JPH0769292B2 - Management method of pH meter for absorbing liquid slurry - Google Patents
Management method of pH meter for absorbing liquid slurryInfo
- Publication number
- JPH0769292B2 JPH0769292B2 JP62244131A JP24413187A JPH0769292B2 JP H0769292 B2 JPH0769292 B2 JP H0769292B2 JP 62244131 A JP62244131 A JP 62244131A JP 24413187 A JP24413187 A JP 24413187A JP H0769292 B2 JPH0769292 B2 JP H0769292B2
- Authority
- JP
- Japan
- Prior art keywords
- meter
- absorbent
- liquid slurry
- slurry
- value
- 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 - Fee Related
Links
- 239000002002 slurry Substances 0.000 title claims description 20
- 239000007788 liquid Substances 0.000 title claims description 13
- 238000007726 management method Methods 0.000 title claims 2
- 230000002745 absorbent Effects 0.000 claims description 20
- 239000002250 absorbent Substances 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 238000001514 detection method Methods 0.000 claims description 10
- 235000019738 Limestone Nutrition 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000006028 limestone Substances 0.000 claims description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 7
- 238000006477 desulfuration reaction Methods 0.000 claims description 7
- 230000023556 desulfurization Effects 0.000 claims description 7
- 239000003546 flue gas Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000010440 gypsum Substances 0.000 claims description 4
- 229910052602 gypsum Inorganic materials 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229940043430 calcium compound Drugs 0.000 claims description 3
- 150000001674 calcium compounds Chemical class 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910016978 MnOx Inorganic materials 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910003174 MnOOH Inorganic materials 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- RTBHLGSMKCPLCQ-UHFFFAOYSA-N [Mn].OOO Chemical compound [Mn].OOO RTBHLGSMKCPLCQ-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- -1 CaCO 3 Substances 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910018654 Mn Ox Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Treating Waste Gases (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は湿式石灰石膏法排煙脱硫装置の吸収剤の供給量
制御用などのpH計の管理方法に関する。TECHNICAL FIELD The present invention relates to a method for managing a pH meter for controlling the supply amount of an absorbent in a wet limestone gypsum flue gas desulfurization apparatus.
従来、湿式石灰石膏法排煙脱硫装置において吸収スラリ
ーのpH測定用のpH計を複数台設置しこれを定期的に塩酸
溶液で交互に洗浄し、洗浄時は当該pH計以外のpH計指示
をもつて吸収液スラリーのpH値としていた。Conventionally, in wet lime gypsum method flue gas desulfurization equipment, multiple pH meters were installed for measuring the pH of the absorbing slurry, and they were periodically washed alternately with hydrochloric acid solution. The pH value of the absorption liquid slurry was always used.
ところが、ボイラー負荷の急激な上昇時、即ち吸収する
SO2量が急激に増加する時、においてpHの検出値が突然
上昇し、数分から数十分にわたつて異常に高い値を指示
する現象やあるいはボイラ負荷が低い状態で長時間運転
を継続した時、即ち吸収するSO2量が少ししかない時に
複数台設置しているpH計相互間の指示値にズレが生じて
くる現象が見られ、特に吸収液スラリーのpH値で吸収剤
の供給流量を制御する時などは問題があつた。However, when the boiler load suddenly rises, that is, it is absorbed
When the amount of SO 2 suddenly increased, the detected value of pH suddenly increased, indicating an abnormally high value for several minutes to several tens of minutes, or continued operation for a long time with a low boiler load. At the time of absorption, that is, when there is only a small amount of SO 2 absorbed, there is a phenomenon that the readings between the pH meters installed in multiple units may deviate. Especially, the supply flow rate of the absorbent depends on the pH value of the absorbent slurry. There was a problem when controlling.
本発明は上記の問題点を解消し、吸収液スラリーpHの連
続安定測定を行ないうる方法を提供しようとするもので
ある。The present invention is intended to solve the above problems and provide a method capable of continuously and stably measuring the pH of an absorbent slurry.
本発明者らは、上記問題点を解決すべく鋭意原因究明の
結果、ボイラー負荷上昇時のpH測定値の突変上昇や長時
間ボイラー低負荷時の複数台設置pH計相互間の指示値の
不一致の原因が下記の反応に起因するものであることを
つきとめた。As a result of diligent investigations to solve the above problems, the inventors of the present invention have determined that the measured values of the pH values when the boiler load is increased suddenly or the long-term boiler has a low load. The cause of the discrepancy was found to be due to the following reaction.
