WO2017018054A1 - Filling method for solid catalyst - Google Patents
Filling method for solid catalyst Download PDFInfo
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- WO2017018054A1 WO2017018054A1 PCT/JP2016/066682 JP2016066682W WO2017018054A1 WO 2017018054 A1 WO2017018054 A1 WO 2017018054A1 JP 2016066682 W JP2016066682 W JP 2016066682W WO 2017018054 A1 WO2017018054 A1 WO 2017018054A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
Definitions
- the present invention relates to a method of filling a reactor with a solid catalyst.
- a target compound by a catalytic reaction using a solid catalyst there are many known methods for producing a target compound by a catalytic reaction using a solid catalyst. Examples of such methods include a method for producing acrolein and / or acrylic acid by a partial oxidation reaction of propylene, a method for producing methacrolein and / or methacrylic acid from isobutylene and / or tertiary butanol, and ethylene oxide from ethylene. Examples thereof include a production method, a method of producing styrene from ethylbenzene, a method of producing 1,3-butadiene from butenes, and hydrodesulfurization and / or hydrodenitrogenation of petroleum.
- a fixed bed reactor composed of several thousand to several tens of thousands of reaction tubes is usually used, and the solid catalyst is usually filled into each reaction tube by gravity drop from the top of the reactor.
- the filling operation is carried out while curing the area around the workplace from the viewpoint of preventing contact between rainwater and the catalyst.
- the filling operation differs depending on the work system of the work and the catalyst, and therefore the filling procedure cannot be generally described, but usually takes about 1 to 30 days. Despite the merit that the operation can be started sooner if the working days are shortened, there have been few reports on attempts to improve the working efficiency by improving the working environment.
- Patent Document 1 describes a method in which a tubular material is inserted into a reaction tube to be filled with a catalyst, and a solid catalyst is filled while releasing a gas from the lower end thereof.
- An object of the present invention is to reduce the impact caused by free fall applied to a catalyst that is easily pulverized and crushed.
- Patent Document 2 describes a method in which the dry gas is supplied from the lower part of the reactor and the humidity in the reactor is reduced to 90% or less by covering the upper part of the reactor.
- the object is to prevent the catalyst performance from being deteriorated by condensation, and to suppress the pulverization of the catalyst during filling as in the invention described in Patent Document 1.
- JP 2003-340266 A Japanese Patent No. 4532391
- the present invention raises the work efficiency by reducing the staying of dust in the filling work place by lowering the dust in the filling work place by blowing air from the upper part of the reactor to the filling work place (filling work space) of the solid catalyst.
- the purpose is to shorten the length.
- the present invention (1) This is a method of filling a fixed bed catalyst reactor with a solid catalyst, and the pressure in the filling work space inside the reactor is reacted by blowing air from at least one place above the reactor into the filling work space inside the reactor.
- a solid catalyst filling method characterized by a positive pressure of 1 Pascal or more of the atmospheric pressure around the vessel, (2) A positive pressure of 1 Pascal or more and 30 Pascals or less of atmospheric pressure around the reactor by blowing air from at least one place above the reactor to the filling work space inside the reactor.
- the solid catalyst filling method according to (1) characterized in that (3) The method for packing a solid catalyst according to any one of (1) and (2), wherein the dust in the reactor is sucked from the lower part of the reactor by a dust collector or a ventilator, About.
- the catalyst filling work environment is maintained and the work efficiency is increased, whereby the time required for the catalyst filling work can be shortened and the plant can be operated quickly.
- a composite oxide catalyst based on bismuth and molybdenum for example, The catalysts described in Japanese Patent No. -016755, Japanese Patent No. 5130562 and the method of using the same can be applied.
- a composite oxide catalyst mainly composed of vanadium and molybdenum for example, a catalyst described in Japanese Patent No. 5680373, Japanese Patent Application Laid-Open No.
- a catalyst mainly composed of phosphorus and molybdenum for example, a catalyst described in Japanese Patent No. 5570142, Japanese Patent Application Laid-Open No. 2015-096497, and a method of using the same are applied. it can.
- a composite oxide catalyst mainly composed of molybdenum and bismuth for example, a catalyst described in International Publication No. 2013/161703, and a method of using the same can be applied.
- the present invention is not limited to the following detailed description and examples.
- the “reactor” described in the present application document means a fixed bed catalytic reaction apparatus composed of a plurality of reaction tubes, and the operation of filling the reactor with a catalyst and / or an inert substance is performed in the reactor. This is the same as the operation of filling the reaction tube constituting the catalyst and / or an inert substance.
- the catalyst can be prepared by a method known per se. What is necessary is just to design the component of a catalyst, preparation conditions, a shape, etc. suitably according to the target product, raw material, and reaction conditions.
- the predetermined filling amount of catalyst per reaction tube can be determined as follows. That is, for example, when a cylindrical reaction tube having a total length of 380 cm and an inner diameter of 25 mm is filled so that the filling height is 200 cm, the filling height is 200 cm using a reaction tube having a similar reaction tube diameter in advance.
- the catalyst weight of is measured.
- a reaction tube having a similar reaction tube diameter is not necessarily the same as the length and the inner diameter of a reaction tube used in an industrial apparatus.
- a reaction tube having an inner diameter of 24 mm and a reaction tube having an inner diameter of 28 mm has a filling height of 200 cm.
- the catalyst weight can be measured, and the necessary catalyst weight in a reaction tube having an inner diameter of 25 mm can be determined by interpolation.
- the catalyst weighed in the required amount is preferably subdivided in advance so that the amount of each reaction tube is one in a container.
- a catalyst such as an automatic filling machine is used to divide the catalyst into a plurality of reactors. It is also possible to fill the reaction tube.
- the catalyst is subdivided into containers in advance, it is preferable to subdivide the catalyst so that the amount of catalyst charged per reaction tube is the same. The same amount indicates a catalyst amount that does not cause a difference of 1 cm or more in the packing height of the catalyst.
- the filling operation by free fall using a funnel is simple and preferable.
- the filling speed is naturally constant by pouring the entire amount of the divided catalyst into the funnel at a stroke. If a bridge is formed in the funnel, it can be resolved by lightly tapping. Tapping the funnel more than necessary is not preferable because it causes the filling speed and, consequently, the catalyst filling height to vary. Even when the catalyst is charged into the reactor using a machine, it is preferable to adjust the machine appropriately so that the catalyst filling speed is the same. After completing the catalyst filling operation, measure the catalyst filling height with a measure etc.
- the standard value for the catalyst packing height is the catalyst packing height required to fully demonstrate the performance of the catalyst used, and varies depending on the target reaction, reaction conditions, and the inner diameter error of the reaction tube used. However, it is usually about ⁇ 1 cm to ⁇ 5 cm of the target filling height. The same applies to the case where another type, shape, or concentration of catalyst is filled on top of a catalyst that has already been filled.
- the pressure in the catalyst filling work place is usually at least 1 Pascal of atmospheric pressure around the reactor by blowing air from at least one place to the catalyst filling work place (filling work space) that is usually the upper space of the reactor, preferably
- the positive pressure is 1 to 30 pascals, more preferably 3 to 20 pascals. Since the optimum value varies depending on the structure and size of the reactor, it cannot be generally stated.
- the pressure in the catalyst filling work area is 1 Pascal of the atmospheric pressure around the reactor in consideration of the suction force of the dust collector and / or the exhaust fan.
- the air flow rate may be determined so that the positive pressure is 1 to 30 Pascals, more preferably 3 to 20 Pascals.
- the pressure in the catalyst filling work place may be a positive pressure of 30 Pascal or more of the atmospheric pressure around the reactor, but it is difficult to obtain an effect commensurate with it.
- the dust collector is not particularly limited as long as it is generally used, but a partition type dust collector that collects dust with a bag filter or the like is simple and preferable.
