JPS63179087A - Chemical washing liquid for scale in geothermal power plant - Google Patents
Chemical washing liquid for scale in geothermal power plantInfo
- Publication number
- JPS63179087A JPS63179087A JP1010587A JP1010587A JPS63179087A JP S63179087 A JPS63179087 A JP S63179087A JP 1010587 A JP1010587 A JP 1010587A JP 1010587 A JP1010587 A JP 1010587A JP S63179087 A JPS63179087 A JP S63179087A
- Authority
- JP
- Japan
- Prior art keywords
- scale
- hot water
- washing liquid
- cleaning solution
- geothermal power
- 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
- 239000000126 substance Substances 0.000 title claims abstract description 17
- 239000007788 liquid Substances 0.000 title abstract description 5
- 238000005406 washing Methods 0.000 title abstract 4
- 238000005260 corrosion Methods 0.000 claims abstract description 17
- 230000007797 corrosion Effects 0.000 claims abstract description 17
- 239000003112 inhibitor Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 35
- 238000004140 cleaning Methods 0.000 claims description 22
- 150000002222 fluorine compounds Chemical class 0.000 claims description 21
- 229910019142 PO4 Inorganic materials 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 11
- 239000010452 phosphate Substances 0.000 claims description 11
- 238000010248 power generation Methods 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 26
- 239000000377 silicon dioxide Substances 0.000 abstract description 16
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 abstract description 4
- 229920000388 Polyphosphate Polymers 0.000 abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 abstract description 3
- 239000011737 fluorine Substances 0.000 abstract description 3
- 239000001205 polyphosphate Substances 0.000 abstract description 3
- 235000011176 polyphosphates Nutrition 0.000 abstract description 3
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 3
- 229910017665 NH4HF2 Inorganic materials 0.000 abstract description 2
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 17
- 235000021317 phosphate Nutrition 0.000 description 11
- 230000007935 neutral effect Effects 0.000 description 10
- 230000002378 acidificating effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- ASZZHBXPMOVHCU-UHFFFAOYSA-N 3,9-diazaspiro[5.5]undecane-2,4-dione Chemical compound C1C(=O)NC(=O)CC11CCNCC1 ASZZHBXPMOVHCU-UHFFFAOYSA-N 0.000 description 5
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 5
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- -1 silica ions Chemical class 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000011698 potassium fluoride Substances 0.000 description 2
- 235000003270 potassium fluoride Nutrition 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 240000002834 Paulownia tomentosa Species 0.000 description 1
- JKALDIASYJJDLK-UHFFFAOYSA-L [O-]OOOOO[O-].[Ca+2] Chemical compound [O-]OOOOO[O-].[Ca+2] JKALDIASYJJDLK-UHFFFAOYSA-L 0.000 description 1
- 229940000488 arsenic acid Drugs 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- TVHALOSDPLTTSR-UHFFFAOYSA-H hexasodium;[oxido-[oxido(phosphonatooxy)phosphoryl]oxyphosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O TVHALOSDPLTTSR-UHFFFAOYSA-H 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- UGTZMIPZNRIWHX-UHFFFAOYSA-K sodium trimetaphosphate Chemical compound [Na+].[Na+].[Na+].[O-]P1(=O)OP([O-])(=O)OP([O-])(=O)O1 UGTZMIPZNRIWHX-UHFFFAOYSA-K 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
Landscapes
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は地熱発電プラントの熱水配管及び熱水が通る機
器類に生Ｆｙ、＋Ｔ着した二酸化けい素（Ｓ １０２
） ７＆：主成分とするスケールｔａ解除去するため
の化学的洗浄液に関する。Detailed Description of the Invention [Industrial Application Field] The present invention provides silicon dioxide (S 102
) 7&: Concerning a chemical cleaning solution for removing scale as a main component.
熱水型坑井から得られる蒸気を使用する地熱発電１ラン
ドにおいては、蒸気の数倍に相当する熱水は環境保護、
公害防止及び地下の水量の維持などの理由から、地下へ
還元するのが最もよいとされており、世界の大部分のサ
イトにおいて熱水輸送管によって地下還元が実施されて
いる。In geothermal power generation using steam obtained from hydrothermal wells, hot water equivalent to several times the amount of steam is used for environmental protection,
For reasons such as preventing pollution and maintaining underground water levels, it is considered best to return water underground, and underground return is carried out using hot water transport pipes at most sites around the world.
