JPH0716609B2 - Regeneration method of spent desulfurization agent in coal gasification gas desulfurization - Google Patents
Regeneration method of spent desulfurization agent in coal gasification gas desulfurizationInfo
- Publication number
- JPH0716609B2 JPH0716609B2 JP1080973A JP8097389A JPH0716609B2 JP H0716609 B2 JPH0716609 B2 JP H0716609B2 JP 1080973 A JP1080973 A JP 1080973A JP 8097389 A JP8097389 A JP 8097389A JP H0716609 B2 JPH0716609 B2 JP H0716609B2
- Authority
- JP
- Japan
- Prior art keywords
- gas
- regeneration reactor
- desulfurization
- oxygen
- coal gasification
- 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.)
- Expired - Lifetime
Links
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- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、石炭ガス化ガスのように硫化水素を含有する
ガスの脱硫に用いた使用済脱硫剤を再生する方法に関す
るものである。TECHNICAL FIELD The present invention relates to a method for regenerating a spent desulfurizing agent used for desulfurizing a gas containing hydrogen sulfide such as coal gasification gas.
従来、石炭ガス化ガスの脱硫方法として、特開昭60−18
582号公報に示されるように、通気性支持体間に粒塊状
の鉄鉱石（Fe2O3が主成分）からなる脱硫剤を充填した
層に、石炭ガス化ガスを通過させて、下記の反応式によ
り脱硫を行う方法が知られている。Conventionally, as a desulfurization method of coal gasification gas, JP-A-60-18
As disclosed in Japanese Patent No. 582, coal gasification gas is allowed to pass through a layer in which a desulfurizing agent composed of agglomerated iron ore (mainly Fe 2 O 3 ) is filled between air-permeable supports, and A method of performing desulfurization by a reaction formula is known.
３Fe2O3＋H2→２Fe3O4＋H2O （１） Fe3O4＋３H2S＋H2→3FeS＋４H2O （２） また、同公報に示されるように、使用済の脱硫剤の層
に、空気、酸素などの酸化剤を供給して、下記の反応式
により酸化鉄に再生する方法が知られている。3Fe 2 O 3 + H 2 → 2Fe 3 O 4 + H 2 O (1) Fe 3 O 4 + 3H 2 S + H 2 → 3FeS + 4H 2 O (2) Also, as shown in the same publication, in the layer of the used desulfurizing agent. A method is known in which an oxidizing agent such as air, oxygen or the like is supplied and iron oxide is regenerated by the following reaction formula.
2FeS＋7/2O2→Fe2O3＋２SO2 （３） 〔発明が解決しようとする課題〕 上記のように、使用済脱硫剤は、酸化雰囲気で吸着した
硫黄分をSO2の形で脱離させることによって、再生させ
ることができる。しかし、脱硫剤再生反応は、通常、発
熱反応であり、使用済脱硫剤と酸化剤とをワンスルーで
接触させる従来方法では、反応速度が大きすぎて、再生
反応器内で局部的な異常温度上昇が生じ、脱硫剤の劣化
や強度低下を招くため、不活性ガス等で酸化剤を希釈し
て再生反応器に供給していた。2FeS + 7 / 2O 2 → Fe 2 O 3 + 2SO 2 (3) [Problems to be solved by the invention] As described above, the spent desulfurization agent desorbs the sulfur content adsorbed in the oxidizing atmosphere in the form of SO 2 . It can be played back. However, the desulfurization agent regeneration reaction is usually an exothermic reaction, and the conventional method in which the used desulfurization agent and the oxidant are brought into contact with each other in a one-through manner causes the reaction rate to be too high, resulting in a local abnormal temperature rise in the regeneration reactor. Therefore, the desulfurizing agent is deteriorated and the strength thereof is lowered. Therefore, the oxidizing agent was diluted with an inert gas or the like and supplied to the regeneration reactor.
本発明は上記の点に鑑みなされたもので、脱硫剤再生過
程において、再生反応器出口ガスのうち、一部を抜き出
してSO2処理工程に送り、残部を再生反応器入口に循環
させることにより、再生反応器内の温度制御を行うこと
ができ、かつ、酸化剤すなわち酸素含有気体の予熱が不
要で、しかも系外に抜き出すSO2含有ガスはSO2が濃縮さ
れているので、SO2後処理工程のコンパクト化を図るこ
とができる石炭ガス化ガス脱硫における使用済脱硫剤の
再生方法を提供することを目的とするものである。The present invention has been made in view of the above points, by extracting a part of the regeneration reactor outlet gas in the desulfurization agent regeneration process and sending it to the SO 2 treatment step, and circulating the remainder to the regeneration reactor inlet. , regeneration reactor temperature control can be performed in, and requires no preheating of the oxidizing agent i.e. oxygen-containing gas, and since sO 2 containing gas withdrawn from the system is sO 2 are concentrated, after sO 2 It is an object of the present invention to provide a method for regenerating a used desulfurizing agent in coal gasification gas desulfurization, which can achieve a compact treatment process.
