JPH0460159B2 - - Google Patents
Info
- Publication number
- JPH0460159B2 JPH0460159B2 JP2488284A JP2488284A JPH0460159B2 JP H0460159 B2 JPH0460159 B2 JP H0460159B2 JP 2488284 A JP2488284 A JP 2488284A JP 2488284 A JP2488284 A JP 2488284A JP H0460159 B2 JPH0460159 B2 JP H0460159B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- alkaline earth
- water
- earth metal
- product
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 83
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 57
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 49
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 48
- 229910052751 metal Inorganic materials 0.000 claims description 45
- 239000002184 metal Substances 0.000 claims description 45
- 150000002989 phenols Chemical class 0.000 claims description 34
- 239000003153 chemical reaction reagent Substances 0.000 claims description 27
- 239000003599 detergent Substances 0.000 claims description 26
- 239000000047 product Substances 0.000 claims description 26
- 239000001569 carbon dioxide Substances 0.000 claims description 24
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 24
- 239000007795 chemical reaction product Substances 0.000 claims description 21
- 238000011282 treatment Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 15
- 229910052717 sulfur Inorganic materials 0.000 claims description 15
- 239000011593 sulfur Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 150000001298 alcohols Chemical class 0.000 claims description 6
- 238000005987 sulfurization reaction Methods 0.000 claims description 6
- 150000004679 hydroxides Chemical class 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 61
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 30
- 238000004821 distillation Methods 0.000 description 25
- 239000002994 raw material Substances 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- 238000007259 addition reaction Methods 0.000 description 13
- 239000003085 diluting agent Substances 0.000 description 13
- -1 ethylhexyl Chemical group 0.000 description 12
- 229960001860 salicylate Drugs 0.000 description 12
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 11
- 210000000988 bone and bone Anatomy 0.000 description 10
- 239000012467 final product Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 238000001914 filtration Methods 0.000 description 9
- 239000003921 oil Substances 0.000 description 7
- 101100492795 Aspergillus flavus atmG gene Proteins 0.000 description 6
- 239000010687 lubricating oil Substances 0.000 description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 206010020751 Hypersensitivity Diseases 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 208000026935 allergic disease Diseases 0.000 description 3
- 239000002199 base oil Substances 0.000 description 3
- 238000000998 batch distillation Methods 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 230000009610 hypersensitivity Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000005486 sulfidation Methods 0.000 description 3
