JPS5935654B2 - How to remove sulfur dioxide gas - Google Patents
How to remove sulfur dioxide gasInfo
- Publication number
- JPS5935654B2 JPS5935654B2 JP51155259A JP15525976A JPS5935654B2 JP S5935654 B2 JPS5935654 B2 JP S5935654B2 JP 51155259 A JP51155259 A JP 51155259A JP 15525976 A JP15525976 A JP 15525976A JP S5935654 B2 JPS5935654 B2 JP S5935654B2
- Authority
- JP
- Japan
- Prior art keywords
- gypsum
- liquid
- sulfur dioxide
- absorption
- dioxide 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.)
- Expired
Links
Landscapes
- Treating Waste Gases (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Description
【発明の詳細な説明】
本発明は硫黄酸化物(以下S02と記す)を含む排ガス
中のS02 を除去する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for removing S02 from exhaust gas containing sulfur oxides (hereinafter referred to as S02).
更に詳しくはスルホカルボン酸塩を含む水溶液を吸収液
としてSOxを吸収し、該SOxを石膏として取り出す
方法であり、この場合に吸収液中の溶存石膏に基づく吸
収塔内における付着物の発生を防止する方法である。More specifically, it is a method of absorbing SOx using an aqueous solution containing a sulfocarboxylate as an absorption liquid and extracting the SOx as gypsum.In this case, the generation of deposits in the absorption tower due to dissolved gypsum in the absorption liquid is prevented. This is the way to do it.
従来排ガス中のS02を湿式吸収して石膏として取り出
す方法としては、例えば亜硫曹−石膏法、石炭−石膏法
等が行なわれている。Conventional methods for wet-absorbing S02 in exhaust gas and extracting it as gypsum include, for example, the sulfite-gypsum method and the coal-gypsum method.
しがし亜硫曹石膏法においては、亜硫酸ナトリウムの一
部が排ガス中の炭素により酸化されて硫酸ナトリウムと
なり、吸収液中に蓄積して(るため、所謂脱芒工程を設
ける必要があり、工程が複雑になる。In the sulfite gypsum method, a portion of the sodium sulfite is oxidized by carbon in the exhaust gas and becomes sodium sulfate, which accumulates in the absorption liquid. The process becomes complicated.
また石灰石膏法においては亜硫曹石膏法におけるような
酸化による不都合は生じないが、SO2の吸収率が低い
ことや、スケールの発生が多いことなどから必らずしも
好ましい方法とは云えない。In addition, although the lime plaster method does not suffer from the disadvantages of oxidation that occur with the sulfurous gypsum method, it cannot necessarily be said to be a preferable method due to its low SO2 absorption rate and large scale formation. .
これらの欠点を解決した他の方法として酢酸、プロピオ
ン酸又は酪酸などの有機酸のアルカリ塩水溶液でSO□
を吸収する方法が提案されている。Another method that solves these drawbacks is SO
A method has been proposed to absorb
この方法におけるSO2吸収工程および石膏生成工程を
反応式で示すと以下のようである。The reaction formula for the SO2 absorption step and gypsum production step in this method is as follows.
S02吸収工程
RCOOM十SO2+H20→RCOOH+MH803
石膏生成工程
RCOOM+MH8O3+3A02→RCOOH十M2
SO42RCOOH+M2 SO4+Ca COs +
H20→2 RCOOM +Ca SO4・2 H2
0↓十co2↑(ここでMはNa、NH4を指しRはC
H3−1C2H6−1C3H7〜を指す)
有機酸アルカリ水溶液を用いる方法においては、亜硫曹
法と同様のS02吸収率を得ることができ、しかも亜硫
曹法の如く脱芒工程を必要としない。S02 absorption process RCOOM 10 SO2 + H20 → RCOOH + MH803
Gypsum generation process RCOOM+MH8O3+3A02→RCOOH1M2
SO42RCOOH+M2 SO4+Ca COs +
H20→2 RCOOM +Ca SO4・2 H2
0↓10co2↑(Here, M stands for Na, NH4, and R stands for C.
