JP2006248919A - Method for vapor-phase oxidation reaction - Google Patents
Method for vapor-phase oxidation reaction Download PDFInfo
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- JP2006248919A JP2006248919A JP2005064017A JP2005064017A JP2006248919A JP 2006248919 A JP2006248919 A JP 2006248919A JP 2005064017 A JP2005064017 A JP 2005064017A JP 2005064017 A JP2005064017 A JP 2005064017A JP 2006248919 A JP2006248919 A JP 2006248919A
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 14
- 239000012808 vapor phase Substances 0.000 title abstract 5
- 239000003054 catalyst Substances 0.000 claims abstract description 76
- 239000002245 particle Substances 0.000 claims abstract description 56
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 10
- 239000011733 molybdenum Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000000126 substance Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 40
- 239000012071 phase Substances 0.000 description 36
- 239000013078 crystal Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000010574 gas phase reaction Methods 0.000 description 6
- 239000003507 refrigerant Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- GDXTWKJNMJAERW-UHFFFAOYSA-J molybdenum(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Mo+4] GDXTWKJNMJAERW-UHFFFAOYSA-J 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000000790 scattering method Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- YLSLSHTYFFBCKG-UHFFFAOYSA-N bismuth;oxomolybdenum Chemical compound [Mo].[Bi]=O YLSLSHTYFFBCKG-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000005465 channeling Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- WUJISAYEUPRJOG-UHFFFAOYSA-N molybdenum vanadium Chemical compound [V].[Mo] WUJISAYEUPRJOG-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
この発明は、気相酸化反応方法に関し、特に気相酸化反応に用いる装置の汚れの防止に関する。 The present invention relates to a gas phase oxidation reaction method, and more particularly to prevention of contamination of an apparatus used for a gas phase oxidation reaction.
気相反応装置中で、モリブデンを含む金属酸化物触媒を用いてアンモ酸化反応等の気相酸化反応を行うと、この気相反応装置を構成する除熱コイルや熱交換器などの冷却装置の冷却効果が徐々に低下していく現象が知られている。 When a gas phase oxidation reaction such as an ammoxidation reaction is performed using a metal oxide catalyst containing molybdenum in a gas phase reaction apparatus, a cooling device such as a heat removal coil or a heat exchanger constituting the gas phase reaction apparatus is used. It is known that the cooling effect gradually decreases.
この、冷却効果が低下した除熱コイル表面の顕微鏡写真を図４に示す。針状結晶は、上記の金属酸化物触媒から遊離したモリブデン化合物が、気相反応装置の表面にモリブデン酸化物の針状結晶として析出したものと考えられ、さらに、針状結晶の間に上記金属酸化物触媒の粒子が取り込まれることで、冷却装置の表面を広く覆ってしまっている。 FIG. 4 shows a photomicrograph of the surface of the heat removal coil with a reduced cooling effect. The acicular crystals are thought to be that molybdenum compounds released from the above metal oxide catalyst were precipitated as molybdenum oxide acicular crystals on the surface of the gas phase reactor. Since the oxide catalyst particles are taken in, the surface of the cooling device is widely covered.
ところで、一般に流動床による反応に用いる触媒粒子は、Ｇｅｌｄａｒｔの粒子分類によるＡ粒子が適当とされ、すなわち、平均粒径が５０〜１００μｍの範囲にあるとよいとされる。また、非特許文献１には、粒径が２５μｍ以下、特に１７．８μｍ以下の粒子を添加することにより流動化開始速度が低下する、すなわち流動性が向上することが示されている。 By the way, generally, the catalyst particles used for the reaction in the fluidized bed are suitably A particles according to Geldart's particle classification, that is, the average particle size is preferably in the range of 50 to 100 μm. Non-Patent Document 1 shows that the addition of particles having a particle size of 25 μm or less, particularly 17.8 μm or less, reduces the fluidization start speed, that is, improves the fluidity.
