JPH05117669A - Apparatus for purifying high-temperature reducing gas - Google Patents
Apparatus for purifying high-temperature reducing gasInfo
- Publication number
- JPH05117669A JPH05117669A JP3284784A JP28478491A JPH05117669A JP H05117669 A JPH05117669 A JP H05117669A JP 3284784 A JP3284784 A JP 3284784A JP 28478491 A JP28478491 A JP 28478491A JP H05117669 A JPH05117669 A JP H05117669A
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- JP
- Japan
- Prior art keywords
- gas
- regeneration
- reaction tower
- pipe
- reaction
- 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.)
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は高温還元性ガス、例え
ば、石炭ガス化プロセスの生成ガス等に含まれる硫化水
素、硫化カルボニル等の硫黄化合物を除去するための精
製装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a refining apparatus for removing a high temperature reducing gas, for example, a sulfur compound such as hydrogen sulfide or carbonyl sulfide contained in a product gas of a coal gasification process.
【０００２】[0002]
【従来の技術】近年、石油資源の枯渇、価格の高騰から
燃料又は原料の多様化が要請され、石炭や重質油（ター
ルサンド油、オイルシェール油、大慶原油、マヤ油ある
いは減圧残油など）の利用技術の開発が進められてい
る。しかし、このガス化生成ガスには原料の石炭や重質
油によって異なるが、数１００〜数１０００ｐｐｍの硫
化水素（Ｈ2 Ｓ）、硫化カルボニル（ＣＯＳ）等の硫黄
化合物を含み、公害防止上あるいは後流機器の腐食防止
のために除去する必要がある。この除去方法としては乾
式法が熱経済的にも有利で、プロセス構成も簡素なこと
から金属酸化物を主成分とする吸収剤を高温で硫化物に
して吸収除去する方法が一般的になっている。2. Description of the Related Art In recent years, due to exhaustion of petroleum resources and soaring prices, diversification of fuels or raw materials has been demanded. ) Is being developed. However, this gasification product gas contains sulfur compounds such as hydrogen sulfide (H 2 S) and carbonyl sulfide (COS) of several hundred to several thousand ppm, though it depends on the raw material coal or heavy oil. Must be removed to prevent corrosion of downstream equipment. As a method for removing this, a dry method is also advantageous in terms of thermo-economics, and since the process configuration is simple, a method of absorbing and removing a sulfide containing a metal oxide as a main component at a high temperature has become common. There is.
【０００３】吸収剤としてはＦｅ，Ｚｎ，Ｃｕ，Ｍｏ，
Ｗなどの金属酸化物が使用され、２５０〜５００℃で硫
化水素や硫化カルボニルと反応させる。以下、Ｆｅ3 Ｏ
4 吸収剤を用いてＨ2 Ｓを除去する場合を例に説明する
と、吸収反応は下記（１）及び（２）式に示すように進
むとされている。 Ｆｅ3 Ｏ4 ＋Ｈ2 ＋３Ｈ2 Ｓ→３ＦｅＳ＋４Ｈ2 Ｏ ・・・（１） Ｆｅ3 Ｏ4 ＋ＣＯ＋３Ｈ2 Ｓ→３ＦｅＳ＋３Ｈ2 Ｏ＋ＣＯ2 ・・・（２）As the absorbent, Fe, Zn, Cu, Mo,
A metal oxide such as W is used and is reacted with hydrogen sulfide or carbonyl sulfide at 250 to 500 ° C. Below, Fe 3 O
4 In the case of removing H 2 S using an absorbent, the absorption reaction is said to proceed as shown in the following formulas (1) and (2). Fe 3 O 4 + H 2 + 3H 2 S → 3FeS + 4H 2 O ... (1) Fe 3 O 4 + CO + 3H 2 S → 3FeS + 3H 2 O + CO 2 ... (2)
【０００４】次いで、吸収反応後の吸収剤は酸素含有ガ
スで下記（３）式に示すように反応して金属酸化物（Ｆ
ｅ2 Ｏ3 ）に再生され、高温還元性ガス中の硫黄化合物
はＳＯ2 ガスとして回収除去される。なお、未反応のＦ
ｅ3 Ｏ4 吸収剤は酸素含有ガスで下記（４）式に示すよ
うに反応して金属酸化物（Ｆｅ3 Ｏ4 ）に再生される。 ４ＦｅＳ＋７Ｏ2 →３Ｆｅ2 Ｏ3 ＋ＳＯ2 ・・・（３） Ｆｅ3 Ｏ4 ＋１／４Ｏ2 →３／２Ｆｅ2 Ｏ3 ・・・（４）Then, the absorbent after the absorption reaction reacts with an oxygen-containing gas as shown in the following formula (3) to react with the metal oxide (F
e 2 O 3 ) and the sulfur compounds in the high-temperature reducing gas are recovered and removed as SO 2 gas. In addition, unreacted F
The e 3 O 4 absorbent reacts with an oxygen-containing gas as shown in the following formula (4) to be regenerated into a metal oxide (Fe 3 O 4 ). 4FeS + 7O 2 → 3Fe 2 O 3 + SO 2 ... (3) Fe 3 O 4 + 1 / 4O 2 → 3 / 2Fe 2 O 3 ... (4)
