JPS6042276B2 - anti-corrosion lubricant - Google Patents
anti-corrosion lubricantInfo
- Publication number
- JPS6042276B2 JPS6042276B2 JP14362081A JP14362081A JPS6042276B2 JP S6042276 B2 JPS6042276 B2 JP S6042276B2 JP 14362081 A JP14362081 A JP 14362081A JP 14362081 A JP14362081 A JP 14362081A JP S6042276 B2 JPS6042276 B2 JP S6042276B2
- Authority
- JP
- Japan
- Prior art keywords
- carbon atoms
- alkyl group
- formula
- lubricating oil
- phenol derivative
- 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
- 238000005260 corrosion Methods 0.000 title description 26
- 239000000314 lubricant Substances 0.000 title 1
- 239000010687 lubricating oil Substances 0.000 claims description 33
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 28
- 150000002989 phenols Chemical class 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 25
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 21
- 229910052717 sulfur Inorganic materials 0.000 claims description 21
- 239000011593 sulfur Substances 0.000 claims description 20
- 239000000654 additive Substances 0.000 claims description 14
- 239000002199 base oil Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002480 mineral oil Substances 0.000 claims description 11
- 235000010446 mineral oil Nutrition 0.000 claims description 11
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 8
- 239000012964 benzotriazole Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims 7
- 230000007797 corrosion Effects 0.000 description 22
- 239000003921 oil Substances 0.000 description 22
- 230000000694 effects Effects 0.000 description 11
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 7
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 7
- 238000010248 power generation Methods 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 7
- 239000004332 silver Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000005536 corrosion prevention Methods 0.000 description 2
- 239000010735 electrical insulating oil Substances 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- SKDGWNHUETZZCS-UHFFFAOYSA-N 2,3-ditert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(O)=C1C(C)(C)C SKDGWNHUETZZCS-UHFFFAOYSA-N 0.000 description 1
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- VQQLTEBUMLSLFJ-UHFFFAOYSA-N 2,6-ditert-butyl-4-nonylphenol Chemical compound CCCCCCCCCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VQQLTEBUMLSLFJ-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 1
- BKZXZGWHTRCFPX-UHFFFAOYSA-N 2-tert-butyl-6-methylphenol Chemical compound CC1=CC=CC(C(C)(C)C)=C1O BKZXZGWHTRCFPX-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 241000219122 Cucurbita Species 0.000 description 1
- 235000009852 Cucurbita pepo Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Landscapes
- Lubricants (AREA)
Description
【発明の詳細な説明】
本発明は含腐食性イオウ雰囲気て防食性を有する地熱タ
ービン用潤滑油に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a lubricating oil for geothermal turbines that has anticorrosive properties in a corrosive sulfur atmosphere.
近年、石油コストの高騰に鑑み代替エネルギーの一つと
して地熱の利用が注目されてきており、特に地熱発電は
実用化の段階に入つている。In recent years, in view of the soaring cost of oil, the use of geothermal energy has been attracting attention as an alternative energy source, and geothermal power generation in particular has entered the stage of practical application.
しかしながら、現在稼動中の地熱発電所においてみられ
る問題点の一つとしてタービン用潤滑油による装置機器
の腐食、特にローター接地装置とフして用いられている
銀ブラシの腐食による黒化現象がある。この銀ブラシの
黒化現象は電気抵抗の増加ばかりでなく歯こぼれ現象を
生ずるため発電装置の解放、補修を必要とするに至る。
本発明者は、地熱発電にみられる上記腐食の原門因につ
いて検討した結果、この腐食現象は地熱発電に用いられ
る蒸気中に含まれる主として硫化水素（Ｈ、Ｓ）と炭酸
ガス（ＣＯ０）から成る酸性ガス（一般にはＨ２５５０
〜１０００ｐｐｍＮＣ０２３００〜３０００ｐｐｍ）に
起因することを確認した。However, one of the problems observed in currently operating geothermal power plants is corrosion of equipment due to turbine lubricating oil, and in particular blackening caused by corrosion of silver brushes used as rotor grounding devices. . This blackening phenomenon of the silver brush not only increases electrical resistance but also causes tooth spillage, which necessitates opening and repair of the power generator.