H3-1C2H6-1C3H7 ~) In the method using an organic acid alkali aqueous solution, the same S02 absorption rate as the sulfurous soda method can be obtained, and unlike the sulfurous soda method, a deawning step is not required.
しかし有機酸アルカリを用いる方法では、SO2吸収の
際に遊離酸を生成するため、有機酸の蒸気圧に応じた割
合で有機酸がガス中に蒸散して損失となる。However, in the method using an organic acid alkali, a free acid is generated when SO2 is absorbed, so the organic acid evaporates into the gas at a rate corresponding to the vapor pressure of the organic acid, resulting in a loss.
また有機酸アルカリ水溶液には少量の石膏が溶解するた
め石灰石膏法に比べると著しく少量であるが、吸収塔内
に付着物の発生がある。Furthermore, since a small amount of gypsum is dissolved in the organic acid alkali aqueous solution, deposits are generated inside the absorption tower, although the amount is significantly smaller than in the lime-gypsum method.
本発明者等は上述の欠点のない脱硫法について更に検討
を加えた結果、有機酸のカルボキシル基の他にスルホン
酸基を有する有機スルホカルボン酸塩を含む水溶液を吸
収液とし、かつ該吸収液中に結晶石膏を存在させておく
ことにより理想的な排ガス脱硫を行なうことができるこ
とを見出した。As a result of further study on a desulfurization method that does not have the above-mentioned drawbacks, the present inventors have found that an aqueous solution containing an organic sulfocarboxylate having a sulfonic acid group in addition to the carboxyl group of an organic acid is used as an absorption liquid, and the absorption liquid It has been discovered that ideal exhaust gas desulfurization can be achieved by allowing crystalline gypsum to exist in the reactor.
即ち本発明に使用する有機スルホンカルボン酸塩は大量
にかつ容易に得られるもので、スルホ酢酸、スルホプロ
ピオン酸又はスルホコハク酸とアルカリ金属、マグネシ
ウム及びアンモニウムより選ばれる1又は2種以上の陽
性基との塩である。That is, the organic sulfonecarboxylate used in the present invention is one that can be easily obtained in large quantities, and is composed of sulfoacetic acid, sulfopropionic acid, or sulfosuccinic acid, and one or more positive groups selected from alkali metals, magnesium, and ammonium. It is salt.
これらスルホカルボン酸のカルボン酸基は炭酸より強(
亜硫酸より弱い酸根であり、またスルホン酸基は亜硫酸
より強い酸根であるので、この有※く機スルホン酸塩が
炭酸ガスと802とを含混合ガスと接触する場合、いず
れの酸基も炭酸ガスと反応しない。The carboxylic acid group of these sulfocarboxylic acids is stronger than carbonic acid (
It is a weaker acid group than sulfite, and the sulfonic acid group is a stronger acid group than sulfite, so when this organic sulfonate comes into contact with a mixed gas containing carbon dioxide and 802, both acid groups will react with carbon dioxide. and does not react.
またSO2はカルボン酸基に結合した陽性基とは反応し
ない。Also, SO2 does not react with positive groups bonded to carboxylic acid groups.
従って802ガスと接触しても、スルホン酸基は常に塩
の形態で残り、この有機物はイオンとして水に溶解して
いるので蒸気圧は全(零であり、どのような稀薄ガスと
接触しても蒸発することがない。Therefore, even if it comes into contact with 802 gas, the sulfonic acid group always remains in the form of a salt, and since this organic substance is dissolved in water as an ion, its vapor pressure is total (zero), and when it comes into contact with any dilute gas, will not evaporate.