しかしながら、非特許文献１に記載の粒子を添加すると反応そのものの効率はよくなるが、モリブデンを含む金属酸化物触媒を用いた気相反応系等の結晶が析出する反応系においては、単に粒径が小さい粒子だけを添加するだけでは、その小さい粒子が図４のように、析出した針状結晶の間に取り込まれて表面を覆ってしまうため、反応以外の冷却や移送などにおいて効率が悪くなってしまう。 However, when the particles described in Non-Patent Document 1 are added, the efficiency of the reaction itself is improved, but in a reaction system in which crystals precipitate, such as a gas phase reaction system using a metal oxide catalyst containing molybdenum, the particle size is simply If only small particles are added, the small particles are taken in between the deposited needle crystals and cover the surface as shown in FIG. End up.
そこでこの発明は、酸化物触媒を使用する気相酸化反応において、その酸化物触媒から遊離した成分の上記表面への付着を抑制することを目的とする。 Accordingly, an object of the present invention is to suppress adhesion of components released from the oxide catalyst to the surface in the gas phase oxidation reaction using the oxide catalyst.
この発明は、気相反応装置中で酸化物触媒を使用して行う気相酸化反応において、上記酸化物触媒は、上記気相反応装置中でその酸化物触媒から遊離する成分が、上記気相反応装置の内表面、上記気相反応装置内部の装置の表面、又はそれらの両方に析出しうるものであって、上記酸化物触媒のうち、粒径が２０μｍ以下である触媒粒子が占める割合を２重量％以下とすることによって上記の課題を解決したのである。 The present invention relates to a gas phase oxidation reaction performed using an oxide catalyst in a gas phase reactor, wherein the oxide catalyst has a component released from the oxide catalyst in the gas phase reactor. The ratio of the catalyst particles having a particle size of 20 μm or less to the oxide catalyst can be deposited on the inner surface of the reactor, the surface of the device inside the gas phase reactor, or both. The above problems have been solved by setting the content to 2% by weight or less.
粒径２０μｍ以下である触媒粒子の割合を２重量％以下とすることで、気相反応装置内部の配管などの表面に析出する針状結晶の間に入り込める大きさの触媒粒子が少なくなるため、触媒粒子が針状結晶に絡まって固まることが少なくなり、除熱コイルの伝熱係数の低下を抑制することができる。また同様の効果により、製品を抜き出す配管の閉塞を防いだり、気相反応装置の内表面が触媒粒子に覆われることを防いだりすることができる。 By setting the ratio of the catalyst particles having a particle size of 20 μm or less to 2% by weight or less, the number of catalyst particles that can enter between the acicular crystals deposited on the surface of the piping inside the gas phase reactor is reduced. The catalyst particles are less likely to get entangled with the needle-like crystals and harden, and the decrease in the heat transfer coefficient of the heat removal coil can be suppressed. Moreover, the same effect can prevent the piping from which the product is extracted from being blocked, and can prevent the inner surface of the gas phase reactor from being covered with the catalyst particles.
以下、この発明について詳細に説明する。
この発明は、気相反応装置中で酸化物触媒を使用して行う気相酸化反応において、上記酸化物触媒は、上記気相反応装置中でその酸化物触媒から遊離する成分が、上記気相反応装置の内表面、上記気相反応装置内部の装置の表面、又はそれらの両方に析出しうるものであって、上記酸化物触媒のうち、粒径が２０μｍ以下である触媒粒子が占める割合が２重量％以下であることを特徴とする、気相酸化反応方法である。
Hereinafter, the present invention will be described in detail.
The present invention relates to a gas phase oxidation reaction performed using an oxide catalyst in a gas phase reactor, wherein the oxide catalyst has a component released from the oxide catalyst in the gas phase reactor. A ratio of catalyst particles having a particle size of 20 μm or less in the oxide catalyst can be deposited on the inner surface of the reactor, the surface of the device inside the gas phase reactor, or both. It is a gas phase oxidation reaction method characterized by being 2% by weight or less.
上記の気相酸化反応とは、粉体状の触媒粒子による流動床で、供給される気体原料と酸素とを反応させる反応であり、例えば、モリブデンを含む酸化物触媒を用いたアンモ酸化反応によるアクリロニトリルの製造やプロピレンの気相酸化によるアクリル酸の製造などが挙げられる。 The gas phase oxidation reaction is a reaction in which a gaseous material to be supplied and oxygen are reacted in a fluidized bed of powdered catalyst particles, for example, by an ammoxidation reaction using an oxide catalyst containing molybdenum. Examples include acrylonitrile production and acrylic acid production by propylene gas phase oxidation.