上記の目的を達成するために、本発明の石炭ガス化ガス
脱硫における使用済脱硫剤の再生方法は、脱硫反応に用
いた使用済脱硫剤を再生反応器で酸素含有気体により酸
化・再生する方法において、再生反応器後流のSO2を含
むガスの一部を系外に抜き出し、再生反応器後流のSO2
を含むガスの残部を再生反応器上流側に循環するととも
に、この循環ガス中に酸素含有気体を供給し、再生反応
器内部の温度を検出しこの温度検出値で酸素含有気体の
流量を調節して再生反応器内部温度を一定範囲内に制御
し、さらに、再生反応器出口のガス圧力を検出しこの圧
力検出値で循環ガス流量を調節して再生反応器および循
環ラインの圧力を一定範囲内に制御するものである。In order to achieve the above object, the method for regenerating a used desulfurizing agent in the coal gasification gas desulfurization of the present invention is a method of oxidizing and regenerating a used desulfurizing agent used in a desulfurization reaction with an oxygen-containing gas in a regeneration reactor in extracts a portion of the gas containing SO 2 regeneration reactor downstream from the system, the regeneration reactor slipstream SO 2
The rest of the gas containing is circulated to the upstream side of the regeneration reactor, and the oxygen-containing gas is supplied into this circulation gas, the temperature inside the regeneration reactor is detected, and the flow rate of the oxygen-containing gas is adjusted by this temperature detection value. Control the internal temperature of the regeneration reactor within a certain range, detect the gas pressure at the outlet of the regeneration reactor, and adjust the circulation gas flow rate by this pressure detection value to adjust the pressure of the regeneration reactor and the circulation line within a certain range. To control.
以下、第１図に基づいて詳細に説明する。１は再生反応
器で、脱硫反応に寄与した使用済脱硫剤を移動床または
固定床に充填して用いられる。この再生反応器１の後流
のSO2を含むガスの一部を系外に抜き出し、再生反応器
１後流のSO2を含むガスの残部を、循環コンプレッサー
２を備えた循環ライン３により、再生反応器１上流側に
循環する。この循環ライン３に酸素含有気体供給管４を
接続している。５はスタートアップ用熱風炉、６は流量
指示調節器、７は圧力指示調節器、８、９は制御弁であ
る。系外に抜き出されるSO2を含むガスは、循環によりS
O2が濃縮されてSO2リッチガスとなり、他の用途に供さ
れる。Hereinafter, a detailed description will be given with reference to FIG. A regeneration reactor 1 is used by filling a moving bed or a fixed bed with the spent desulfurizing agent that has contributed to the desulfurization reaction. A part of the gas containing SO 2 in the downstream of the regeneration reactor 1 is extracted to the outside of the system, and the remaining gas containing SO 2 in the downstream of the regeneration reactor 1 is circulated by a circulation line 3 equipped with a circulation compressor 2. It circulates on the upstream side of the regeneration reactor 1. An oxygen-containing gas supply pipe 4 is connected to the circulation line 3. Reference numeral 5 is a hot-air stove for start-up, 6 is a flow rate indicator controller, 7 is a pressure indicator controller, and 8 and 9 are control valves. The SO 2 -containing gas extracted outside the system is circulated by S
O 2 is concentrated to SO 2 rich gas, which is used for other purposes.
本発明の方法において、酸素含有気体としては、空気、
酸素、酸素富化空気などが用いられる。また、脱硫剤と
しては、鉄、亜鉛などを含む鉱物そのもの、それらを成
型したもの、他に担体にこれらの金属を担持したもの、
または担体成分と金属成分とを混合した後、焼成したも
のなどが用いられる。In the method of the present invention, the oxygen-containing gas is air,
Oxygen, oxygen-enriched air, etc. are used. Further, as the desulfurizing agent, minerals themselves containing iron, zinc, etc., those molded of them, other those supporting these metals on a carrier,
Alternatively, a mixture obtained by mixing the carrier component and the metal component and then firing the mixture is used.