As a result of studying the causes of the above-mentioned corrosion observed in geothermal power generation, the present inventor found that this corrosion phenomenon is mainly caused by hydrogen sulfide (H, S) and carbon dioxide gas (CO0) contained in the steam used in geothermal power generation. acidic gas (generally H2550)
~1000ppmNC02300~3000ppm).
すなわ１ち、長期間の運転中に潤滑油中に混入してくる
Ｈ２Ｓ及びＨ２Ｓの油中での酸化により生成する遊離イ
オウｓが潤滑油と接触する装置機器部分及び銀ブラシを
腐食するに至る。本発明者は上述したごときＨ２Ｓ及び
遊離イオウに起因する腐食現象の防食について検討した
結果、本発明をなすに至つた。In other words, H2S mixed into the lubricating oil during long-term operation and free sulfur produced by oxidation of H2S in the oil corrode the parts of the equipment and silver brushes that come into contact with the lubricating oil. reach. The present inventor has completed the present invention as a result of studies on corrosion prevention against the corrosion phenomenon caused by H2S and free sulfur as described above.
したがつて、本発明の目的は、含腐食性イオウ雰囲気で
の運転において優れた防食性を有する地熱タービツ用潤
滑油を提供することにある。Therefore, an object of the present invention is to provide a lubricating oil for geothermal turbines that has excellent anticorrosive properties when operating in a corrosive sulfur atmosphere.
以下本発明を詳しく説明する。本発明に係る潤滑油は鉱
油を基油とし、添加剤として２−メルカプトベンゾチア
ゾールとフェノール誘導体、特に下記式（Ｉ）、（■）
及び（■）で表わされる群のフェノール誘導体から選択
される１種もしくは２種以上を含有することを特徴とす
る。The present invention will be explained in detail below. The lubricating oil according to the present invention uses mineral oil as a base oil, and uses 2-mercaptobenzothiazole and phenol derivatives as additives, particularly those of the following formulas (I) and (■).
It is characterized by containing one or more phenol derivatives selected from the group represented by (■) and (■).
・・・・ ・・・・・・ （Ｉ）
ゾトリアゾールとを含有することを特徴とする含腐食性
イオウ雰囲気下で防食性を有する地熱タービン用潤滑油
。...... (I) A lubricating oil for geothermal turbines having anticorrosive properties in a corrosive sulfur atmosphere, characterized by containing zotriazole.
６ フェノール誘導体が下記式（１）で表わされる特許
請求の範囲第５項記載の潤滑油。6. The lubricating oil according to claim 5, wherein the phenol derivative is represented by the following formula (1).
（式中Ｒ１およびＲ３は炭素数１乃至４個のアルキル基
を示し、Ｒ２は水素又は炭素数１乃至９のアルキル基を
示す）。(In the formula, R1 and R3 represent an alkyl group having 1 to 4 carbon atoms, and R2 represents hydrogen or an alkyl group having 1 to 9 carbon atoms).
７ フェノール誘導体が下記式（■）で表わされる特許
請求の範囲築５項記載の潤滑油。7. The lubricating oil according to claim 5, wherein the phenol derivative is represented by the following formula (■).
（式中Ｒ１およびＲ１″は炭素数１乃至４個のアルキル
基を示し、Ｒ２及びＲ２″は水素又は炭素数１乃至４個
のアルキル基を示し、Ｒ３及びＲ４は水素又は炭素数１
乃至３個のアルキル基を示す）。(In the formula, R1 and R1'' represent an alkyl group having 1 to 4 carbon atoms, R2 and R2'' represent hydrogen or an alkyl group having 1 to 4 carbon atoms, and R3 and R4 represent hydrogen or an alkyl group having 1 to 4 carbon atoms.
to 3 alkyl groups).
８ フェノール誘導体が下記式（■）で表わされる特許
請求の範囲第５項記載の潤滑油。8. The lubricating oil according to claim 5, wherein the phenol derivative is represented by the following formula (■).
（式中Ｒｌ，Ｒ２，Ｒ３，Ｒ４，Ｒｌ″及びＲ２″は上
記式．（■）におけると同じ意味を示す）。(In the formula, Rl, R2, R3, R4, Rl'' and R2'' have the same meanings as in the above formula (■)).