この発明で用いる上記酸化物触媒は、反応中の上記気相反応装置内の環境において、その成分の一部又は全部が気相に遊離した後、上記気相反応装置の内表面や、気相と接触する除熱コイルなどの装置の表面に析出しうるものである。このように析出した結晶は、上記気相反応装置内のこれらの表面において、上記酸化物触媒の触媒粒子と絡んで、この触媒粒子を表面に固めてしまうことがあるが、この発明はその現象の進行を抑制するものである。この現象が起こり得る上記酸化物触媒としては、例えば、モリブデン−ビスマス酸化物触媒や、モリブデン−バナジウム酸化触媒などのモリブデンを含む酸化物触媒が挙げられる。これらのモリブデンを含む酸化物触媒は、環境中に水が存在すると、モリブデンの酸化物がモリブデンの水酸化物として固相から気相に遊離する性質がある。アンモ酸化反応では副生成物として水が生成するため、この水によりモリブデンが気相に遊離する。この遊離した成分であるモリブデン水酸化物が、上記気相反応装置内部の表面に、酸化モリブデンの結晶として析出する。 The oxide catalyst used in the present invention is the environment inside the gas phase reactor during the reaction, after some or all of its components are released into the gas phase, the inner surface of the gas phase reactor, the gas phase It can be deposited on the surface of a device such as a heat removal coil that comes into contact with the device. The crystals thus precipitated may become entangled with the catalyst particles of the oxide catalyst on these surfaces in the gas phase reactor, and the catalyst particles may be solidified on the surface. It suppresses the progress of Examples of the oxide catalyst in which this phenomenon can occur include oxide catalysts containing molybdenum such as a molybdenum-bismuth oxide catalyst and a molybdenum-vanadium oxidation catalyst. These oxide catalysts containing molybdenum have the property that, when water is present in the environment, the molybdenum oxide is liberated from the solid phase to the gas phase as molybdenum hydroxide. In the ammoxidation reaction, water is generated as a by-product, and molybdenum is liberated into the gas phase by this water. Molybdenum hydroxide, which is a free component, is precipitated as molybdenum oxide crystals on the surface inside the gas phase reactor.
上記の気相反応装置は、内部に原料や製品を供給したり排出したりするための配管や、冷却用のコイルなどの装置を備えたものであり、このような気相反応装置としては、例えば、図１に示すアクリロニトリル製造装置が挙げられる。この気相反応装置は、本体１１に、下方の空気導入管１２から空気ａを導入して、吹き出し口１３から吹き出させることで触媒１４を浮遊させ流動床として反応を行うものである。この環境中に、原料導入管１５から上記の反応物質としてプロピレンとアンモニアとの混合気体ｂを導入して、これらを空気中の酸素により酸化させて、１当量のアクリロニトリルと、３当量の水を得る。ただし、この反応に適切な温度に保つために、冷媒ｄを通した除熱コイル１６で本体１１内部の上記の混合気体を冷却しつつ上記の反応を行う。生成したアクリロニトリルはサイクロン１９で触媒を分離され、反応ガスｃとして抜き出される。この反応ガスを熱交換器１８で冷却した後アンモニア分離、アクリロニトリル精製系に送られる。 The above gas phase reaction apparatus is provided with devices such as piping for supplying and discharging raw materials and products, and a coil for cooling, and as such a gas phase reaction apparatus, For example, the acrylonitrile manufacturing apparatus shown in FIG. 1 is mentioned. In this gas phase reaction apparatus, air a is introduced into a main body 11 from a lower air introduction pipe 12 and blown out from a blow-out port 13, whereby the catalyst 14 is floated and reacted as a fluidized bed. In this environment, a mixed gas b of propylene and ammonia is introduced from the raw material introduction pipe 15 as the above-mentioned reactant, and these are oxidized by oxygen in the air, so that 1 equivalent of acrylonitrile and 3 equivalents of water are obtained. obtain. However, in order to maintain a temperature suitable for this reaction, the above reaction is performed while cooling the mixed gas inside the main body 11 by the heat removal coil 16 through which the refrigerant d has passed. The produced acrylonitrile is separated from the catalyst by a cyclone 19 and extracted as a reaction gas c. The reaction gas is cooled by a heat exchanger 18 and then sent to an ammonia separation and acrylonitrile purification system.