【０００５】さらに再生反応後、Ｈ2 ，ＣＯ等の還元性
ガスを通すことにより、吸収剤は下記（５）及び（６）
式に示すように元のＦｅ3 Ｏ4 に変化する。このように
吸収反応、再生反応、還元反応を繰り返すことにより、
金属酸化物（Ｆｅ2 Ｏ3 ）を有効に利用して高温還元性
ガスから硫化物を除去することができる。 ３Ｆｅ2 Ｏ3 ＋Ｈ2 →２Ｆｅ3 Ｏ4 ＋Ｈ2 Ｏ ・・・（５） ３Ｆｅ2 Ｏ3 ＋ＣＯ→２Ｆｅ3 Ｏ4 ＋ＣＯ2 ・・・（６） このプロセスで使用される吸収剤は上記の金属酸化物を
単独で、あるいは耐熱性の多孔質物質に担持したものを
球状、円柱状、ハニカム状に成形したものが通常使用さ
れる。Further, after the regeneration reaction, a reducing gas such as H 2 or CO is passed through to make the absorbent into the following (5) and (6)
As shown in the formula, the original Fe 3 O 4 is changed. By repeating the absorption reaction, regeneration reaction, and reduction reaction in this way,
The sulfide can be removed from the high-temperature reducing gas by effectively utilizing the metal oxide (Fe 2 O 3 ). 3Fe 2 O 3 + H 2 → 2Fe 3 O 4 + H 2 O (5) 3Fe 2 O 3 + CO → 2Fe 3 O 4 + CO 2 (6) The absorbent used in this process is the above metal. The oxide is used alone, or one obtained by supporting a heat-resistant porous material into a spherical, columnar or honeycomb shape is usually used.
【０００６】次に、従来装置について図２〜図５を用い
て説明する。図２は反応塔１が吸収工程、反応塔２が還
元工程、反応塔３が再生工程にそれぞれ置かれた段階に
おける高温還元性ガスの精製装置のプロセスフローを示
した図であり、図３は反応塔１，２，３の配管とバルブ
の総ての関係を示した図であって、白抜きバルブは開放
を黒塗りバルブは閉鎖した状態を示しており、図２に対
応した状態を示したものである。図４は３つの反応塔が
吸収工程、再生工程、還元工程に切換えるサイクルのタ
イムチャートを示した図、図５は図３の総てのバルブの
開閉状態を経時的に示した図である。Next, a conventional device will be described with reference to FIGS. FIG. 2 is a diagram showing a process flow of the refining apparatus for high temperature reducing gas at a stage where the reaction tower 1 is placed in the absorption step, the reaction tower 2 is placed in the reduction step, and the reaction tower 3 is placed in the regeneration step. [Fig. 3] Fig. 3 is a diagram showing the relationship between all of the pipes and valves of the reaction towers 1, 2 and 3, wherein the open valves are open and the black valves are closed, and the state corresponding to Fig. 2 is shown. It is a thing. FIG. 4 is a diagram showing a time chart of a cycle in which three reaction towers are switched to an absorption process, a regeneration process, and a reduction process, and FIG. 5 is a diagram showing open / closed states of all the valves in FIG. 3 with time.
【０００７】処理を受ける高温還元性ガスは配管１０及
び配管４４を介して吸収工程の反応塔１に流入され、反
応塔１内に充填された吸収剤（Ｆｅ3 Ｏ4 ）１００と接
触して上記（１）及び（２）式の反応により、被処理ガ
ス中の硫化物が吸収除去され、精製ガスは配管４５及び
配管１１を介して回収され、例えば燃料等として後続機
器のタービン等に送られる。また、精製ガスの一部は配
管４５から分岐された配管１３を介して還元工程の反応
塔２に導入され、精製ガス中の還元性成分（Ｈ2 ，Ｃ
Ｏ）と再生工程を経た吸収剤（Ｆｅ2 Ｏ3 ）とを反応さ
せて上記（５）及び（６）式の反応により、吸収剤はＦ
ｅ3 Ｏ4 に還元される。その際、反応塔２に接続される
配管１３に流量検出調節計３０及びバルブ３１を設置す
ることにより、反応塔２に供給される精製ガスの流量を
所定の一定量に制御することができる。The high-temperature reducing gas to be treated is introduced into the reaction tower 1 in the absorption step through the pipe 10 and the pipe 44, and comes into contact with the absorbent (Fe 3 O 4 ) 100 filled in the reaction tower 1. By the reactions of the above formulas (1) and (2), sulfides in the gas to be treated are absorbed and removed, and the purified gas is recovered through the pipe 45 and the pipe 11 and sent to a turbine or the like of a subsequent device as fuel or the like. Be done. Further, a part of the purified gas is introduced into the reaction tower 2 in the reduction step via the pipe 13 branched from the pipe 45, and the reducing component (H 2 , C in the purified gas is contained.