また、循環ガスの流量を調節するために、再生反応器内
部の温度を検出して、酸素含有気体供給ラインの流量指
示調節器６を制御し、温度が設定値より上昇した場合
は、酸素含有気体供給量を減少させ、逆に温度が低下し
た場合は、酸素含有気体供給量を増加させることによっ
て、再生反応器内部温度の制御を行う。Further, in order to adjust the flow rate of the circulating gas, the temperature inside the regeneration reactor is detected and the flow rate instruction controller 6 of the oxygen-containing gas supply line is controlled. When the gas supply amount is decreased, and conversely the temperature decreases, the oxygen-containing gas supply amount is increased to control the internal temperature of the regeneration reactor.
酸素含有気体供給量を変えても再生反応器および循環ラ
インの圧力を変動させないために、SO2リッチ抜出量を
コントロールして循環ガス流量を調節する。このため、
再生反応器出口のガス圧力を検出して、圧力指示調節器
７でSO2リッチガス抜出ラインの制御弁９を制御する。In order not to change the pressure in the regeneration reactor and the circulation line even when the oxygen-containing gas supply amount is changed, the SO 2 rich withdrawal amount is controlled to adjust the circulation gas flow rate. For this reason,
The gas pressure at the outlet of the regeneration reactor is detected, and the pressure indicating controller 7 controls the control valve 9 of the SO 2 rich gas extraction line.
以下、本発明の実施例を挙げて説明する。 Examples of the present invention will be described below.
実施例１ 使用済の酸化鉄系脱硫剤の再生を、酸素含有気体として
空気を用いて第１図に示すフローに従って行った。Example 1 The used iron oxide-based desulfurizing agent was regenerated by using air as an oxygen-containing gas according to the flow shown in FIG.
処理脱硫剤（使用済脱硫剤）の組成は、Fe3O482wt％、F
eS6wt％、残SiO2、Al2O3、処理量は100Kg/hrであった。
また、空気は常温で46Nm3/hr（水分5.0vol％）を供給
し、循環ラインの循環量は180Nm3/hrであり、再生反応
器の温度は743℃±８℃に保持した。The composition of the treated desulfurization agent (used desulfurization agent) is Fe 3 O 4 82wt%, F
eS 6 wt%, residual SiO 2 , Al 2 O 3 , and treatment amount was 100 Kg / hr.
Further, as the air, 46 Nm 3 / hr (water content: 5.0 vol%) was supplied at room temperature, the circulation rate of the circulation line was 180 Nm 3 / hr, and the temperature of the regeneration reactor was maintained at 743 ° C. ± 8 ° C.
処理後の脱硫剤（再生脱硫剤）の組成は、Fe2O3 98wt
％、Fe2O3＜1wt％、FeS＜0.1wt％であり、排出量は98.6
Kg/hrであった。また系外へ抜き出す排出ガス量は41Nm3
/hrで、その組成は、SO2 10.0vol％、H2O 5.6vol％、H2
S＜2000ppmであった。The composition of the desulfurizing agent (regenerated desulfurizing agent) after treatment is Fe 2 O 3 98wt
%, Fe 2 O 3 <1wt%, FeS <0.1wt%, emission amount is 98.6
It was Kg / hr. The amount of exhaust gas extracted from the system is 41 Nm 3
/ hr, the composition is SO 2 10.0vol%, H 2 O 5.6vol%, H 2
It was S <2000ppm.
上記の通り、ほぼ安定して脱硫剤を再生することができ
た。As described above, the desulfurizing agent could be regenerated almost stably.
本発明は上記のように構成されているので、つぎのよう
な効果を奏する。Since the present invention is configured as described above, it has the following effects.
（１）再生ガスを循環し、その循環量によって、ガス中
の酸素濃度を調節することができ、また過剰な循環ガス
を流すことによって、熱拡散が促進されるので、再生反
応器内の温度制御を行うことができる。さらに、再生反
応器内部の温度を検出しこの温度検出値で酸素含有気体
の流量を調節することにより、より確実に再生反応内部
温度を一定範囲内に制御することができ、かつ、再生反
応器出口のガス圧力を検出しこの圧力検出値で循環ガス
流量を調節することにより、再生反応器および循環ライ
ンの圧力を一定範囲内に制御することができる。(1) Circulating a regeneration gas, the oxygen concentration in the gas can be adjusted by the amount of the circulation, and flowing an excessive amount of the circulation gas promotes thermal diffusion. Control can be performed. Further, by detecting the temperature inside the regeneration reactor and adjusting the flow rate of the oxygen-containing gas with this temperature detection value, the internal temperature of the regeneration reaction can be controlled more reliably within a certain range, and the regeneration reactor can be controlled. By detecting the gas pressure at the outlet and adjusting the circulating gas flow rate with this pressure detection value, the pressure in the regeneration reactor and the circulation line can be controlled within a certain range.