各坑口の気水分離器で分難された熱水には多量のシリカ
イオン（地熱地帯によって異なるが５００〜＋ ２ Ｑ
Ｏｐｐ＋ｎ程度）が含まれているため、地下還元井ま
での熱水輸送管にシリカを主成分とするスケールが析出
、付着することによって管内の閉塞をきたし、地下還元
井への熱水容量減衰を生じ、地熱の開発にとって大きな
問題となっている。The hot water separated by the steam separator at each wellhead contains a large amount of silica ions (depending on the geothermal area, 500 to +2 Q).
(approximately Opp+n), scale mainly composed of silica precipitates and adheres to the hot water transport pipe leading to the underground reinjection well, causing blockage in the pipe and reducing the hot water capacity to the underground reinjection well. This is a major problem for geothermal development.
熱水輸送管内に析出、付着するスケールは硬くて強固な
無定形シリカの結晶であり、熱水輸送管より採叡したス
ケールの化学組成の１例を示すと、８１０２１８６．８
％、ＡＩ！２０３； ２．５％、ｃｔｈＧＯ３ｉ ５．
２％、Ｆｅ２Ｏ２ｐ ００２％及び水分５．０％で３１
０２ｆ主成分とし、その他にＡ／２０３．Ｃａｃｏ３等
が数％含有されている。The scale that precipitates and adheres to hot water transport pipes is hard and strong amorphous silica crystals, and an example of the chemical composition of scale collected from a hot water transport pipe is 8102186.8.
%, AI! 203; 2.5%, cthGO3i 5.
2%, Fe2O2p 002% and moisture 5.0% 31
02f main component, and A/203. Contains several percent of Caco3 and the like.
このよりな５１０２全主成分とするスケールの除去対策
については、一部で試験が実施されているようであるが
、まだ実用化には至っていないようで、熱水輸送管が閉
塞する前に、新しい熱水輸送管と取替交換しているのが
現状であり、それに要する経済的損失が大きい欠点があ
る。It seems that some tests have been conducted on measures to remove scale, which is mainly composed of all 5102, but it seems that it has not yet been put into practical use. Currently, hot water transport pipes are replaced with new ones, which has the drawback of causing a large economic loss.
本発明ζ上記事実に鑑み、地熱発電プラントの熱水配管
及び熱水が通る機器類に生成付着した８１０２ ｋ主
成分とするスケールを溶解除去する化学的洗浄液を提供
しようとするものである。The present invention ζ In view of the above facts, it is an object of the present invention to provide a chemical cleaning solution that dissolves and removes scale mainly composed of 8102k that has formed and adhered to hot water piping and equipment through which hot water passes in a geothermal power plant.
熱水輸送管内に析出、付着したシリカを主成分とするス
ケールに対し溶解除去力がすぐれており、しかも熱水輸
送管内の鋼材腐食に対しても全く問題のない洗浄剤を提
供する必要性から、本発明者等は次のようにすぐれた洗
浄剤を見出し本発明に到達したものである。Based on the need to provide a cleaning agent that has excellent ability to dissolve and remove scale mainly composed of silica that has precipitated and adhered to hot water transport pipes, and also has no problem with corrosion of steel materials in hot water transport pipes. The present inventors discovered the following excellent cleaning agent and arrived at the present invention.
即ち、本発明はフッ化水素アンモニウム、フッ１ヒ水素
カリウム、フッ化水素ナトリウム、フッ化アンモニウム
、フッ化カリウム及びフッ化ナトＩＪウム等のフッ素化
合物の少なくとも１橿以上に、フッ化水素酸を添加し、
これに重合りん酸塩及び酸腐食抑制剤を添加してなる地
熱発電プラントのスケール化学的洗浄である。That is, the present invention involves adding hydrofluoric acid to at least one fluorine compound such as ammonium hydrogen fluoride, potassium hydrogen fluoride, sodium hydrogen fluoride, ammonium fluoride, potassium fluoride, and sodium fluoride. Add,
This is a scale chemical cleaning method for geothermal power plants that is made by adding polymerized phosphate and acid corrosion inhibitors to this.
この本発明化学的洗浄液は、これ全６０〜７０Ｃの温度
範囲で使用することにより、シリカを主成分とする硬質
スケールに対し、非常にすぐれた溶解力を有し、かつ鋼
材に対する酸腐食も無視できる程度である。By using the chemical cleaning solution of the present invention in a temperature range of 60 to 70C, it has an extremely excellent dissolving power for hard scale mainly composed of silica, and also ignores acid corrosion on steel materials. As much as possible.
