JPS59230090A - Purification of gas - Google Patents
Purification of gasInfo
- Publication number
- JPS59230090A JPS59230090A JP10412783A JP10412783A JPS59230090A JP S59230090 A JPS59230090 A JP S59230090A JP 10412783 A JP10412783 A JP 10412783A JP 10412783 A JP10412783 A JP 10412783A JP S59230090 A JPS59230090 A JP S59230090A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- coke oven
- hydrogenation
- dienes
- oven gas
- 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
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- Industrial Gases (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の利用分野〕
本発明は、コークス炉ガスの精製方法に係り、特にコー
クス炉ガス中に含まれるジエン類、酸素、オレフィン類
、硫黄化合物をコークス炉ガス中の水素で水添して精製
する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a method for purifying coke oven gas, particularly for purifying dienes, oxygen, olefins, and sulfur compounds contained in coke oven gas. This invention relates to a method of purification by hydrogenation with hydrogen.
従来のコークス炉ガスの精製方法としてはニッケルーモ
リブデン系触媒或はコバルト−モリブデン系触媒を用い
た一段水添方法が用いられている。As a conventional method for purifying coke oven gas, a one-stage hydrogenation method using a nickel-molybdenum catalyst or a cobalt-molybdenum catalyst is used.
しかしながら、従来の方法では、触媒活性を発揮させる
ために入口温度を高くする必要があり、その結果、ガム
状物質が生成して、触媒層前段の配管機器及び触媒層の
閉そく並びに水添触媒の活性低下を引起す欠点があった
。However, in the conventional method, it is necessary to raise the inlet temperature in order to exhibit the catalyst activity, and as a result, a gummy substance is generated, which blocks the piping equipment and the catalyst layer in the front stage of the catalyst layer, as well as the hydrogenation catalyst. It had the disadvantage of causing a decrease in activity.
本発明の目的は、上記した従来技術の欠点をなくシ、コ
ークス炉ガスに含まれるジエン類、酸素、オレフィン類
及び硫黄化合物をコークス炉ガス中の水素で水添して精
製する新しい方法を提供することにある。The purpose of the present invention is to eliminate the above-mentioned drawbacks of the prior art and provide a new method for purifying dienes, oxygen, olefins, and sulfur compounds contained in coke oven gas by hydrogenating them with hydrogen in coke oven gas. It's about doing.
本発明を概説すれば、本発明は、不純物としてジエン類
、酸素、オレフィン類及び硫黄化合物を含有するコーク
ス炉ガスを、該コークス炉ガス中の水素で水添して精製
する方法において、主にジエン類と酸素とを接触水添す
る第１工程及び残存したオレフィン類と硫黄化合物とを
接触水添する第２工程を包含することを特徴とするガス
の精製方法に関する。To summarize the present invention, the present invention mainly provides a method for purifying coke oven gas containing dienes, oxygen, olefins, and sulfur compounds as impurities by hydrogenating the coke oven gas with hydrogen in the coke oven gas. The present invention relates to a gas purification method comprising a first step of catalytically hydrogenating dienes and oxygen and a second step of catalytically hydrogenating remaining olefins and a sulfur compound.
本発明者らはコークス炉ガス中に含まれるジエン類が重
合してガム状物質を生成し、触媒層及び触媒層前段の配
管機器を閉そくしたシ、触媒活性を低下させたシするこ
とを実験により確認した。The present inventors conducted an experiment in which the dienes contained in coke oven gas polymerized to form a gummy substance, which blocked the catalyst layer and the piping equipment in front of the catalyst layer, and reduced the catalyst activity. Confirmed by.
この重合物の生成を防ぐために、オレフィン類と硫黄化
合物を水添する工程の前に低温域でジエン類と酸素を水
添処理する工程を設けたところ、オレフィン類と硫黄化
合物の水添触媒の活性低下も非常に小さくなることを確
認し、本発明に至った。In order to prevent the formation of this polymer, we installed a process to hydrogenate dienes and oxygen at a low temperature before the process of hydrogenating olefins and sulfur compounds. It was confirmed that the decrease in activity was also very small, leading to the present invention.