（２）再生反応は、一定温度以上でなければ進行しない
が、余熱を有する再生ガスを循環することにより、供給
する酸素含有気体の予熱が不要となる。(2) The regeneration reaction does not proceed unless the temperature is equal to or higher than a certain temperature, but preheating of the oxygen-containing gas to be supplied becomes unnecessary by circulating the regeneration gas having residual heat.
（３）再生反応器で生成したSO2は循環ガス中に蓄積さ
れ、濃縮されてから後処理工程に送られるので、SO2後
処理工程がコンパクトになり、かつ、効率的に処理され
る。(3) Since the SO 2 produced in the regeneration reactor is accumulated in the circulating gas, concentrated and then sent to the post-treatment process, the SO 2 post-treatment process becomes compact and is efficiently treated.
第１図は本発明の石炭ガス化ガス脱硫における使用済脱
硫剤の再生方法を実施する装置の一例を示すフローシー
トである。 １…再生反応器、２…循環コンプレッサー、３…循環ラ
イン、４…酸素含有気体供給管、５…スタートアップ用
熱風炉、６…流量指示調節器、７…圧力指示調節器、
８、９…制御弁FIG. 1 is a flow sheet showing an example of an apparatus for carrying out a method for regenerating a used desulfurizing agent in coal gasification gas desulfurization according to the present invention. DESCRIPTION OF SYMBOLS 1 ... Regeneration reactor, 2 ... Circulation compressor, 3 ... Circulation line, 4 ... Oxygen-containing gas supply pipe, 5 ... Hot-air stove for start-up, 6 ... Flow rate indicator regulator, 7 ... Pressure indicator regulator,
8, 9 ... Control valve
Claims (1)
脱硫剤を再生反応器で酸素含有気体により酸化・再生す
る方法において、再生反応器後流のSO2を含むガスの一
部を系外に抜き出し、再生反応器後流のSO2を含むガス
の残部を再生反応器上流側に循環するとともに、この循
環ガス中に酸素含有気体を供給し、再生反応器内部の温
度を検出しこの温度検出値で酸素含有気体の流量を調節
して再生反応器内部温度を一定範囲内に制御し、さら
に、再生反応器出口のガス圧力を検出しこの圧力検出値
で循環ガス流量を調節して再生反応器および循環ライン
の圧力を一定範囲内に制御することを特徴とする石炭ガ
ス化ガス脱硫における使用済脱硫剤の再生方法。1. A method of oxidizing and regenerating a spent desulfurizing agent used in a desulfurization reaction of coal gasification gas with an oxygen-containing gas in a regeneration reactor, wherein a part of a gas containing SO 2 in the downstream of the regeneration reactor is It is extracted to the outside of the system, and the rest of the gas containing SO 2 in the downstream of the regeneration reactor is circulated to the upstream side of the regeneration reactor, and an oxygen-containing gas is supplied into this circulating gas to detect the temperature inside the regeneration reactor. The temperature detection value is used to control the flow rate of the oxygen-containing gas to control the internal temperature of the regeneration reactor within a certain range.Furthermore, the gas pressure at the outlet of the regeneration reactor is detected, and the circulation gas flow rate is adjusted with this pressure detection value. A method for regenerating a used desulfurization agent in coal gasification gas desulfurization, which comprises controlling the pressure of a regeneration reactor and a circulation line within a certain range.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1080973A JPH0716609B2 (en) | 1989-03-30 | 1989-03-30 | Regeneration method of spent desulfurization agent in coal gasification gas desulfurization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1080973A JPH0716609B2 (en) | 1989-03-30 | 1989-03-30 | Regeneration method of spent desulfurization agent in coal gasification gas desulfurization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02258059A JPH02258059A (en) | 1990-10-18 |
| JPH0716609B2 true JPH0716609B2 (en) | 1995-03-01 |
Family
ID=13733457
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1080973A Expired - Lifetime JPH0716609B2 (en) | 1989-03-30 | 1989-03-30 | Regeneration method of spent desulfurization agent in coal gasification gas desulfurization |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0716609B2 (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5929285B2 (en) * | 1976-03-24 | 1984-07-19 | バブコツク日立株式会社 | Sulfur recovery equipment tail gas purification method |
-
1989
- 1989-03-30 JP JP1080973A patent/JPH0716609B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02258059A (en) | 1990-10-18 |
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