また、この化学的洗浄液の使用態様としては、熱水輸送
管内のスケール厚みが１０〜１５１程度まで成長した時
点で予備配管と取替交換し、取外したスケール付き熱水
輸送管は別途洗浄ループに取付は固定してから本発明化
学的洗浄液を６０〜７０Ｃに加温しながらルーフ内にポ
ンプで注入循環して熱水輸送管内に析出付着したシリカ
を主成分とするスケールを溶解除去するようにすればよ
い。In addition, as for how to use this chemical cleaning solution, when the scale thickness inside the hot water transport pipe grows to about 10 to 151 cm, it is replaced with a spare pipe, and the removed hot water transport pipe with scale is placed in a separate cleaning loop. After the installation is fixed, the chemical cleaning solution of the present invention is pumped into the roof while being heated to 60-70C and circulated to dissolve and remove the scale mainly composed of silica deposited in the hot water transport pipe. do it.
本発明化学的洗浄液の７リカを主成分とするスケールの
溶解力は使用すフッ素化合物が酸性か中性かによって、
それと組合せるフッ１ヒ水素酸の量も異なる。酸性フッ
素化合物とフッ化水素酸の組合せの溶解力は酸性フッ素
化合物の濃度とフッ化水素酸濃度との配合比にも左右さ
れ、かつフッ素化合物の濃度は洗浄対象物に生成付着シ
たスケール量によって決定されるが効果的な洗浄力全達
成するためには、フッ化水素アンモニウム（ＮＨ４ＨＦ
２）、フッ化水素カリウム（ＫＨＦ２）、フッ化水素カ
リウム（ＮａＨＦ２） 等の酸性フッ化物ＶＣ対する
７ン１ヒ水素酸（ＨＦ） との混合比は、それぞれを
Ｆ量に換算して４：１〜Ｉ：４の範囲が取適であり、ま
たフッ化アンモニウム（ＮＨ４Ｆ）、フッ化ナトリウム
（ＮａＦ） 、フッ化カリウム（ＫＦ ）等の中性フッ
化物に対するフッ化水素酸（ＨＦ）との混合比はそれぞ
れｒｔに換算して２：５〜１：４の範囲が最適である。The dissolving power of the scale mainly composed of 7 Lika in the chemical cleaning solution of the present invention depends on whether the fluorine compound used is acidic or neutral.
The amount of fluorohydrohydric acid combined therewith also differs. The dissolving power of a combination of an acidic fluorine compound and hydrofluoric acid depends on the mixing ratio of the acidic fluorine compound concentration and the hydrofluoric acid concentration, and the concentration of the fluorine compound depends on the amount of scale formed and adhered to the object to be cleaned. To achieve full effective cleaning power determined by ammonium hydrogen fluoride (NH4HF)
2) The mixing ratio of 7-1 arsenic acid (HF) to acidic fluoride VC such as potassium hydrogen fluoride (KHF2) and potassium hydrogen fluoride (NaHF2) is 4: A range of 1 to I:4 is suitable, and hydrofluoric acid (HF) is suitable for neutral fluorides such as ammonium fluoride (NH4F), sodium fluoride (NaF), and potassium fluoride (KF). The optimum mixing ratio is in the range of 2:5 to 1:4 in terms of rt.
いずれの場合もその全濃度はフッ素（Ｆｌ ｔがＳ ｗ
ｔ％以上にすべきで１０ ｗｔ％を超えても効果上差異
がないで経済性を考えて５〜ｌ Ｏｗｔ％の範囲にすべ
きである。In either case, the total concentration is fluorine (Fl t is S w
The content should be at least 10 wt%, and even if it exceeds 10 wt%, there will be no difference in effectiveness, so considering economic efficiency, it should be in the range of 5 to 1 Owt%.
本発明化学洗浄液は重合りん酸塩の添加により、スケー
ル中のカル／ラムと反応して可廖性の錯化合物を生成す
るため、フッ化水素酸によるシリカの溶解力が増加する
。その重合りん酸塩の添加濃度はスケール中のカルシウ
ム濃度によって決まるが、カルシウムに対し１当量のみ
加で十分である。By adding the polymerized phosphate, the chemical cleaning solution of the present invention reacts with Cal/Rum in the scale to form a flexible complex compound, thereby increasing the ability of hydrofluoric acid to dissolve silica. The concentration of the polymerized phosphate added is determined by the calcium concentration in the scale, but it is sufficient to add only 1 equivalent to calcium.