- the installation location is not particularly limited as long as it is a location where the falling dust generated when the catalyst is filled can be collected, but 1 to 10 dust collectors are installed on the stage installed at the bottom of the reactor. Things are preferable.
- the blower and the exhaust fan are not particularly limited as long as they are generally used, but a centrifugal type and an axial flow type are preferable. It is preferable to install 1 to 10 dust collectors on the stage installed in the upper part of the reactor in order to bring the catalyst filling workplace under positive pressure, and the exhaust fan on the stage installed in the lower part of the reactor in the same manner as the dust collector.
- the blowing air contains not only air but also air enriched by supplying pure oxygen and saturated steam at a temperature of about 35 ° C. Air or the like can also be used.
- the pressure in the catalyst filling work area and the atmospheric pressure around the reactor can be measured using a commercially available pressure measuring device.
- the working place for filling the catalyst is the upper part of the reactor, but the reactor is structured so that different reactors are vertically connected, and the middle part of the successive reactors is filled with the catalyst.
- the present invention is also applied to a reactor as a work place. Further, the present invention can also be achieved by covering the upper part of the reactor with a structure such as a tent and setting the inside of the structure to the positive pressure described above.
- Example 1 While heating and stirring 3000 parts by weight of distilled water, 423.8 parts by weight of ammonium molybdate and 3.0 parts by weight of potassium nitrate were dissolved to obtain an aqueous solution (A1). Separately, 302.7 parts by weight of cobalt nitrate, 162.9 parts by weight of nickel nitrate, and 145.4 parts by weight of ferric nitrate are dissolved in 1000 parts by weight of distilled water to prepare an aqueous solution (B1), and 42 parts by weight of concentrated nitric acid. In addition, 164.9 parts by weight of bismuth nitrate was dissolved in 200 parts by weight of distilled water acidified to prepare aqueous solutions (C1).
- the aqueous solution (B1) and the aqueous solution (C1) are sequentially mixed with the aqueous solution (A1) with vigorous stirring, and the resulting suspension is dried using a spray drier and calcined at 440 ° C. for 6 hours and pre-calcined powder (D1 )
- a powder obtained by mixing 100 parts by weight of the pre-fired powder (D1) with 5 parts by weight of crystalline cellulose into an inert carrier (a spherical substance having a diameter of 4.5 mm mainly composed of alumina and silica) is applied to the catalyst after molding.
- a supported catalyst (E1) was obtained by supporting and molding into a spherical shape having a diameter of 5.2 mm using a 20% by weight aqueous glycerin solution as a binder so as to account for 50% by weight.
- the supported catalyst (E1) was calcined in an air atmosphere at a calcining temperature of 550 ° C. for 4 hours to obtain a catalyst (F1).
- an aqueous solution (A2) was obtained by dissolving 423.8 parts by weight of ammonium molybdate and 2.0 parts by weight of potassium nitrate while heating and stirring 3000 parts by weight of distilled water.
- 302.7 parts by weight of cobalt nitrate, 162.9 parts by weight of nickel nitrate, and 145.4 parts by weight of ferric nitrate were dissolved in 1000 parts by weight of distilled water to prepare an aqueous solution (B2), and 42 parts by weight of concentrated nitric acid.
- An aqueous solution (C2) was prepared by dissolving 164.9 parts by weight of bismuth nitrate in 200 parts by weight of distilled water acidified by adding.
- the aqueous solution (B2) and the aqueous solution (C2) are sequentially mixed with the aqueous solution (A2) with vigorous stirring, and the resulting suspension is dried using a spray dryer and calcined at 440 ° C. for 6 hours, and then pre-calcined powder (D2 )
- a powder obtained by mixing 100 parts by weight of the pre-fired powder (D2) with 5 parts by weight of crystalline cellulose into an inert carrier (a spherical substance having a diameter of 4.5 mm mainly composed of alumina and silica) is applied to the catalyst after molding.
- a supported catalyst (E2) was obtained by supporting and molding into a spherical shape having a diameter of 5.2 mm using a 20% by weight glycerin aqueous solution as a binder so as to account for 50% by weight.
- the supported catalyst (E2) was calcined at 510 ° C. for 4 hours to obtain a catalyst (F2).
- an inert sphere with a diameter of 7 mm is filled at the source gas outlet part so that the filling height is 60 cm,
- the catalyst (F2) is packed to a packing height of 230 cm, and a mixture of 80% by weight of the catalyst (F1) and 20% by weight of inert spheres having a diameter of 5.2 mm is further packed to a height of 120 cm.
- Comparative Example 1 In the same plant as in Example 1, the work was performed without adjusting the pressure of the catalyst filling work place in the reactor without using the blower at the upper part of the reactor and the dust collector at the lower part of the reactor. The pressure was less than ⁇ 1 Pascal of atmospheric pressure around the reactor. It took 15 days from the start of the catalyst filling to the completion of the work to keep the catalyst filling length within the standard value.
- Example 2 In the same plant as in Example 1, the work was performed using only the blower at the top of the reactor, and the pressure of the catalyst filling work place in the reactor was 5 Pascal or more and 20 Pascal or less of the atmospheric pressure around the reactor on that day. When the operation was continued while adjusting the air flow rate so as to be positive pressure, it took 13 days from the start of the catalyst filling to the completion of the operation for keeping the catalyst filling length within the standard value.
- Comparative Example 2 In the same plant as in Example 1, air was circulated from the lower part of the reactor to the catalyst filling work place in the reactor, and the pressure in the catalyst filling work place in the reactor was changed to 5 to 20 pascals of atmospheric pressure around the reactor on that day. When working with the following positive pressure, the amount of dust in the catalyst filling work area was large, making it difficult to carry out the work continuously.From the start of catalyst filling to the completion of work to keep the catalyst filling length within the standard value It took 20 days. Most of the catalyst powder collected by the dust collector used in the lower part of the reactor in Example 1 is likely to stay or scatter in the catalyst filling work area or its surroundings, which is problematic in terms of contact with workers and environmental conservation. there is a possibility.
- the work efficiency is improved by blowing air from the upper part of the reactor to the catalyst filling work place in the reactor and setting the catalyst filling work place in the reactor to a positive pressure of 1 to 30 pascals of atmospheric pressure around the reactor.
- the number of days until the target plant operation was able to be reduced.
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Abstract
The purpose of the present invention is to increase the work efficiency by suppressing retention of dust in a filling workplace (filling workspace) for a solid catalyst by blowing air from the upper part of a reactor in the filling workplace and making the filling workplace be under positive pressure and to shorten plant stoppage periods. The present invention provides a filling method for a solid catalyst, which is a method for filling a solid catalyst into a fixed bed catalytic reactor, wherein the method is characterized by blowing air from at least one location of the upper part of the reactor in a filling workspace inside the reactor and making the pressure in the filling workspace inside the reactor a positive pressure of 1 pascal higher or more than the atmospheric pressure in the vicinity of the reactor.
Description
本発明は、固体触媒を反応器に充填する方法に関する。
The present invention relates to a method of filling a reactor with a solid catalyst.
固体触媒を用いた接触反応により、目的化合物を製造する方法は多く知られている。そのような方法として、例えば、プロピレンの部分酸化反応によりアクロレインおよび／またはアクリル酸を製造する方法、イソブチレンおよび／またはターシャリーブタノールからメタクロレインおよび／またはメタクリル酸を製造する方法、エチレンからエチレンオキサイドを製造する方法、エチルベンゼンからスチレンを製造する方法、ブテン類から１，３－ブタジエンを製造する方法、石油の水素化脱硫および／または水素化脱窒素反応などが例示される。
There are many known methods for producing a target compound by a catalytic reaction using a solid catalyst. Examples of such methods include a method for producing acrolein and / or acrylic acid by a partial oxidation reaction of propylene, a method for producing methacrolein and / or methacrylic acid from isobutylene and / or tertiary butanol, and ethylene oxide from ethylene. Examples thereof include a production method, a method of producing styrene from ethylbenzene, a method of producing 1,3-butadiene from butenes, and hydrodesulfurization and / or hydrodenitrogenation of petroleum.