（式中Ｒ１およびＲ３は炭素数１〜４個のアルキル基を
示し、Ｒ２は水素又は炭素数１〜９のアル発明の詳細な
説明本発明は含腐食性イオウ雰囲気て防食性を有する地
熱タービン用潤滑油に関する。(In the formula, R1 and R3 represent an alkyl group having 1 to 4 carbon atoms, and R2 is hydrogen or an alkyl group having 1 to 9 carbon atoms.) Regarding lubricating oil for use.
近年、石油コストの高騰に鑑み代替エネルギーの一つと
して地熱の利用が注目されてきており、特に地熱発電は
実用化の俊階に入つている。In recent years, in view of the soaring cost of oil, the use of geothermal energy has been attracting attention as an alternative energy source, and geothermal power generation in particular is on the verge of practical application.
しかしながら、現在稼動中の地熱発電所においてみられ
る問題点の一つとしてタービン用潤滑油による装置機器
の腐食、特にローター接地装置とフして用いられている
銀ブラシの腐食による黒化現象がある。この銀ブラシの
黒化現象は電気抵抗の増加ばかりでなく歯こぼれ現象を
生ずるため発電装置の解放、補修を必要とするに至る。
本発明者は、地熱発電にみられる上記腐食の原門因につ
いて検討した結果、この腐食現象は地熱発電に用いられ
る蒸気中に含まれる主として硫化水素（Ｈ２Ｓ）と炭酸
ガス（ＣＯ２）から成る酸性ガス（一般にはＨ２Ｓ５Ｏ
〜１０００ｐｐｍ．．Ｃ０２３００〜３０００ｐｐｍ）
に起因することを確認した。However, one of the problems observed in currently operating geothermal power plants is corrosion of equipment due to turbine lubricating oil, and in particular blackening caused by corrosion of silver brushes used as rotor grounding devices. . This blackening phenomenon of the silver brush not only increases electrical resistance but also causes tooth spillage, which necessitates opening and repair of the power generator.
As a result of studying the causes of the above-mentioned corrosion observed in geothermal power generation, the present inventor found that this corrosion phenomenon is caused by the acidity mainly composed of hydrogen sulfide (H2S) and carbon dioxide gas (CO2) contained in the steam used for geothermal power generation. gas (generally H2S5O
~1000ppm. ．． C02300~3000ppm)
It was confirmed that this was caused by
すなわｌち、長期間の運転中に潤滑油中に混入してくる
Ｈ２Ｓ及びＨ２Ｓの油中での酸化により生成する遊離イ
オウＳが潤滑油と接触する装置機器部分及び銀ブラシを
腐食するに至る。本発明者は上述したごときＨ２Ｓ及び
遊離イオウに起因する腐食現象の防食について検討した
結果、本発明をなすに至つた。In other words, H2S mixed into the lubricating oil during long-term operation and free sulfur S produced by oxidation of H2S in the oil corrode the parts of the equipment and silver brushes that come into contact with the lubricating oil. reach. The present inventor has completed the present invention as a result of studies on corrosion prevention against the corrosion phenomenon caused by H2S and free sulfur as described above.
したがつて、本発明の目的は、含腐食性イオウ雰囲気で
の運転において優れた防食性を有する地熱タービン用潤
滑油を提供することにある。Accordingly, an object of the present invention is to provide a lubricating oil for geothermal turbines that has excellent corrosion resistance when operating in a corrosive sulfur atmosphere.
以下本発明の詳細な説明する。本発明に係る潤滑油は鉱
油を基油とし、添加剤として２−メルカプトベンゾチア
ゾールとフェノール誘導体、特に下記式（１），（■）
及び（■）で表わされる群のフェノール誘導体から選択
される１種もしくは２種以上を含有することを特徴とす
る。The present invention will be explained in detail below. The lubricating oil according to the present invention uses mineral oil as a base oil, and uses 2-mercaptobenzothiazole and a phenol derivative as additives, particularly the following formulas (1) and (■).
It is characterized by containing one or more phenol derivatives selected from the group represented by (■) and (■).
キル基を示す）。(indicates a kill group).