本発明の主にジエン類と酸素とを接触水添する第１工程
に使用する触媒としては、ニッケル及び／又はコバルト
を含む触媒、あるいは白金族金属を含む触媒を使用する
ことが好ましい。これらの触媒はジエン類の選択水添性
能が画期的に優れているものである。As the catalyst used in the first step of catalytically hydrogenating dienes and oxygen in the present invention, it is preferable to use a catalyst containing nickel and/or cobalt, or a catalyst containing a platinum group metal. These catalysts have revolutionary superior performance for selective hydrogenation of dienes.
また、オレフィン類と硫黄化合物を水添する第２工程に
は、ニッケル及び／又はコバルトとモリブデンとを含む
触媒を用いるのが好適である。例を挙げれば、ＮＩＯＭ
ｏｏｎ 、 ｋｔ２０ｓ 、Ｃｏ０−Ｍ ｏ Ｏｓ
ＡＬｚ Ｏｓなどであり、通常使用に際しては還元され
る。また水添脱硫活性を高めるために硫化してから使用
することが多い。Further, in the second step of hydrogenating olefins and sulfur compounds, it is preferable to use a catalyst containing nickel and/or cobalt and molybdenum. For example, NIOM
oon, kt20s, Co0-M o Os
ALzOs, etc., and is reduced during normal use. In addition, it is often used after being sulfurized to increase the hydrodesulfurization activity.
第１工程における選択水添反応の温度は１００〜４５０
Ｃが好ましい。更に好ましくは１５０〜３５０Ｃである
。４５０Ｃを超えるとオレフィンの水添反応及びＣ０１
ＣＯ２のメタネーション反応の進行が大きく触媒層の温
度上昇が大きくなり、触媒の半融現象をひき起こす。１
００Ｃ未満では選択水添活性が充分でなく、ジエン類が
第１工程から第２工程に流出する。コークス炉ガスの供
給速度は空間速度で５００〜５０．０００１１−”が好
ましい。空間速度が５００ ｈ −１未満では使用する
触媒量が多くなって経済的でなくなり、一方５０．００
０３１−１を超えると水添活性が充分でなくなる。圧力
は２〜１００気圧で良いが特に限定されない。The temperature of the selective hydrogenation reaction in the first step is 100-450
C is preferred. More preferably it is 150-350C. If it exceeds 450C, olefin hydrogenation reaction and C01
The progress of the methanation reaction of CO2 is large, and the temperature rise of the catalyst layer becomes large, causing a half-melting phenomenon of the catalyst. 1
If the temperature is less than 00C, the selective hydrogenation activity will not be sufficient and dienes will flow from the first step to the second step. The coke oven gas supply rate is preferably 500 to 50.00011-'' in terms of space velocity.If the space velocity is less than 500 h-1, the amount of catalyst to be used increases, making it uneconomical;
If it exceeds 031-1, the hydrogenation activity will not be sufficient. The pressure may be 2 to 100 atmospheres, but is not particularly limited.
第２工程におけろ水添脱硫反応を行う温度は２５０〜５
００Ｃが好ましく、更に好ましくは３００〜４５０Ｃで
ある。５００Ｃを超えると炭化水素の分解による炭素析
出のトラブルを招くことが１７．２５０ｔｌｌ’未満で
は水添脱硫活性が充分でない。ガスの供給速度は空間速
度で５００〜５０．０００ｈ−１の範囲が好ましい。水
添脱硫後の硫化水素の除去方法としては公知の方法がい
ずれも使用されうる。例を挙げれば、ＺｎＯ１Ｆｅ２０
３、ＣｕＯ％活性炭などの固体吸着剤を使用する方法で
ある。The temperature at which the hydrodesulfurization reaction is carried out in the second step is 250-5
00C is preferred, and more preferably 300-450C. If it exceeds 500C, troubles such as carbon precipitation due to decomposition of hydrocarbons will occur, and if it is less than 17.250tll', the hydrodesulfurization activity will not be sufficient. The gas supply rate is preferably in the range of 500 to 50,000 h-1 in terms of space velocity. Any known method can be used to remove hydrogen sulfide after hydrodesulfurization. For example, ZnO1Fe20
