JPH05279269A - Method for hydrogenation reaction of unsaturated hydrocarbon compound - Google Patents
Method for hydrogenation reaction of unsaturated hydrocarbon compoundInfo
- Publication number
- JPH05279269A JPH05279269A JP10593092A JP10593092A JPH05279269A JP H05279269 A JPH05279269 A JP H05279269A JP 10593092 A JP10593092 A JP 10593092A JP 10593092 A JP10593092 A JP 10593092A JP H05279269 A JPH05279269 A JP H05279269A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- unsaturated hydrocarbon
- hydrocarbon compound
- pressure loss
- hydrogenating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- B01J8/06—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 in tube reactors; the solid particles being arranged in tubes
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は多管式熱交換型水素添加
反応装置による不飽和炭化水素化合物の水素添加反応方
法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrogenation reaction method for unsaturated hydrocarbon compounds using a multi-tube heat exchange type hydrogenation reactor.
【０００２】[0002]
【従来の技術】多管式熱交換型水素添加反応装置による
不飽和炭化水素化合物の水素添加反応は、固定床用触媒
を充填した複数の反応管内を水素ガスおよび不飽和炭化
水素化合物を流通させ、該反応管の外側を熱媒を用いて
加熱して、連続して水素添加反応反応を行なわせるもの
であり、反応熱の制御が容易等の利点がある（特開昭６
３−１４１６３８号、特開平２−５６２３８号など）。
しかしこの装置を用いた水素添加反応では、各反応管へ
の流量が均一に分配されることが必要であり、不均一な
流れになった場合には各反応管における水素添加反応が
バラつき、副反応が起きたり、反応率が低下するなどの
問題が生じる。2. Description of the Related Art The hydrogenation reaction of an unsaturated hydrocarbon compound in a multi-tube heat exchange type hydrogenation reactor is carried out by flowing hydrogen gas and an unsaturated hydrocarbon compound in a plurality of reaction tubes filled with a fixed bed catalyst. The outer side of the reaction tube is heated by using a heating medium to continuously carry out the hydrogenation reaction, which is advantageous in that the heat of reaction can be easily controlled.
3-141638, JP-A-2-56238, etc.).
However, in the hydrogenation reaction using this device, it is necessary that the flow rate to each reaction tube be evenly distributed, and if the flow becomes non-uniform, the hydrogenation reaction in each reaction tube will vary and Problems such as a reaction occurring and a decrease in the reaction rate occur.
【０００３】[0003]
【発明が解決しようとする課題】本発明はこのような背
景のもと、多管式熱交換型水素添加反応装置において固
定床用触媒を充填した複数の反応管内への流量を均一に
すべくなされたものである。本発明者らは、前記課題を
解決すべく研究の結果、固定床用触媒を充填した各反応
管における圧力損失を一定の範囲内に制御することによ
り均一な水素添加反応反応が進むことを見出し、この知
見に基いて本発明を完成した。Under the circumstances described above, the present invention aims to make uniform the flow rate into a plurality of reaction tubes filled with a fixed bed catalyst in a multi-tube heat exchange type hydrogenation reactor. It was made. As a result of research to solve the above problems, the present inventors have found that a uniform hydrogenation reaction reaction proceeds by controlling the pressure loss in each reaction tube filled with a fixed bed catalyst within a certain range. The present invention has been completed based on this finding.
【０００４】[0004]
【課題を解決するための手段】かくして本発明によれ
ば、多管式熱交換型水素添加反応装置を用いて不飽和炭
化水素化合物の水素添加反応を行うにあたり、固定床用
触媒を充填したときの反応管の圧力損失の標準偏差
（σ）の、反応管の圧力損失の平均値（Ｘ）に対する割
合（σ／Ｘ）が１０％以下であることを特徴とする不飽
和炭化水素化合物の水素添加反応方法が提供される。Thus, according to the present invention, when a fixed bed catalyst is packed in carrying out a hydrogenation reaction of an unsaturated hydrocarbon compound using a multitubular heat exchange type hydrogenation reactor, Of the standard deviation (σ) of the pressure loss of the reaction tube to the average value (X) of the pressure loss of the reaction tube (σ / X) is 10% or less, the hydrogen of the unsaturated hydrocarbon compound. An addition reaction method is provided.