（式（■），（■）においてＲｌ，Ｒｌ″は炭素数１〜
４個のアルキル基を示し、Ｒ２，Ｒ２″は水素又は炭素
数１〜４個のアルキル基を示し、Ｒ３，Ｒ４は水素又は
炭素数１〜３個のアルキル基を示す。(In formulas (■) and (■), Rl and Rl'' have 1 to 1 carbon atoms.
4 alkyl groups are shown, R2 and R2'' are hydrogen or an alkyl group having 1 to 4 carbon atoms, and R3 and R4 are hydrogen or an alkyl group having 1 to 3 carbon atoms.
更に、本発明に係る潤滑油は上記添加剤に加えてベンゾ
トリアゾールを含有することを特徴とするものも包含す
る。本発明において基油に対する添加剤として用いる２
−メルカプトベンゾチアゾールは従来電気絶縁油中のイ
オウＳによる該油中の裸銅部の防食に使用することが知
られている（特公昭５２−４０４吋公報）。Furthermore, the lubricating oil according to the present invention also includes one characterized in that it contains benzotriazole in addition to the above additives. 2 used as an additive to base oil in the present invention
-Mercaptobenzothiazole has been known to be used to prevent corrosion of bare copper parts in electrical insulating oil due to sulfur S (Japanese Patent Publication No. 404/1983).
しかしながら、地熱タービン用潤滑油のごとき含腐食性
イオウ雰囲気下で用いる潤滑油では２−メルカプトベン
ゾチアゾール単独を添加剤として含有させても防食効果
、特にＡｇの防食効果が十分でないので上記（１），（
■）及び（■）を有する群のフェノール誘導体から選択
されるものの併用が必要である。本発明で用いるフェノ
ール誘導体は油溶性であり、酸化防止剤として公知のも
のであり、上記式（１）て表わされるフェノール誘導体
として２，６−ジーｔ−ブチルーｐ−クレゾール，２−
メチルー６−ｔ−ブチルーｐ−クレゾール、２，６−ジ
ーｔ−ブチルフェノール、２，６−ジーｔ−ブチルー４
−ノニルフェノールを例示し得る。However, in lubricating oils used in corrosive sulfur atmospheres such as lubricating oils for geothermal turbines, even if 2-mercaptobenzothiazole is added alone as an additive, the anticorrosive effect, especially the anticorrosive effect of Ag, is insufficient, so (1) ，(
It is necessary to use a combination of phenol derivatives selected from the group consisting of (1) and (2). The phenol derivative used in the present invention is oil-soluble and is known as an antioxidant, and the phenol derivative represented by the above formula (1) is 2,6-di-t-butyl-p-cresol, 2-
Methyl-6-t-butyl-p-cresol, 2,6-di-t-butylphenol, 2,6-di-t-butyl-4
-nonylphenol can be exemplified.
また上記式（■）で表わされるフェノール誘導体として
は、４，４″−メチレンビス（２，６−ジーｔ−ブチル
フェノール）、４，４″−メチレンビス（６−ｔ−ブチ
ルー２−メチルフェノール）、４，４″−プチリデンビ
ス（６−ｔ−ブチルー３−メチルフェノール）を例示し
得る。また上記式（■）で表わされるフェノール誘導体
としては２，２′−メチレンビス（６−ｔ−ブチルー４
−メチルフェノール）、２，７−メチレンビス（６−ｔ
−ブチルフェノール）を例示し得る。In addition, the phenol derivatives represented by the above formula (■) include 4,4''-methylenebis(2,6-di-t-butylphenol), 4,4''-methylenebis(6-t-butyl-2-methylphenol), 4,4''-methylenebis(2,6-di-t-butylphenol), , 4''-butylidene bis(6-t-butyl-3-methylphenol). Examples of the phenol derivative represented by the above formula (■) include 2,2'-methylenebis(6-t-butyl-4-methylphenol).
-methylphenol), 2,7-methylenebis(6-t
-butylphenol).
以下に、基油としての鉱油に２−メルカプトベンゾチア
ゾール単独及び上記フェノール誘導体と併用したものを
それぞれ添加剤として添加した試作油についてＡｇ板の
防食テストを行つた結果を下記表１に例示する。Table 1 below shows the results of a corrosion protection test on Ag plates for trial oils in which 2-mercaptobenzothiazole alone and in combination with the above phenol derivative were added as additives to mineral oil as a base oil.