この気相反応装置の上記遊離した成分が析出しうる表面としては、特に、気相と接触して冷却を行う除熱コイル１６の表面や、圧力が急激に変化する製品排出管１７の入り口付近の表面、熱交換器１８の冷却チューブ表面が挙げられ、これらの表面では上記の結晶の析出が起こりやすい。なお、冷媒ｄとしては、本体１１の内部より低温である高圧の熱水や水蒸気が挙げられ、本体１１の熱をこの冷媒ｄに移して外に取り除いている。 The surface of the gas phase reactor on which the liberated components can be deposited is particularly the surface of the heat removal coil 16 that cools in contact with the gas phase, or the vicinity of the inlet of the product discharge pipe 17 where the pressure changes rapidly. And the surface of the cooling tube of the heat exchanger 18, and the precipitation of the crystals is likely to occur on these surfaces. In addition, as the refrigerant | coolant d, the high pressure hot water and water vapor | steam which are low temperature from the inside of the main body 11 are mentioned, The heat | fever of the main body 11 is moved to this refrigerant | coolant d, and is removed outside.
この発明で用いる酸化物触媒は、粒径が２０μｍ以下である触媒粒子が占める割合が２重量％以下であることが必要であり、１．５重量％以下であるとより好ましい。なお、この値は低いほど好ましく、０％が最も好ましい。粒径が２０μｍ以下である触媒粒子は、上記気相反応装置の表面に析出した結晶間に絡むことで捕捉される可能性が高く、この大きさの触媒粒子が２重量％を超えると、上記の結晶間に触媒粒子が絡みやすくなり、さらにそれらの触媒粒子同士の間が析出する結晶で固まることで、上記気相反応装置内部の装置表面や、上記気相反応装置の内表面全体が析出した上記結晶と捕捉された上記触媒粒子とに覆われてしまうおそれが高くなる。 In the oxide catalyst used in the present invention, the proportion of the catalyst particles having a particle size of 20 μm or less needs to be 2% by weight or less, and more preferably 1.5% by weight or less. In addition, this value is so preferable that it is low, and 0% is the most preferable. The catalyst particles having a particle size of 20 μm or less are highly likely to be trapped by being entangled between crystals deposited on the surface of the gas phase reactor, and when the size of the catalyst particles exceeds 2% by weight, The catalyst particles are easily entangled between the crystals, and further solidified with crystals that deposit between the catalyst particles, so that the apparatus surface inside the gas phase reactor and the entire inner surface of the gas phase reactor are precipitated. There is a high possibility that the crystals and the trapped catalyst particles are covered.
一方で、粒径が４４μｍ以下である触媒粒子の割合が、２０重量％以上であり５０重量％以下であると好ましい。気相酸化反応においては、「化学工学．第３４巻．第１０号（１９７０）Ｐ１０１３〜１０９０」に示されるように、４４μｍ以下の粒子はＧｏｏｄ ｆｒａｃｔｉｏｎと呼ばれ、それが２０〜５０重量％の範囲で存在すると適切であることが示されている。２０重量％未満では流動改善効果はなく、５０重量％を超えるとチャネリングの傾向が現れるためである。 On the other hand, the ratio of catalyst particles having a particle size of 44 μm or less is preferably 20% by weight or more and 50% by weight or less. In the gas phase oxidation reaction, as shown in “Chemical Engineering, Vol. 34, No. 10 (1970) P1013-1090”, particles of 44 μm or less are referred to as Good fraction, which is 20 to 50% by weight. It has been shown to be appropriate to exist in range. This is because if it is less than 20% by weight, there is no flow improvement effect, and if it exceeds 50% by weight, channeling tends to occur.
なお、この発明において用いる粒子の割合の値は、球相当径の体積分布基準による粒度分布で示したものであり、このような値を測定する方法としては、レーザー回折散乱法が挙げられる。 In addition, the value of the ratio of the particles used in the present invention is shown by the particle size distribution based on the volume distribution standard of the equivalent sphere diameter, and a method of measuring such a value includes a laser diffraction scattering method.