もし重合りん酸塩が無添加であると、スケール中のカル
シウムはフッ素と反応して酸に不溶性のフッ化カルシウ
ム（ｃａＦ２） ｋ生成するので、その７ツ化カルシ
ウムがスケールの主成分であるシリカ（ＳｌＯ２）の表
面ヲ棟って、フッ素化合物によるシリカの溶解力を阻害
することになる。If polymerized phosphate is not added, the calcium in the scale will react with fluorine to produce acid-insoluble calcium fluoride (caF2), and the calcium heptoxide will react with silica, which is the main component of the scale. The surface roughness of (SlO2) inhibits the ability of fluorine compounds to dissolve silica.
効果的な重合りん酸塩としてはピロりん酸塩（ピロりん
酸、ピロりん酸ナトリウム）、ポリりん酸塩（トリポリ
りん酸ナトリウム、テトラりん酸ナトリウム、ヘキサジ
ん酸ナトリウム）、メタりん酸塩（ヘキサメタりん酸ナ
トリウム、トリメタりん酸ナトリウム）、及びウルトラ
りん酸塩（ウルトラりん酸す） ＩＪウム）等がある。Effective polymeric phosphates include pyrophosphates (pyrophosphoric acid, sodium pyrophosphate), polyphosphates (sodium tripolyphosphate, sodium tetraphosphate, sodium hexadate), and metaphosphates ( These include sodium hexametaphosphate, sodium trimetaphosphate), and ultraphosphate (ultraphosphate IJium).
又本発明化学的洗浄液には酸腐食抑制剤を加える必要が
あるが、酸腐食抑制剤としては、それが鋼材に対し表面
吸着作用全発揮して腐食抑制効果を奏するものならば、
公知の酸腐食抑制剤が適宜選択して使用し得る。Furthermore, it is necessary to add an acid corrosion inhibitor to the chemical cleaning solution of the present invention, but as an acid corrosion inhibitor, if it exerts its full surface adsorption effect on steel materials and exhibits a corrosion inhibiting effect,
Known acid corrosion inhibitors may be selected and used as appropriate.
例えばヒビロンＡ−１００（杉村化学工業株式会社製、
有機アミン系インヒビター、商品名）ヒビロンに−４（
杉村化学工業株式会社製；有機アミン糸インヒビター；
商品名）、イビット（住友化学工業株式会社製、有機ア
ミン糸インヒビター、商品名）等があげられる。使用濃
度は０．６〜０．５ ｗｔ％で十分である。For example, Hibiron A-100 (manufactured by Sugimura Chemical Industry Co., Ltd.)
Organic amine inhibitor, trade name) Hiviron ni-4 (
Manufactured by Sugimura Chemical Industry Co., Ltd.; Organic amine thread inhibitor;
(trade name), Ivit (manufactured by Sumitomo Chemical Co., Ltd., organic amine thread inhibitor, trade name), etc. A concentration of 0.6 to 0.5 wt% is sufficient.
本発明において使用するフッ化水素酸とフッ化水素アン
モニ９ム、フッ化水素カリウム、フッ化水素す） Ｉ）
ラム等のフッ素化合物との混合洗浄液によるシリカスケ
ールの溶解作用はフッ素化合物としてフッ化水素アンモ
ニウム（ＮＨ４ＨＦ２）全例にとって示すと下記第１式
で推測される。Hydrofluoric acid, ammonium hydrogen fluoride, potassium hydrogen fluoride, hydrogen fluoride used in the present invention) I)
The dissolving action of silica scale by a cleaning solution mixed with a fluorine compound such as ram is estimated by the following equation 1 for all cases of ammonium hydrogen fluoride (NH4HF2) as a fluorine compound.
２５１０ ＋ ６ＨＦ ＋３ＮＨ４）ＩＦ２＋Ｈ２０→
２Ｈ２Ｆ３１Ｆ６十３ＮＨ４０Ｈ＋２８２０ ・・・
第１式第１表に本発明による実施例（一部比較例）を示
す。2510 + 6HF +3NH4) IF2+H20→
2H2F31F6 3NH40H+2820...
Formula 1 Table 1 shows examples (some comparative examples) according to the present invention.