O) and the absorbent (Fe 2 O 3 ) which has undergone the regeneration step are reacted to react with the above formulas (5) and (6), whereby the absorbent is F
It is reduced to e 3 O 4 . At this time, by installing the flow rate detection controller 30 and the valve 31 in the pipe 13 connected to the reaction tower 2, the flow rate of the purified gas supplied to the reaction tower 2 can be controlled to a predetermined fixed amount.
【０００８】他方、再生工程にある反応塔３には配管２
３，２４，２５及び１５を介して酸素含有ガスが導入さ
れ、前記（３）式により吸収剤に吸収されている硫黄成
分（ＦｅＳ）と酸素とを反応させてＳＯ2 ガスを発生さ
せるとともに、吸収剤はＦｅＳからＦｅ2 Ｏ3 に再生さ
れる。On the other hand, a pipe 2 is installed in the reaction tower 3 in the regeneration process.
An oxygen-containing gas is introduced via 3, 24, 25 and 15, and the sulfur component (FeS) absorbed in the absorbent by the formula (3) is reacted with oxygen to generate SO 2 gas, The absorbent is regenerated from FeS to Fe 2 O 3 .
【０００９】再生された吸収剤は上記の還元工程に移さ
れＦｅ3 Ｏ4 まで還元される。還元工程の反応塔２及び
再生工程の反応塔３からの排出ガスは配管１２，１４及
び１６を介して一体化され、再生工程で酸化反応熱で高
温となった排出ガスは熱交換器４で上記酸素含有ガスと
熱交換して冷却され、さらに配管１７を介して冷却器５
に送られる。その際、被処理ガスの流入配管１０を分岐
した配管２７を上記配管１７に接続して被処理ガスの一
部を上記排出ガスに添加する。この被処理ガスの添加量
はガス流量検出調節計３２でバルブ３３を操作して制御
される。そして、該排出ガスは冷却器５において配管２
８に供給される冷媒で冷却され、さらに配管１８を介し
て還元反応器６に導入され、還元触媒１０１と接触して
下記（７）及び（８）式のように反応して単体硫黄Ｓｘ
を生成する。還元反応器６内の温度は前記（７）及び
（８）式の反応が進み易い温度（例えば２５０℃）にな
るように、温度検出調節計３４と冷却器５の冷媒流量を
操作するバルブ３５によって制御される。 ＳＯ2 ＋２Ｈ2 →（１／ｘ）Ｓｘ＋２Ｈ2 Ｏ（ｘ＝２〜８）・・・（７） ＳＯ2 ＋２ＣＯ→（１／ｘ）Ｓｘ＋２ＣＯ2 （ｘ＝２〜８）・・・（８）The regenerated absorbent is transferred to the above reduction step and reduced to Fe 3 O 4 . The exhaust gas from the reaction tower 2 of the reduction process and the reaction tower 3 of the regeneration process are integrated via the pipes 12, 14 and 16, and the exhaust gas which has become high temperature due to the heat of oxidation reaction in the regeneration process is transferred to the heat exchanger 4. It is cooled by exchanging heat with the oxygen-containing gas, and is further cooled through the pipe 17 to the cooler 5.
Sent to. At that time, a pipe 27 branched from the inflow pipe 10 for the gas to be treated is connected to the pipe 17 to add a part of the gas to be treated to the exhaust gas. The addition amount of the gas to be processed is controlled by operating the valve 33 with the gas flow rate detection controller 32. Then, the exhaust gas is supplied to the pipe 2 in the cooler 5.
It is cooled by the refrigerant supplied to 8 and is further introduced into the reduction reactor 6 through the pipe 18, and comes into contact with the reduction catalyst 101 to react as in the following formulas (7) and (8) to react with elemental sulfur Sx.
To generate. A valve 35 for controlling the flow rate of the refrigerant in the temperature detection controller 34 and the cooler 5 so that the temperature in the reduction reactor 6 becomes a temperature (for example, 250 ° C.) in which the reactions of the above equations (7) and (8) easily proceed. Controlled by. SO 2 + 2H 2 → (1 / x) Sx + 2H 2 O (x = 2 to 8) (7) SO 2 + 2CO → (1 / x) Sx + 2CO 2 (x = 2 to 8) (8)
【００１０】還元反応器６から配管１９を介して流出し
た単体硫黄の蒸気を含むガスは冷却器７で配管２９で供
給される冷媒により冷却され、配管２０を介してコンデ
ンサー８に導入され、液状の単体硫黄として配管７７に
より回収される。その際、コンデンサー８内の温度は硫
黄の凝縮温度以下になるように温度検出調節計３６と冷
却器７の冷媒流量を操作するバルブ３７によって制御さ
れる。The gas containing the vapor of elemental sulfur flowing out from the reduction reactor 6 through the pipe 19 is cooled by the refrigerant supplied through the pipe 29 in the cooler 7, introduced into the condenser 8 through the pipe 20, and is in the liquid state. Is recovered by the pipe 77 as the elemental sulfur. At this time, the temperature inside the condenser 8 is controlled by the temperature detection controller 36 and the valve 37 that controls the flow rate of the refrigerant in the cooler 7 so that the temperature becomes equal to or lower than the condensation temperature of sulfur.