なお、試験方法はＪｌＳＣ２ｌＯｌの電気絶縁油腐食試
験方法に準拠して行つた（ただし、試料油へのＮ２吹込
みとコック閉めの操作は行なわない）。The test method was conducted in accordance with the electrical insulating oil corrosion test method of JlSC2lOl (however, the injection of N2 into the sample oil and the operation of closing the cock were not performed).
６×２５瓢の〜板を試料とし、一方上記試作油２５０ｍ
１に結晶イオウを溶解して油中の遊離イオウの濃度を調
整したものの各々に上記試料を１４０℃で一定時間接触
させた後のＡｇ板の変色状態を観察することにより行な
つた。A 6 x 25 gourd board was used as a sample, while 250 m of the above prototype oil was used as a sample.
The concentration of free sulfur in the oil was adjusted by dissolving crystalline sulfur in No. 1, and the samples were brought into contact at 140° C. for a certain period of time, and then the state of discoloration of the Ag plate was observed.
（４）〜板の防食評価は下記基準による。(4) The corrosion protection evaluation of the board is based on the following criteria.
上記表１にみられるごとく、２−メルカプトベンゾチア
ゾールル単独を添加剤として含む油では遊離イオウの含
量が２０〜３０ｐｐｍ程度で、且つ接触時間が短い場合
には無添加のものに比しＡｇに対する防食効果はみられ
るが、試験時間が１２０時記間に達するともはや防食効
果は殆んどみられなくなる。As shown in Table 1 above, in oils containing 2-mercaptobenzothiazole alone as an additive, when the free sulfur content is about 20 to 30 ppm and the contact time is short, the oil has a higher Ag content than that without additives. Although an anticorrosive effect is observed, when the test time reaches 120 hours, the anticorrosive effect is almost no longer observed.
これに対し、２−メルカプトベンゾチアゾールと共に前
記式のフェノール誘導体を併用して添加した油では遊離
イオウ含量が２０〜３０ｐｐｍ程度で試験時間が１叫間
の場合にはＡｇの腐食は実質上みられず、また試験時間
が１２叫間に達しても防食効果がある。On the other hand, in the case of oil in which the phenol derivative of the above formula is added together with 2-mercaptobenzothiazole, when the free sulfur content is about 20 to 30 ppm and the test time is 1 hour, virtually no corrosion of Ag is observed. Moreover, the anticorrosion effect is maintained even when the test time reaches 12 hours.
一方、フェノール誘導体単独を添加剤として用いた油で
は防食効果は殆んどみられない。On the other hand, oil containing only a phenol derivative as an additive has almost no anticorrosion effect.
したがつて、上記試験結果に照らし、本発明においては
２−メルカプトベンゾチアゾールとフェノール誘導体は
〜に対する防食効果上相乗的に作用していると言い得る
。Therefore, in light of the above test results, it can be said that in the present invention, 2-mercaptobenzothiazole and the phenol derivative act synergistically in terms of the anticorrosion effect against ~.
次に、本発明では添加剤として更にベンゾトリアゾール
を含む潤滑油をも対象として包含するものてあり、この
添加剤を添加することにより潤滑油のＮに対する防食性
が一そう高くなる。Next, the present invention further includes lubricating oils containing benzotriazole as an additive, and by adding this additive, the corrosion resistance of the lubricating oil against N is further increased.
上述した試験方法に基き、基油としての鉱油に２−メル
カプトベンゾチアゾール、フェノール誘導体及びベンゾ
トリアゾールを添加した試作油についてＡｇ板の防食テ
ストを行つた結果を下記表２に例示する。Based on the above-mentioned test method, a corrosion protection test was conducted on Ag plates using a prototype oil prepared by adding 2-mercaptobenzothiazole, a phenol derivative, and benzotriazole to mineral oil as a base oil. The results are shown in Table 2 below.