本発明は有機スルホカルボン酸塩および結晶石膏を含む
水溶液を吸収塔に供給し、そこでSO2を含む排ガスと
接触させSO2を亜硫酸水素アルカリとして捕集する吸
収工程、得られる吸収液に空気又は酸素を吹ぎ込んで該
液中の亜硫酸水素アルカリを硫酸アルカリとする酸化工
程、該酸化処理した液に消石灰または石灰石を加え有機
スルホカルボン酸塩および結晶石膏を含む液を再生する
工程および前記酸化工程出液または再生液より吸収した
SQ訝目当量の石膏を分離する工程よりなる。The present invention involves an absorption process in which an aqueous solution containing an organic sulfocarboxylate and crystalline gypsum is supplied to an absorption tower, where it is brought into contact with an exhaust gas containing SO2, and SO2 is collected as an alkali hydrogen sulfite. An oxidation step in which the alkali hydrogen sulfite in the solution is converted into an alkali sulfate by blowing into the solution, a step in which slaked lime or limestone is added to the oxidized solution to regenerate a solution containing an organic sulfocarboxylate and crystalline gypsum, and a step in which the oxidation step is started. This process consists of separating the SQ equivalent amount of gypsum absorbed from the liquid or regenerated liquid.
本発明に用いる有機スルホカルボン酸塩としてスルホ酢
酸ナトリウムを用いた場合を例にとり、各工程を次に化
学式で示す。Taking as an example the case where sodium sulfoacetate is used as the organic sulfocarboxylate used in the present invention, each step is shown below using chemical formulas.
吸収工程
本発明においては吸収液の再生工程で生成する結晶石膏
を分離することなく、もしくはその一部のみを分離し、
再生液を吸収塔に導入する。Absorption process In the present invention, the crystalline gypsum produced in the absorption liquid regeneration process is not separated, or only a part of it is separated,
The regeneration liquid is introduced into the absorption tower.
このように結晶石膏の存在する状態で再生液を吸収塔に
導入することにより吸収塔内での石膏溶解度の低下に基
づく溶存石膏の析出が結晶石膏を種晶としておこるため
析出してくる石膏の機器への付着を防止することができ
るだけでなく、付着防止のだめの結晶石膏を別途供給す
る手段を採る必要がない。In this way, by introducing the regenerating liquid into the absorption tower in the presence of crystalline gypsum, precipitation of dissolved gypsum occurs due to the decrease in gypsum solubility in the absorption tower, using the crystalline gypsum as a seed crystal. Not only can adhesion to equipment be prevented, but there is no need to separately supply crystalline gypsum to prevent adhesion.
結晶石膏の含有濃度は2〜10重量%とするのが望まし
い。The concentration of crystalline gypsum is preferably 2 to 10% by weight.
本発明において吸収したSO2相当量の石膏の分離は酸
化工程の出液または再生液のいずれより行なってもよい
。In the present invention, the absorbed gypsum equivalent to SO2 may be separated from either the effluent of the oxidation step or the regenerated solution.
酸化工程出液より結晶石膏の分離をするときは吸収液の
再生により生成する結晶石膏が吸収工程、酸化工程を経
る間に結晶の成長がみられるので結晶石膏を沢過し易い
状態で分離できる。When separating crystalline gypsum from the effluent of the oxidation process, the crystalline gypsum produced by regenerating the absorption liquid undergoes crystal growth during the absorption process and oxidation process, so it can be separated in a state where it is easy to pass through the crystalline gypsum. .
また石膏生成後直ちに分離するときは得られる石膏がア
ルカリ性を示し石膏ボード等の反相としては不適当なも
のとなるが、このような不都合も回避することができる
。Furthermore, when the gypsum is separated immediately after it is produced, the resulting gypsum becomes alkaline and becomes unsuitable for use as a reversible material for gypsum boards, etc., but this inconvenience can also be avoided.
しかし得られる石膏の用途によっては勿論石膏生成直後
、即ち再生液より分離してよい。However, depending on the use of the obtained gypsum, it may of course be separated immediately after the gypsum is produced, ie, separated from the regenerated liquid.
結晶石膏の分離は吸収塔で吸収したS02相当量の結晶
石膏を分離すればよく、酸化工程出液より行なうとぎは
その全量もしくはその一部より分離する。The crystalline gypsum can be separated by separating an amount equivalent to the S02 absorbed in the absorption tower, and the removal from the effluent of the oxidation process is performed by separating the entire amount or a part thereof.