- 230000001052 transient effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000007806 chemical reaction intermediate Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000010705 motor oil Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 150000003870 salicylic acids Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- PVULMDLILHXVIO-UHFFFAOYSA-N 2-nonoxybenzoic acid Chemical compound CCCCCCCCCOC1=CC=CC=C1C(O)=O PVULMDLILHXVIO-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 206010066364 Hypersexuality Diseases 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241000218231 Moraceae Species 0.000 description 1
- 235000008708 Morus alba Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001944 continuous distillation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000003747 fuel oil additive Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 125000001802 myricyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- VNCXHTZWYIBJTA-UHFFFAOYSA-N nonyl 2-hydroxybenzoate Chemical compound CCCCCCCCCOC(=O)C1=CC=CC=C1O VNCXHTZWYIBJTA-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Lubricants (AREA)
Description
本発明は、潤滑油または燃料油の清浄剤あるい
はアルカリ清浄剤として有用な塩基性あるいは過
塩基性のアルカリ土類金属フエネート型清浄剤ま
たは硫化アルカリ土類金属フエネート型清浄剤
（以下特記を要さない限り塩基性アルカリ土類金
属フエネート型清浄剤という。）を工業的に有利
に製造する方法に関するものである。一般に塩基
性フエネート型清浄剤は内燃機用潤滑油に使用さ
れ、オキシ酸や硫酸などの酸類、それにスラツ
ジ、ラツカー、カーボンなどを中和あるいは分散
し、腐食磨耗、リンググループ閉塞、およびピス
トンリング膠着等を防止するに著効を示すもので
ある。
先に本発明者らは（特願昭57−142393号）、フ
エノール類、二価アルコール、及びアルカリ土類
金属酸化物あるいは水酸化物（以下アルカリ土類
金属試薬という。）を、又はこれらに硫黄を加え
たものを反応させて、フエノール類の金属付加
を、又は金属付加と硫化を同時に行わせる反応に
おいて、反応系中に適当な量の水を添加すること
により、金属付加又は金属付加と硫化の反応が著
しく促進され、過剰の二価アルコールの使用が必
要とせず１回の反応当りのアルカリ土類金属試薬
の製品への転化率を著しく高くすることが可能で
あることを見出している。
一般的に種々の方法で工業的に製造される塩基
性アルカリ土類金属フエネート型清浄剤中には潤
滑油基油に代表される希釈溶剤に不溶または難溶
の副生成物あるいは微量の未反応アルカリ土類金
属試薬が懸濁状態で混在しており、これら微量の
不溶解性物質は未反応フエノール類等の回収前あ
るいは回収後に過、遠心分離などの手段で除去
する必要がある。未発明者らによつて見出された
前記の塩基性アルカリ土類金属フエネート型清浄
剤の製造法（特願昭57−142393号）においても、
特に反応生成物から回収したフエノール類を原料
として用いかつその使用量が少ない場合、二価ア
ルコールの使用量が少ない場合、あるいは水の添
加量が多い場合などには過の困難な不溶解性も
しくは難溶解性物質が副生することがあることが
判つた。
このような不溶解性物質の除去を工業的規模で
実施する方法としては過法が設備投資および運
転経費の面から優れた方法である。しかし過の
困難な不溶解性物質の量が多くなると、フイルタ
ープレス型の過機を用いる場合においては目詰
りを起して単位面積当りの過速度が著しく小さ
くなり必然的に操作圧を高くせざるをえなくな
り、液硫を循環するザイツ型やフンダー型の過
機を用いる場合においては原液当りの過助剤の
量を増したり、過のサイクル数を増やさざるを
得なくなる結果作業時間および労力が増加するう
えに操作に伴なう有効物質の損失量も増加するな
ど好ましくない現象をひき起す。
本発明者らはこのようなごく微量の不溶解性物
質、懸濁物質が過性に著しく悪影響を与える現
象について鋭意検討を加えた結果、水を添加して
行なつたフエノール類への金属付加又は硫化−金
属付加反応後、系内に存在する遊離の水を実質上
完全に除去し、さらに反応生成物と付加又は反応
している少量の水（非遊離水）も除去してから通
常の炭酸化反応を行なうと、驚くべきことに、
過性を著しく悪化させる原因となる物質は副生し
ないという事実を見出して本発明を完成したもの
である。過すべき懸濁物質の大部分は過性に
悪影響を与えない。そして得られた生成物は未反
応アルカリ土類金属試薬や雑多な副生成物を含有
しているので、そのうちどの成分が過性を悪化
させる原因物質であるかを見極めるのはきわめて
困難であり、しかもそれらは金属付加、硫化、炭
酸化などの種々の反応を経由して生成するため、
その厳密な化学構造および成因を追求するのは不
可能に近い。
上述の如き処理を行なうことによつて、アルカ
リ土類金属試薬反応率、炭酸化反応速度、生成す
る塩基性アルカリ土類金属フエネート型清浄剤の
組成、効果などに実質上悪影響を与えることな
く、懸濁物質中に存在する過性悪化物質の量を
激減させるか無くすことができるというのは予想
外の知見である。
従つて本発明の主たる目的は過性に優れた塩
基性アルカリ土類金属フエネート型清浄剤の製造
法を提供することにある。
すなわち本発明の要旨は、フエノール類、二価
アルコール、およびアルカリ土類金属化物およ
び／または水酸化物からなるアルカリ土類金属試
薬よりなる出発原料混合物に水を添加し反応させ
てフエノール類の金属付桑を、またはこれらの硫
黄を加えたものを反応させて金属付加と硫化とを
同時に行なわせ、反応生成物をその後二酸化炭素
で処理することにより塩基性アルカリ土類金属フ
エネート型清浄剤の製法において、金属付加もし
くは硫化−金属付加工程後二酸化炭素処理工程前
に系内の遊離水の実質上全部、および生成物に付
加もしくは反応している水の少なくとも一部を除
去することを特徴とする塩基性アルカリ土類金属
フエネート型清浄剤の製法に存する。
本発明方法の好ましい一実施例態様は、金属付
加もしくは硫化−金属付加工程後二酸化炭素処理
工程前に、系内の遊離水の大部分を留去したのち
もしくは留去操作を行なわず、減圧下２価アルコ
ールの沸とう条件下少なくとも約10分間以上還流
して、その間に系内に発生する水の実質上全部を