表２にみられるごとく、ベンゾトリアゾールを更に含む
潤滑油は遊離イオウを３０ｐｐｍ含み且つ１錫時間（７
日間）の試験時間でも防食効果を示す。As seen in Table 2, the lubricating oil further containing benzotriazole contains 30 ppm free sulfur and 1 tin hour (7
It shows anti-corrosion effect even after a test time of 1 day).
本発明における添加剤の基油に対する添加量は２−メル
カプトベンゾチアゾールでは基油中の遊離イオウ含量に
応て定められるが通常は５〜２００ｐｐｍであり、２０
０ｐｐｍを越えると基油に対する溶解度が低減するので
好ましくない。The amount of additive added to the base oil in the present invention is determined depending on the free sulfur content in the base oil for 2-mercaptobenzothiazole, but is usually 5 to 200 ppm, and 20
If it exceeds 0 ppm, the solubility in the base oil will decrease, which is not preferable.
フェノー゛ル誘導体は通常基油に対して０．４−１．呼
量％添加するのが潤滑油の酸化安定性及び経済上の観点
からすれば好ましく、また１重量％を越えてもＡｇの防
食効果は平衡状態になるので経済上から得策でない。ま
た、ベンゾトリアゾールは通常基油に対して３０〜１０
０ｐｐｍ添加するとよく、１００ｐｐｍを越えると基油
に対する溶解性が悪くなるので留意する必要がある。以
上は本発明に係る潤滑油の銀に対する防食効果を述べた
が、２−メルカプトベンゾチアゾールをフェノール誘導
体と併用すると下記に示すごとく銅に対する防食性も一
そう向上する。Phenol derivatives are usually used at a ratio of 0.4-1.0% to the base oil. It is preferable to add Ag in an amount of % by weight from the viewpoint of oxidation stability of the lubricating oil and from an economic point of view, and even if it exceeds 1% by weight, the anticorrosive effect of Ag will be in an equilibrium state, so it is not economical. Also, benzotriazole is usually 30 to 10% of the base oil.
It is best to add 0 ppm, and care must be taken because if it exceeds 100 ppm, the solubility in the base oil will deteriorate. The anti-corrosion effect on silver of the lubricating oil according to the present invention has been described above, but when 2-mercaptobenzothiazole is used in combination with a phenol derivative, the anti-corrosion effect on copper is further improved as shown below.
試験方法：
Ａｇ板の代りにＣｕ板を用いる以外は前記のＡｇ板防食
試験の方法と同じてある。Test method: The method was the same as the above-mentioned Ag plate corrosion protection test except that a Cu plate was used instead of the Ag plate.
試験結果は下記表３のとおりてある。叙上のごとく、本
発明によると、地熱発電タービンにおけるごとき含腐食
性イオウ雰囲気下で用いられる潤滑油において防食性の
高い潤滑油を提供し得るようになる。The test results are shown in Table 3 below. As described above, according to the present invention, it is possible to provide a lubricating oil with high corrosion resistance for use in a corrosive sulfur atmosphere such as in a geothermal power generation turbine.
以下に実施例を示して本発明を更に具体的に説明する。
なお、各実施例て用いた鉱油の性状及び防食試験は下記
のとおりである。鉱油の性状：
中東原油を常圧蒸留、真空蒸留して得られる留出油をフ
ルフラール溶剤抽出、水素化処理および溶剤脱ろう処理
して精製し、表４に示す性状の鉱油を基油として用いた
。EXAMPLES The present invention will be explained in more detail with reference to Examples below.
The properties of the mineral oil used in each example and the corrosion resistance test are as follows. Properties of mineral oil: The distillate oil obtained by atmospheric distillation and vacuum distillation of Middle Eastern crude oil was purified by furfural solvent extraction, hydrogenation treatment, and solvent dewaxing treatment, and the mineral oil with the properties shown in Table 4 was used as a base oil. there was.
銀板および銅板防食試験：
前掲のとおりＪＩＳＣ２ｌＯｌ−１９７８に定める方法
に準拠した。Silver plate and copper plate corrosion protection test: As mentioned above, the method specified in JISC21Ol-1978 was followed.
ただし窒素ガスの吹込みおよび空気との遮断は行わない
。遊離硫黄濃度は単体硫黄を試料油に溶解して調整した
。However, neither nitrogen gas injection nor air isolation is performed. Free sulfur concentration was adjusted by dissolving elemental sulfur in sample oil.
