reaction product aniline is used as a solvent and the catalyst is dispersed.
As the catalyst, a palladium catalyst, a palladium-platinum supported catalyst, a nickel catalyst, a cobalt catalyst, or the like is used.
The reaction is carried out at about 150 ° C to 250 ° C.
第一反応器にニトロベンゼンを供給するとともに反応に必要な量に対して過剰の水素ガスを供給する。第一反応器はいわゆる連続完全混合槽であり、反応を完結させることが困難であると同時にニトロベンゼンの転化率が１００％に近づくと、逐次反応による不純物生成が促進されるため、ニトロベンゼンの転化率を、使用する触媒等にもよるが、通常は約８０〜９９．９％に抑制する。
一般的に逐次反応をともなう有機化合物の合成反応では、選択率と転化率とは相対する関係にあり、転化率が高く原料濃度が低い領域では目的化合物の選択率が低下する。ニトロベンゼンの水素還元反応では、転化率を高く維持すると目的化合物のアニリンに対する過水添が生じ、選択率が著しく低下する。従って、転化率を所定の範囲になるよう反応を精度良く制御する必要がある。
Nitrobenzene is supplied to the first reactor and excess hydrogen gas is supplied relative to the amount required for the reaction. The first reactor is a so-called continuous complete mixing tank, and it is difficult to complete the reaction. At the same time, when the conversion rate of nitrobenzene approaches 100%, impurity generation by sequential reaction is promoted. Depending on the catalyst used, etc., it is usually suppressed to about 80-99.9%.
In general, in a synthesis reaction of an organic compound accompanied by a sequential reaction, the selectivity and the conversion rate are in a relative relationship, and the selectivity of the target compound decreases in a region where the conversion rate is high and the raw material concentration is low. In the hydrogen reduction reaction of nitrobenzene, when the conversion rate is kept high, perhydrogenation of the target compound to aniline occurs, and the selectivity is significantly lowered. Therefore, it is necessary to accurately control the reaction so that the conversion rate falls within a predetermined range.
第一反応器においては、未反応のニトロベンゼンおよび反応生成物（アニリンおよび水）は過剰の水素ガスに同伴され蒸発する。このガスを第二反応器に供給し、未反応のニトロベンゼンについて気相反応を行ない、完全に反応させる。ニトロベンゼンとアニリンの沸点が近く、精製分離に負荷がかかるので完全に反応させるのが好ましい。
触媒としては、銅−クロム系触媒などが使用される。
反応は約１００〜２４５℃で行なわれる。
In the first reactor, unreacted nitrobenzene and reaction products (aniline and water) are entrained with excess hydrogen gas and evaporated. This gas is supplied to the second reactor, and a gas phase reaction is performed on unreacted nitrobenzene to complete the reaction. Since the boiling points of nitrobenzene and aniline are close to each other and a load is imposed on purification separation, it is preferable to completely react.
A copper-chromium-based catalyst or the like is used as the catalyst.
The reaction is carried out at about 100-245 ° C.
第二反応器では、第一反応器から導入された反応生成物中の未反応のニトロベンゼンの量に比例して発熱が生じる。第一反応器における転化率が高いと第二反応器に導入されるニトロベンゼンの量が少なくなり、第一反応器における転化率が低いと第二反応器に導入されるニトロベンゼンの量が多くなる。本発明においては、第二反応器における発熱量と第一反応器における転化率との関係を予め求めておく。そして、実際の反応の際に、第二反応器における発熱量を求め、求めた発熱量と前記関係とから、第一反応器における転化率を求める。
ところで、第二反応器における反応が相変化をともなわない断熱反応であれば、発熱量と温度上昇とはほぼ比例関係にある。すなわち、第二反応器における反応が相変化をともなわない断熱反応であれば、温度上昇を測定することは、発熱量を求めることと同等であり、第二反応器における温度上昇と第一反応器における転化率との関係から第一反応器における転化率を求めることも可能である。除熱や相変化をともなう反応器であれば、冷却媒体の温度変化および流量を加味して第二反応器の発熱量を算出することが可能である。
In the second reactor, heat is generated in proportion to the amount of unreacted nitrobenzene in the reaction product introduced from the first reactor. When the conversion rate in the first reactor is high, the amount of nitrobenzene introduced into the second reactor decreases, and when the conversion rate in the first reactor is low, the amount of nitrobenzene introduced into the second reactor increases. In the present invention, the relationship between the calorific value in the second reactor and the conversion rate in the first reactor is determined in advance. In the actual reaction, the calorific value in the second reactor is obtained, and the conversion rate in the first reactor is obtained from the obtained calorific value and the relationship.