第１表に示す組成の洗浄液＋００ｍｊ全２００１のポリ
エチレン製ビーカにとり、これに５ＴＰＴ桐の短冊形の
テストピース（表面積３２ｃｒｎ２）及び実機の熱水輸
送管よシ採取したシリカを主成分とするスケール（３１
０２； ８６−８％、”２０！！ ’２．５％、０ａＣ
Ｏ＃ ５−２％、ｒ１５２０ｓ ； ０．２％、水分；
５．０％）を５〜７龍角程度に砕いて入れ、サランラン
プでポリエチレン製ビーカヲ苫閉後、６５Ｃの恒温水槽
に４時間（その間１５分間毎に１回の割合でと一カ中の
洗浄液を手動で攪拌した）浸漬し友。その後ビーカ中の
テストピース及び不溶解性スケールを取り出して、テス
トピースについては水洗後、アルコール、エーテルで洗
浄乾燥し、試験前後の重量差より腐食減ｔｔｌ−５不溶
解分スケールについては十分水洗後乾燥して重量を測定
し、試験前後の重量差よりスケールの溶解率を求めた。A cleaning solution with the composition shown in Table 1 + 00mj total 2001 was placed in a polyethylene beaker, and a 5TPT paulownia rectangular test piece (surface area 32crn2) and a scale containing silica as a main component (collected from a hot water transport pipe of an actual machine) were added to it. 31
02; 86-8%, "20!! '2.5%, 0aC
O# 5-2%, r1520s; 0.2%, moisture;
5.0%) was crushed into about 5 to 7 cubes, and after closing the polyethylene beaker with a saran lamp, it was placed in a constant temperature water bath at 65C for 4 hours (during which time, it was poured once every 15 minutes. The cleaning solution was stirred manually). After that, the test piece and insoluble scale in the beaker are taken out, and the test piece is washed with water, then washed with alcohol and ether, and dried.The difference in weight between before and after the test shows that corrosion is reduced.TTL-5 Insoluble scale is washed thoroughly with water. After drying, the weight was measured, and the scale dissolution rate was determined from the difference in weight before and after the test.
第１表から明らかなように試験番号（１）乃至（９）は
中性フッ素化合物に重合りん酸塩、酸腐食抑制剤（イン
ヒビター）を添加し、これにフッ化水素酸の重加濃度を
変化させて中性フッ素化合物との合計がＦ情として５Ｘ
ＧＣなるよう調整した洗浄液である。実機スケールの溶
解率は中性フッ素化合物対フフ化水素酸の混合比に影響
しており、フッ素化合物の単独あるいは３株併用のイロ
１れも中性フッ素化合物対フッ化水素酸の混合比の最適
範囲は２：３〜ｉ：４であり、その場合の実機スケール
の溶解率はほぼ９９％を示している。また本発明洗浄液
による熱水輸送管用材のテストピース（５ＴＰＴ材）に
対する腐食減量は非常に小さく腐食状態も全面均一腐食
であり、全く問題ない。As is clear from Table 1, in test numbers (1) to (9), a polymerized phosphate and an acid corrosion inhibitor (inhibitor) were added to a neutral fluorine compound, and a polyconcentration of hydrofluoric acid was added to the neutral fluorine compound. The total amount with neutral fluorine compounds is 5X as F condition.
This is a cleaning solution adjusted to be GC. The dissolution rate on an actual scale is affected by the mixing ratio of neutral fluorine compounds to hydrofluoric acid, and the mixing ratio of neutral fluorine compounds to hydrofluoric acid affects the mixing ratio of neutral fluorine compounds to hydrofluoric acid. The optimal range is 2:3 to i:4, and in that case, the dissolution rate on an actual scale is approximately 99%. Further, the corrosion loss caused by the cleaning solution of the present invention on the test piece (5TPT material) of hot water transport pipe material was very small, and the corrosion state was uniform corrosion over the entire surface, so there was no problem at all.
試験番号ａｌ乃至１１ｎは酸性フッ素化合物に重合りん
酸塩、酸腐食抑制剤（インヒビター）ｋ′ＩＩＳ加し、
これにフッ化水素酸の添加＠ｔｌｋ変化させて酸性７ツ
素化合物との合計がＦ賛として５％になるよう調整した
洗浄液である。実機スケールの醪Ｍ−率は試験番号（１
１乃至（９）と同様にフッ素化合物ダ・ｊフッ化水素酸
の混合比に影響しており、酸性フッ素化合物の単独ある
いは３種併用の何ｎもその混合比の最適範囲は４：１〜
１：４であり、その場合の実機スケールの溶解率はほぼ
９５％以上を示している。また本発明洗浄液によるテス
トピース（５ＴＰＴ材）に対する腐食減量も試験番号（
２）乃至（９）と殆んど差異々く問題ない。In test numbers al to 11n, polymerized phosphate and acid corrosion inhibitor k'IIS were added to the acidic fluorine compound,
This is a cleaning liquid that was adjusted by adding hydrofluoric acid @tlk so that the total amount with the acidic heptadium compound was 5% as F. The actual scale M-rate is the test number (1
Similar to 1 to (9), fluorine compounds influence the mixing ratio of hydrofluoric acid, and the optimum range of the mixing ratio for acidic fluorine compounds alone or in combination is 4:1 to 4:1.