3. A method using a solid adsorbent such as CuO% activated carbon.
本発明においては、このようにして精製されたコークス
炉ガスの一部を第１工程の前段に循環する工程を含んで
もよい。ガスを循環することによ乞
シ第１工程の選択水添反応の温度制御が容易に行うこと
ができるという効果がある。この時のガスの循環量は原
料コークス炉ガスの１０〜１０００％の範囲にあること
が好ましい。循環するガス量としては第１工程の温度を
３５０Ｃ以下に抑えるような範囲が選ばれ、ガス量が調
節される。The present invention may include a step of circulating a part of the coke oven gas purified in this way to a stage before the first step. Circulating the gas has the effect that the temperature of the selective hydrogenation reaction in the first step can be easily controlled. The amount of gas circulated at this time is preferably in the range of 10 to 1000% of the raw coke oven gas. The amount of gas to be circulated is selected within a range that keeps the temperature in the first step below 350C, and the amount of gas is adjusted.
次に本発明を実施するためのプロセスを図面によって具
体的に説明する。すなわち第１図は、本発明の一実施の
態様を示す工程図であり、１はコークス炉ガス、２は第
１水添塔、３は加熱炉、４は第２水添塔、５は硫化水素
吸収塔そして６は精製ガスを意味する。また、第２図は
、本発明において、精製ガスの一部を第１水添塔の前段
に循環を行う場合の一実施の態様を示す工程図であり、
１〜６は第１図と同義であり、７は精製ガス循環ライン
を意味する。図面は本発明を理解するために必要な主要
部のみを含み、本発明を理解するのに必要のない冷却器
、昇圧器、制御装置及びその他の装置は簡単にするため
に省略しである。Next, a process for carrying out the present invention will be specifically explained with reference to the drawings. That is, FIG. 1 is a process diagram showing an embodiment of the present invention, in which 1 is a coke oven gas, 2 is a first hydrogenation tower, 3 is a heating furnace, 4 is a second hydrogenation tower, and 5 is a sulfiding tower. Hydrogen absorption tower and 6 means purified gas. Further, FIG. 2 is a process diagram showing an embodiment of the present invention in which a part of the purified gas is circulated to the front stage of the first hydrogenation column,
1 to 6 have the same meanings as in FIG. 1, and 7 means a purified gas circulation line. The drawings include only main parts necessary for understanding the present invention, and coolers, boosters, control devices, and other devices that are not necessary for understanding the present invention are omitted for the sake of simplicity.
次に本発明を実施例により更に具体的に説明するが、本
発明はこれにより限定されない。Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.
実施例１
第１図においてコークス炉ガス１の主な成分の組成は、
Ｈ２５３，２５チ、Ｃ０５，８９チ、ｃｏ、 ２．２０
饅、ＣＨ４３０，６７％、Ｃ２Ｈ４１，６０チ、ＣａＨ
ａ １．６０チ、０２０．５０慢、Ｃ４Ｈ，０，１０チ
、硫黄化合物０．０１％、Ｎ２４−１８チなどである。Example 1 In FIG. 1, the composition of the main components of coke oven gas 1 is as follows:
H253, 25chi, C05,89chi, co, 2.20
Steamed rice, CH430, 67%, C2H41, 60chi, CaH
a 1.60%, 020.50%, C4H, 0.10%, sulfur compound 0.01%, N24-18%, etc.