これらの反応には通常、数千から数万本の反応管からなる固定床反応装置が用いられ、固体触媒は通常、１本ずつの反応管に反応器上部より重力落下によって充填される。充填作業は雨水と触媒との接触防止の観点から作業場周辺を養生しながら実施される。充填作業は、その作業の勤務体系や触媒に応じて充填手順が異なるため一概には言えないが通常１日から３０日程度を要する。この作業日数が短縮されれば早くに運転を開始できるというメリットがあるにもかかわらず、作業環境の改善により作業効率をあげるという試みはほとんど報告されていない。
For these reactions, a fixed bed reactor composed of several thousand to several tens of thousands of reaction tubes is usually used, and the solid catalyst is usually filled into each reaction tube by gravity drop from the top of the reactor. The filling operation is carried out while curing the area around the workplace from the viewpoint of preventing contact between rainwater and the catalyst. The filling operation differs depending on the work system of the work and the catalyst, and therefore the filling procedure cannot be generally described, but usually takes about 1 to 30 days. Despite the merit that the operation can be started sooner if the working days are shortened, there have been few reports on attempts to improve the working efficiency by improving the working environment.
特許文献１には触媒を充填しようとする反応管に管状物を挿入し、その下部先端から気体を放出させながら固体触媒を充填する方法が記載されている。この発明の目的は、粉化・破砕しやすい触媒に加わる自由落下による衝撃を低下させるものである。
Patent Document 1 describes a method in which a tubular material is inserted into a reaction tube to be filled with a catalyst, and a solid catalyst is filled while releasing a gas from the lower end thereof. An object of the present invention is to reduce the impact caused by free fall applied to a catalyst that is easily pulverized and crushed.
特許文献２には反応器下部より乾燥ガスを供給し、かつ反応器上部に覆いを付けることで反応器内の湿度を９０％以下にする方法が記載されている、この発明は反応器内の結露によって触媒性能を低下させることを防ぐこと、また特許文献１に記載の発明と同様に、充填する際の触媒の粉化を抑制することを目的としている。
Patent Document 2 describes a method in which the dry gas is supplied from the lower part of the reactor and the humidity in the reactor is reduced to 90% or less by covering the upper part of the reactor. The object is to prevent the catalyst performance from being deteriorated by condensation, and to suppress the pulverization of the catalyst during filling as in the invention described in Patent Document 1.
これらの特許文献に記載される従来技術は、反応器下部より反応器上部の触媒充填作業場に気体を導入することが共通点であるが、本発明者らの検討によればこの方法では、
１）反応器上部の触媒充填作業場に触媒の粉じんが滞留しやすく、触媒充填作業環境が悪化する場合がある、
２）触媒の粉じんが作業者と接触することによって頻繁に保護具を交換したり、作業者を交代したりする必要があり、作業効率が低下する場合がある、
３）触媒の粉化により発生した触媒粉末が反応器内に滞留する事で、触媒粉末が反応管内に混入する可能性がある、
４）反応器下部より反応器上部の触媒充填作業場に供給した気体の流れに沿って触媒粉末が反応器外に飛散する可能性があり、環境保全上好ましくない、
という問題点が挙げられ、結果として作業効率が悪化し想定していたスケジュールよりも作業が遅延する事があった。 The prior art described in these patent documents is common in that gas is introduced from the lower part of the reactor into the catalyst filling work place at the upper part of the reactor, but according to the study by the present inventors, in this method,
1) Dust of the catalyst tends to stay in the catalyst filling work place at the top of the reactor, and the catalyst filling work environment may be deteriorated.
2) It is necessary to change the protective equipment frequently or change the worker due to the catalyst dust coming into contact with the worker, which may reduce the work efficiency.
3) The catalyst powder generated by the catalyst pulverization may stay in the reactor, so that the catalyst powder may be mixed in the reaction tube.
4) The catalyst powder may be scattered outside the reactor along the gas flow supplied from the lower part of the reactor to the catalyst filling work place at the upper part of the reactor.
As a result, the work efficiency deteriorated and the work was sometimes delayed from the expected schedule.
１）反応器上部の触媒充填作業場に触媒の粉じんが滞留しやすく、触媒充填作業環境が悪化する場合がある、
２）触媒の粉じんが作業者と接触することによって頻繁に保護具を交換したり、作業者を交代したりする必要があり、作業効率が低下する場合がある、
３）触媒の粉化により発生した触媒粉末が反応器内に滞留する事で、触媒粉末が反応管内に混入する可能性がある、
４）反応器下部より反応器上部の触媒充填作業場に供給した気体の流れに沿って触媒粉末が反応器外に飛散する可能性があり、環境保全上好ましくない、
という問題点が挙げられ、結果として作業効率が悪化し想定していたスケジュールよりも作業が遅延する事があった。 The prior art described in these patent documents is common in that gas is introduced from the lower part of the reactor into the catalyst filling work place at the upper part of the reactor, but according to the study by the present inventors, in this method,
1) Dust of the catalyst tends to stay in the catalyst filling work place at the top of the reactor, and the catalyst filling work environment may be deteriorated.
2) It is necessary to change the protective equipment frequently or change the worker due to the catalyst dust coming into contact with the worker, which may reduce the work efficiency.
3) The catalyst powder generated by the catalyst pulverization may stay in the reactor, so that the catalyst powder may be mixed in the reaction tube.
4) The catalyst powder may be scattered outside the reactor along the gas flow supplied from the lower part of the reactor to the catalyst filling work place at the upper part of the reactor.
As a result, the work efficiency deteriorated and the work was sometimes delayed from the expected schedule.
固体触媒を反応器に充填する作業は過酷を極めるため、作業環境の保全と作業者の体調維持が重要となる。本発明は、固体触媒の充填作業場（充填作業空間）に反応器上部より送風することで充填作業場を陽圧下とし、充填作業場における粉じんの滞留を抑制する事で作業効率を上げ、プラントの停止期間を短くすることを目的とするものである。
Since the work of filling the solid catalyst into the reactor is extremely harsh, it is important to maintain the work environment and maintain the physical condition of the worker. The present invention raises the work efficiency by reducing the staying of dust in the filling work place by lowering the dust in the filling work place by blowing air from the upper part of the reactor to the filling work place (filling work space) of the solid catalyst. The purpose is to shorten the length.
すなわち本発明は、
（１）固定床触媒反応装置に固体触媒を充填する方法であり、反応器内部の充填作業空間に少なくとも反応器上部の一カ所から送風することで反応器内部の充填作業空間の圧力をその反応器周辺の大気圧の１パスカル以上の陽圧とすることを特徴とする固体触媒の充填方法、
（２）反応器内部の充填作業空間に少なくとも反応器上部の一カ所から送風することで反応器内部の充填作業空間の圧力をその反応器周辺の大気圧の１パスカル以上３０パスカル以下の陽圧とすることを特徴とする（１）に記載の固体触媒の充填方法、
（３）反応器下部より集塵機もしくは排風機によって反応器内の粉じんを吸引することを特徴とする（１）または（２）のいずれか１項に記載の固体触媒の充填方法、
に関する。 That is, the present invention
(1) This is a method of filling a fixed bed catalyst reactor with a solid catalyst, and the pressure in the filling work space inside the reactor is reacted by blowing air from at least one place above the reactor into the filling work space inside the reactor. A solid catalyst filling method characterized by a positive pressure of 1 Pascal or more of the atmospheric pressure around the vessel,
(2) A positive pressure of 1 Pascal or more and 30 Pascals or less of atmospheric pressure around the reactor by blowing air from at least one place above the reactor to the filling work space inside the reactor. The solid catalyst filling method according to (1), characterized in that
(3) The method for packing a solid catalyst according to any one of (1) and (2), wherein the dust in the reactor is sucked from the lower part of the reactor by a dust collector or a ventilator,
About.