【００１１】一方、コンデンサー８で硫黄を除いた不活
性ガス（主成分Ｎ2）は配管２１を介して循環ブロワ９
に入り、配管２１に設置したバルブ３９と流量検出調節
計３８によって循環流量は一定に制御される。この不活
性ガスは循環ブロワ９から配管２２及び２４を介し、配
管２３からの空気又は酸素と一体化されて上記熱交換器
４に入り加熱される。On the other hand, the inert gas (main component N 2 ) from which sulfur has been removed by the condenser 8 is circulated through the pipe 21 to the circulation blower 9
Then, the circulation flow rate is controlled to be constant by the valve 39 and the flow rate detection controller 38 installed in the pipe 21. This inert gas is integrated with the air or oxygen from the pipe 23 from the circulation blower 9 via the pipes 22 and 24, and enters the heat exchanger 4 where it is heated.
【００１２】配管２４内の酸素濃度は酸素濃度検出調節
計４０とバルブ４１によって所定の値に制御される。か
かる酸素含有ガスは熱交換器４によって加熱され、配管
２５及び１５を介して再生工程の反応器３に入る。The oxygen concentration in the pipe 24 is controlled to a predetermined value by the oxygen concentration detection controller 40 and the valve 41. The oxygen-containing gas is heated by the heat exchanger 4 and enters the reactor 3 in the regeneration process via the pipes 25 and 15.
【００１３】また、配管２２の不活性ガスの一部は配管
２６を介して被処理ガス導入用配管１０に接続され合流
される。そして、配管２６にはバルブ４３が設置されて
おり、循環ブロワ９の圧力が一定になるように圧力検出
調節計４２で制御される。Further, a part of the inert gas in the pipe 22 is connected to the processing gas introducing pipe 10 via the pipe 26 and merges. A valve 43 is installed in the pipe 26 and is controlled by the pressure detection controller 42 so that the pressure of the circulation blower 9 becomes constant.
【００１４】吸収工程をある時間続けると、吸収剤のＦ
ｅ3 Ｏ4は．全量ＦｅＳに変化するため、反応器１から
硫化物が流出するようになる。そこで、硫化物が流出す
る以前に、図３に示したバルブ６１，６４，６８，７
０，７５を閉鎖し、バルブ６２，６３，６９，７１，７
３を開放することにより、反応器１を吸収工程から再生
工程に、反応器２を還元工程から吸収工程に、反応器３
を再生工程から還元工程に移行させる。If the absorption process is continued for a certain period of time, the F
e 3 O 4 is. Since the total amount is changed to FeS, the sulfide comes to flow out from the reactor 1. Therefore, before the sulfide flows out, the valves 61, 64, 68, 7 shown in FIG.
0, 75 closed, valves 62, 63, 69, 71, 7
By opening 3, reactor 1 from the absorption step to the regeneration step, reactor 2 from the reduction step to the absorption step, reactor 3
Is transferred from the regeneration step to the reduction step.
【００１５】図４は各工程の持続時間を４時間として、
各反応器の切換えの状況を示したもので、図５は図４に
対応して図３中のバルブ６１〜７５の開閉状態を示した
ものである。このように３つの反応器を順次切換えるこ
とにより、還元性ガスの脱硫精製を連続的に行うもので
ある。In FIG. 4, the duration of each process is 4 hours,
FIG. 5 shows the switching state of each reactor, and FIG. 5 shows the opened / closed state of the valves 61 to 75 in FIG. 3 corresponding to FIG. By sequentially switching the three reactors in this manner, desulfurization purification of the reducing gas is continuously performed.
【００１６】[0016]
【発明が解決しようとする課題】上記の精製装置では再
生工程にある反応器３に送りこまれる再生ガスはバルブ
４１で一定Ｏ2 濃度に、またバルブ３９で一定流量とな
るよう制御されている。この精製装置は一般的に石炭ガ
ス化複合発電用であり、石炭ガス化複合発電所はベース
ロード電力供給ではなく負荷変動時の調節用と考えられ
ている。このことはガス化炉から配管１０を通して該装
置に流入する高温還元性ガスの流量が変動し、吸収工程
で吸収される硫黄の量が変動することを意味する。In the above refining apparatus, the regeneration gas sent to the reactor 3 in the regeneration step is controlled by the valve 41 so as to have a constant O 2 concentration and the valve 39 so as to have a constant flow rate. This refiner is generally for integrated coal gasification combined cycle power generation, and it is considered that the integrated coal gasification combined cycle power plant is not for base load power supply but for adjustment during load changes. This means that the flow rate of the high-temperature reducing gas flowing from the gasification furnace through the pipe 10 into the apparatus fluctuates, and the amount of sulfur absorbed in the absorption step fluctuates.