【０００５】本発明においては、固定床触媒を充填した
複数の反応管を有し、水素ガスと不飽和炭化水素化合物
とを反応管の下部から上部へ流通させ、連続して水素化
反応を行なわせるようにした多管式熱交換型水素添加反
応装置を使用する。本発明で使用する多管式熱交換型水
素添加反応装置の代表的な例を図１に示した。In the present invention, a plurality of reaction tubes filled with a fixed bed catalyst are provided, and hydrogen gas and an unsaturated hydrocarbon compound are circulated from the lower part to the upper part of the reaction tube to continuously carry out the hydrogenation reaction. A multi-tube heat exchange type hydrogenation reactor is used. A typical example of the multi-tube heat exchange type hydrogenation reactor used in the present invention is shown in FIG.
【０００６】[0006]
【図１】[Figure 1]
【０００７】１は固定床触媒９を充填した反応管であ
る。熱媒体は熱媒体入口３から流入し熱媒体出口４へ流
出する。原料不飽和炭化水素化合物は入口６から供給さ
れ、水素ガスは入口５から供給されて、反応管１の下部
から上部へ流通して、反応物は７から抜き出される。ま
た、未反応水素ガスは８から抜き出される。反応装置下
部には気体分散板２が取り付けられている。Reference numeral 1 is a reaction tube filled with a fixed bed catalyst 9. The heat medium flows in from the heat medium inlet 3 and flows out to the heat medium outlet 4. The raw material unsaturated hydrocarbon compound is supplied from the inlet 6, the hydrogen gas is supplied from the inlet 5, flows from the lower part to the upper part of the reaction tube 1, and the reaction product is extracted from 7. Further, unreacted hydrogen gas is extracted from 8. A gas dispersion plate 2 is attached to the lower part of the reactor.
【０００８】本発明で使用する固定床用触媒は、従来か
ら不飽和炭化水素化合物や不飽和石油樹脂の水素添加反
応に使用されているものであれば特に限定されないが、
通常は、ニッケル、白金、パラジウム、ロジウムなどの
金属種を、アルミナ、シリカ、カーボン、チタニアなど
の担体に担持させた粉末触媒を、打錠、押し出し等の方
法でペレット状に成型したものや、あらかじめ円筒形、
ペレット状、球状等に成型した担体表面に、前記金属種
を担持した触媒が用いられる。触媒の大きさは、その有
効面積と反応器内の圧力損失を勘案して、直径０．３〜
１０ｍｍ、好ましくは０．６〜５ｍｍの大きさである。The fixed bed catalyst used in the present invention is not particularly limited as long as it has been conventionally used in the hydrogenation reaction of unsaturated hydrocarbon compounds and unsaturated petroleum resins.
Usually, nickel, platinum, palladium, metal species such as rhodium, alumina, silica, carbon, powder catalyst supported on a carrier such as titania, tableting, those molded into pellets by a method such as extrusion, Pre-cylindrical,
A catalyst in which the metal species is supported on the surface of a carrier formed into a pellet shape, a spherical shape, or the like is used. The size of the catalyst should be 0.3-diameter in consideration of its effective area and pressure loss in the reactor.
The size is 10 mm, preferably 0.6 to 5 mm.
【０００９】これら固定床触媒は複数の反応管にそれぞ
れ充填される。固定床触媒を充填した反応管は、不活性
ガスを一定流量で流したときの圧力損失を一本ずつ測定
する。反応管の圧力損失は、触媒を充填した反応管頂部
から不活性ガスを一定流量で連続的に流入させ、反応管
底部を開放したときの反応管頂部における圧力の値であ
る。通常不活性ガスは窒素を使用する。測定条件は特に
限定されないが、通常は、窒素ガス流量３〜１０（ｍ3
／時間）（標準状態）で、そのときの反応管の圧力損失
は触媒充填層当り５００〜２０００（ｍｍＨ2 Ｏ／ｍ）
の範囲である。These fixed bed catalysts are packed in a plurality of reaction tubes, respectively. The reaction tube filled with the fixed bed catalyst measures the pressure loss one by one when the inert gas is flown at a constant flow rate. The pressure loss of the reaction tube is the value of the pressure at the top of the reaction tube when the bottom of the reaction tube is opened by continuously flowing an inert gas at a constant flow rate from the top of the reaction tube filled with the catalyst. Nitrogen is usually used as the inert gas. The measurement conditions are not particularly limited, but usually the nitrogen gas flow rate is 3 to 10 (m 3
/ Hour) (standard state), the pressure loss of the reaction tube at that time is 500 to 2000 (mmH 2 O / m) per catalyst packed bed.