全量より分離したときはその涙液を、一部より分離した
ときはその涙液および残部の酸化工程出液と併せて再生
工程に送る。If the tear fluid is separated from the entire amount, the tear fluid is sent to the regeneration step together with the tear fluid and the remaining oxidation step exudate when the tear fluid is separated from a portion of the tear fluid.
また再生液より結晶石膏を分離するときは再生液の一部
より行ない涙液は残部の再生液と併せて吸収塔へ導く。When crystalline gypsum is separated from the regenerated liquid, a portion of the regenerated liquid is separated, and the lachrymal fluid is led to the absorption tower together with the remaining regenerated liquid.
上述の如(本発明においては蒸気圧を有しない有機スル
ホカルボン酸塩を吸収剤として含む水溶液を用いること
により亜硫酸アルカリ法や有機酸アルカリ法と同様のS
02の除去ができ、しかも亜硫酸アルカリ法の如く脱芒
工程を必要とせず、また有機酸アルカリ法の如(吸収剤
の損失を伴なわない。As described above (in the present invention, by using an aqueous solution containing an organic sulfocarboxylate as an absorbent that has no vapor pressure, S
Moreover, unlike the alkali sulfite method, a de-awning process is not required, and unlike the organic acid-alkali method, there is no loss of absorbent.
また結晶石膏を吸収液中に存在させることにより溶解石
膏による吸収塔での石膏の析出による付着を防止し得、
しかも吸収液中に種晶を加えるための特別な手段を必要
としない。In addition, by making crystalline gypsum present in the absorption liquid, it is possible to prevent adhesion due to gypsum precipitation in the absorption tower due to dissolved gypsum.
Furthermore, no special means for adding seed crystals to the absorption liquid is required.
また本発明によれば吸収塔で一度排ガスと接触した吸収
液を全て酸化工程、再生工程へと循環させるため吸収液
中の有機スルホカルボン酸塩の濃度が吸収塔内を一度通
過する際にSO2を十分吸収し得る濃度であればよいの
で、低濃度の有機スルホカルボン酸塩水溶液を吸収液と
して使用することができる。Furthermore, according to the present invention, all the absorbent that has once contacted exhaust gas in the absorption tower is circulated to the oxidation process and the regeneration process, so that the concentration of organic sulfocarboxylate in the absorbent decreases to SO2 when it passes through the absorption tower once. As long as the concentration is sufficient to absorb the absorbent, a low-concentration organic sulfocarboxylate aqueous solution can be used as the absorption liquid.
以下実施例により具体的に説明する。This will be explained in detail below using examples.
実施例中%は重量%を意味する。In the examples, % means weight %.
実施例 1
スルホ酢酸ナトリウム2%、硫酸ナトリウム3%および
結晶石膏2%を含む水溶液7771”/ hを用いて5
O21000ppmを含む燃焼排ガス500ONm’/
hを吸収塔で接触処理した。Example 1 Using 7771"/h of an aqueous solution containing 2% sodium sulfoacetate, 3% sodium sulfate and 2% crystalline gypsum
Combustion exhaust gas containing 1000ppm O2 500ONm'/
h was subjected to contact treatment in an absorption tower.
この場合吸収塔を出た吸収液に空気を接触させて該吸収
液に含有される亜硫酸水素ナトリウムを酸化して硫酸ナ
トリウムとして、ついでこのように酸化処理上た液の%
から結晶石膏を分離し、得られる涙液と該酸化処理した
液の残部とを併せて、これに消石灰を添加してそのpH
を6.6〜7.0に調整してからこの液を吸収塔に循環
させることにより燃焼排ガスの処理を168時間行なっ
た。In this case, air is brought into contact with the absorption liquid exiting the absorption tower to oxidize the sodium bisulfite contained in the absorption liquid to form sodium sulfate, and then the percentage of the oxidized liquid is
The crystalline gypsum is separated from the lachrymal fluid, the resulting tear fluid is combined with the remainder of the oxidized fluid, and slaked lime is added to this to adjust its pH.