除去することである。また他の好ましい一実施態
様は、金属付加もしくは硫化−金属付加工程後二
酸化炭素処理工程前に、系内の遊離水の大部分を
留去したのちもしくは留去操作を行なわず、使用
アルカリ土類金属試薬１グラム式量当り少なくと
も約0.2モル以上の二価アルコールを系内に添加
しその全量を再留去することである。
本発明において遊離の水とは蒸留など混合物中
の水を除去する通常の方法で除去できる水を意味
する。例えば本発明における金属付加もしくは硫
化−金属付加工程後の生成物から遊離水を回分式
蒸留で留去する場合、まず水が留出し、その量が
徐々に減ると共に塔頂留出物温度が下り、さらに
蒸留を続けると留出物温度が再上昇し、二価アル
コール留分が留出する。二価アルコールが留出し
初めるまでに留出する水が本発明にいう遊離水で
あり、遊離水留出の終点は塔頂留出物の温度が上
昇する過程における約80℃、25mmＨｇに相当する
揮発度の点である。その後後述する種々の処理を
行なうことによつて再び生成してくる水が反応中
間体と付加または反応している非遊離水である。
本発明において問題とする過性に関しては、
工業的規模での優劣を判定する尺度としては、同
一条件での単位面積当りの過速度が最も妥当で
あるが、この値は過機のタイプの違い、及び
過条件の違いによつて著しく異なり、普遍性のあ
るデーターとはなりにくい。本発明では少量のサ
ンプルで簡単に測定が可能であり、被過原液の
本質的な難度を示すと思われる目詰り指数
（Silting Index、SI）をもつて過の難易を判定
する基準とした。すなわち、SIと過性との関係
は次の通りである。
０＜SI＜10 過性 きわめて良好
10≦SI＜20 〃 良
20≦SI＜100 〃 やゝ不良
100≦SI 〃 きわめて不良
（注） 試験条件
ミリボアー社：シルテイング・インデツクス装
置（XX68−013−00）を使用。試料を30倍の１
号流パラで稀釈し、シルテイグ・ヘツド
（Silting Head）：４番、フイルター（Filter）：
シルテイング・インデツクス用（08μ）フイルタ
ーを使用して測定する。
これらの指数値が実際の過速度ときわめて良
好な対応を示すことを確認している。
尚本明細書中単体とよび化合物の量について、
硫黄１グラム式量は化学式のいかんにかかわらず
Ｓに換算した量で表わすものとし、無機化合物は
グラム式量またはグラム当量で表わす。化学当量
について、一価のフエノール類１モルは１グラム
等量である。
本発明で使用する反応原料について述べる。本
発明に使用されるフエノール類としては炭素数４
〜36個、好ましくは炭素数８〜32個の炭化水素側
鎖、例えばアルキル基、アルケニル基、アラルキ
ル基等を有するフエノール類を挙げることができ
る。具体的にはブチル、アミル、オクチル、ノニ
ル、ドデシル、セチル、エチルヘキシル、トリア
コンチル等の炭化水素基、あるいは流動パラフイ
ン、ワツクス、オレフイン重合体（ポリエチレ
ン、ポリプロピレン、ポリブテン等）の石油炭化
水素から誘導される基を有するフエノール類が単
独、あるいはこれらの混合物として使用される。
通常約130℃、好ましくは約120℃で液状となり得
るものが望ましい。
アルカリ土類金属試薬としてはアルカリ土類金
属の酸化物、あるいは水酸化物、例えばカルシウ
ム、バリウム、ストロンチウム、マグネシウム等
の酸化物あるいは水酸化物が用いられる。フエノ
ール類に対するアルカリ土類金属試薬の使用量は
広い範囲をとることができ、例えばアルカリ土類
金属試薬は使用フエノール流１グラム当量り約
0.01〜20グラム当量、より好適には約0.05〜６グ
ラム当量の量で使用することが好ましい。フエノ
ール類に対するアルカリ土類金属試薬の特に好ま
しい配合比率は0.05〜0.99グラム当量／グラム当
量、殊に0.20〜0.80グラム当量／グラム当量、最
も好適には0.30〜0.70グラム当量／グラム当量で
ある。フエノール類とアルカリ土類金属試薬の使
用量は一方が過大に多すぎるとそれだけ無駄にな
り、未反応原料を回収するのに費用がかかるなど
不利になる。
次に二価アルコールとしては比較的低沸点かつ
低粘度で反応性に富むものが使用される。二価ア
ルコールは炭素数２〜６を有するものが好まし
く、特にエチレングリコール、プロピレングリコ
ールが好ましい。二価アルコールの使用量はアル
カリ土類金属試薬１グラム式量当り約0.15〜1.5
モル、特に約0.3〜1.4モルが好ましい。二価アル
コールはフエノール類とアルカリ土類金属試薬と
の反応による油溶性物質への転化を助け、安定化
し、一部は製品のフエネート中に取りこまれて多
当量化フエネートを構成するものである。従来方
法においては二価アルコールは実際に製品フエネ
ート型清浄剤中に取り込まれる量よりも大過剰に
用いる必要があつた。すなわち従来方法において
は二価アルコールの使用量が少なすぎると反応原
料特にアルカリ土類金属試薬の製品転化率が低下
してしまうという現象がみられた。しかし本発明
者らによる前述のフエネート型清浄剤の製造法
（特願昭57−142393号）においては、反応促進剤
として水を添加することにより二価アルコールの
使用量を製品フエネート型清浄剤中にとりこまれ
る量またはそれよりごくわずかに過剰な量まで少
なくすることが可能になつた。二価アルコールの
使用量が多すぎるとフエノール類への金属付加反
応は円滑に進行するが、反応生成物から過剰の二
価アルコールを蒸留留去する時間およびユーテイ
リテイーが過大にかかつてしまう。
硫黄（単体硫黄）は本発明において極小量から
大多量まで広範囲の量で用いることができる。通
常の使用量はアルカリ土類金属試薬１グラム式量
当り約4.0グラム式量以下、特に約0.05〜3.0グラ
ム式量が好ましい。硫黄の使用量は多すぎると塩
基性のフエネート型清浄剤が得にくくなる。硫黄
は使用しないで反応を行なつてもよい。硫黄の使
用量が多すぎると製品の色相が濃くなつてしま
う。
フエノール類へのアルカリ土類金属試薬の金属
付加反応工程において反応を促進するため反応系
中へ添加する水は、蒸留水はもちろん缶水や工業
用水、金属付加反応で生成する水などが使用出来
その品質に特に制限はなく、冷水、温水、水蒸気
等どのような状態の水でも使用出来る。水の反応
器への添加は水単独又はその一部あるいは全部を
アルキルフエノールや二価アルコール、高級アル
コールなど他の原料との混合物として添加しても
よい。反応器への水の添加時期は特に制限はな
く、水以外の全反応原料が混合される前でも後で
もよいが、全反応原料混合約１時間以内に添加す
るのが好ましい。反応系中への水の添加量は使用
するアルカリ土類金属試薬１グラム式量当り約
0.01〜10グラム式量望ましくは0.1〜2.0グラム式
量である。外部から水を反応系中に添加して金属
付加反応を行なうと、水を添加しない以外は同一
の条件で反応を行なう場合に較べて、反応は円滑
に進行し、反応原料特にアルカリ土類金属試薬の
製品転化率は高くなる。
本発明に於いて、反応物、反応中間体、あるい
は製品等の取扱いを容易にするために適当な粘度
を有する希釈剤もしくは溶剤（以下希釈剤とい
う。）を加えることができる。たとえば金属付加
反応工程または二酸化炭素処理を終えたのちの反
応生成物中から過剰の未反応フエノール類を蒸留