By the way, if the reaction in the second reactor is an adiabatic reaction that does not involve a phase change, the calorific value and the temperature rise are in a substantially proportional relationship. That is, if the reaction in the second reactor is an adiabatic reaction with no phase change, measuring the temperature rise is equivalent to obtaining the calorific value, and the temperature rise in the second reactor and the first reactor It is also possible to obtain the conversion rate in the first reactor from the relationship with the conversion rate in. If it is a reactor with heat removal or phase change, it is possible to calculate the calorific value of the second reactor in consideration of the temperature change and flow rate of the cooling medium.
第二反応器において検知した温度上昇により、または温度上昇ならびに冷却媒体の温度変化および流量により、発熱量を求め、第一反応器における転化率を求め、第一反応器における転化率が所定の範囲になるように反応条件を操作して反応を制御する。第一反応器にて操作される反応条件として、滞留時間、触媒濃度、触媒活性、反応温度、反応圧力、攪拌速度などが挙げられ、これらのうちのいずれかを変更するか、またはこれらのいずれかを組み合わせて変更し、第一反応器の反応を制御することができる。 The calorific value is obtained by the temperature rise detected in the second reactor or by the temperature rise and the temperature change and flow rate of the cooling medium, the conversion rate in the first reactor is obtained, and the conversion rate in the first reactor is within a predetermined range. The reaction is controlled by manipulating the reaction conditions so that The reaction conditions operated in the first reactor include residence time, catalyst concentration, catalyst activity, reaction temperature, reaction pressure, stirring speed, etc., either of which can be changed or any of these These can be combined and changed to control the reaction in the first reactor.
図１に実施例における第二反応器における温度上昇と第一反応器における転化率との関係を示す。予めこの関係を求めておき、第二反応器における温度上昇を測定することによって、この関係からリアルタイムに第一反応器における転化率を求めることができる。従って、転化率が所定の範囲になるように容易に反応を制御できる。 FIG. 1 shows the relationship between the temperature rise in the second reactor and the conversion rate in the first reactor in the examples. By calculating this relationship in advance and measuring the temperature rise in the second reactor, the conversion in the first reactor can be determined in real time from this relationship. Therefore, the reaction can be easily controlled so that the conversion rate falls within a predetermined range.
触媒濃度および触媒活性によって第一反応器の転化率を制御する場合の例を以下に示す。
予め新触媒を溶媒に分散させておき、このスラリーをポンプで第一反応器に連続的に供給するとともに、反応に利用されて活性の低下した触媒は反応液とともに反応器から連続的に抜き出されるプロセスの場合、転化率は反応器内に滞留している触媒濃度と触媒の活性（新しさ）によって変わる。従って、第二反応器における温度上昇幅が規定値を上回った場合は、第一反応器の転化率が規定値より低いことを意味しているため、新触媒のスラリー供給速度を増加する。逆に第二反応器における温度上昇幅が規定値を下回った場合、第一反応器の転化率が規定値より高いことを意味しているため、新触媒のスラリー供給量を減少させるか、または第一反応器からの触媒抜き出し量を増加させる。
同様に反応速度が反応温度に依存する反応プロセスの場合であれば、第二反応器の温度上昇に対して第一反応器の反応温度などを変化させることによって、第一反応器における転化率を所定の範囲になるように反応を制御しても良い。
An example in which the conversion rate of the first reactor is controlled by the catalyst concentration and the catalyst activity is shown below.