（１）固定床触媒反応装置に固体触媒を充填する方法であり、反応器内部の充填作業空間に少なくとも反応器上部の一カ所から送風することで反応器内部の充填作業空間の圧力をその反応器周辺の大気圧の１パスカル以上の陽圧とすることを特徴とする固体触媒の充填方法、
（２）反応器内部の充填作業空間に少なくとも反応器上部の一カ所から送風することで反応器内部の充填作業空間の圧力をその反応器周辺の大気圧の１パスカル以上３０パスカル以下の陽圧とすることを特徴とする（１）に記載の固体触媒の充填方法、
（３）反応器下部より集塵機もしくは排風機によって反応器内の粉じんを吸引することを特徴とする（１）または（２）のいずれか１項に記載の固体触媒の充填方法、
に関する。 That is, the present invention
(1) This is a method of filling a fixed bed catalyst reactor with a solid catalyst, and the pressure in the filling work space inside the reactor is reacted by blowing air from at least one place above the reactor into the filling work space inside the reactor. A solid catalyst filling method characterized by a positive pressure of 1 Pascal or more of the atmospheric pressure around the vessel,
(2) A positive pressure of 1 Pascal or more and 30 Pascals or less of atmospheric pressure around the reactor by blowing air from at least one place above the reactor to the filling work space inside the reactor. The solid catalyst filling method according to (1), characterized in that
(3) The method for packing a solid catalyst according to any one of (1) and (2), wherein the dust in the reactor is sucked from the lower part of the reactor by a dust collector or a ventilator,
About.
本発明によれば、触媒充填作業環境が保全され、作業効率が上がることで触媒充填作業にかかる時間を短縮することが出来、早くにプラント運転が可能になる。
According to the present invention, the catalyst filling work environment is maintained and the work efficiency is increased, whereby the time required for the catalyst filling work can be shortened and the plant can be operated quickly.
次に本発明の好ましい実施形態を説明する。
プロピレン、イソブチレン、および／またはターシャリーブタノールの部分酸化反応により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には、ビスマスおよびモリブデンを主成分とする複合酸化物触媒、例えば特開２０１４－０１９６７５号公報、特許第５１３０５６２号公報などに記載される触媒およびその使用方法が適用できる。アクロレインの部分酸化反応によりアクリル酸を製造するには、バナジウムおよびモリブデンを主成分とする複合酸化物触媒、例えば特許第５６８０３７３号公報、特開２０１５－０９６４９７号公報などに記載される触媒およびその使用方法が適用できる。メタクロレインの部分酸化反応によりメタクリル酸を製造するには、リンおよびモリブデンを主成分とする触媒、例えば特許第５５７０１４２号公報、特開２０１５－０９６４９７号公報などに記載の触媒およびその使用方法が適用できる。ブテン類から共役ジエン類を製造するには、モリブデンおよびビスマスを主成分とする複合酸化物触媒、例えば国際公開第２０１３／１６１７０３号などに記載される触媒およびその使用方法が適用できる。 Next, a preferred embodiment of the present invention will be described.
In order to produce a corresponding unsaturated aldehyde and / or unsaturated carboxylic acid by partial oxidation reaction of propylene, isobutylene and / or tertiary butanol, a composite oxide catalyst based on bismuth and molybdenum, for example, The catalysts described in Japanese Patent No. -016755, Japanese Patent No. 5130562 and the method of using the same can be applied. In order to produce acrylic acid by the partial oxidation reaction of acrolein, a composite oxide catalyst mainly composed of vanadium and molybdenum, for example, a catalyst described in Japanese Patent No. 5680373, Japanese Patent Application Laid-Open No. 2015-096497, and the use thereof The method is applicable. In order to produce methacrylic acid by a partial oxidation reaction of methacrolein, a catalyst mainly composed of phosphorus and molybdenum, for example, a catalyst described in Japanese Patent No. 5570142, Japanese Patent Application Laid-Open No. 2015-096497, and a method of using the same are applied. it can. In order to produce conjugated dienes from butenes, a composite oxide catalyst mainly composed of molybdenum and bismuth, for example, a catalyst described in International Publication No. 2013/161703, and a method of using the same can be applied.
プロピレン、イソブチレン、および／またはターシャリーブタノールの部分酸化反応により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には、ビスマスおよびモリブデンを主成分とする複合酸化物触媒、例えば特開２０１４－０１９６７５号公報、特許第５１３０５６２号公報などに記載される触媒およびその使用方法が適用できる。アクロレインの部分酸化反応によりアクリル酸を製造するには、バナジウムおよびモリブデンを主成分とする複合酸化物触媒、例えば特許第５６８０３７３号公報、特開２０１５－０９６４９７号公報などに記載される触媒およびその使用方法が適用できる。メタクロレインの部分酸化反応によりメタクリル酸を製造するには、リンおよびモリブデンを主成分とする触媒、例えば特許第５５７０１４２号公報、特開２０１５－０９６４９７号公報などに記載の触媒およびその使用方法が適用できる。ブテン類から共役ジエン類を製造するには、モリブデンおよびビスマスを主成分とする複合酸化物触媒、例えば国際公開第２０１３／１６１７０３号などに記載される触媒およびその使用方法が適用できる。 Next, a preferred embodiment of the present invention will be described.
In order to produce a corresponding unsaturated aldehyde and / or unsaturated carboxylic acid by partial oxidation reaction of propylene, isobutylene and / or tertiary butanol, a composite oxide catalyst based on bismuth and molybdenum, for example, The catalysts described in Japanese Patent No. -016755, Japanese Patent No. 5130562 and the method of using the same can be applied. In order to produce acrylic acid by the partial oxidation reaction of acrolein, a composite oxide catalyst mainly composed of vanadium and molybdenum, for example, a catalyst described in Japanese Patent No. 5680373, Japanese Patent Application Laid-Open No. 2015-096497, and the use thereof The method is applicable. In order to produce methacrylic acid by a partial oxidation reaction of methacrolein, a catalyst mainly composed of phosphorus and molybdenum, for example, a catalyst described in Japanese Patent No. 5570142, Japanese Patent Application Laid-Open No. 2015-096497, and a method of using the same are applied. it can. In order to produce conjugated dienes from butenes, a composite oxide catalyst mainly composed of molybdenum and bismuth, for example, a catalyst described in International Publication No. 2013/161703, and a method of using the same can be applied.
以下にプロピレンの部分酸化反応によるアクロレインおよび／またはアクリル酸製造用触媒を反応器に充填する方法を例に本発明の詳細を記載するが、当然のことながら本発明はその趣旨を逸脱しない限り、以下の詳細説明および実施例に限定されるものではなく、固体触媒ならびに固体触媒を使用して目的化合物を製造するために必要な、当該反応に不活性な固体物質を反応器に充填する場合にも適用できる。尚、本出願書類で記載される「反応器」は、複数の反応管から構成される固定床触媒反応装置を意味し、反応器に触媒および／または不活性物質を充填する作業は、反応器を構成する反応管に触媒および／または不活性物質を充填する作業と同一のものである。
Details of the present invention will be described below by way of example of a method of charging a reactor with a catalyst for producing acrolein and / or acrylic acid by partial oxidation reaction of propylene, but it goes without saying that the present invention does not depart from the spirit of the present invention. The present invention is not limited to the following detailed description and examples. When the reactor is filled with a solid material that is inert to the reaction and is necessary for producing the target compound using the solid catalyst. Is also applicable. The “reactor” described in the present application document means a fixed bed catalytic reaction apparatus composed of a plurality of reaction tubes, and the operation of filling the reactor with a catalyst and / or an inert substance is performed in the reactor. This is the same as the operation of filling the reaction tube constituting the catalyst and / or an inert substance.