コークス炉排ガス１は約１５０〜２００Ｃの温度で第１
水添塔２に導入される。ニッケル１５重量係、残りアル
ミナよりなる選択水添触媒により、コークス炉ガス中の
ジエン類、酸素、オレフィン類、硫黄化金物のうち、主
にジエン類と酸素を選択的に水添処理する効果を有する
。第１水添塔出口の主な成分のガス組成は、Ｈｘ ５３
．５２％、ＣＯ５，９２％、ＣＯ２２，２１条、ＣＨ４
３０，８２％、Ｃ２Ｈ４１，６１％、Ｃａ Ｈａ １．
６１％、Ｃ４ＨＩＯ０，１％、硫黄化合物ｏ、ｏｉ％
、Ｎ ２４．２０％である。上記ガスは約１９０〜２４
０Ｃの温度で次の加熱炉３に導入され、約２５０〜３５
０Ｃの温度に加熱される。加熱後のコークス炉ガスは第
２水添塔４に導入される。コバルト３重量％、モリブデ
ン１４重量％、残りアルミナよりなる水添触媒により、
コークス炉ガス中のオレフィン類はパラフィン類に転化
され、硫黄化合物は硫化水素に転化される。第２水添塔
４出口の主な成分のガス組成は、Ｎｚ５３．５２％、Ｃ
０５，９２％ 、ＣＯ２２，２１％、ＣＨ４３０，８２
％、Ｃ，Ｈ，１，６１％、ＣａＨｅ １．６１ ％ 、
Ｃ４Ｈ１００，１０％、Ｎ２４．２０％、Ｈｚ ８０．
０１％であり、上記生成ガスは約３００〜４０００の温
度で第２水添塔を出る。第２水添塔を出たガスは第２水
添塔４出口のガス温度を維持しながら、硫化水素吸収塔
５に導入される。硫化水素吸収塔５ではガス中の硫化水
素が吸着除去される。かくして精製された精製ガス６の
主な成分の組成は、Ｈ２５３，５３％、ＣＯ５，９２チ
、ＣＯ２２−２１％、ＣＨ４３０，８２チ、Ｃ２Ｈ６１
，６１％、ＣａＨｓ １．６１％、Ｃ４Ｈｔｏ ０．１
％、Ｎｚ４．２０％となる。The coke oven exhaust gas 1 is at a temperature of about 150-200C.
It is introduced into the hydrogenation tower 2. A selective hydrogenation catalyst consisting of 15 parts by weight of nickel and the rest alumina has the effect of selectively hydrogenating mainly dienes and oxygen among dienes, oxygen, olefins, and sulfurized metals in coke oven gas. have The gas composition of the main components at the outlet of the first hydrogenation tower is Hx 53
．． 52%, CO5, 92%, CO22, 21st article, CH4
30.82%, C2H41.61%, Ca Ha 1.
61%, C4HIO0,1%, sulfur compounds o, oi%
, N 24.20%. The above gas is about 190~24
It is introduced into the next heating furnace 3 at a temperature of 0C, about 250-35
It is heated to a temperature of 0C. The coke oven gas after heating is introduced into the second hydrogenation tower 4. With a hydrogenation catalyst consisting of 3% by weight of cobalt, 14% by weight of molybdenum, and the remainder alumina,
Olefins in the coke oven gas are converted to paraffins, and sulfur compounds are converted to hydrogen sulfide. The gas composition of the main components at the outlet of the second hydrogenation tower 4 is Nz53.52%, C
05.92%, CO22.21%, CH430.82
%, C, H, 1.61%, CaHe 1.61%,
C4H100, 10%, N24.20%, Hz 80.
01%, and the product gas leaves the second hydrogenation column at a temperature of about 300-4000°C. The gas exiting the second hydrogenation tower is introduced into the hydrogen sulfide absorption tower 5 while maintaining the gas temperature at the outlet of the second hydrogenation tower 4. In the hydrogen sulfide absorption tower 5, hydrogen sulfide in the gas is adsorbed and removed. The composition of the main components of the purified gas 6 thus purified is: H253.53%, CO5.92%, CO22-21%, CH430.82%, C2H61
,61%, CaHs 1.61%, C4Hto 0.1
%, Nz 4.20%.
第２図に示した精製ガスの一部を第１水添塔の前段に循
環する場合においても、先の実施例と同様に効率良くコ
ークス炉ガスの精製が行われる。Even in the case where a part of the purified gas shown in FIG. 2 is circulated upstream of the first hydrogenation column, the coke oven gas is efficiently purified as in the previous embodiment.