で回収する際、高沸点で、かつ適当なる粘度を有
した希釈剤の存在下で蒸留を行なうことによつて
生成物（塔底物）は液状の望ましい状態で得るこ
とができる。なお、通常は未反応フエノール類の
溜出に伴つて希釈剤の一部も溜出する。したがつ
て、回収フエノール類を繰り返し、反応に供する
場合には希釈剤としては反応に直接悪影響を与え
ないものが好ましい。また希釈剤の存在下に反応
を行なつてもよい。好ましい希釈剤の例としては
パラフイン系、ナフテン系、芳香族系、あるいは
混合系の基油などの適当な粘度の石油留分、例え
ば沸点約220〜550℃で粘度が100℃で約２〜40cSt
の潤滑油留分を挙げることができる。その他の有
機溶媒でも疎水性、かつ、親油性を示し、反応時
や製品の用途面において無害であれば希釈剤とし
て用いることができる。例えば炭素数８〜24の高
級アルコールも使用することができる。
本発明における塩基性フエネート型清浄剤の主
なる製造工程及び運転条件は下記のとおりであ
る。
(イ) 金属付加もしくは硫化−金属付加工程金属付
加反応工程はフエノール類、二価アルコール
類、およびアルカリ土類金属試薬の反応原料に
水を反応前または反応途中で添加してあるいは
さらに硫黄を加えて反応を行なう。反応温度約
60〜200℃、好ましくは約90〜190℃の範囲で反
応させる。反応は常圧下に行なうこともできる
が、反応を促進するために添加した水を系内の
液相中にとどめておくため加圧下好ましくは０
〜10atmGの加圧下に行なつてもよい。
また各原料の反応釜への仕込順序は反応を円
滑に進行させるため以下の順序で行なうのが最
も好ましい。
アルカリ土類金属試薬はフエノール類のあと
で仕込み、最後に二価アルコールおよび水を加
える。二価アルコールと水とは同時にもしくは
別々にてどちらかが先でもよい。）加え得る。
硫黄を使用した場合フエノール類の金属付加反
応と硫化反応が同時に生起し、反応中硫化水素
が発生するが、反応中に反応系外へ除去するこ
とが望ましい。本反応は通常約１〜９時間の範
囲内でほぼ終了する。
その後につづく蒸留工程において、反応系に
添加した水および反応により生成する水よりな
る遊離水の実質上全部、および反応生成物に付
加または反応している水（非遊離水）の少なく
とも一部を反応混合物から脱離・留去すること
が過性の良好な塩基性アルカリ土類金属フエ
ノール型清浄剤の製造にとつて不可欠である。
遊離水の除去は通常の蒸留方法によるこたがで
き、例えば回分式蒸留の場合は大部分の水が留
出し、次に塔頂留出物の温度が低下し、そして
塔頂留出物の温度が約80℃、25mmＨｇに相当す
る揮発度の点まで再上昇するまで蒸留を続けれ
ばよい。連続式蒸留の場合も回分式蒸留の遊離
水が留出するように蒸留すればよい。非遊離水
の除去は、減圧下二価アルコールの沸とう条件
下に加熱して少なくとも約10分間以上二価アル
コールを含む留分を還流させ、その間系内に発
生してくる水の少なくとも一部を除去すること
によつて行なうことができる。この操作の好ま
しい温度は約80〜120℃、時間は約10分〜２時
間である。二価アルコールの還流中に発生して
くる水は、この操作中留出物を相分離して水に
富む層を系外に除去しても、この操作後水を蒸
留留去してもよい。非遊離水の除去はまた、使
用アルカリ土類金属試薬１グラム式量当り少な
くとも約0.2モル以上の二価アルコール、特に
エチレグリコールを系内に添加しその全量を再
留去することによつて水を同時に除去すること
ができる。この操作の好ましい温度は約80〜
120℃、二価アルコールの好ましい添加量は使
用アルカリ土類金属試薬１グラム式量当り約
0.2〜１モルである。これら非遊離水の除去操
作はもはや水が生成してこなくなるまで継続し
て非遊離水の全部を除去することが好ましい
が、非遊離水はその一部例えばその約５〜80％
を除去するだけでもよい。また遊離水を除去す
る上記の通常の蒸留操作を行なうことなく、反
応生成物を直接上記した非遊離水除去操作に付
しても非遊離水の少なくとも一部と共に遊離水
の実質上全部を除去することができるが、処理
時間が長くなつたり二価アルコールの添加量が
増えたりする。これらの水除去操作後の中間製
品中にとりこまれた二価アルコール対アルカリ
土類金属試薬の比が小さい領域では最終製品の
アルカリ価や金属付加当量比が小さくなるの
で、上記の比は約0.2〜0.6、特に約0.45〜0.60
モル／グラム式量の範囲とすることが好まし
い。
(ロ) 二酸化炭素処理工程
製品の安定性および油溶性をさらに増すため
次に、前記の硫化−金属付加反応工程を完結し
た液状蒸留残留物をオートクレーブに入れ、反
応温度約50〜230℃、好ましくは約80〜200℃、
反応圧力約０〜50atmG、好ましくは約０〜
20amGの条件で二酸化炭素と反応させる。必
要ならば、この生成物を更に二酸化炭素のふん
囲気下、好ましくは加圧下（０〜50atmG、好
ましくは０〜20atmG）、約100〜230℃におい
て数分〜十数時間好ましくは約0.5〜10時間保
持する。二酸化炭素処理工程において二酸化炭
素は反応してフエノール類の側鎖およびフエノ
ール性芳香族核に導入される。反応生成物を分
析したところフエネート骨核のほかサリチレー
ト骨核も検出された。二酸化炭素処理により生
成物は潤滑油添加剤、燃料油添加剤として性能
（なかでもエンジン油に添加したときのエンジ
ン油の清浄性、安定性）がさらに向上する。
また、必要ならば、二酸化炭素処理後の反応
生成物にアルカリ土類金属試薬と二価アルコー
ルを添加し、再び上記のような金属付加反応を
行ない、次いで、二酸化炭素処理する一連の操
作を１回以上繰り返すことによつてさらに金属
付加をすることも可能である。二酸化炭素処理
後の反応生成物中の未反応フエノール類は経済
上などの面から、これらの一部、もしくは大部
分を回収することが好ましく、またこの回収フ
エノール類を原料として再使用することもでき
る。また金属付加もしくは硫化−金属付加工程
にて余剰となつた二価アルコールは二酸化炭素
処理工程後に未反応フエノール類などと共に回
収してもよい。二酸化炭素処理前および処理後
に回収する二価アルコールの量は、最終製品中
にとりこまれた二価アルコール対アルカリ土類
金属試薬の量の比が約0.50モル／グラム式量以
下、特に約0.45モル／グラム式量以下となる量
とすることが添加剤としての効果の面では好ま
しい。
ここで未反応フエノール類の蒸留をフエネー
ト型清浄剤の通常の希釈剤である潤滑油のベー
スオイルなどの存在下で行うと、蒸留残留物は
液状の好ましい状態で得ることができる。残存
する少量の不溶解性物質は、フエノール類の回
収前、あるいは回収後に過または遠心分離な
どの操作により除去することができる。
本発明方法の反応生成物の正確な構造の詳細
は不明であるが、反応生成物を加水分解し、加
水分解物をヘキサンのような溶剤で抽出して得
られる油層にサリチル酸類とフエノール類の両
者が検出されることから原料フエノール類はそ
の一部が二酸化炭素との反応によりサリチレー
トに転化したものと考えられる。また反応生成
物はフエノール類およびサリチル酸類の合計グ
ラム当量当り理論量以上のアルカリ土類金属元
素を含有することから生成物は塩基性アルカリ
土類金属サリチレートもしくは塩基性硫化アル
カリ土類金属サリチレートと塩基性アルカリ土