また、この発明で用いる酸化物触媒の平均粒径は、３０μｍ以上であると好ましく、４０μｍ以上であるとより好ましい。平均粒径が３０μｍ未満であると、析出した結晶間に取り込まれる小さな触媒粒子が多すぎて、酸化物触媒の触媒粒子が表面を覆いやすくなってしまう。一方で、上記の平均粒径は１００μｍ以下であると好ましい。１００μｍを超えると、触媒粒子が大きすぎて触媒としての効率が低下してしまうためである。 The average particle size of the oxide catalyst used in the present invention is preferably 30 μm or more, and more preferably 40 μm or more. If the average particle size is less than 30 μm, there are too many small catalyst particles taken in between the precipitated crystals, and the catalyst particles of the oxide catalyst tend to cover the surface. On the other hand, the average particle size is preferably 100 μm or less. If it exceeds 100 μm, the catalyst particles are too large and the efficiency as a catalyst is reduced.
上記のような粒度分布の酸化物触媒を得る方法としては、例えば、分級を行って触媒粒子を選び出して求める粒度分布に調整する方法や、上記酸化物触媒の触媒粒子を製造する際にスプレーのノズル径を調整する方法等が挙げられる。 Examples of the method for obtaining an oxide catalyst having the above particle size distribution include, for example, a method of performing classification to select catalyst particles and adjusting the obtained particle size distribution, and a method of spraying when producing the catalyst particles of the oxide catalyst. For example, a method for adjusting the nozzle diameter may be used.
上記のような粒子の割合の粒度分布である酸化物触媒を用いて気相酸化反応を行うことにより、上記酸化物触媒から遊離した成分が表面に析出した結晶の間に、上記酸化物触媒が捕捉されにくくなるので、表面が酸化物触媒で汚れにくくなり、その表面の伝熱係数の低下を抑制したり、配管の閉塞を抑制したりできる。また、表面に捕捉されにくくなるため、上記酸化物触媒の消費量も抑制できる。 By performing a gas phase oxidation reaction using an oxide catalyst having a particle size distribution as described above, the oxide catalyst is formed between crystals in which components released from the oxide catalyst are deposited on the surface. Since it becomes difficult to be trapped, the surface becomes difficult to be stained with the oxide catalyst, and it is possible to suppress a decrease in the heat transfer coefficient of the surface or to block the piping. Moreover, since it becomes difficult to be trapped on the surface, consumption of the oxide catalyst can also be suppressed.
この発明について、実施例を挙げてより具体的に説明する。 The present invention will be described more specifically with reference to examples.
（実施例１）
図１に示す気相反応装置の内径２５ｃｍ、容積０．８ｍ３である本体１１に、分級して得られた平均粒径５０μｍ、２０μｍ以下の触媒粒子の粒度分布が１．２重量％のモリブデンを有する触媒（触媒組成、Ｍｏ：Ｂｉ：Ｆｅ：Ｃｅ：Ｃｒ：Ｎｉ：Ｍｇ：Ｃｏ：Ｋ：Ｒｂ：Ｏ：ＳｉＯ２＝１２：０．５：２：０．５：０．４：４：１．５：１：０．０７：０．０６：Ｘ：４２。なお、Ｘは残分を示す。）を８４ｋｇ導入した。なお、この粒度分布の値は、（株）島津製作所製、ＳＡＬＤ−２０００Ｊ（レーザー回折散乱法）により測定した。次いで、原料導入管１５より反応気体としてプロピレン７．８ｋｇ／ｈ及びアンモニア３．５ｋｇ／ｈを、空気導入管１２から吹き出し口１３を経由して空気５４ｋｇ／ｈを本体１１に供給し、４４０℃でアンモ酸化反応を行い、アクリロニトリルを得た。また、反応と同時に、本体１１中のＳＴＰＡ２３製除熱コイル１６に冷媒ｄとして１４１℃の水蒸気を１５０ｋｇ／ｈの流量で流通させ、反応熱の除熱を行った。
Example 1
Molybdenum having an average particle size of 50 μm and a catalyst particle size of 20 μm or less obtained by classification on a main body 11 having an inner diameter of 25 cm and a volume of 0.8 m 3 of the gas phase reactor shown in FIG. (Catalyst composition, Mo: Bi: Fe: Ce: Cr: Ni: Mg: Co: K: Rb: O: SiO 2 = 12: 0.5: 2: 0.5: 0.4: 4: 1.5: 1: 0.07: 0.06: X: 42, where X represents the remainder. The particle size distribution was measured by SALD-2000J (Laser Diffraction Scattering Method) manufactured by Shimadzu Corporation. Next, 7.8 kg / h of propylene and 3.5 kg / h of ammonia are supplied as reaction gases from the raw material introduction pipe 15, and 54 kg / h of air is supplied from the air introduction pipe 12 through the outlet 13 to the main body 11. Ammoxidation reaction was carried out to obtain acrylonitrile. Simultaneously with the reaction, 141 ° C. water vapor was circulated at a flow rate of 150 kg / h as refrigerant d through the heat removal coil 16 made of STPA23 in the main body 11 to remove the heat of reaction.