実施例１表４に示した鉱油に２−メルカプトベンゾチア
ゾール１００ｐｐｍと酸化防止剤２，６−ジーｔ−ブチ
ルー４−メチルフェノール０．５Ｗｔ％を加熱溶解させ
試料油（１）を得た。Example 1 Sample oil (1) was obtained by heating and dissolving 100 ppm of 2-mercaptobenzothiazole and 0.5 wt% of the antioxidant 2,6-di-t-butyl-4-methylphenol in the mineral oil shown in Table 4.
実施例２
表４に示した鉱油に２−メルカプトベンゾチアゾール１
００ｐｐｍと酸化防止剤４，４″−メチレンビス（２，
６，ジーｔ−ブチルフェノール）を１Ｗｔ％加熱溶解さ
せ、試料油（２）を得た。Example 2 2-mercaptobenzothiazole 1 was added to the mineral oil shown in Table 4.
00ppm and antioxidant 4,4″-methylenebis(2,
6, di-t-butylphenol) was dissolved by heating to obtain a sample oil (2).
実施例３
上記試料油（１）にベンゾトリアゾール５０ｐｐｍを溶
解して試料油（３）を得た。Example 3 50 ppm of benzotriazole was dissolved in the above sample oil (1) to obtain sample oil (3).
実施例４
上記試料油（２）にベンゾトリアゾール５０ｐｐｍを溶
解して試料油（４）を得た。Example 4 50 ppm of benzotriazole was dissolved in the above sample oil (2) to obtain sample oil (4).
試料油（１）〜（４）の各性状を表５に示す。Table 5 shows the properties of sample oils (1) to (4).
Claims (1)
ゾチアゾール及びフェノール誘導体を含有することを特
徴とする含腐食性イオウ雰囲気下で防食性を有する地熱
タービン用潤滑油。 ２ フェノール誘導体が下記式（ I ）で表わされる特
許請求の範囲第１項記載の潤滑油。 ▲数式、化学式、表等があります▼（ I ）（式中Ｒ＿
１およびＲＣは炭素数１乃至４個のアルキル基を示し、
Ｒ＿２は水素又は炭素数１乃至９のアルキル基を示す）
。 ３ フェノール誘導体が下記式（II）で表わされる特許
請求の範囲第１項記載の潤滑油。 ▲数式、化学式、表等があります▼（II）（式中Ｒ＿１
およびＲ＿１′は炭素数１乃至４個のアルキル基を示し
、Ｒ＿２及びＲ＿２′は水素又は炭素数１乃至４個のア
ルキル基を示し、Ｒ＿３及びＲ＿４は水素又は炭素数１
乃至３個のアルキル基を示す）。 ４ フェノール誘導体が下記式（III）で表わされる特
許請求の範囲第１項記載の潤滑油。 ▲数式、化学式、表等があります▼（III）（式中Ｒ＿
１、Ｒ＿２、Ｒ＿３、Ｒ＿４、Ｒ＿１′及びＲ＿２′は
上記式（II）におけると同じ意味を示す）。 ５ 鉱油を基油とし、添加剤として２−メルカプトベン
ゾチアゾールとフェノール誘導体及びベンゾトリアゾー
ルとを含有することを特徴とする含腐食性イオウ雰囲気
下で防食性を有する地熱タービン用潤滑油。６ フェノ
ール誘導体が下記式（ I ）で表わされる特許請求の範
囲第５項記載の潤滑油。 ▲数式、化学式、表等があります▼（ I ）（式中Ｒ＿
１およびＲ＿３は炭素数１乃至４個のアルキル基を示し
、Ｒ＿２は水素又は炭素数１乃至９のアルキル基を示す
）。 ７ フェノール誘導体が下記式（II）で表わされる特許
請求の範囲第５項記載の潤滑油。 ▲数式、化学式、表等があります▼（II）（式中Ｒ＿１
およびＲ＿１′は炭素数１乃至４個のアルキル基を示し
、Ｒ＿２及びＲ＿２′は水素又は炭素数１乃至４個のア
ルキル基を示し、Ｒ＿３及びＲ＿４は水素又は炭素数１
乃至３個のアルキル基を示す）。 ８ フェノール誘導体が下記式（III）で表わされる特
許請求の範囲第５項記載の潤滑油。 ▲数式、化学式、表等があります▼（III）（式中Ｒ＿
１、Ｒ＿２、Ｒ＿３、Ｒ＿４、Ｒ＿１′及びＲ＿２′は
上記式（II）におけると同じ意味を示す）。 ▲数式、化学式、表等があります▼・・・・・（ I ）
（式中Ｒ＿１およびＲ＿３は炭素数１〜４個のアルキル
基を示し、Ｒ＿２は水素又は炭素数１〜９のアルキル基
を示す）。[Scope of Claims] 1. A lubricating oil for geothermal turbines having anticorrosive properties in a corrosive sulfur atmosphere, characterized by using mineral oil as a base oil and containing 2-mercaptobenzothiazole and a phenol derivative as additives. 2. The lubricating oil according to claim 1, wherein the phenol derivative is represented by the following formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (R_ in the formula
1 and RC represent an alkyl group having 1 to 4 carbon atoms,
R_2 represents hydrogen or an alkyl group having 1 to 9 carbon atoms)
. 3. The lubricating oil according to claim 1, wherein the phenol derivative is represented by the following formula (II). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (R_1 in the formula
and R_1' represents an alkyl group having 1 to 4 carbon atoms, R_2 and R_2' represent hydrogen or an alkyl group having 1 to 4 carbon atoms, and R_3 and R_4 represent hydrogen or an alkyl group having 1 to 4 carbon atoms.