The combustion exhaust gas was treated for 168 hours by adjusting the liquid to 6.6 to 7.0 and circulating the liquid to the absorption tower.
この結果吸収塔から出るガス中のS02は1〜2ppm
テアリ、また吸収塔へのカルシウム塩の付着は全(見ら
れなかった。As a result, the S02 in the gas coming out of the absorption tower is 1 to 2 ppm.
No accumulation of calcium salts or calcium salts on the absorption tower was observed.
また副生じた石膏も50×200μの柱状結晶であって
、この結晶10%懸濁水のpHは5.2〜5.8であり
、非常に良質な石膏であった。The gypsum produced as a by-product was also columnar crystals of 50 x 200 microns, and the pH of the 10% suspension of crystals was 5.2 to 5.8, indicating that the gypsum was of very good quality.
実施例 2
スルホ酢酸ナトリウム5%、硫酸ナトリウム4%および
結晶石膏6.7%を含む吸収液2.6 m3/ hを用
いてSO2]、 OOOppmを含む燃焼排ガス500
0 Nrrl/ hを接触処理した。Example 2 Flue gas containing 500 ppm SO2], OOOppm using an absorption liquid 2.6 m3/h containing 5% sodium sulfoacetate, 4% sodium sulfate and 6.7% crystalline gypsum
A contact treatment of 0 Nrrl/h was carried out.
この場合吸収塔を出た吸収液に空気を接触させて、該吸
収液に含有される亜硫酸水素ナトリウムを酸化して硫酸
ナトリウムとなし、ついでこのような酸化処理した液の
%から結晶石膏を分離し、得られる涙液と該酸化処理し
た液の残部とを併せて、これに石灰石微粉末を添加して
そのpHを5.5〜5.6に調整してからこの液を吸収
塔に循環させることにより燃焼排ガスの処理を120時
間行なった。In this case, the absorption liquid exiting the absorption tower is brought into contact with air to oxidize the sodium bisulfite contained in the absorption liquid to sodium sulfate, and then crystalline gypsum is separated from the oxidized liquid. Then, the obtained tear fluid and the remainder of the oxidized fluid are combined, fine limestone powder is added thereto to adjust the pH to 5.5 to 5.6, and this fluid is circulated to the absorption tower. The combustion exhaust gas was treated for 120 hours.
この結果吸収塔から出るガス中のSO2は3〜8 pp
mであり、また、吸収塔へのカルシウム塩の付着は全く
見られなかった。As a result, the SO2 in the gas coming out of the absorption tower is 3 to 8 pp.
m, and no calcium salts were observed to adhere to the absorption tower.
また副生じた石膏も50X200μの柱状結晶であって
、この結晶10%懸濁水のpHは5.2〜5.5であり
、非常に良質な石膏であった。The gypsum produced as a by-product was also columnar crystals measuring 50×200 μm, and the pH of the 10% suspension of the crystals was 5.2 to 5.5, indicating that the gypsum was of very good quality.