実施例２（運転初期段階）
第１図において実施例１と同一成分を有するコークス炉
ガス１は約１５０〜２００Ｃの温度で第コークス炉ガス
中のジエン類、酸素、オレフィン類、硫黄化合物のうち
、主にジエン類、酸素およびオレフィン類を選択的に水
添処理する。第１水添塔出口の主な成分のガス組成は、
Ｈ２５３，５２％、ＣＯ５゜９２％、ＣＯｚ ２．２１
％、ＣＨ４３０，８２％、Ｃ２Ｈ６１，６１％、ＣｓＨ
６１，６１％、Ｃ４Ｈ１００，１％、硫黄化合物０．０
１％、Ｎ２４．２（１ｑ６である。上記ガスは２４０〜
２９０Ｃの温度で次の加熱炉３に導入され、約２５０〜
３５０Ｃの温度に加熱される。加熱後のコークス炉ガス
は第２水添塔４に導入される。コバルト３重量％、モリ
ブデン１４重量％、アルミナ８３重量％よりなる水添触
媒により、コークス炉ガス中の硫黄化合物は硫化水素に
転化される。第２水添塔４出口の主な成分のガス組成は
、Ｎｚ５３．５２％、ＣＯ５，９２チ、ＣＯ２２，２１
チ、ＣＨ４３０，８２％、Ｃ２Ｈ６１，６１チ、ＣａＨ
ｓ １．６１％、Ｃ４Ｈ１００，１０％、Ｎ２４．２０
％、Ｈ２ＳＯ，０１チであり、上記生成ガスは約３００
〜４００ｔ：’の温度で第２水添塔を出る。第２水添塔
を出たガスは第２水添塔４出口のガス温度を維持しなが
ら、硫化水素吸収塔５に導入される。硫化水素吸収塔５
ではガス中の硫化水素が吸着除去される。かくして精製
された精製ガス６の主な成分の組成は、Ｎｚ５３．５３
％、Ｃ０５，９２ｑ６、Ｃ０２２，２１チ、ＣＨ４３０
，８２チ、Ｃ２Ｈ６１，６１チ、Ｃ３Ｈｓ １．６１チ
、Ｃ４Ｈ１Ｇ ０．１％、Ｎ２４．２０％となる。Example 2 (initial stage of operation) In FIG. 1, a coke oven gas 1 having the same components as in Example 1 is heated at a temperature of about 150 to 200C to remove dienes, oxygen, olefins, and sulfur compounds from the coke oven gas. , selectively hydrogenating mainly dienes, oxygen and olefins. The gas composition of the main components at the outlet of the first hydrogenation tower is:
H253,52%, CO5°92%, COz 2.21
%, CH430,82%, C2H61,61%, CsH
61.61%, C4H100.1%, sulfur compound 0.0
1%, N24.2 (1q6. The above gas is 240~
It is introduced into the next heating furnace 3 at a temperature of 290C, and about 250~
Heated to a temperature of 350C. The coke oven gas after heating is introduced into the second hydrogenation tower 4. Sulfur compounds in the coke oven gas are converted to hydrogen sulfide by a hydrogenation catalyst consisting of 3% by weight of cobalt, 14% by weight of molybdenum, and 83% by weight of alumina. The gas composition of the main components at the outlet of the second hydrogenation tower 4 is 53.52% Nz, 5.92% CO, and 22.21% CO2.
CH430,82%, C2H61,61CH, CaH
s 1.61%, C4H100,10%, N24.20
%, H2SO, 01%, and the above generated gas is about 300%
It leaves the second hydrogenation column at a temperature of ~400t:'. The gas exiting the second hydrogenation tower is introduced into the hydrogen sulfide absorption tower 5 while maintaining the gas temperature at the outlet of the second hydrogenation tower 4. Hydrogen sulfide absorption tower 5
The hydrogen sulfide in the gas is adsorbed and removed. The composition of the main components of the purified gas 6 thus purified is Nz53.53
%, C05,92q6, C022,21chi, CH430
, 82chi, C2H61,61chi, C3Hs 1.61chi, C4H1G 0.1%, and N24.20%.