A new catalyst is dispersed in advance in a solvent, and this slurry is continuously supplied to the first reactor by a pump. The catalyst whose activity has been reduced due to the reaction is continuously extracted from the reactor together with the reaction solution. In the process, the conversion varies depending on the concentration of catalyst remaining in the reactor and the activity (newness) of the catalyst. Therefore, when the temperature rise in the second reactor exceeds the specified value, it means that the conversion rate of the first reactor is lower than the specified value, and therefore the slurry supply rate of the new catalyst is increased. Conversely, if the temperature rise in the second reactor falls below the specified value, it means that the conversion rate of the first reactor is higher than the specified value, so the slurry supply amount of the new catalyst is decreased, or Increase the amount of catalyst removed from the first reactor.
Similarly, in the case of a reaction process in which the reaction rate depends on the reaction temperature, the conversion rate in the first reactor can be increased by changing the reaction temperature of the first reactor with respect to the temperature increase in the second reactor. You may control reaction so that it may become a predetermined range.
以下、本発明を実施例で詳細に説明するが、本発明はこの実施例に限定されるものではない。
１リットルのオートクレーブ（第一反応器）に攪拌機、ガス導入管、触媒投入口、反応液抜出口、ニトロベンゼン導入口、アニリン導入口、蒸気発生口、コンデンサーを取り付けた。
第一反応器にアニリン３５０ｇと、活性炭にパラジウムを５重量％担持させた触媒を７０ｍｇ仕込んだ。第一反応器を２００℃まで昇温した後、ニトロベンゼンを１７５ｇ／ｈｒの速さで、系内の全圧を０．５ＭＰａ−Ｇに保ちつつ水素を５リットル／分の速さで導入し、反応を開始した。この後、活性炭にパラジウムを５重量％担持させた触媒を３．５ｍｇ／ｈｒの速さで追加し、内容液を１７．５ｇ／ｈｒの速さで抜き出した。内容物の液量および温度、圧力を一定に保ち、発生した蒸気を過剰の水素とともに抜き出してコンデンサーで凝縮させ、受器に粗アニリンを捕集した。
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to this Example.
A stirrer, a gas inlet tube, a catalyst inlet, a reaction liquid outlet, a nitrobenzene inlet, an aniline inlet, a steam generator, and a condenser were attached to a 1 liter autoclave (first reactor).
The first reactor was charged with 350 g of aniline and 70 mg of a catalyst in which 5% by weight of palladium was supported on activated carbon. After raising the temperature of the first reactor to 200 ° C., hydrogen was introduced at a rate of 175 g / hr and hydrogen was introduced at a rate of 5 liters / minute while maintaining the total pressure in the system at 0.5 MPa-G. The reaction was started. Thereafter, a catalyst in which 5% by weight of palladium was supported on activated carbon was added at a rate of 3.5 mg / hr, and the content liquid was extracted at a rate of 17.5 g / hr. The liquid volume, temperature and pressure of the contents were kept constant, and the generated vapor was extracted together with excess hydrogen and condensed with a condenser, and the crude aniline was collected in a receiver.
第一反応器中のニトロベンゼン濃度を、その目標値である１．０重量％前後に保つために、捕集された粗アニリン中のニトロベンゼン濃度を逐次的にガスクロマトグラフにより分析し、その結果をもとに追加する触媒の量を１．０〜５．２ｍｇ／ｈｒの間で変化させた。その結果、第一反応器中のニトロベンゼン濃度を０．３〜２重量％に保ちながら、５６時間反応を続けた。 In order to keep the nitrobenzene concentration in the first reactor at around 1.0% by weight, which is the target value, the nitrobenzene concentration in the collected crude aniline was sequentially analyzed by gas chromatography, and the results were also obtained. The amount of catalyst added to was varied between 1.0 and 5.2 mg / hr. As a result, the reaction was continued for 56 hours while maintaining the nitrobenzene concentration in the first reactor at 0.3 to 2% by weight.
受器に捕集された粗アニリンはやや黄色を帯びた透明液で、ニトロベンゼンが０．４重量％、シクロヘキシルアミンが８０ｐｐｍ（重量）、シクロヘキサノンが５００ｐｐｍ（重量）、Ｎ−シクロヘキシルアニリンが３５０ｐｐｍ（重量）であった。原料のニトロベンゼンに対するアニリンの収率は、９９．４％であった。 The crude aniline collected in the receiver is a slightly yellowish transparent liquid, 0.4% by weight of nitrobenzene, 80 ppm (by weight) of cyclohexylamine, 500 ppm (by weight) of cyclohexanone, and 350 ppm (by weight of N-cyclohexylaniline). )Met. The yield of aniline with respect to the raw material nitrobenzene was 99.4%.