The range is.
【００１０】複数の反応管すべてについて圧力損失を測
定した後、圧力損失の平均値（Ｘ）と、圧力損失の標準
偏差（σ）を求める。標準偏差の、圧力損失の平均値に
対する割合（σ／Ｘ）が１０％を超える場合は、反応管
内の触媒量を増減させて調整し、標準偏差の圧力損失の
平均値に対する割合（σ／Ｘ）が１０％以内になるまで
調整を繰り返す。After measuring the pressure loss in all of the plurality of reaction tubes, the average value (X) of the pressure loss and the standard deviation (σ) of the pressure loss are obtained. When the ratio of standard deviation to the average value of pressure loss (σ / X) exceeds 10%, the amount of catalyst in the reaction tube is increased or decreased to adjust, and the ratio of standard deviation to the average value of pressure loss (σ / X) ) Is adjusted to 10% or less.
【００１１】固定床触媒を充填した反応管は反応装置内
に並列に設置される。反応管は通常内径２０〜７０ｍ
ｍ、長さ２〜８ｍであり、また反応装置内に設置される
本数は５０〜２００本である。The reaction tubes filled with the fixed bed catalyst are installed in parallel in the reactor. Reaction tube usually has an inner diameter of 20 to 70 m
m, the length is 2 to 8 m, and the number installed in the reactor is 50 to 200.
【００１２】本発明で使用する不飽和炭化水素化合物は
特に限定されないが、たとえばオレフィン化合物、芳香
族炭化水素化合物が挙げられる。オレフィン化合物とし
ては、ブテン、ペンテン、ヘキセン、ヘプテン、オクテ
ン、ブタジエン、イソプレン、シクロペンテン、ジシク
ロペンタジエン、シクロペンタジエン、オクタジエンな
ど；芳香族炭化水素化合物としては、ベンゼン、スチレ
ン、α−メチルスチレン、インデンなどである。また、
石油ナフサの熱分解物などをフリーデルクラック触媒の
存在下に重合して得られる炭化水素樹脂の水素添加反応
を行うことも可能である。The unsaturated hydrocarbon compound used in the present invention is not particularly limited, and examples thereof include an olefin compound and an aromatic hydrocarbon compound. Examples of olefin compounds include butene, pentene, hexene, heptene, octene, butadiene, isoprene, cyclopentene, dicyclopentadiene, cyclopentadiene, octadiene; aromatic hydrocarbon compounds include benzene, styrene, α-methylstyrene, indene, etc. Is. Also,
It is also possible to carry out a hydrogenation reaction of a hydrocarbon resin obtained by polymerizing a thermal decomposition product of petroleum naphtha in the presence of a Friedel crack catalyst.
【００１３】水素添加反応条件については、水素添加反
応率、反応時間、反応器仕様などを考慮して適宜決定さ
れるが、通常は、反応圧力２０〜３００ｋｇ／ｃｍ2 、
反応温度は３０〜３５０℃、水素ガス供給量は、原料不
飽和炭化水素化合物の理論水素吸収量の１〜３０倍であ
る。また、原料不飽和水素炭化水素化合物の供給量は、
ＷＨＳＶ（Ｗｅｉｇｈｔ Ｈｏｕｒｌｙ Ｓｐａｃｅ
Ｖｅｌｏｃｉｔｙ、１時間当りの原料供給量／触媒充填
量）が０．０１〜１０の範囲になるようにその流量を決
定する。The hydrogenation reaction conditions are appropriately determined in consideration of the hydrogenation reaction rate, reaction time, reactor specifications, etc., but usually the reaction pressure is 20 to 300 kg / cm 2 ,
The reaction temperature is 30 to 350 ° C., and the hydrogen gas supply amount is 1 to 30 times the theoretical hydrogen absorption amount of the raw material unsaturated hydrocarbon compound. In addition, the supply amount of the raw material unsaturated hydrogen hydrocarbon compound is
WHSV (Weight Hourly Space)
The flow rate is determined so that the velocity, the amount of the raw material supplied / the amount of the catalyst filled per hour) is in the range of 0.01 to 10.