この運転を３ヶ月（約２０００時間）連続して行い、除熱コイル１６の総括伝熱係数Ｕの変化を、測定した値から下記式（１）により算出した。なお、式中、Ｃｐは流通させた水蒸気の定圧比熱（ｋｃａｌ／ｋｇ・℃）、Ｗは蒸気流量（ｋｇ／ｈｒ）、Ｔｏｕｔは除熱コイル１６の出口における水蒸気温度（℃）、Ｔｉｎは除熱コイル１６の入口における水蒸気温度（℃）、ＴＲは反応装置内温度（℃）を示し、Ａは除熱コイルの伝熱面積（ｍ２）を示す。その結果を図２に示す。総括伝熱係数Ｕは徐々に低下したが、その変化は緩やかなものとなった。 This operation was performed continuously for 3 months (about 2000 hours), and the change in the overall heat transfer coefficient U of the heat removal coil 16 was calculated from the measured value by the following equation (1). In the formula, C p is the constant-pressure specific heat of the circulated water vapor (kcal / kg · ° C.), W is the steam flow rate (kg / hr), T out is the water vapor temperature (° C.) at the outlet of the heat removal coil 16, T in the steam temperature at the inlet of the heat removal coil 16 (℃), T R denotes a reactor internal temperature (° C.), a represents the heat transfer area of the heat removal coil (m 2). The result is shown in FIG. The overall heat transfer coefficient U gradually decreased, but the change was gradual.
運転停止後に、除熱コイル１６に付着した付着物を採取して顕微鏡で撮影した写真を図３に示す。 The photograph which extract | collected the deposit | attachment adhering to the heat removal coil 16 after the operation stop and image | photographed with the microscope is shown in FIG.
（比較例１）
実施例１において、触媒を分級せずに、粒径が２０μｍ以下の触媒粒子の割合が５重量％であるモリブデンを有する触媒（触媒組成は実施例１と同じ。）をそのまま用いた以外は実施例１と同様に３ヶ月間運転してアクリロニトリルを得た。また同様に、除熱コイル１６の総括伝熱係数の変化を測定した。その結果を図２に示す。総括伝熱係数は時間経過とともにはっきりと低下していき、３ヶ月で半分以下にまで低下した。
(Comparative Example 1)
Example 1 Example 1 was carried out except that the catalyst was not classified and the catalyst having molybdenum (the catalyst composition is the same as that of Example 1) having a particle size of 20 μm or less was 5% by weight. The acrylonitrile was obtained by operating for 3 months in the same manner as in Example 1. Similarly, the change in the overall heat transfer coefficient of the heat removal coil 16 was measured. The result is shown in FIG. The overall heat transfer coefficient clearly decreased over time and decreased to less than half in 3 months.
運転停止後に、除熱コイル１６に付着した付着物を採取して顕微鏡で撮影した写真を図４に示す。図３ではほとんど見られなかった粒径１０〜２０μｍ程度の微粒子が厚く付着していた。微粒子が多いことにより、それらがＭｏＯ３の結晶中に取り込まれる率が高くなって表面への付着量を増大させ、伝熱を悪化させたと考えられる。 FIG. 4 shows a photograph taken after the operation was stopped, and collected with a microscope after collecting the adhering material adhering to the heat removal coil 16. In FIG. 3, fine particles having a particle size of about 10 to 20 μm, which was hardly seen, were attached thickly. It is considered that the large amount of fine particles increased the rate of their incorporation into the MoO 3 crystals, increasing the amount of adhesion to the surface and deteriorating heat transfer.