触媒の調製
触媒の調製はそれ自身公知の方法を採用することが出来る。目的とする生成物、原料、反応条件に応じて適宜触媒の構成成分、調製条件、形状などを設計すればよい。 Preparation of catalyst The catalyst can be prepared by a method known per se. What is necessary is just to design the component of a catalyst, preparation conditions, a shape, etc. suitably according to the target product, raw material, and reaction conditions.
触媒の調製はそれ自身公知の方法を採用することが出来る。目的とする生成物、原料、反応条件に応じて適宜触媒の構成成分、調製条件、形状などを設計すればよい。 Preparation of catalyst The catalyst can be prepared by a method known per se. What is necessary is just to design the component of a catalyst, preparation conditions, a shape, etc. suitably according to the target product, raw material, and reaction conditions.
触媒の充填
反応管１本あたりの触媒の所定充填量は以下のようにして決定することができる。すなわち、例えば触媒を充填高さが２００ｃｍとなるように、全長３８０ｃｍ内径２５ｍｍの円柱状反応管に充填する場合、予め類似の反応管径の反応管を使用して充填高さが２００ｃｍになるための触媒重量を測定する。類似の反応管径の反応管とは、必ずしも工業装置で使用する反応管と長さや内径と同一でなくともよく、例えば内径２４ｍｍの反応管と内径２８ｍｍの反応管で充填高さが２００ｃｍとなる触媒重量を測定し、内径２５ｍｍの反応管での必要触媒重量を内挿で求めることも出来る。 Catalyst filling The predetermined filling amount of catalyst per reaction tube can be determined as follows. That is, for example, when a cylindrical reaction tube having a total length of 380 cm and an inner diameter of 25 mm is filled so that the filling height is 200 cm, the filling height is 200 cm using a reaction tube having a similar reaction tube diameter in advance. The catalyst weight of is measured. A reaction tube having a similar reaction tube diameter is not necessarily the same as the length and the inner diameter of a reaction tube used in an industrial apparatus. For example, a reaction tube having an inner diameter of 24 mm and a reaction tube having an inner diameter of 28 mm has a filling height of 200 cm. The catalyst weight can be measured, and the necessary catalyst weight in a reaction tube having an inner diameter of 25 mm can be determined by interpolation.
反応管１本あたりの触媒の所定充填量は以下のようにして決定することができる。すなわち、例えば触媒を充填高さが２００ｃｍとなるように、全長３８０ｃｍ内径２５ｍｍの円柱状反応管に充填する場合、予め類似の反応管径の反応管を使用して充填高さが２００ｃｍになるための触媒重量を測定する。類似の反応管径の反応管とは、必ずしも工業装置で使用する反応管と長さや内径と同一でなくともよく、例えば内径２４ｍｍの反応管と内径２８ｍｍの反応管で充填高さが２００ｃｍとなる触媒重量を測定し、内径２５ｍｍの反応管での必要触媒重量を内挿で求めることも出来る。 Catalyst filling The predetermined filling amount of catalyst per reaction tube can be determined as follows. That is, for example, when a cylindrical reaction tube having a total length of 380 cm and an inner diameter of 25 mm is filled so that the filling height is 200 cm, the filling height is 200 cm using a reaction tube having a similar reaction tube diameter in advance. The catalyst weight of is measured. A reaction tube having a similar reaction tube diameter is not necessarily the same as the length and the inner diameter of a reaction tube used in an industrial apparatus. For example, a reaction tube having an inner diameter of 24 mm and a reaction tube having an inner diameter of 28 mm has a filling height of 200 cm. The catalyst weight can be measured, and the necessary catalyst weight in a reaction tube having an inner diameter of 25 mm can be determined by interpolation.
こうして必要量計量された触媒は予め容器に反応管１本ずつの量になるように小分けするのが好ましいが、自動充填機のような機械を用いて触媒を、反応器を構成する複数本の反応管に充填することも可能である。触媒を予め容器に小分けする場合は、反応管１本あたりに充填する触媒量が同一になるように小分けするのが好ましい。同一量とは触媒の充填高さに１ｃｍ以上の差を生じさせない程度の触媒量を示す。
The catalyst weighed in the required amount is preferably subdivided in advance so that the amount of each reaction tube is one in a container. However, a catalyst such as an automatic filling machine is used to divide the catalyst into a plurality of reactors. It is also possible to fill the reaction tube. When the catalyst is subdivided into containers in advance, it is preferable to subdivide the catalyst so that the amount of catalyst charged per reaction tube is the same. The same amount indicates a catalyst amount that does not cause a difference of 1 cm or more in the packing height of the catalyst.
反応器への充填作業としては漏斗を使用した自由落下による充填作業が簡便で好ましい。この際、触媒を予め容器等に小分けする場合、小分けされた触媒の全量を漏斗に一気に注ぎ込むことで充填スピードはおのずと一定になる。万一、漏斗内でブリッジを形成した場合は軽くタッピングすることで解消することが出来る。必要以上に漏斗をタッピングするのは充填スピード、ひいては触媒充填高さをばらつかせる原因となるので、好ましくない。機械を用いて触媒を反応器に充填する場合も触媒充填スピードが同一になるよう、適宜機械を調整して作業に当たるのが好ましい。触媒の充填作業が完了したら、全ての反応管に対してメジャーなどで触媒充填高さを測定しながら、触媒充填高さが規格値の範囲内になるように必要な量の触媒を追加する作業を行う。触媒充填高さの規格値とは、使用する触媒の性能を十分に発揮するために必要な触媒充填高さであり、目的とする反応、反応条件や使用する反応管の内径誤差により異なるため一概には言えないが、通常目標とする充填高さの±１ｃｍから±５ｃｍ程度である。更に別の種類や形状、濃度の触媒をすでに充填が完了した触媒の上部に充填する場合も同様である。
As the filling operation to the reactor, the filling operation by free fall using a funnel is simple and preferable. At this time, when the catalyst is divided into containers or the like in advance, the filling speed is naturally constant by pouring the entire amount of the divided catalyst into the funnel at a stroke. If a bridge is formed in the funnel, it can be resolved by lightly tapping. Tapping the funnel more than necessary is not preferable because it causes the filling speed and, consequently, the catalyst filling height to vary. Even when the catalyst is charged into the reactor using a machine, it is preferable to adjust the machine appropriately so that the catalyst filling speed is the same. After completing the catalyst filling operation, measure the catalyst filling height with a measure etc. for all reaction tubes and add the required amount of catalyst so that the catalyst filling height is within the standard range. I do. The standard value for the catalyst packing height is the catalyst packing height required to fully demonstrate the performance of the catalyst used, and varies depending on the target reaction, reaction conditions, and the inner diameter error of the reaction tube used. However, it is usually about ± 1 cm to ± 5 cm of the target filling height. The same applies to the case where another type, shape, or concentration of catalyst is filled on top of a catalyst that has already been filled.