【００１４】また、反応装置底部には、水素ガスを分散
させるために、必要に応じて気体分散板を取り付けるこ
とができる。気体分散板は特に限定されないが、たとえ
ば径０．１〜２ｍｍ程度の微細な穴を多数有する多孔
板、メッシュサイズ１〜１００μｍ程度の焼結金属フィ
ルター、金属繊維フィルターが挙げられる。Further, a gas dispersion plate can be attached to the bottom of the reaction apparatus, if necessary, in order to disperse hydrogen gas. The gas dispersion plate is not particularly limited, and examples thereof include a porous plate having a large number of fine holes having a diameter of about 0.1 to 2 mm, a sintered metal filter having a mesh size of about 1 to 100 μm, and a metal fiber filter.
【００１５】[0015]
【実施例】以下に実施例を挙げて本発明を説明する。 （実施例１〜３、比較例１、２）図１に準じた構造の多
管式熱交換型水素添加反応装置を使用して、シクロペン
タジエンを水素添加してシクロペンテンを製造した。反
応温度は８０℃、圧力は２５ｋｇ／ｃｍ2 を保持し、水
素供給量は６０ｍ3／時間（標準状態）、シクロペンタ
ジエンは、シクロペンタジエン濃度１５重量％のトルエ
ン溶液を４００（ｌ／時間）供給した。また固定床触媒
はシリカアルミナ担体の０．５％パラジウムを使用し、
反応管は、内径２５ｍｍ、長さ３ｍ（触媒充填層長さ
２．５ｍ）のものを１５７本並列に設置した。また気体
分散板としてメッシュサイズ５μｍの焼結金属フィルー
タを使用した。結果を表１に示す。なお、反応率は、水
素添加反応に消費されたシクロペンタジエン量（モル）
の原料シクロペンタジエン量（モル）に対する割合であ
り、選択率は、シクロペンテン量（モル）の原料シクロ
ペンタジエン量（モル）に対する割合であり、また、収
率は、反応率の値に選択率の値を乗じたものである。EXAMPLES The present invention will be described below with reference to examples. (Examples 1 to 3 and Comparative Examples 1 and 2) Cyclopentadiene was hydrogenated to produce cyclopentene using a multitubular heat exchange type hydrogenation reactor having a structure according to FIG. The reaction temperature was 80 ° C., the pressure was 25 kg / cm 2 , the hydrogen supply rate was 60 m 3 / hour (standard state), and cyclopentadiene was 400 (l / hour) toluene solution having a cyclopentadiene concentration of 15% by weight. did. The fixed bed catalyst uses 0.5% palladium on silica-alumina carrier,
As the reaction tubes, 157 tubes having an inner diameter of 25 mm and a length of 3 m (catalyst packed bed length of 2.5 m) were installed in parallel. A sintered metal filler having a mesh size of 5 μm was used as the gas dispersion plate. The results are shown in Table 1. The reaction rate is the amount (mol) of cyclopentadiene consumed in the hydrogenation reaction.
Is the ratio of the starting material cyclopentadiene amount (mol), the selectivity is the ratio of the cyclopentene amount (mol) to the starting material cyclopentadiene amount (mol), and the yield is the reaction value. Is multiplied by.
【００１６】[0016]
【表１】 [Table 1]
【００１７】表１から、固定床用触媒を充填したときの
反応管の圧力損失の標準偏差の平均値に対する割合が１
０％以下に調整された複数の反応管を使用するとシクロ
ペンタジエンの水素添加反応が効率良く行われることが
わかる。From Table 1, the ratio of the standard deviation of the pressure loss of the reaction tube when the catalyst for fixed bed is filled to the average value is 1
It can be seen that the hydrogenation reaction of cyclopentadiene is efficiently carried out by using a plurality of reaction tubes adjusted to 0% or less.
【００１８】[0018]
【発明の効果】かくして本発明によれば、不飽和炭化水
素化合物の水素添加反応生成物が高収率で製造できる。As described above, according to the present invention, a hydrogenation reaction product of an unsaturated hydrocarbon compound can be produced in high yield.
【図１】本発明で使用する多管式熱交換型水素添加反応
装置の具体的構造の一例を示す図である。FIG. 1 is a diagram showing an example of a specific structure of a multitubular heat exchange type hydrogenation reaction device used in the present invention.