１１ （気相反応装置の）本体
１２ 空気導入管
１３ 吹き出し口
１４ 触媒
１５ 原料導入管
１６ 除熱コイル
１７ 製品排出管
１８ 熱交換器
１９ サイクロン
ａ 空気
ｂ 混合気体
ｃ 反応ガス
ｄ 冷媒
11 Main body (of gas phase reactor) 12 Air introduction pipe 13 Outlet 14 Catalyst 15 Raw material introduction pipe 16 Heat removal coil 17 Product discharge pipe 18 Heat exchanger 19 Cyclone a Air b Gas mixture c Reaction gas d Refrigerant
Claims (4)
上記酸化物触媒は、上記気相反応装置中でその酸化物触媒から遊離する成分が、上記気相反応装置の内表面、上記気相反応装置内部の装置の表面、又はそれらの両方に析出しうるものであって、
上記酸化物触媒のうち、粒径が２０μｍ以下である触媒粒子が占める割合が２重量％以下であることを特徴とする、気相酸化反応方法。 In a gas phase oxidation reaction using an oxide catalyst in a gas phase reactor,
In the oxide catalyst, components liberated from the oxide catalyst in the gas phase reactor are deposited on the inner surface of the gas phase reactor, the surface of the device inside the gas phase reactor, or both. It can be
A gas phase oxidation reaction method characterized in that the proportion of catalyst particles having a particle size of 20 μm or less in the oxide catalyst is 2% by weight or less.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007063089A (en) * | 2005-09-01 | 2007-03-15 | Mitsubishi Rayon Co Ltd | Method and device for producing nitrile compound |
| WO2009081758A1 (en) | 2007-12-26 | 2009-07-02 | Asahi Kasei Chemicals Corporation | Process for producing oxide catalyst |
| JP2010095451A (en) * | 2008-10-14 | 2010-04-30 | Asahi Kasei Chemicals Corp | Gas-phase exothermic reaction method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997033863A1 (en) * | 1996-03-12 | 1997-09-18 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for preparing unsaturated nitrile |
| WO1999003825A1 (en) * | 1997-07-14 | 1999-01-28 | Mitsubishi Chemical Corporation | Method for gas phase catalytic oxidation of hydrocarbon |
| JPH11349545A (en) * | 1998-06-02 | 1999-12-21 | Asahi Chem Ind Co Ltd | Production of alpha, beta-unsaturated nitrile |
| JP2001029788A (en) * | 1999-07-21 | 2001-02-06 | Mitsubishi Rayon Co Ltd | Production of fluidized bed catalyst comprising molybdenum-bismuth-iron-containing metal oxide |
-
2005
- 2005-03-08 JP JP2005064017A patent/JP2006248919A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997033863A1 (en) * | 1996-03-12 | 1997-09-18 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for preparing unsaturated nitrile |
| WO1999003825A1 (en) * | 1997-07-14 | 1999-01-28 | Mitsubishi Chemical Corporation | Method for gas phase catalytic oxidation of hydrocarbon |
| JPH11349545A (en) * | 1998-06-02 | 1999-12-21 | Asahi Chem Ind Co Ltd | Production of alpha, beta-unsaturated nitrile |
| JP2001029788A (en) * | 1999-07-21 | 2001-02-06 | Mitsubishi Rayon Co Ltd | Production of fluidized bed catalyst comprising molybdenum-bismuth-iron-containing metal oxide |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007063089A (en) * | 2005-09-01 | 2007-03-15 | Mitsubishi Rayon Co Ltd | Method and device for producing nitrile compound |
| WO2009081758A1 (en) | 2007-12-26 | 2009-07-02 | Asahi Kasei Chemicals Corporation | Process for producing oxide catalyst |
| JP5191008B2 (en) * | 2007-12-26 | 2013-04-24 | 旭化成ケミカルズ株式会社 | Method for producing oxide catalyst |
| US9731285B2 (en) | 2007-12-26 | 2017-08-15 | Asahi Kasei Chemicals Corporation | Process for producing oxide catalysts |
| JP2010095451A (en) * | 2008-10-14 | 2010-04-30 | Asahi Kasei Chemicals Corp | Gas-phase exothermic reaction method |
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