上記作業実施に当たり、通常は反応器上部空間である触媒充填作業場（充填作業空間）に少なくとも一カ所から送風することで触媒充填作業場の圧力をその反応器周辺の大気圧の１パスカル以上、好ましくは１パスカル以上３０パスカル以下、より好ましくは３パスカル以上２０パスカル以下の陽圧とする。送風量は反応器の構造や大きさによって最適値が異なるため、一概には言えない。後述する、反応器下部に設置する集塵機および／または排風機を使用する場合は、その集塵機および／または排風機の吸引力も考慮して触媒充填作業場の圧力がその反応器周辺の大気圧の１パスカル以上、好ましくは１パスカル以上３０パスカル以下、より好ましくは３パスカル以上２０パスカル以下の陽圧となるように送風量を決定すればよい。触媒充填作業場の圧力をその反応器周辺の大気圧の３０パスカル以上の陽圧としても差し支えないが、それに見合った効果は得られにくい傾向にある。
In carrying out the above operation, the pressure in the catalyst filling work place is usually at least 1 Pascal of atmospheric pressure around the reactor by blowing air from at least one place to the catalyst filling work place (filling work space) that is usually the upper space of the reactor, preferably The positive pressure is 1 to 30 pascals, more preferably 3 to 20 pascals. Since the optimum value varies depending on the structure and size of the reactor, it cannot be generally stated. When using a dust collector and / or an exhaust fan installed at the lower part of the reactor, which will be described later, the pressure in the catalyst filling work area is 1 Pascal of the atmospheric pressure around the reactor in consideration of the suction force of the dust collector and / or the exhaust fan. The air flow rate may be determined so that the positive pressure is 1 to 30 Pascals, more preferably 3 to 20 Pascals. The pressure in the catalyst filling work place may be a positive pressure of 30 Pascal or more of the atmospheric pressure around the reactor, but it is difficult to obtain an effect commensurate with it.
集塵機は一般的に使用されるものであれば特に限定されないが、バグフィルターなどで粉じんを捕集する、隔壁式集塵機が簡便で好ましい。設置場所は触媒を充填した際に発生し、落下してくる粉じんを捕集できる場所であれば特に制限はないが、反応器下部に設置したステージなどに１台から１０台の集塵機を設置する事が好ましい。
The dust collector is not particularly limited as long as it is generally used, but a partition type dust collector that collects dust with a bag filter or the like is simple and preferable. The installation location is not particularly limited as long as it is a location where the falling dust generated when the catalyst is filled can be collected, but 1 to 10 dust collectors are installed on the stage installed at the bottom of the reactor. Things are preferable.
送風機、排風機は一般的に使用されるものであれば特に限定されないが、遠心式、軸流式が好ましい。送風機は触媒充填作業場を陽圧下にするために反応器上部に、排風機は集塵機と同様に反応器下部に設置したステージなどに１台から１０台の集塵機を設置する事が好ましい。
The blower and the exhaust fan are not particularly limited as long as they are generally used, but a centrifugal type and an axial flow type are preferable. It is preferable to install 1 to 10 dust collectors on the stage installed in the upper part of the reactor in order to bring the catalyst filling workplace under positive pressure, and the exhaust fan on the stage installed in the lower part of the reactor in the same manner as the dust collector.
本発明の本質は、触媒充填作業場を、送風により陽圧下に保つことであるので、送風には空気のみならず純酸素を供給して富化した空気や、気温３５℃程度の飽和水蒸気を含む空気等も用いる事が出来る。尚、触媒充填作業場の圧力および反応器周辺の大気圧は、市販の圧力測定装置を使用して測定することが出来る。通常、触媒を充填する作業場所（触媒充填作業場）は反応器の上部であるが、異なる反応器が縦に連続している構造の反応器であって、連続する反応器の中間部分を触媒充填作業場とする反応器においても本発明は適用される。また、反応器上部をテントのような構造物で覆い、その構造物内を上記の陽圧にすることでも本発明を達成することが出来る。
Since the essence of the present invention is to maintain the catalyst filling work place under a positive pressure by blowing air, the blowing air contains not only air but also air enriched by supplying pure oxygen and saturated steam at a temperature of about 35 ° C. Air or the like can also be used. Note that the pressure in the catalyst filling work area and the atmospheric pressure around the reactor can be measured using a commercially available pressure measuring device. Normally, the working place for filling the catalyst (catalyst filling work place) is the upper part of the reactor, but the reactor is structured so that different reactors are vertically connected, and the middle part of the successive reactors is filled with the catalyst. The present invention is also applied to a reactor as a work place. Further, the present invention can also be achieved by covering the upper part of the reactor with a structure such as a tent and setting the inside of the structure to the positive pressure described above.
実施例１
蒸留水３０００重量部を加熱攪拌しながらモリブデン酸アンモニウム４２３．８重量部と硝酸カリウム３．０重量部を溶解して水溶液（Ａ１）を得た。別に、硝酸コバルト３０２．７重量部、硝酸ニッケル１６２．９重量部、硝酸第二鉄１４５．４重量部を蒸留水１０００重量部に溶解して水溶液（Ｂ１）を、また濃硝酸４２重量部を加えて酸性にした蒸留水２００重量部に硝酸ビスマス１６４．９重量部を溶解して水溶液（Ｃ１）をそれぞれ調製した。 Example 1
While heating and stirring 3000 parts by weight of distilled water, 423.8 parts by weight of ammonium molybdate and 3.0 parts by weight of potassium nitrate were dissolved to obtain an aqueous solution (A1). Separately, 302.7 parts by weight of cobalt nitrate, 162.9 parts by weight of nickel nitrate, and 145.4 parts by weight of ferric nitrate are dissolved in 1000 parts by weight of distilled water to prepare an aqueous solution (B1), and 42 parts by weight of concentrated nitric acid. In addition, 164.9 parts by weight of bismuth nitrate was dissolved in 200 parts by weight of distilled water acidified to prepare aqueous solutions (C1).
蒸留水３０００重量部を加熱攪拌しながらモリブデン酸アンモニウム４２３．８重量部と硝酸カリウム３．０重量部を溶解して水溶液（Ａ１）を得た。別に、硝酸コバルト３０２．７重量部、硝酸ニッケル１６２．９重量部、硝酸第二鉄１４５．４重量部を蒸留水１０００重量部に溶解して水溶液（Ｂ１）を、また濃硝酸４２重量部を加えて酸性にした蒸留水２００重量部に硝酸ビスマス１６４．９重量部を溶解して水溶液（Ｃ１）をそれぞれ調製した。 Example 1
While heating and stirring 3000 parts by weight of distilled water, 423.8 parts by weight of ammonium molybdate and 3.0 parts by weight of potassium nitrate were dissolved to obtain an aqueous solution (A1). Separately, 302.7 parts by weight of cobalt nitrate, 162.9 parts by weight of nickel nitrate, and 145.4 parts by weight of ferric nitrate are dissolved in 1000 parts by weight of distilled water to prepare an aqueous solution (B1), and 42 parts by weight of concentrated nitric acid. In addition, 164.9 parts by weight of bismuth nitrate was dissolved in 200 parts by weight of distilled water acidified to prepare aqueous solutions (C1).
上記水溶液（Ａ１）に水溶液（Ｂ１）および水溶液（Ｃ１）を順次、激しく攪拌しながら混合し、生成した懸濁液をスプレードライヤーを用いて乾燥し４４０℃で６時間焼成し予備焼成粉末（Ｄ１）を得た。このとき得られた予備焼成粉末（Ｄ１）における触媒活性成分の酸素を除いた組成比は原子比でＭｏ＝１２、Ｂｉ＝１．７、Ｎｉ＝２．８、Ｆｅ＝１．８、Ｃｏ＝５．２、Ｋ＝０．１５であった。
The aqueous solution (B1) and the aqueous solution (C1) are sequentially mixed with the aqueous solution (A1) with vigorous stirring, and the resulting suspension is dried using a spray drier and calcined at 440 ° C. for 6 hours and pre-calcined powder (D1 ) The composition ratio excluding oxygen of the catalytically active component in the pre-fired powder (D1) obtained at this time is atomic ratio: Mo = 12, Bi = 1.7, Ni = 2.8, Fe = 1.8, Co = 5.2, K = 0.15.