排煙脱硫の吸収剤としては、CaCO3,Ca（OH）2,CaOのよ
うなカルシウム化合物が使用されるが、これらは通常石
灰石より得られるものである。石灰石中には微量（約30
〜100mg/kg）のマンガンを含有しているため、石灰石を
原料として得られたCaCO3,Ca（OH）２又はCaOなどを主
成分とするSO2吸収液中にも微量なマンガンを必然的に
含有している。亜硫酸の酸化において、この原料吸収剤
中に微量含まれるマンガンが次のように酸化反応に関与
している。As the flue gas desulfurization absorbent, calcium compounds such as CaCO 3 , Ca (OH) 2 and CaO are used, and these are usually obtained from limestone. Trace amount (about 30) in limestone
(~ 100mg / kg) manganese, so a small amount of manganese is inevitable even in the SO 2 absorbent containing CaCO 3 , Ca (OH) 2 or CaO as the main component obtained from limestone. Contained in. In the oxidation of sulfurous acid, a small amount of manganese contained in this raw material absorbent is involved in the oxidation reaction as follows.
Mn2+＋HSO3 -＋H+〔Mn・SO2〕２＋H2O （１） ２〔Mn・SO2〕2+＋O2＋5H2O2MnOOH↓ ＋HSO3 -＋SO4 2-＋7H+ （２） 上記（２）式の反応でオキシ水酸化マンガン（MnOOH）
を生じ、これはさらに次の反応によつて酸化反応を促進
する。 Mn 2+ + HSO 3 - + H + [Mn · SO 2] 2 + H 2 O (1) 2 [Mn · SO 2] 2+ + O 2 + 5H 2 O2MnOOH ↓ + HSO 3 - + SO 4 2+ 7H + (2) above ( Manganese oxyhydroxide (MnOOH) by the reaction of formula 2)
Which further accelerates the oxidation reaction by the following reaction.
2MnOOH↓＋HSO3 -＋3H+→2Mn2+＋SO4 2-＋3H2O （３） 通常ボイラー負荷が高く吸収するSO2量が多いときに
は、吸収液スラリー中に亜硫酸が充分存在するために、
オキシ水酸化マンガンは中間的に存在するのみで、実際
に固相に存在することはないが、ボイラー負荷が低く吸
収するSO2量が少なくなると、（２）式の反応で生成し
たオキシ水酸化マンガンの一部は、次の反応によつてマ
ンガン酸化物として析出する。2MnOOH ↓ ＋ HSO 3 − ＋ 3H + → 2Mn 2+ ＋ SO 4 2 ＋ 3H 2 O (3) Usually, when the boiler load is high and the amount of SO 2 to be absorbed is large, there is sufficient sulfurous acid in the absorbing solution slurry,
Manganese oxyhydroxide exists only in the intermediate state and does not actually exist in the solid phase. However, when the boiler load is low and the amount of SO 2 absorbed is small, the oxyhydroxide produced by the reaction of formula (2) is generated. A part of manganese is precipitated as manganese oxide by the following reaction.
MnOOH↓→MnOx↓＋1/2H2O （４） このマンガン酸化物MnOxのｘの値は通常１以上２以下の
値であり、析出したMnOxは非晶質の固体であり、pH値の
検出器の表面や、吸収液スラリー配管の内壁に沈着す
る。又、このMnOxはボイラーの負荷が上昇し、再びSO2
の吸収量が増加すると、次の反応によつて溶解する。MnOOH ↓ → MnOx ↓ + 1 / 2H 2 O (4) The x value of this manganese oxide MnOx is usually 1 or more and 2 or less, and the precipitated MnOx is an amorphous solid and has a pH value detector. On the inner surface of the absorption liquid slurry pipe. In addition, the load on the boiler of this MnOx increases, and SO 2
When the absorption amount of is increased, it is dissolved by the next reaction.
MnOx＋HSO3 -＋H+→Mn2+＋SO4 2-＋H2O （５） 即ち、ボイラーが低負荷時が長期継続する場合、pH計の
検出部には経時的にMnOxの沈着量が増加し、pH計の感度
の低下を招き、一方、ボイラー負荷が上昇すると沈着Mn
Oxが溶解することとなり、溶解時に（５）式から判るよ
うに、pH検出部周囲の水素イオンH+を消費するため見掛
け上pHの検出値が高くなる現象を呈する訳であり、さら
に、前記MnOxは塩酸には難溶性の物質であり、通常の塩
酸水溶液の洗浄では溶解量は皆無に近く、従つて従来の
洗浄方法では間隔の解決をみなかつた訳である。MnOx ＋ HSO 3 − ＋ H + → Mn 2+ ＋ SO 4 2 ＋ H 2 O (5) That is, when the load of the boiler continues for a long period of time, the amount of MnOx deposited on the detection part of the pH meter increases with time, If the boiler load increases, the deposition of Mn
Ox is dissolved, and as it is understood from the formula (5) when dissolved, the phenomenon that the detected value of pH is apparently increased due to consumption of the hydrogen ion H + around the pH detection part, MnOx is a substance that is hardly soluble in hydrochloric acid, and the amount of dissolved MnOx is almost zero in the usual washing with a hydrochloric acid aqueous solution, so that the conventional washing method can solve the gap.