【００１７】再生工程では前記再生反応（３）式によ
り、吸収した硫黄分をＳＯ2 ガスとして回収するもの
で、吸収した硫黄分の変動に関係なく、一定流量、一定
酸素濃度の再生ガスを供給することによって吸収剤の再
生不良や余分なＯ2 ガスが配管１４−１７−１８を通し
て還元反応器６に流入し還元反応器触媒１０１の劣化を
発生させることになっていた。In the regeneration step, the absorbed sulfur content is recovered as SO 2 gas by the above-mentioned regeneration reaction (3). Regardless of the fluctuation of the absorbed sulfur content, the regeneration gas having a constant flow rate and a constant oxygen concentration is supplied. As a result, defective regeneration of the absorbent and excess O 2 gas flow into the reduction reactor 6 through the pipes 14-17-18 to cause deterioration of the reduction reactor catalyst 101.
【００１８】そこで、本発明では、上記の精製装置の欠
点を解消し、吸収剤の再生を確実に行うこと、また還元
反応器内触媒の劣化を防止することのできる高温還元性
ガスの精製装置を提供しようとするものである。Therefore, in the present invention, the refining apparatus for high temperature reducing gas which can solve the above-mentioned drawbacks of the refining apparatus, surely regenerate the absorbent, and prevent the catalyst in the reduction reactor from deteriorating. Is to provide.
【００１９】[0019]
【課題を解決するための手段】本発明は高温還元性ガス
中の硫黄化合物を吸収する吸収剤を充填した少なくとも
３つの反応塔と、該反応塔に被処理ガス、酸素含有再生
ガス並びに高純度還元性ガスを供給及び排出する配管を
バルブを介して接続し、該バルブの開閉により上記反応
塔を吸収工程、再生工程並びに還元工程に順次変更可能
とし、再生工程における反応塔に再生ガスを供給する再
生ガス循環ラインの配管に酸素濃度検出調節計と該調節
計の出力信号で操作される空気又は酸素流量調節バルブ
とを備えた高温還元性ガスの精製装置において、吸収工
程における反応塔に高温還元性ガスを供給及び排出する
配管に硫黄化合物ガス濃度検出器を設置し、該検出器の
検出信号を入力して減算をする減算器、該減算器の出力
信号と高温還元性ガス供給配管に設置したガス流量検出
器の検出信号を入力して乗算を行う乗算器、該乗算器の
出力信号を入力して還元工程から吸収工程に切換えた直
後から再生工程に切換えるまでの積算を行う積算器およ
び反応塔の吸収工程から再生工程切換時、該積算器の出
力信号を入力して設定値を出力する関数発生器を設け、
該関数発生器からの出力信号を再生ガス循環ラインの配
管に設けた酸素濃度検出調節計の設定値として入力し、
空気又は酸素ガス流量調節バルブを調節し、再生工程に
ある反応塔への再生ガスの酸素濃度を制御可能としたこ
とを特徴とする高温還元性ガスの精製装置である。The present invention is directed to at least three reaction columns filled with an absorbent for absorbing a sulfur compound in a high-temperature reducing gas, and the reaction columns to be treated gas, oxygen-containing regenerated gas and high purity. A pipe for supplying and discharging a reducing gas is connected through a valve, and by opening and closing the valve, the reaction tower can be sequentially changed to an absorption step, a regeneration step and a reduction step, and the regeneration gas is supplied to the reaction tower in the regeneration step. In a refining apparatus for a high temperature reducing gas equipped with an oxygen concentration detection controller in a pipe of a regeneration gas circulation line and an air or oxygen flow rate control valve operated by an output signal of the controller, a high temperature is generated in a reaction tower in an absorption step. A sulfur compound gas concentration detector is installed in a pipe for supplying and discharging reducing gas, and a subtractor for inputting a detection signal of the detector to perform subtraction, an output signal of the subtractor and high temperature reducibility A multiplier that inputs the detection signal of the gas flow rate detector installed in the gas supply pipe and performs multiplication, and an integration of the output signal of the multiplier from immediately after switching from the reduction process to the absorption process until switching to the regeneration process A function generator that inputs the output signal of the integrator and outputs a set value when the regeneration process is switched from the absorption process of the integrator and the reaction tower to perform the
Input the output signal from the function generator as the set value of the oxygen concentration detection controller provided in the pipe of the regenerated gas circulation line,
This is a refining apparatus for high-temperature reducing gas, characterized in that the oxygen concentration of the regenerated gas to the reaction tower in the regeneration step can be controlled by adjusting the air or oxygen gas flow rate control valve.
【００２０】[0020]
【作用】本発明は再生工程の反応塔に供給する再生ガス
中の酸素濃度を吸収剤の再生に必要である最適な量に制
御することによって、吸収剤の再生不良や過剰Ｏ2 ガス
排出による還元反応器内触媒の劣化を防止しようとした
ものである。According to the present invention, by controlling the oxygen concentration in the regeneration gas supplied to the reaction column in the regeneration step to the optimum amount required for regeneration of the absorbent, it is possible to prevent defective regeneration of the absorbent and discharge of excess O 2 gas. It is intended to prevent deterioration of the catalyst in the reduction reactor.