to 3 alkyl groups). 4. The lubricating oil according to claim 1, wherein the phenol derivative is represented by the following formula (III). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (R_ in the formula
1, R_2, R_3, R_4, R_1' and R_2' have the same meanings as in the above formula (II)). 5. A geothermal turbine lubricating oil having anticorrosive properties in a corrosive sulfur atmosphere, characterized by using mineral oil as a base oil and containing 2-mercaptobenzothiazole, a phenol derivative, and benzotriazole as additives. 6. The lubricating oil according to claim 5, wherein the phenol derivative is represented by the following formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (R_ in the formula
1 and R_3 represent an alkyl group having 1 to 4 carbon atoms, and R_2 represents hydrogen or an alkyl group having 1 to 9 carbon atoms). 7. The lubricating oil according to claim 5, wherein the phenol derivative is represented by the following formula (II). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (R_1 in the formula
and R_1' represents an alkyl group having 1 to 4 carbon atoms, R_2 and R_2' represent hydrogen or an alkyl group having 1 to 4 carbon atoms, and R_3 and R_4 represent hydrogen or an alkyl group having 1 to 4 carbon atoms.
to 3 alkyl groups). 8. The lubricating oil according to claim 5, wherein the phenol derivative is represented by the following formula (III). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (R_ in the formula
1, R_2, R_3, R_4, R_1' and R_2' have the same meanings as in the above formula (II)). ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(I)
(In the formula, R_1 and R_3 represent an alkyl group having 1 to 4 carbon atoms, and R_2 represents hydrogen or an alkyl group having 1 to 9 carbon atoms.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14362081A JPS6042276B2 (en) | 1981-09-11 | 1981-09-11 | anti-corrosion lubricant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14362081A JPS6042276B2 (en) | 1981-09-11 | 1981-09-11 | anti-corrosion lubricant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5845291A JPS5845291A (en) | 1983-03-16 |
| JPS6042276B2 true JPS6042276B2 (en) | 1985-09-20 |
Family
ID=15342978
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14362081A Expired JPS6042276B2 (en) | 1981-09-11 | 1981-09-11 | anti-corrosion lubricant |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6042276B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS625576A (en) * | 1985-06-28 | 1987-01-12 | 日本圧着端子製造株式会社 | Electric connector |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH025868Y2 (en) * | 1985-12-03 | 1990-02-13 |
-
1981
- 1981-09-11 JP JP14362081A patent/JPS6042276B2/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS625576A (en) * | 1985-06-28 | 1987-01-12 | 日本圧着端子製造株式会社 | Electric connector |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5845291A (en) | 1983-03-16 |
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