以上の知見から、ボイラー負荷上昇時の吸収液スラリー
のpHの突変上昇はpH計の検出器周囲に生じた特異現象に
依存したpH値であり、吸収液スラリー本体のpH値ではな
いpH値を検知していたものであり、又ボイラー負荷低負
荷継続時の複数台のpH計相互間の検出pH値の相違は、検
出器に沈着したMnOxの沈着量或いは沈着状況の相違によ
つてpH計相互間の検出感度の相違が原因となつて生じた
現象であつたことを解明した。From the above findings, the sudden increase in the pH of the absorbent slurry when the boiler load increases is a pH value that depends on a unique phenomenon that occurs around the detector of the pH meter, and not the pH value of the absorbent slurry body. In addition, the difference in the detected pH value between multiple pH meters when the boiler load and low load continue is due to the amount of MnOx deposited on the detector or the difference in the deposition status. It was clarified that this was a phenomenon caused by the difference in detection sensitivity between the two instruments.
本発明は、以上の知見に基づきなされたものであり、カ
ルシウム化合物を吸収剤として用いる湿式石灰石膏法排
煙脱硫装置の吸収液スラリーのpHをpH計を用いて直結測
定するに際し、吸収液スラリーから該pH計の検出器を間
欠的に隔離し、該検出器を過酸化水素水と塩酸または硫
酸との混合溶液で洗浄し、洗浄後再び吸収液スラリーの
pH検出に寄与させることを特徴とする湿式排煙脱硫装置
における吸収液スラリー用pH計の管理方法に関する。The present invention has been made based on the above findings, when directly measuring the pH of the absorbent liquid slurry of a wet limestone gypsum method flue gas desulfurization apparatus using a calcium compound as an absorbent, the absorbent liquid slurry The detector of the pH meter is intermittently isolated from the above, and the detector is washed with a mixed solution of hydrogen peroxide solution and hydrochloric acid or sulfuric acid, and after washing, the absorbent slurry
The present invention relates to a method for controlling a pH meter for absorbing liquid slurry in a wet flue gas desulfurization device, which contributes to pH detection.
上記（３）式におけるマンガン酸化物MnOxを過酸化水素
水と塩酸または硫酸との混合溶液で洗浄すると、次の反
応によつてMnOxは速やかに溶解する。When manganese oxide MnOx in the above formula (3) is washed with a mixed solution of hydrogen peroxide solution and hydrochloric acid or sulfuric acid, MnOx is rapidly dissolved by the following reaction.
即ち、pH計の検出部に沈着していたMnOxは上記反応で洗
浄される。 That is, MnOx deposited on the detection part of the pH meter is washed by the above reaction.
〔実施例−１〕 本発明による一実施例を第１図によつて説明する。第１
図では、２台のpH計を用いて、２時間に１回吸収液スラ
リーからpH計の検出部を抜き出し洗浄を行ない、２台の
pH計の洗浄周期は一時間ズラした。又pH計の検出器引抜
き10分間に指示値を採用するpH計は他方のpH洗浄液とし
て10％塩酸10に30％過酸化水素水１を添加し、これ
に過酸化水素の分解遅延剤として10mlのリン酸を添加し
たものを用いた。この洗浄液での洗浄は２分とした。第
１図は、ボイラー負荷上昇時の実施例を示したものであ
る。また、ボイラー低負荷が継続した状態下での実施例
を第２図に示した。[Example-1] An example of the present invention will be described with reference to FIG. First
In the figure, using two pH meters, once every two hours, the pH meter's detection unit was pulled out from the absorbent slurry and washed.
The cleaning cycle of the pH meter was staggered for one hour. In addition, the pH meter that uses the indicated value for 10 minutes from the withdrawal of the detector of the pH meter adds 30% hydrogen peroxide solution 1 to 10% hydrochloric acid 10 as the other pH cleaning solution, and add 10 ml as a hydrogen peroxide decomposition retarder. The phosphoric acid added was used. The cleaning with this cleaning solution was performed for 2 minutes. FIG. 1 shows an embodiment when the boiler load is increased. Further, FIG. 2 shows an embodiment under the condition that the low load of the boiler is continued.