その後、予備焼成粉末（Ｄ１）１００重量部に結晶セルロース５重量部を混合した粉末を不活性担体（アルミナおよびシリカを主成分とする直径４．５ｍｍの球状物質）に成型後の触媒に対して５０重量％を占める割合になるよう２０重量％グリセリン水溶液をバインダーとして直径５．２ｍｍの球状に担持成型して担持触媒（Ｅ１）を得た。担持触媒（Ｅ１）を、焼成温度５５０℃で４時間、空気雰囲気下で焼成することで触媒（Ｆ１）を得た。
Thereafter, a powder obtained by mixing 100 parts by weight of the pre-fired powder (D1) with 5 parts by weight of crystalline cellulose into an inert carrier (a spherical substance having a diameter of 4.5 mm mainly composed of alumina and silica) is applied to the catalyst after molding. A supported catalyst (E1) was obtained by supporting and molding into a spherical shape having a diameter of 5.2 mm using a 20% by weight aqueous glycerin solution as a binder so as to account for 50% by weight. The supported catalyst (E1) was calcined in an air atmosphere at a calcining temperature of 550 ° C. for 4 hours to obtain a catalyst (F1).
次に、蒸留水３０００重量部を加熱攪拌しながらモリブデン酸アンモニウム４２３．８重量部と硝酸カリウム２．０重量部を溶解して水溶液（Ａ２）を得た。別に、硝酸コバルト３０２．７重量部、硝酸ニッケル１６２．９重量部、および硝酸第二鉄１４５．４重量部を蒸留水１０００重量部に溶解して水溶液（Ｂ２）を、また濃硝酸４２重量部を加えて酸性にした蒸留水２００重量部に硝酸ビスマス１６４．９重量部を溶解して水溶液（Ｃ２）をそれぞれ調製した。
Next, an aqueous solution (A2) was obtained by dissolving 423.8 parts by weight of ammonium molybdate and 2.0 parts by weight of potassium nitrate while heating and stirring 3000 parts by weight of distilled water. Separately, 302.7 parts by weight of cobalt nitrate, 162.9 parts by weight of nickel nitrate, and 145.4 parts by weight of ferric nitrate were dissolved in 1000 parts by weight of distilled water to prepare an aqueous solution (B2), and 42 parts by weight of concentrated nitric acid. An aqueous solution (C2) was prepared by dissolving 164.9 parts by weight of bismuth nitrate in 200 parts by weight of distilled water acidified by adding.
上記水溶液（Ａ２）に水溶液（Ｂ２）および水溶液（Ｃ２）を順次、激しく攪拌しながら混合し、生成した懸濁液をスプレードライヤーを用いて乾燥し４４０℃で６時間焼成し予備焼成粉末（Ｄ２）を得た。このとき得られた予備焼成粉末（Ｄ２）における触媒活性成分の酸素を除いた組成比は原子比でＭｏ＝１２、Ｂｉ＝１．７、Ｎｉ＝２．８、Ｆｅ＝１．８、Ｃｏ＝５．２、Ｋ＝０．１であった。
The aqueous solution (B2) and the aqueous solution (C2) are sequentially mixed with the aqueous solution (A2) with vigorous stirring, and the resulting suspension is dried using a spray dryer and calcined at 440 ° C. for 6 hours, and then pre-calcined powder (D2 ) The composition ratio excluding oxygen of the catalytically active component in the pre-fired powder (D2) obtained at this time is atomic ratio Mo = 12, Bi = 1.7, Ni = 2.8, Fe = 1.8, Co = 5.2, K = 0.1.
その後、予備焼成粉末（Ｄ２）１００重量部に結晶セルロース５重量部を混合した粉末を不活性担体（アルミナおよびシリカを主成分とする直径４．５ｍｍの球状物質）に成型後の触媒に対して５０重量％を占める割合になるよう２０重量％グリセリン水溶液をバインダーとして直径５．２ｍｍの球状に担持成型して担持触媒（Ｅ２）を得た。担持触媒（Ｅ２）を５１０℃で４時間焼成して触媒（Ｆ２）を得た。
Thereafter, a powder obtained by mixing 100 parts by weight of the pre-fired powder (D2) with 5 parts by weight of crystalline cellulose into an inert carrier (a spherical substance having a diameter of 4.5 mm mainly composed of alumina and silica) is applied to the catalyst after molding. A supported catalyst (E2) was obtained by supporting and molding into a spherical shape having a diameter of 5.2 mm using a 20% by weight glycerin aqueous solution as a binder so as to account for 50% by weight. The supported catalyst (E2) was calcined at 510 ° C. for 4 hours to obtain a catalyst (F2).
全長３８０ｃｍで内径２５ｍｍの反応管１００００本を備えた固定床接触式多管反応器に対し、原料ガス出口部分に直径７ｍｍの不活性球を充填高さが６０ｃｍとなるように充填し、その上部に触媒（Ｆ２）を充填高さが２３０ｃｍとなるように充填し、さらにその上部に触媒（Ｆ１）８０重量％と直径５．２ｍｍの不活性球２０重量％との混合物を充填高さが１２０ｃｍとなるように充填することにした。充填作業を実施するに当たり、反応器内の触媒充填作業場（充填作業空間）に対して反応器上部のマンホールより送風器にて空気を供給（送風）し、反応器下部には集塵機を設置した。両者を稼働させながら反応器内の触媒充填作業場の圧力がその日の反応器周辺の大気圧の５パスカル以上２０パスカル以下の陽圧となるように送風量を調整しながら作業を継続したところ触媒の充填開始から、触媒充填長を規格値内に収める作業を完了するまでにかかった日数は１０日であった。反応器下部で使用した集塵機で吸引した触媒粉末の合計量は約８０ｋｇであった。
In a fixed bed contact type multi-tube reactor equipped with 10000 reaction tubes with a total length of 380 cm and an inner diameter of 25 mm, an inert sphere with a diameter of 7 mm is filled at the source gas outlet part so that the filling height is 60 cm, The catalyst (F2) is packed to a packing height of 230 cm, and a mixture of 80% by weight of the catalyst (F1) and 20% by weight of inert spheres having a diameter of 5.2 mm is further packed to a height of 120 cm. It was decided to fill so that In carrying out the filling work, air was supplied (blowed) from the manhole at the top of the reactor to the catalyst filling work place (filling work space) in the reactor by a blower, and a dust collector was installed at the bottom of the reactor. The operation of the catalyst was continued while adjusting the air flow rate so that the pressure in the catalyst filling work area in the reactor became a positive pressure of 5 Pascal or more and 20 Pascal or less of the atmospheric pressure around the reactor while operating both. It took 10 days from the start of filling to the completion of the work of keeping the catalyst filling length within the standard value. The total amount of catalyst powder sucked by the dust collector used in the lower part of the reactor was about 80 kg.
比較例１
実施例１と同一のプラントにて、反応器上部の送風機、反応器下部の集塵機を使用せず、反応器内の触媒充填作業場の圧力を調節することなく作業を行ったところ、触媒充填作業場の圧力は反応器周辺の大気圧の±１パスカル未満であった。触媒の充填開始から、触媒充填長を規格値内に収める作業を完了するまでにかかった日数は１５日であった。 Comparative Example 1
In the same plant as in Example 1, the work was performed without adjusting the pressure of the catalyst filling work place in the reactor without using the blower at the upper part of the reactor and the dust collector at the lower part of the reactor. The pressure was less than ± 1 Pascal of atmospheric pressure around the reactor. It took 15 days from the start of the catalyst filling to the completion of the work to keep the catalyst filling length within the standard value.
実施例１と同一のプラントにて、反応器上部の送風機、反応器下部の集塵機を使用せず、反応器内の触媒充填作業場の圧力を調節することなく作業を行ったところ、触媒充填作業場の圧力は反応器周辺の大気圧の±１パスカル未満であった。触媒の充填開始から、触媒充填長を規格値内に収める作業を完了するまでにかかった日数は１５日であった。 Comparative Example 1
In the same plant as in Example 1, the work was performed without adjusting the pressure of the catalyst filling work place in the reactor without using the blower at the upper part of the reactor and the dust collector at the lower part of the reactor. The pressure was less than ± 1 Pascal of atmospheric pressure around the reactor. It took 15 days from the start of the catalyst filling to the completion of the work to keep the catalyst filling length within the standard value.