【００２１】すなわち、吸収工程の反応塔へ供給される
ガスと排出されるガス中の硫黄化合物ガス濃度を検出す
ることにより吸収工程で反応塔吸収剤に吸収された硫黄
化合物の量を把握することにより、再生に必要な酸素ガ
ス濃度を算出し、適性な酸素濃度の再生ガス供給を行お
うとするものである。That is, the amount of the sulfur compound absorbed in the reaction tower absorbent in the absorption step is grasped by detecting the concentration of the sulfur compound gas in the gas supplied to and discharged from the reaction tower in the absorption step. According to the above, the oxygen gas concentration required for regeneration is calculated, and the regeneration gas is supplied with an appropriate oxygen concentration.
【００２２】具体的には、吸収工程にある反応塔に高温
還元性ガスを供給および排出する配管に硫黄化合物ガス
濃度検出器とガス流量検出器を設置し、該濃度検出器の
各検出信号を減算器に入力し、該減算器の出力信号とガ
ス流量検出器の検出信号を乗算器および積算器に入力す
る。Specifically, a sulfur compound gas concentration detector and a gas flow detector are installed in the pipe for supplying and discharging the high-temperature reducing gas to the reaction tower in the absorption step, and each detection signal of the concentration detector is detected. It is input to the subtractor, and the output signal of the subtractor and the detection signal of the gas flow rate detector are input to the multiplier and the integrator.
【００２３】吸収工程にある反応塔を再生工程に切換え
時、該積算器の出力信号を入力して酸素濃度設定値を出
力する関数発生器を設置し、該関数発生器の出力信号を
再生ガス循環ラインの配管に設けた酸素濃度検出調節計
の設定値として入力し、該配管の空気又は酸素ガス流量
調節バルブを作動させて、再生ガス中の酸素濃度を制御
可能にするものである。When the reaction tower in the absorption process is switched to the regeneration process, a function generator for inputting the output signal of the integrator and outputting the oxygen concentration set value is installed, and the output signal of the function generator is used as the regeneration gas. The oxygen concentration in the regeneration gas can be controlled by inputting it as a set value of an oxygen concentration detection controller provided in the piping of the circulation line and operating the air or oxygen gas flow rate control valve of the piping.
【００２４】[0024]
【実施例】本発明の実施例を図１を参照して説明する。
図１の装置は図２の従来装置において、吸収工程にある
反応塔１の入口配管４４と出口配管４５に硫黄化合物ガ
ス濃度検出器８２，８３を設置し、該検出器８２，８３
の検出信号を減算器８４に入力して硫黄化合物ガス入側
濃度と出側濃度の差を算出する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described with reference to FIG.
The apparatus of FIG. 1 is different from the conventional apparatus of FIG. 2 in that sulfur compound gas concentration detectors 82, 83 are installed in the inlet pipe 44 and the outlet pipe 45 of the reaction tower 1 in the absorption process.
Is input to the subtractor 84 to calculate the difference between the sulfur compound gas inlet side concentration and the outlet side concentration.
【００２５】該減算器８４の出力信号と反応塔１の入口
配管４４に設置したガス流量検出器８１の検出信号を乗
算器８５に入力し乗算を行い、反応塔１で吸収された硫
黄化合物ガス量を算出し、該乗算器８５の出力信号を入
力して還元工程から吸収工程に切換えた直後からの再生
工程に切換えるまでの積算を行う積算器８６に入力し、
積算を行う。The output signal of the subtractor 84 and the detection signal of the gas flow rate detector 81 installed in the inlet pipe 44 of the reaction tower 1 are input to the multiplier 85 for multiplication, and the sulfur compound gas absorbed in the reaction tower 1 is multiplied. The amount is calculated, and the output signal of the multiplier 85 is input to the integrator 86 that performs integration from immediately after switching from the reduction process to the absorption process until switching to the regeneration process,
Accumulate.
【００２６】反応塔が吸収工程から再生工程へ切換え時
該積算器８６出力信号を関数発生器８７に入力して設定
値を出力し、該出力信号を再生ガス供給ラインである配
管２４に設けた酸素濃度検出調節計４０に入力し、配管
２３の空気又は酸素ガス流量調節バルブ４１を調節して
再生ガス中の酸素濃度を制御する。再生循環ラインの配
管２１−２２−２４−２５を経て再生工程にある反応塔
に再生ガスが供給される。When the reaction tower switches from the absorption step to the regeneration step, the output signal of the integrator 86 is input to the function generator 87 to output the set value, and the output signal is provided in the pipe 24 which is the regeneration gas supply line. It is input to the oxygen concentration detection controller 40, and the oxygen concentration in the regeneration gas is controlled by adjusting the air or oxygen gas flow rate control valve 41 in the pipe 23. Regeneration gas is supplied to the reaction tower in the regeneration process via the piping 21-22-24-25 of the regeneration circulation line.