前記のニトロベンゼンの水素還元反応において、第一反応器の転化率と第二反応器における温度上昇の関係を解析的に求めた。
ニトロベンゼンの水素還元反応は、C6H5NO2+3H2→C6H5NH2+2H2O の反応であり、反応に必要な理論水素量は、ニトロベンゼン１モルに対して水素３モルであるが、通常は第一反応器には過剰の水素を吹き込んで反応を行う。第二反応器には、反応生成物であるアニリンと水、未反応原料であるニトロベンゼンと過剰の水素が導入される。
In the hydrogen reduction reaction of nitrobenzene, the relationship between the conversion rate of the first reactor and the temperature rise in the second reactor was analytically determined.
The hydrogen reduction reaction of nitrobenzene is a reaction of C 6 H 5 NO 2 + 3H 2 → C 6 H 5 NH 2 + 2H 2 O. The theoretical amount of hydrogen required for the reaction is 3 mol of hydrogen per 1 mol of nitrobenzene. However, the reaction is usually carried out by blowing excess hydrogen into the first reactor. In the second reactor, the reaction product aniline and water, the unreacted raw material nitrobenzene and excess hydrogen are introduced.
第二反応器を気相断熱反応とすれば、第二反応器における反応ガスの温度上昇は、第二反応器におけるニトロベンゼンの水素化による反応熱を、第二反応器を通過するガスの顕熱で割ることで理論的に求まる。だだし、第二反応器を通過するガスの顕熱は水素の過剰量に大きく依存する。したがって、温度上昇と転化率との関係は、反応条件によって変わる。
ここでは、第一反応器に供給されるニトロベンゼンに対する水素のモル比を１０とし、第二反応器へのガスの導入温度を２１０℃で行った場合の、第二反応器における温度上昇の理論値を求めた。この温度上昇と第一反応器の転化率との関係を図１に示す。
この関係を用いて、第二反応器の温度上昇の実測値から第一反応器における転化率を求めることが可能になる。温度上昇が１５℃であった場合、第一反応器の転化率は、９８．６になる。
If the second reactor is a gas phase adiabatic reaction, the temperature rise of the reaction gas in the second reactor is caused by the sensible heat of the gas passing through the second reactor by the reaction heat due to the hydrogenation of nitrobenzene in the second reactor. Divide by to get it theoretically. However, the sensible heat of the gas passing through the second reactor greatly depends on the excess amount of hydrogen. Therefore, the relationship between temperature rise and conversion varies depending on the reaction conditions.
Here, the theoretical value of the temperature increase in the second reactor when the molar ratio of hydrogen to nitrobenzene supplied to the first reactor is 10 and the gas introduction temperature into the second reactor is 210 ° C. Asked. The relationship between this temperature rise and the conversion rate of the first reactor is shown in FIG.
Using this relationship, the conversion rate in the first reactor can be obtained from the actually measured value of the temperature rise in the second reactor. When the temperature rise is 15 ° C., the conversion rate of the first reactor is 98.6.
Claims (4)
後段反応器における発熱量と前段反応器における転化率との関係を予め求めておき、実際の反応を行う際に、後段反応器における発熱量を求め、求めた発熱量と前記関係とから前段反応器における転化率を求め、求めた転化率をもとに前段反応器の反応を制御する反応制御方法。 A exothermic reaction process having a multi-stage reactor, a reactor preceding reactor of the reactor of a two-stage continuous in series carry out the reaction by gas-liquid contact, evaporator subsequent reactor in the previous stage reactor In an exothermic reaction process that is a reactor that completely performs a gas phase reaction on the unreacted raw material gas and a reactor that performs an adiabatic reaction without phase change,
The relationship between the calorific value in the post-reactor and the conversion rate in the pre-reactor is obtained in advance, and when performing the actual reaction, the calorific value in the post-reactor is obtained, and the pre-reaction is determined from the obtained calorific value and the relationship. The reaction control method which calculates | requires the conversion rate in a reactor and controls reaction of a prestage reactor based on the calculated | required conversion rate.
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