類金属フエネートもしくは塩基性硫化アルカリ
土類金属フエネートの骨核を含有するものと考
えられる。一方反応生成物はサリチレート骨核
のみよりなる分子とフエネート骨核のみよりな
る分子との混合物であるのか、１分子中にサリ
チレート骨核とフエネート骨核との両者を有す
る化合物なのか、またサリチレート骨核および
フエネート骨核とアルカリ土類金属元素、反応
した硫黄および反応した二価アルコールとの結
合様式については詳細不明であり、さらに反応
した二酸化炭素のうちサリチレートへの転化に
費された以外の二酸化炭素の生成物中における
結合様式は詳細不明であり、本発明の反応生成
物は塩基性硫化アルカリ土類金属サリチレート
もしくは塩基性アルカリ土類金属サリチレート
と塩基性アルカリ土類金属フエネートもしくは
塩基性硫化アルカリ土類金属フエネートとの複
合物（complex）とも呼ばれうるものである。
以上の通り本発明の反応生成物の詳細な構造は
不明であるが、塩基性アルカリ土類金属サリチ
レート骨核もしくは塩基性硫化アルカリ土類金
属サリチレート骨核と比較的多割合の塩基性硫
化アルカリ土類金属フエネート骨核もしくは塩
基性アルカリ土類金属フエネート骨核とを有す
るので、本明細書において反応生成物は塩基性
アルカリ土類金属フエネート型清浄剤と記述す
る。しかしながらこの呼称は上記したように正
確な化学品名を記述するものではないし、また
本発明は上記した推定あるいは理論に何ら拘束
されるものではなく、単に理解に便なため上記
の呼称を用いる。
以上本発明によればフエノール類当りの多量の
アルカリ土類金属を付加した過の良好な塩基性
アルカリ土類金属フエネート型清浄剤を、使用金
属に関し収率よく（高い製品転化率）製造するこ
とができる。
以下実施例により本発明を説明する。
実施例 １
撹拌機、滴下ロート、窒素ガス導入管および温
度計を装着したステンレス製オートクレーブ内に
純度89.3wt％のノニルフエノール（ｐ−ノニルフ
エノール55.4％、ｏ−ノニルフエノール33.9％お
よび鉱油10.7％から成る。ノニルフエノール含有
量3.0モル。）、酸化カルシウム1.0グラム式量おび
硫黄0.7グラム式量（22.47ｇ）を入れ、撹拌しな
がらこの懸濁液にエチレングリコール0.55モル
（34.2ｇ）と水0.8グラム式量との混合液を窒素気
流中1atmGの加圧下125℃で30分間で添加し、内
容物を130℃、2atmGで５時間加熱撹拌して硫化
水素を除去しながら硫化−金属付加反応を行なつ
た。反応終了後滴下ロートを冷却管につけ替えた
のち反応系内を徐々に減圧しながら添加した水お
よび反応で生成する水を蒸留留去した。この際の
最終留出温度はトツプ48.5℃（10mmＨｇ）であつ
た。この遊離水の留出が終つた後もオートクレー
ブの加熱を続け、ボトム温度175℃（30mmＨｇ）
の条件下（エチレングリコールの沸とう条件下）
全還流をかけながら熱処理を行なうと新たに系内
から少量の水（非遊離水）が発生してくるのが観
察された。1.5時間熱処理を続けたのち、処理中
に発生した水およびごく少量のエチレングリコー
ルを蒸留留去した。
得られた上記の蒸留残留物を加圧下（０〜
5atmG、最高5atmG）温度120℃で30分間二酸化
炭素を吸収させた。次いで二酸化炭素による加圧
下（5atmG）175℃で２時間保持して反応生成物
溶液を得た。この反応生成物溶液を希釈剤150ニ
ユートラル油（粘度5.39cS（99℃）のパラフイン
系潤滑油）242.3ｇで希釈し、生成混合物を過
して極少量の不溶解分1.18ｇを除去し、液を得
た。生成混合物の過に際し、その過の難易を
示す指数として目詰り指数（SI値）を測定したと
ころ6.4であつた。２用２口梨型フラスコにこ
の液を入れ、減圧蒸留して液中に混在する未
反応のエチレングリコールとノニルフエノールの
大部分を留去し、最終製品として蒸留残留物
536.8ｇを得た。その際の最終留出物温度は158℃
（１mmＨｇ）であつた。最終製品の塩基性アルカ
リ土類金属フエネート型清浄剤について原料の製
品化率および最終製品の性状（反応CO2含有量は
原料の物質収支から算出した。）を第１表に示す。
第１表中原料の製品転化率は最終製品中にとりこ
まれた原料の割合を云い、金属付加当量比は最終
製品中にとりこまれたアルカリ土類金属試薬フエ
ノール類（遊離フエノール類を除く。）のグラム
当量比を云う。
第１表に示す性状を有する最終製品の一部をシ
リカゲルを吸着剤とし、ｎ−ヘキサンを置換剤と
するカラム・クロマトを行つた活性成分を単離し
た。
単離した淡黄色粉末の活性成分を過剰の
1NH2SO4水溶液を用いて加水分解し、得られた
油層を液体クロマトグラフイーで分析したとこ
ろ、活性成分を構成するノニルウフエノールの
10.8モル％がノニルアサリチル酸であることが判
つた。
実施例 ２
実施例１と同様の反応を行なつた。
金属付加および硫化反応終了後、圧力を減じな
がら、添加水および生成水を留去した。
その後系へ0.3mol／CaOグラム式量のエチレ
ングリコールを添加し、撹拌しながらオートクレ
ーブを加熱・減圧条件に保持して添加したエチレ
ングリコールに相当する量のエチレングリコール
を再び留出せしめたが、その際新たに水が発生し
て同時に留去されるのが観察された。最終留出条
件はトツプ温度74℃（５mmＨｇ）であつた。
実施例１と同一条件にて炭酸化反応後、希釈剤
150ニユートラル油242.3ｇを加えたのち、液のSI
値を測定したところ、4.4であつた。
最終製品の性状は第１表に示すとおりであつ
た。また活性成分を構成するノニルフエノールの
105％がノニルサリチレートに転化していた。
実施例 ３
ノニルフエノールを3.0モルの代りに2.0モル使
用し、遊離水留去後エチレングリコールを酸化カ
ルシウム１グラム式量当り0.3モルの代りに0.5モ
ル添加し、かつ二酸化炭素の吹込み温度を120℃
の代りに150℃とした以外は、実施例２と全く同
様にして硫化−金属付加、蒸留、炭酸化処理、
過および蒸留を行なつて、塩基性アルカリ土類金
属フエネート型清浄剤を製造した。
炭酸化反応希釈剤150ニユートラル油242.3ｇを
加えた後の生成液のSI値を測定したところ5.3で
あつた。最終製品の性状は第１表に示すとおりで
あつた。
比較例 １
実施例１と同様の反応を行なつた。金属付加お
よび硫化反応終了跡、反応系内を徐々に減圧にし
ながら添加した水および反応で生成する水とごく
少量のエチレングリコールを蒸留留去した。この
際の最終留出温度は48.0℃（10mmＨｇ）であつ
た。
得られた液状蒸留残留物はそれ以上の処理を行
わず、ただちに、実施例１と同一条件にて炭酸化
反応を行ない、この反応生成物溶液を希釈剤150
ニユートラル油242.3ｇで希釈し、溶液のSI値を
測定したところ131であつた。
過工程は実施例１〜３に較べて著しく困難で
あつた。最終製品の性状は第１表に示す通りであ
つた。