【００２７】図１では再生工程にある反応塔は反応塔３
である。酸素濃度検出調節計４０の設定値は反応塔３が
吸収工程で吸収した硫黄化合物ガス量から、再生工程切
換え時関数発生器８７で出力した信号を設定したもので
ある。すなわち、図１の装置は再生工程にある反応塔に
供給する再生ガス中の酸素濃度を制御するようにしたの
で、その他の装置構成は図３と差異はないので、その他
の装置構成については図２と同一の部材について、同一
の符号を付し説明を省略する。In FIG. 1, the reaction tower in the regeneration step is the reaction tower 3
Is. The setting value of the oxygen concentration detection controller 40 is set by the signal output from the function generator 87 at the time of switching the regeneration process from the amount of the sulfur compound gas absorbed by the reaction tower 3 in the absorption process. That is, since the apparatus of FIG. 1 is designed to control the oxygen concentration in the regeneration gas supplied to the reaction tower in the regeneration step, other apparatus configurations are the same as those of FIG. The same members as those in No. 2 are given the same reference numerals and the description thereof will be omitted.
【００２８】積算器８６の出力信号を入力して、再生ガ
ス中の酸素濃度設定値を出力する関数発生器８７に設定
する関数の一例を図６に示す。図６に示す関数は吸収硫
黄化合物ガス量に対して図４および図５のサイクルで各
操作を行うために、４時間で反応塔全体の再生反応を終
了できる再生ガスの酸素濃度を示すものである。図６の
Ｘ0 は吸収硫黄化合物ガス量ゼロの場合で反応塔内吸収
剤のＦｅ3 Ｏ4 を酸化するために必要な量｛前記（４）
式の反応に必要な酸素ガス量｝である。FIG. 6 shows an example of a function which is input to the output signal of the integrator 86 and is set in the function generator 87 which outputs the oxygen concentration set value in the regeneration gas. The function shown in FIG. 6 indicates the oxygen concentration of the regenerated gas that can complete the regeneration reaction of the entire reaction tower in 4 hours in order to carry out each operation in the cycles of FIGS. 4 and 5 with respect to the absorbed sulfur compound gas amount. is there. X 0 in FIG. 6 is the case where the amount of absorbed sulfur compound gas is zero, and the amount required to oxidize Fe 3 O 4 of the absorbent in the reaction tower {(4) above
The amount of oxygen gas required for the reaction in the formula}.
【００２９】[0029]
【発明の効果】本発明は上記の構成を採用することによ
り、吸収工程で吸収した硫黄分を検出して、再生工程の
反応塔に供給する再生ガス中の酸素濃度を吸収剤の再生
に必要である最適値に制御することによって、吸収剤の
再生不良や過剰Ｏ2 ガス排出で還元反応器内触媒の劣化
を防止することができる。According to the present invention, by adopting the above-mentioned constitution, the sulfur content absorbed in the absorption step is detected, and the oxygen concentration in the regeneration gas supplied to the reaction tower in the regeneration step is necessary for the regeneration of the absorbent. It is possible to prevent deterioration of the catalyst in the reduction reactor due to defective regeneration of the absorbent and discharge of excess O 2 gas by controlling the value to be the optimum value.
【図１】本発明の一実施例の精製装置のプロセスフロー
を示した図。FIG. 1 is a diagram showing a process flow of a refining apparatus according to an embodiment of the present invention.
【図２】従来のプロセスフローを示した図。FIG. 2 is a diagram showing a conventional process flow.
【図３】反応塔の配管とバルブの総ての関係を示した
図。FIG. 3 is a diagram showing the relationship between all the pipes and valves of the reaction tower.
【図４】３つの反応塔の各工程に切換えるサイクルタイ
ムチャートを示した図。FIG. 4 is a diagram showing a cycle time chart for switching to each process of three reaction towers.
【図５】図３の総てのバルブの開閉状態を経時的に示し
た図。FIG. 5 is a view showing the open / closed states of all the valves in FIG. 3 with time.
【図６】本発明の一実施例で関数発生器に設定する関数
の一具体例を示した図。FIG. 6 is a diagram showing a specific example of a function set in a function generator according to an embodiment of the present invention.