第２図に示した精製ガスの一部を第１水添塔の前段に循
環する場合においても、先の実施例と同様に効率良くコ
ークス炉ガスの精製が行われる。Even in the case where a part of the purified gas shown in FIG. 2 is circulated upstream of the first hydrogenation column, the coke oven gas is efficiently purified as in the previous embodiment.
実施例３（運転開始から４０００時間経過後）第１図に
おいて実施例１と同一成分を有するコークス炉ガス１は
約１５０〜２００ｃの温度で第チ、アルミナが９９゜５
−よりなる水添触媒により、コークス炉ガス中のジエン
類、酸素、オレフィン類、硫黄化合物のうち、主にジエ
ン類、酸素およびオレフィン類を選択的に水添処理する
。第１水添塔出口の主な成分のガス組成は、Ｈ２５３，
５２％、Ｃ０５，９２％、ＣＯ２２，２１％、ＣＨ４３
０，８２％、Ｃ＊Ｈ４０，３２％、Ｃ２Ｈ６１，２９％
、Ｃｓ Ｈ６０，３２％、Ｃ５Ｈｓ １．２９％、Ｃ４
Ｈｔｏ ０．１ ％、硫黄化合物０．０１チ、Ｎｚ ４
．２０ ％である。上記ガスは２４０〜２９０Ｃの温度
で次の加熱炉３に導入され、約２５０〜３５０Ｃの温度
に加熱される。加熱後のコークス炉ガスは第２水添塔４
に導入される。コバルト３重量％、モリブデン１４重量
％、アルミナ８３重量％よりなる水添触媒によシ、コー
クス炉ガス中の残存オレフィン類及び硫黄化合物は硫化
水素に転化される。第２水添塔４出口の主な成分のガス
組成は、Ｈ２５３，５２％、ＣＯ５，９２％、Ｃ０２２
，２１チ、ＣＨ４３０，８２チ、Ｃ，Ｈ，１，６１チ、
Ｃ，ｓＨｓ １．６１％、Ｃ４ＨＩＤ ０．１０ ’％
、Ｎ２４．２０％、ＨｚＳｏ、０１％であシ、上記生
成ガスは約３００〜４００Ｃの温度で第２水添塔を出る
。第２水添塔を出たガスは第２水添塔４出口のガス温度
を維持しながら、硫化水素吸収塔５に導入される。硫化
水素吸収塔５ではガス中の硫化水素が吸着除去される。Example 3 (After 4000 hours from the start of operation) In FIG. 1, coke oven gas 1 having the same components as in Example 1 was heated at a temperature of about 150 to 200°C, and alumina was 99°5.
Among dienes, oxygen, olefins, and sulfur compounds in coke oven gas, mainly dienes, oxygen, and olefins are selectively hydrogenated using a hydrogenation catalyst consisting of -. The gas composition of the main components at the outlet of the first hydrogenation tower is H253,
52%, CO5, 92%, CO22, 21%, CH43
0.82%, C*H40.32%, C2H61.29%
, Cs H60, 32%, C5Hs 1.29%, C4
Hto 0.1%, sulfur compound 0.01%, Nz 4
．． 20%. The gas is introduced into the next heating furnace 3 at a temperature of 240-290C and heated to a temperature of about 250-350C. The coke oven gas after heating is sent to the second hydrogenation tower 4.
will be introduced in Residual olefins and sulfur compounds in the coke oven gas are converted to hydrogen sulfide by a hydrogenation catalyst consisting of 3% by weight of cobalt, 14% by weight of molybdenum, and 83% by weight of alumina. The gas composition of the main components at the outlet of the second hydrogenation tower 4 is H253, 52%, CO5, 92%, CO22
,21chi,CH430,82chi,C,H,1,61chi,
C,sHs 1.61%, C4HID 0.10'%
, N24.20%, HzSo, 01% and the above product gas exits the second hydrogenation tower at a temperature of about 300-400C. The gas exiting the second hydrogenation tower is introduced into the hydrogen sulfide absorption tower 5 while maintaining the gas temperature at the outlet of the second hydrogenation tower 4. In the hydrogen sulfide absorption tower 5, hydrogen sulfide in the gas is adsorbed and removed.