The present invention relates to basic or overbased alkaline earth metal phenate type detergents or sulfurized alkaline earth metal phenate type detergents (unless otherwise specified) that are useful as lubricating or fuel oil detergents or alkaline detergents. The present invention relates to an industrially advantageous method for producing a basic alkaline earth metal phenate type detergent (unless otherwise specified). Generally, basic phenate type detergents are used in lubricating oils for internal combustion engines, and neutralize or disperse acids such as oxyacids and sulfuric acids, as well as sludge, lacquer, carbon, etc., and prevent corrosion, wear, ring group clogging, and piston ring sticking. It has been shown to be highly effective in preventing. Previously, the present inventors (Japanese Patent Application No. 142393/1982) used phenols, dihydric alcohols, and alkaline earth metal oxides or hydroxides (hereinafter referred to as alkaline earth metal reagents), or In a reaction in which sulfur is added to metal addition of phenols, or metal addition and sulfidation are carried out simultaneously, metal addition or metal addition can be achieved by adding an appropriate amount of water to the reaction system. It has been found that the sulfidation reaction is significantly accelerated, and it is possible to significantly increase the conversion rate of alkaline earth metal reagent to product per reaction without using excess dihydric alcohol. . Generally, basic alkaline earth metal phenate type detergents produced industrially by various methods contain by-products that are insoluble or sparingly soluble in diluting solvents such as lubricant base oils, or trace amounts of unreacted substances. Alkaline earth metal reagents are mixed in a suspended state, and it is necessary to remove these minute amounts of insoluble substances by means such as filtration or centrifugation before or after recovering unreacted phenols and the like. In the method for producing the basic alkaline earth metal phenate type detergent discovered by the uninventors (Japanese Patent Application No. 142393/1982),
In particular, when phenols recovered from reaction products are used as a raw material and the amount used is small, when the amount of dihydric alcohol used is small, or when the amount of water added is large, insoluble or It was found that poorly soluble substances may be produced as by-products. As a method for removing such insoluble substances on an industrial scale, the filtration method is an excellent method in terms of equipment investment and operating costs. However, when the amount of insoluble substances that are difficult to filter increases, when using a filter press type filter, clogging occurs and the overspeed per unit area decreases significantly, making it necessary to increase the operating pressure. When using a Seitz-type or Hunder-type filtration machine that circulates liquid sulfur, it is necessary to increase the amount of filtration agent per stock solution or increase the number of filtration cycles, resulting in increased work time and labor. This causes undesirable phenomena such as an increase in the amount of active substance lost during operation. The present inventors have conducted intensive studies on the phenomenon in which extremely small amounts of insoluble and suspended substances have a significant adverse effect on transient properties, and have found that metal addition to phenols is carried out by adding water. Or, after the sulfurization-metal addition reaction, the free water present in the system is substantially completely removed, and a small amount of water (non-free water) that has been added or reacted with the reaction product is also removed, and then the usual Surprisingly, when the carbonation reaction is carried out,