Claims (1)
る吸収剤を充填した少なくとも３つの反応塔と、該反応
塔に被処理ガス、酸素含有再生ガス並びに高純度還元性
ガスを供給及び排出する配管をバルブを介して接続し、
該バルブの開閉により上記反応塔を吸収工程、再生工程
並びに還元工程に順次変更可能とし、再生工程における
反応塔に再生ガスを供給する再生ガス循環ラインの配管
に酸素濃度検出調節計と該調節計の出力信号で操作され
る空気又は酸素流量調節バルブとを備えた高温還元性ガ
スの精製装置において、吸収工程における反応塔に高温
還元性ガスを供給及び排出する配管に硫黄化合物ガス濃
度検出器を設置し、該検出器の検出信号を入力して減算
をする減算器、該減算器の出力信号と高温還元性ガス供
給配管に設置したガス流量検出器の検出信号を入力して
乗算を行う乗算器、該乗算器の出力信号を入力して還元
工程から吸収工程に切換えた直後から再生工程に切換え
るまでの積算を行う積算器および反応塔の吸収工程から
再生工程切換時、該積算器の出力信号を入力して設定値
を出力する関数発生器を設け、該関数発生器からの出力
信号を再生ガス循環ラインの配管に設けた酸素濃度検出
調節計の設定値として入力し、空気又は酸素ガス流量調
節バルブを調節し、再生工程にある反応塔への再生ガス
の酸素濃度を制御可能としたことを特徴とする高温還元
性ガスの精製装置。1. At least three reaction towers filled with an absorbent that absorbs a sulfur compound in a high-temperature reducing gas, and a gas to be treated, an oxygen-containing regenerating gas, and a high-purity reducing gas are supplied to and discharged from the reaction towers. Connect the piping to be connected through the valve,
By opening and closing the valve, the reaction tower can be sequentially changed to an absorption step, a regeneration step, and a reduction step, and an oxygen concentration detection controller and the controller are installed in a pipe of a regeneration gas circulation line for supplying a regeneration gas to the reaction tower in the regeneration step. In a refining apparatus for a high temperature reducing gas equipped with an air or oxygen flow rate control valve operated by the output signal of a sulfur compound gas concentration detector in a pipe for supplying and discharging the high temperature reducing gas to the reaction tower in the absorption step. A subtractor that is installed and inputs the detection signal of the detector to perform subtraction, and a multiplication that inputs and multiplies the output signal of the subtractor and the detection signal of the gas flow rate detector installed in the high temperature reducing gas supply pipe When the output signal of the multiplier is input and the integrating process from immediately after switching from the reduction process to the absorption process until switching to the regeneration process and when the regeneration process is switched from the absorption process of the reaction tower, Provide a function generator that inputs the output signal of the integrator and outputs the set value, and input the output signal from the function generator as the set value of the oxygen concentration detection controller provided in the pipe of the regeneration gas circulation line, A refining apparatus for high-temperature reducing gas, characterized in that the oxygen concentration of the regenerated gas to the reaction tower in the regeneration step can be controlled by adjusting the air or oxygen gas flow rate control valve.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3284784A JP2891577B2 (en) | 1991-10-30 | 1991-10-30 | High-temperature reducing gas purification equipment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3284784A JP2891577B2 (en) | 1991-10-30 | 1991-10-30 | High-temperature reducing gas purification equipment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05117669A true JPH05117669A (en) | 1993-05-14 |
| JP2891577B2 JP2891577B2 (en) | 1999-05-17 |
Family
ID=17682977
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3284784A Expired - Lifetime JP2891577B2 (en) | 1991-10-30 | 1991-10-30 | High-temperature reducing gas purification equipment |
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| Country | Link |
|---|---|
| JP (1) | JP2891577B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101505163B1 (en) * | 2013-01-30 | 2015-03-23 | 현대제철 주식회사 | Apparatus for treating exhaust gas and method therof |
| JP2016187792A (en) * | 2015-03-30 | 2016-11-04 | 積水化学工業株式会社 | Gas purification method and device, and valuable generation method and device |
| WO2017047730A1 (en) * | 2015-09-17 | 2017-03-23 | 積水化学工業株式会社 | Gas treatment method |
| WO2017047731A1 (en) * | 2015-09-17 | 2017-03-23 | 積水化学工業株式会社 | Gas treatment method and apparatus |
| JP2020073252A (en) * | 2019-08-29 | 2020-05-14 | 積水化学工業株式会社 | Gas purification method and device, and valuable material production method and device |
-
1991
- 1991-10-30 JP JP3284784A patent/JP2891577B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101505163B1 (en) * | 2013-01-30 | 2015-03-23 | 현대제철 주식회사 | Apparatus for treating exhaust gas and method therof |
| JP2016187792A (en) * | 2015-03-30 | 2016-11-04 | 積水化学工業株式会社 | Gas purification method and device, and valuable generation method and device |
| WO2017047730A1 (en) * | 2015-09-17 | 2017-03-23 | 積水化学工業株式会社 | Gas treatment method |
| WO2017047731A1 (en) * | 2015-09-17 | 2017-03-23 | 積水化学工業株式会社 | Gas treatment method and apparatus |
| JPWO2017047730A1 (en) * | 2015-09-17 | 2018-07-05 | 積水化学工業株式会社 | Gas processing method |
| JPWO2017047731A1 (en) * | 2015-09-17 | 2018-07-05 | 積水化学工業株式会社 | Gas processing method and apparatus |
| US10786782B2 (en) | 2015-09-17 | 2020-09-29 | Sekisui Chemical Co., Ltd. | Gas treatment method |
| JP2020073252A (en) * | 2019-08-29 | 2020-05-14 | 積水化学工業株式会社 | Gas purification method and device, and valuable material production method and device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2891577B2 (en) | 1999-05-17 |
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