かくして精製された精製ガス６の主な成分の組成は、Ｈ
２５３，５３％ 、ＣＯ５，９２％、ＣＯｘ ２．２１
チ、ＣＨ，３０，８２％、Ｃ２Ｈａ １．６１％、０３
Ｈｓ１．６１％、Ｃ４Ｈ１００，１％、Ｎ２４．２０％
となる。The composition of the main components of the purified gas 6 thus purified is H
253.53%, CO5.92%, COx 2.21
CH, CH, 30,82%, C2Ha 1.61%, 03
Hs1.61%, C4H100.1%, N24.20%
becomes.
第２図に示した精製ガスの一部を第１水添塔の前段に循
環する場合においても、先の実施例と同様に効率良くコ
ークス炉ガスの精製が行われる。Even in the case where a part of the purified gas shown in FIG. 2 is circulated upstream of the first hydrogenation column, the coke oven gas is efficiently purified as in the previous embodiment.
以上詳細な説明から明らかなように、本発明にヨレハ、
コークス炉ガスに含まれるジエン類、酸素、オレフィン
類、硫黄化合物のうち、まず、選択水添触媒を用いた第
１工程により、低温で主にジエン類と酸素を選択的に水
添し、第２工程で残存したオレフィン類と硫黄化合物を
水添できるので、ジエン類重合によるガム状物質の生成
を抑制し、効率良くコークス炉ガスの精製ができるとい
う顕著な効果を持っている。As is clear from the above detailed description, the present invention includes
Among the dienes, oxygen, olefins, and sulfur compounds contained in coke oven gas, the first step is to selectively hydrogenate mainly dienes and oxygen at low temperature using a selective hydrogenation catalyst. Since remaining olefins and sulfur compounds can be hydrogenated in two steps, it has the remarkable effect of suppressing the formation of gummy substances due to diene polymerization and efficiently purifying coke oven gas.
第１図は本発明の一実施の態様を示す工程図、第２図は
本発明において、精製ガスの一部の循環を行う場合の一
実施の態様を示す工程図である。
１・・・コークス炉ガス、２・・・第１水添塔出炉、４
・・・第２水添塔、５・・・硫化水素吸収塔、６・・・
精製ガス、７・・・精製ガス循環ライン。
（
第１頁の続き
■出 願 人 株式会社日立製作所
東京都千代田区丸の内−丁目５
番１号
＝６４１−FIG. 1 is a process diagram showing an embodiment of the present invention, and FIG. 2 is a process diagram showing an embodiment of the present invention in which part of the purified gas is circulated. 1... Coke oven gas, 2... First hydrogenation tower discharge, 4
...Second hydrogenation tower, 5...Hydrogen sulfide absorption tower, 6...