〔実施例−２〕 実施例−１における洗浄液を、10％硫酸10中に30％過
酸化水素水１を添加し、これに過酸化水素の分解遅延
剤としてリン酸10mlを添加したものを使用した結果、効
果及び状況は第１図及び第２図のそれと全く同様であつ
た。[Example-2] The cleaning solution used in Example-1 was prepared by adding 30% hydrogen peroxide solution 1 in 10% sulfuric acid 10 and adding 10 ml of phosphoric acid as a decomposition retarder for hydrogen peroxide. As a result, the effect and the situation were exactly the same as those of FIGS. 1 and 2.
ボイラー負荷上昇時の場合に、実施例−１の洗浄液の代
りに10％塩酸を用いたときの状況を第３図に示した。FIG. 3 shows the situation when 10% hydrochloric acid was used instead of the cleaning liquid of Example-1 when the boiler load was increased.
又第４図に、上記と同じ洗浄液を用いた時のボイラー低
負荷が継続したときの状況を示した。又基本的な洗浄サ
イクル等は実施例−１と同じである。Further, FIG. 4 shows the situation when the low load of the boiler is continued when the same cleaning liquid as above is used. The basic cleaning cycle and the like are the same as in Example-1.
第４図においてpH計Ａの方がMnOxによる検出部の感度不
良が大きく、約５時間経過時位から影響を受けており、
pH計Ａの指示値が高目の指示をするために、pH計Ａの指
示値が採用されている間はpHを下げるため吸収剤石灰石
が少ししか供給されずこのためpH計Ｂの指示はこの間低
下の傾向を示し、逆にpH計Ｂの指示値が採用されるとpH
を上げるべく吸収剤石灰石の供給が増加されるための現
象であつた。In Fig. 4, the pH meter A has a larger sensitivity defect of the detection unit due to MnOx, and is affected by about 5 hours.
Since the indication value of the pH meter A gives a higher indication, a small amount of absorbent limestone is supplied to lower the pH while the indication value of the pH meter A is adopted. During this period, it shows a tendency to decrease, and conversely when the indicated value of pH meter B is adopted,
It was a phenomenon because the supply of absorbent limestone was increased in order to raise the rate.
本発明によつて、pH値の検出部表面への沈着物による吸
収液スラリーpH値の誤検出を解消し、常に正常な吸収液
スラリーpHを連続安定して測定できた。According to the present invention, the erroneous detection of the pH value of the absorption liquid slurry due to the deposit on the surface of the detection part of the pH value was eliminated, and the normal absorption liquid slurry pH could always be measured continuously and stably.
第１図及び第２図は本発明効果説明図、第３図及び第４
図は従来法の状況図である。1 and 2 are explanatory views of the effect of the present invention, FIG. 3 and FIG.
The figure shows the situation of the conventional method.
Claims (1)
式石灰石膏法排煙脱硫装置の吸収液スラリーのpHをpH計
を用いて連続測定するに際し、吸収液スラリーから該pH
計の検出器を間欠的に隔離し、該検出器を過酸化水素と
塩酸または硫酸との混合溶液で洗浄し、洗浄後再び吸収
液スラリーのpH検出に寄与させることを特徴とする湿式
排煙脱硫装置における吸収液スラリー用pH計の管理方
法。1. When continuously measuring the pH of an absorbent liquid slurry of a wet limestone gypsum method flue gas desulfurization apparatus using a calcium compound as an absorbent, the pH of the absorbent liquid slurry is measured when the pH is measured.
Wet flue gas, characterized in that the detector of the meter is intermittently isolated, the detector is washed with a mixed solution of hydrogen peroxide and hydrochloric acid or sulfuric acid, and after washing, it contributes again to the pH detection of the absorbent slurry. Management method of pH meter for absorbing liquid slurry in desulfurization equipment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62244131A JPH0769292B2 (en) | 1987-09-30 | 1987-09-30 | Management method of pH meter for absorbing liquid slurry |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62244131A JPH0769292B2 (en) | 1987-09-30 | 1987-09-30 | Management method of pH meter for absorbing liquid slurry |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6488243A JPS6488243A (en) | 1989-04-03 |
| JPH0769292B2 true JPH0769292B2 (en) | 1995-07-26 |
Family
ID=17114226
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62244131A Expired - Fee Related JPH0769292B2 (en) | 1987-09-30 | 1987-09-30 | Management method of pH meter for absorbing liquid slurry |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0769292B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116106384B (en) * | 2023-02-26 | 2025-03-21 | 包钢集团矿山研究院（有限责任公司） | A device and method for quickly detecting active calcium oxide in lime |
-
1987
- 1987-09-30 JP JP62244131A patent/JPH0769292B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6488243A (en) | 1989-04-03 |
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