The present invention was completed by discovering the fact that no by-product is produced that causes a significant deterioration of hypersensitivity. Most of the suspended matter that should be filtered does not have a negative effect on the filter. Since the obtained product contains unreacted alkaline earth metal reagents and miscellaneous by-products, it is extremely difficult to determine which components are responsible for worsening hypersensitivity. Moreover, since they are produced through various reactions such as metal addition, sulfurization, and carbonation,
It is nearly impossible to pursue its exact chemical structure and origin. By carrying out the above-mentioned treatment, the reaction rate of the alkaline earth metal reagent, the carbonation reaction rate, the composition and effectiveness of the basic alkaline earth metal phenate type detergent to be produced, etc. are substantially not adversely affected. It is an unexpected finding that the amount of transient aggravating substances present in suspended matter can be drastically reduced or eliminated. Therefore, the main object of the present invention is to provide a method for producing a basic alkaline earth metal phenate type detergent having excellent permeability. That is, the gist of the present invention is to add water to a starting material mixture consisting of a phenol, a dihydric alcohol, and an alkaline earth metal reagent consisting of an alkaline earth metal compound and/or hydroxide, and to react with the phenol metal. A method for producing a basic alkaline earth metal phenate type detergent by reacting mulberries or their sulfur-added products to simultaneously perform metal addition and sulfidation, and then treating the reaction product with carbon dioxide. After the metal addition or sulfurization-metal addition step and before the carbon dioxide treatment step, substantially all of the free water in the system and at least a portion of the water that has been added to or reacted with the product are removed. A method for producing a basic alkaline earth metal phenate type detergent. In a preferred embodiment of the method of the present invention, after most of the free water in the system is distilled off after the metal addition or sulfurization-metal addition step and before the carbon dioxide treatment step, or without performing a distillation operation, the water is removed under reduced pressure. The method is to reflux the dihydric alcohol under boiling conditions for at least about 10 minutes, and substantially all of the water generated in the system is removed during that time. In another preferred embodiment, after most of the free water in the system is distilled off after the metal addition or