Claims (1)
プロピオン酸、スルホコハク酸より選ばれる有機スルホ
カルボン酸の塩および結晶石膏を含有する液に接触させ
て該亜硫酸ガスを亜硫酸水素アルカリの形態で該液中に
吸収させる吸収工程、亜硫酸ガスを吸収した吸収液に空
気または酸素を吹き込んで該液中の亜硫酸水素アルカリ
を硫酸アルカリに酸化する酸化工程、亜硫酸水素アルカ
リを硫酸アルカリに酸化した酸化工程出液に石灰石又は
消石灰を添加して有機スルホカルボン酸塩を再生する再
生工程および酸化工程出液もしくは再生工程出液より吸
収した亜硫酸ガス相当量の結晶・石膏を分離する工程よ
りなり、再生工程出液を吸収工程に循環させることを特
徴とする亜硫酸ガスの除去方法。1. Exhaust gas containing sulfur dioxide gas is brought into contact with a liquid containing a salt of an organic sulfocarboxylic acid selected from sulfoacetic acid, sulfopropionic acid, and sulfosuccinic acid and crystalline gypsum, and the sulfur dioxide gas is contained in the liquid in the form of alkali hydrogen sulfite. an oxidation process in which the alkali hydrogen sulfite in the liquid is oxidized to alkali sulfate by blowing air or oxygen into the absorption liquid that has absorbed sulfur dioxide gas; It consists of a regeneration step in which limestone or slaked lime is added to regenerate organic sulfocarboxylic acid salts, and a step in which crystals and gypsum are separated from the effluent of the oxidation step or crystals and gypsum in an amount equivalent to the amount of sulfur dioxide absorbed from the effluent of the regeneration step. A method for removing sulfur dioxide gas characterized by circulating it in an absorption process.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP51155259A JPS5935654B2 (en) | 1976-12-23 | 1976-12-23 | How to remove sulfur dioxide gas |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP51155259A JPS5935654B2 (en) | 1976-12-23 | 1976-12-23 | How to remove sulfur dioxide gas |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5378978A JPS5378978A (en) | 1978-07-12 |
JPS5935654B2 true JPS5935654B2 (en) | 1984-08-30 |
Family
ID=15601996
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP51155259A Expired JPS5935654B2 (en) | 1976-12-23 | 1976-12-23 | How to remove sulfur dioxide gas |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5935654B2 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107285344B (en) * | 2017-07-26 | 2023-07-21 | 沈阳化工研究院有限公司 | Treatment process and device for byproduct mixed waste salt in phenol production process |
-
1976
- 1976-12-23 JP JP51155259A patent/JPS5935654B2/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
JPS5378978A (en) | 1978-07-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
USRE31236E (en) | Method of removing sulfur dioxide from combustion exhaust gas | |
CA1130987A (en) | Removing carbon oxysulfide from gas streams | |
US3846535A (en) | Method for absorbing sulfur oxides from gaseous mixtures and regenerating the absorbent | |
US4696805A (en) | Method for desulfurizing exhaust gas | |
JPS5829251B2 (en) | Wet flue gas desulfurization gypsum recovery method | |
US4454102A (en) | Method of purifying flue gases from sulphur dioxide | |
CA1091898A (en) | Method for removing sulfur dioxide from exhaust gas | |
US4038367A (en) | Process for the removal of SOx and NOx from waste gases using alkali metal or alkaline earth metal iodide | |
JPS5935654B2 (en) | How to remove sulfur dioxide gas | |
ES2211782T3 (en) | PROCEDURE FOR PURIFYING WATER TAMPON SOLUTIONS. | |
US4014978A (en) | Air pollution control system and method | |
JPS5836619B2 (en) | Treatment method for sulfur oxides in exhaust gas | |
JPS62193629A (en) | Method for removing sulfur oxide contained in exhaust gas | |
US4277451A (en) | Wet process for the desulfurization of exhaust gas | |
US4038368A (en) | Process for removing oxides of nitrogen and sulfur from exhaust gases | |
US4313924A (en) | Process for removal of sulfur dioxide from gas streams | |
CA1079030A (en) | Sulfur dioxide scrubbing system | |
Tseng | CALCIUM-SULFITE HEMIHYDRATE DISSOLUTION AND CRYSTALLIZATION (FLUE GAS, DESULFURIZATION) | |
JPS5825492B2 (en) | Iousankabutsunojiyokiyohouhou | |
CA1148331A (en) | Method of removing sulfur dioxide | |
JPH09122440A (en) | Method for scrubbing sulfur dioxide being accompanied with formation of pure product of magnesium sulfite | |
JPS6242738Y2 (en) | ||
SU1711953A1 (en) | Method of producing absorbent for cleaning gases from hydrogen sulfide and carbon dioxide | |
JPS6254050B2 (en) | ||
GB2046231A (en) | Method for removal of sulphur dioxide from exhaust gas |