１ 反応管 ２ 気体分散板 ３ 熱媒体入口 ４ 熱媒体出口 ５ 水素ガス入口 ６ 不飽和炭化水素化合物入口 ７ 反応生成物出口 ８ 未反応水素ガス出口 ９ 固定床触媒 1 Reaction Tube 2 Gas Dispersion Plate 3 Heat Medium Inlet 4 Heat Medium Outlet 5 Hydrogen Gas Inlet 6 Unsaturated Hydrocarbon Compound Inlet 7 Reaction Product Outlet 8 Unreacted Hydrogen Gas Outlet 9 Fixed Bed Catalyst
Claims (1)
て不飽和炭化水素化合物の水素添加反応を行なうにあた
り、固定床用触媒を充填したときの反応管の圧力損失の
標準偏差（σ）の、圧力損失の平均値（Ｘ）に対する割
合（σ／Ｘ）が１０％以下であることを特徴とする不飽
和炭化水素化合物の水素添加反応方法。1. When performing a hydrogenation reaction of an unsaturated hydrocarbon compound using a multitubular heat exchange type hydrogenation reactor, the standard deviation (σ ) To the average value (X) of the pressure loss is 10% or less, a method for hydrogenation reaction of unsaturated hydrocarbon compounds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10593092A JPH05279269A (en) | 1992-03-31 | 1992-03-31 | Method for hydrogenation reaction of unsaturated hydrocarbon compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10593092A JPH05279269A (en) | 1992-03-31 | 1992-03-31 | Method for hydrogenation reaction of unsaturated hydrocarbon compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05279269A true JPH05279269A (en) | 1993-10-26 |
Family
ID=14420578
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10593092A Pending JPH05279269A (en) | 1992-03-31 | 1992-03-31 | Method for hydrogenation reaction of unsaturated hydrocarbon compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05279269A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08169851A (en) * | 1994-12-16 | 1996-07-02 | Daikin Ind Ltd | Production of 1,1,1,2,3,3-hexafluoropropane |
| EP1466883A1 (en) * | 2001-12-28 | 2004-10-13 | Mitsubishi Chemical Corporation | Method for vapor phase catalytic oxidation |
| JP2006150357A (en) * | 2005-12-16 | 2006-06-15 | Sumitomo Chemical Co Ltd | Multitubular reaction apparatus |
| CZ298994B6 (en) * | 2005-03-18 | 2008-03-26 | Vysoká škola chemicko - technologická | Process for continuously preparing cyclopentene of polymerization purity |
| JP2008246284A (en) * | 2007-03-29 | 2008-10-16 | Sumitomo Chemical Co Ltd | Method for packing catalyst |
| US7850928B2 (en) | 2001-01-25 | 2010-12-14 | Nippon Shokubai Co., Ltd. | Fixed-bed shell-and-tube reactor and its usage |
-
1992
- 1992-03-31 JP JP10593092A patent/JPH05279269A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08169851A (en) * | 1994-12-16 | 1996-07-02 | Daikin Ind Ltd | Production of 1,1,1,2,3,3-hexafluoropropane |
| US7850928B2 (en) | 2001-01-25 | 2010-12-14 | Nippon Shokubai Co., Ltd. | Fixed-bed shell-and-tube reactor and its usage |
| EP1466883A1 (en) * | 2001-12-28 | 2004-10-13 | Mitsubishi Chemical Corporation | Method for vapor phase catalytic oxidation |
| EP1466883A4 (en) * | 2001-12-28 | 2006-09-06 | Mitsubishi Chem Corp | Method for vapor phase catalytic oxidation |
| US7528281B2 (en) | 2001-12-28 | 2009-05-05 | Mitsubishi Chemical Corporation | Method for vapor phase catalytic oxidation |
| US7667072B2 (en) | 2001-12-28 | 2010-02-23 | Mitsubishi Chemical Corporation | Method for vapor phase catalytic oxidation |
| CZ298994B6 (en) * | 2005-03-18 | 2008-03-26 | Vysoká škola chemicko - technologická | Process for continuously preparing cyclopentene of polymerization purity |
| JP2006150357A (en) * | 2005-12-16 | 2006-06-15 | Sumitomo Chemical Co Ltd | Multitubular reaction apparatus |
| JP4549290B2 (en) * | 2005-12-16 | 2010-09-22 | 住友化学株式会社 | Multi-tube reactor |
| JP2008246284A (en) * | 2007-03-29 | 2008-10-16 | Sumitomo Chemical Co Ltd | Method for packing catalyst |
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