Purified gas, 7... Purified gas circulation line. (Continued from page 1 ■Applicant: Hitachi, Ltd. No. 1-5 Marunouchi, Chiyoda-ku, Tokyo = 641-
Claims (1)
黄化合物を含有するコークス炉ガスを、該コークス炉ガ
ス中の水素で水添して精製する方法において、主にジエ
ン類と酸素とを接触水添する第１工程及び残存したオレ
フィン類と硫黄化合物とを接触水添する第２工程を包含
することを特徴とするガスの精製方法。 ２、第１工程に使用する触媒が、ニッケル及び／又はコ
バルトを含有する触媒、あるいは白金族金属を含有する
触媒である特許請求の範囲第１項記載のガスの精製方法
。 ３、第２工程に使用する触媒が、ニッケル及び／又はコ
バルトと、モリブデンとを含有する触媒である特許請求
の範囲第１項記載のガスの精製方法。 ４、第１水添工程の入口温度を１００〜２３０Ｃの範囲
内の温度とすることを特徴とする特許請求の範囲第１項
又は第２項記載のガスの精製方法。 ５、精製ガスの一部を第１工程の前段に循環する特許請
求の範囲第１項記載のガスの精製方法。 ６、ガスの循環量が、原料コークス炉ガスの１０〜１０
００％である特許請求の範囲第４項又は第５項記載のガ
スの精製方法。 ７、ガスの循環量を、第１工程の温度が３５０Ｃ以下及
び第２水添工程の出口温度が４５０Ｃを超えないように
維持されるように調節する特許請求の範囲第５項記載の
ガスの精製方法。[Claims] 1. A method for purifying coke oven gas containing dienes, oxygen, olefins, and sulfur compounds as impurities by hydrogenating it with hydrogen in the coke oven gas, which mainly contains dienes and sulfur compounds. A method for purifying gas, comprising a first step of catalytic hydrogenation with oxygen and a second step of catalytic hydrogenation of remaining olefins and a sulfur compound. 2. The gas purification method according to claim 1, wherein the catalyst used in the first step is a catalyst containing nickel and/or cobalt, or a catalyst containing a platinum group metal. 3. The method for purifying gas according to claim 1, wherein the catalyst used in the second step is a catalyst containing nickel and/or cobalt and molybdenum. 4. The gas purification method according to claim 1 or 2, characterized in that the inlet temperature of the first hydrogenation step is within the range of 100 to 230C. 5. The gas purification method according to claim 1, wherein a part of the purified gas is circulated before the first step. 6. The gas circulation amount is 10 to 10 of the raw material coke oven gas.
00% of the gas purification method according to claim 4 or 5. 7. The gas circulation amount according to claim 5 is adjusted so that the temperature in the first step is maintained at 350C or less and the outlet temperature in the second hydrogenation step does not exceed 450C. Purification method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10412783A JPS59230090A (en) | 1983-06-13 | 1983-06-13 | Purification of gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10412783A JPS59230090A (en) | 1983-06-13 | 1983-06-13 | Purification of gas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS59230090A true JPS59230090A (en) | 1984-12-24 |
Family
ID=14372448
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10412783A Pending JPS59230090A (en) | 1983-06-13 | 1983-06-13 | Purification of gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59230090A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6189294A (en) * | 1984-10-09 | 1986-05-07 | Kawasaki Steel Corp | Method of purifying coke oven gas |
| WO2008126242A1 (en) * | 2007-03-30 | 2008-10-23 | Kawasaki Plant Systems Kabushiki Kaisha | Gum-like substance monitoring apparatus and detecting method and gas turbine equipment |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5339302A (en) * | 1976-09-23 | 1978-04-11 | Conoco Methanation Co | Process for converting organic sulfur compounds to hydrogen sulfide |
| JPS5812318A (en) * | 1981-07-16 | 1983-01-24 | ティーディーケイ株式会社 | Chip condenser |
-
1983
- 1983-06-13 JP JP10412783A patent/JPS59230090A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5339302A (en) * | 1976-09-23 | 1978-04-11 | Conoco Methanation Co | Process for converting organic sulfur compounds to hydrogen sulfide |
| JPS5812318A (en) * | 1981-07-16 | 1983-01-24 | ティーディーケイ株式会社 | Chip condenser |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6189294A (en) * | 1984-10-09 | 1986-05-07 | Kawasaki Steel Corp | Method of purifying coke oven gas |
| JPH0349960B2 (en) * | 1984-10-09 | 1991-07-31 | Kawasaki Seitetsu Kk | |
| WO2008126242A1 (en) * | 2007-03-30 | 2008-10-23 | Kawasaki Plant Systems Kabushiki Kaisha | Gum-like substance monitoring apparatus and detecting method and gas turbine equipment |
| US8499620B2 (en) | 2007-03-30 | 2013-08-06 | Kawasaki Jukogyo Kabushiki Kaisha | Gum substance monitoring apparatus, gum substance detecting method, and gas turbine system |
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