The ratio is 1:4, and the dissolution rate on an actual scale in that case is approximately 95% or more. In addition, the corrosion loss of the test piece (5TPT material) using the cleaning solution of the present invention was also determined by the test number (
There are almost no problems compared to 2) to (9).
試験番号０８及びａ９は重合りん酸塩を添加してない中
性７ツ素化合物とフッ化水素酸の２＝５の混合液、試験
番号■及びａｎは重合りん酸塩を添加してない酸性フッ
素化合物とフッ化水素酸の５＝２の混合液であるが何れ
の混合液においても重合りん酸塩の添加された同一混合
洗浄液に比して実機スケールの溶解率は約３０％以上低
下する。Test numbers 08 and a9 are a 2=5 mixture of a neutral heptadium compound and hydrofluoric acid to which no polymeric phosphate is added, and test numbers ■ and an are acidic to which no polymeric phosphate is added. Although it is a 5=2 mixed solution of fluorine compound and hydrofluoric acid, the dissolution rate on an actual scale is about 30% lower than that of the same mixed cleaning solution with polymerized phosphate added. .
本発明化学的洗浄液により次のような効果が奏せられた
。The chemical cleaning solution of the present invention produced the following effects.
＋１１ フッ化水素アンモニウム、フッ化水素カリウ
ム、フッ化水素ナトリウム等の酸性７ツ化物及びフッ化
アンモニウム、フッ化ナトリウム、フッ化カリウム等の
中性フッ化物にフッ化水素酸を適量併用添加することに
より、シリカを主成分とするスケール溶解に対し顕著な
効果を発揮した。+11 Adding an appropriate amount of hydrofluoric acid to acidic heptadides such as ammonium hydrogen fluoride, potassium hydrogen fluoride, and sodium hydrogen fluoride, and neutral fluorides such as ammonium fluoride, sodium fluoride, and potassium fluoride. This showed a remarkable effect on dissolving scales mainly composed of silica.
（２）洗浄液に重合りん酸塩を併用添加したことにより
スケール中のカルシウムによるシリカの溶解力阻害を防
止した。(2) By adding polymerized phosphate to the cleaning solution, inhibition of the dissolving power of silica by calcium in the scale was prevented.
（３） 上記（１）及び（２）の相乗効果により、地
熱水よシ生成するシリカを主成分とするスケールの溶解
除去に対し、実用的に極めて顕著な効果を発揮した。(3) Due to the synergistic effect of (1) and (2) above, an extremely significant practical effect was exhibited in dissolving and removing scale mainly composed of silica produced by geothermal water.
Claims (1)
加し、これに重合りん酸塩及び酸腐食抑制剤を添加して
なることを特徴とする地熱発電プラントのスケール化学
的洗浄液。A scale chemical cleaning solution for geothermal power generation plants, characterized in that hydrofluoric acid is added to at least one kind of fluorine compound, and a polymerized phosphate and an acid corrosion inhibitor are added thereto.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1010587A JPS63179087A (en) | 1987-01-21 | 1987-01-21 | Chemical washing liquid for scale in geothermal power plant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1010587A JPS63179087A (en) | 1987-01-21 | 1987-01-21 | Chemical washing liquid for scale in geothermal power plant |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63179087A true JPS63179087A (en) | 1988-07-23 |
Family
ID=11741033
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1010587A Pending JPS63179087A (en) | 1987-01-21 | 1987-01-21 | Chemical washing liquid for scale in geothermal power plant |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63179087A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022202164A1 (en) * | 2021-03-25 | 2022-09-29 | 富士電機株式会社 | Method for selecting scale solubilizer |
-
1987
- 1987-01-21 JP JP1010587A patent/JPS63179087A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022202164A1 (en) * | 2021-03-25 | 2022-09-29 | 富士電機株式会社 | Method for selecting scale solubilizer |
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