実施例２
実施例１と同一のプラントにて、反応器上部の送風機のみを使用して作業を行い、反応器内の触媒充填作業場の圧力がその日の反応器周辺の大気圧の５パスカル以上２０パスカル以下の陽圧となるように送風量を調整しながら作業を継続したところ触媒の充填開始から、触媒充填長を規格値内に収める作業を完了するまでにかかった日数は１３日であった。 Example 2
In the same plant as in Example 1, the work was performed using only the blower at the top of the reactor, and the pressure of the catalyst filling work place in the reactor was 5 Pascal or more and 20 Pascal or less of the atmospheric pressure around the reactor on that day. When the operation was continued while adjusting the air flow rate so as to be positive pressure, it took 13 days from the start of the catalyst filling to the completion of the operation for keeping the catalyst filling length within the standard value.
実施例１と同一のプラントにて、反応器上部の送風機のみを使用して作業を行い、反応器内の触媒充填作業場の圧力がその日の反応器周辺の大気圧の５パスカル以上２０パスカル以下の陽圧となるように送風量を調整しながら作業を継続したところ触媒の充填開始から、触媒充填長を規格値内に収める作業を完了するまでにかかった日数は１３日であった。 Example 2
In the same plant as in Example 1, the work was performed using only the blower at the top of the reactor, and the pressure of the catalyst filling work place in the reactor was 5 Pascal or more and 20 Pascal or less of the atmospheric pressure around the reactor on that day. When the operation was continued while adjusting the air flow rate so as to be positive pressure, it took 13 days from the start of the catalyst filling to the completion of the operation for keeping the catalyst filling length within the standard value.
比較例２
実施例１と同一のプラントにて、反応器下部より反応器内の触媒充填作業場に空気を流通し反応器内の触媒充填作業場の圧力をその日の反応器周辺の大気圧の５パスカル以上２０パスカル以下の陽圧として作業したところ、触媒充填作業場での粉じん量が多く、作業を連続して行うことが困難となり触媒の充填開始から、触媒充填長を規格値内に収める作業を完了するまでにかかった日数は２０日であった。実施例１の反応器下部で使用した集塵機で収集した触媒粉末の多くは触媒充填作業場もしくはその周辺外部に滞留、飛散した可能性が強く、作業者との接触や環境保全の面で問題となる可能性がある。 Comparative Example 2
In the same plant as in Example 1, air was circulated from the lower part of the reactor to the catalyst filling work place in the reactor, and the pressure in the catalyst filling work place in the reactor was changed to 5 to 20 pascals of atmospheric pressure around the reactor on that day. When working with the following positive pressure, the amount of dust in the catalyst filling work area was large, making it difficult to carry out the work continuously.From the start of catalyst filling to the completion of work to keep the catalyst filling length within the standard value It took 20 days. Most of the catalyst powder collected by the dust collector used in the lower part of the reactor in Example 1 is likely to stay or scatter in the catalyst filling work area or its surroundings, which is problematic in terms of contact with workers and environmental conservation. there is a possibility.
実施例１と同一のプラントにて、反応器下部より反応器内の触媒充填作業場に空気を流通し反応器内の触媒充填作業場の圧力をその日の反応器周辺の大気圧の５パスカル以上２０パスカル以下の陽圧として作業したところ、触媒充填作業場での粉じん量が多く、作業を連続して行うことが困難となり触媒の充填開始から、触媒充填長を規格値内に収める作業を完了するまでにかかった日数は２０日であった。実施例１の反応器下部で使用した集塵機で収集した触媒粉末の多くは触媒充填作業場もしくはその周辺外部に滞留、飛散した可能性が強く、作業者との接触や環境保全の面で問題となる可能性がある。 Comparative Example 2
In the same plant as in Example 1, air was circulated from the lower part of the reactor to the catalyst filling work place in the reactor, and the pressure in the catalyst filling work place in the reactor was changed to 5 to 20 pascals of atmospheric pressure around the reactor on that day. When working with the following positive pressure, the amount of dust in the catalyst filling work area was large, making it difficult to carry out the work continuously.From the start of catalyst filling to the completion of work to keep the catalyst filling length within the standard value It took 20 days. Most of the catalyst powder collected by the dust collector used in the lower part of the reactor in Example 1 is likely to stay or scatter in the catalyst filling work area or its surroundings, which is problematic in terms of contact with workers and environmental conservation. there is a possibility.
以上より、反応器上部より反応器内の触媒充填作業場に送風し、反応器内の触媒充填作業場を反応器周辺の大気圧の１パスカル以上３０パスカル以下の陽圧とすることで作業効率が向上し、目的とするプラント稼働までの日数を削減することが出来た。
As described above, the work efficiency is improved by blowing air from the upper part of the reactor to the catalyst filling work place in the reactor and setting the catalyst filling work place in the reactor to a positive pressure of 1 to 30 pascals of atmospheric pressure around the reactor. In addition, the number of days until the target plant operation was able to be reduced.
Claims (3)
- 固定床触媒反応装置に固体触媒を充填する方法であり、反応器内部の充填作業空間に少なくとも反応器上部の一カ所から送風することで反応器内部の充填作業空間の圧力をその反応器周辺の大気圧の１パスカル以上の陽圧とすることを特徴とする固体触媒の充填方法。 This is a method of filling a fixed bed catalyst reactor with a solid catalyst. By blowing air from at least one place above the reactor into the filling work space inside the reactor, the pressure in the filling work space inside the reactor is increased around the reactor. A method for filling a solid catalyst, wherein the positive pressure is at least 1 Pascal of atmospheric pressure.
- 反応器内部の充填作業空間に少なくとも反応器上部の一カ所から送風することで反応器内部の充填作業空間の圧力をその反応器周辺の大気圧の１パスカル以上３０パスカル以下の陽圧とすることを特徴とする請求項１に記載の固体触媒の充填方法。 By blowing air from at least one place above the reactor into the filling work space inside the reactor, the pressure in the filling work space inside the reactor is set to a positive pressure between 1 Pascal and 30 Pascals of the atmospheric pressure around the reactor. The method for filling a solid catalyst according to claim 1.
- 反応器下部より集塵機もしくは排風機によって反応器内の粉じんを吸引することを特徴とする請求項１または２のいずれか１項に記載の固体触媒の充填方法。 3. The solid catalyst filling method according to claim 1, wherein the dust in the reactor is sucked from the lower part of the reactor by a dust collector or a ventilator.
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| JPS5617933B2 (en) * | 1977-05-10 | 1981-04-25 | ||
| JP2004506781A (en) * | 2000-08-16 | 2004-03-04 | ボレアリス テクノロジー オイ | Catalyst supply system |
| JP2008246284A (en) * | 2007-03-29 | 2008-10-16 | Sumitomo Chemical Co Ltd | Method for packing catalyst |
| WO2010001732A1 (en) * | 2008-06-30 | 2010-01-07 | 株式会社日本触媒 | Method of packing solid particulate substance into fixed-bed multitubular reactor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5617933B2 (en) * | 1977-05-10 | 1981-04-25 | ||
| JP2004506781A (en) * | 2000-08-16 | 2004-03-04 | ボレアリス テクノロジー オイ | Catalyst supply system |
| JP2008246284A (en) * | 2007-03-29 | 2008-10-16 | Sumitomo Chemical Co Ltd | Method for packing catalyst |
| WO2010001732A1 (en) * | 2008-06-30 | 2010-01-07 | 株式会社日本触媒 | Method of packing solid particulate substance into fixed-bed multitubular reactor |
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