sulfurization-metal addition step and before the carbon dioxide treatment step, or without performing a distillation operation, the alkaline earth At least about 0.2 mole or more of dihydric alcohol per gram of metal reagent is added to the system and the entire amount is redistilled. In the present invention, free water means water that can be removed by a conventional method for removing water from a mixture, such as distillation. For example, when free water is distilled off from the product after the metal addition or sulfurization-metal addition step in the present invention by batch distillation, water is first distilled out, and as the amount of water gradually decreases, the temperature of the top distillate decreases. As the distillation continues, the temperature of the distillate rises again, and a dihydric alcohol fraction is distilled out. The water that is distilled out before the dihydric alcohol begins to be distilled off is the free water referred to in the present invention, and the end point of free water distillation corresponds to about 80°C and 25 mmHg in the process of increasing the temperature of the top distillate. It's a matter of volatility. The water that is regenerated by various treatments described later is non-free water that has been added to or reacted with the reaction intermediate. Regarding hypersensitivity, which is a problem in the present invention,
The most appropriate measure for determining superiority or inferiority on an industrial scale is the overspeed per unit area under the same conditions, but this value varies significantly depending on the type of overpressure machine and the overconditions. , it is difficult to obtain universal data. In the present invention, the silting index (SI), which can be easily measured with a small amount of sample and is considered to indicate the essential difficulty of the analyte, was used as a standard for determining the difficulty of analysing. That is, the relationship between SI and hypersexuality is as follows. 0<SI<10 Transient Very good 10≦SI<20 〃 Good 20≦SI＜100 〃 Very poor 100≦SI 〃 Very poor (Note) Test conditions Millibore: Silting indexing device (XX68-013-00) use. 30 times the sample
Dilute with Goryu Para, Silting Head: No. 4, Filter:
Measure using a silting index (08μ) filter. It has been confirmed that these index values show a very good correspondence with the actual overspeed. In addition, in this specification, regarding the amount of a simple substance and a compound,
The formula weight of 1 gram of sulfur is expressed as an amount converted to S regardless of the chemical formula, and inorganic compounds are expressed as a gram formula weight or gram equivalent. Regarding chemical equivalents, 1 mole of monovalent phenols is equivalent to 1 gram. The reaction raw materials used in the present invention will be described. The phenols used in the present invention have 4 carbon atoms.
Mention may be made of phenols having a hydrocarbon side chain having ~36 carbon atoms, preferably 8 to 32 carbon atoms, such as an alkyl group, an alkenyl group, an aralkyl group, and the like. Specifically, it is derived from hydrocarbon groups such as butyl, amyl, octyl, nonyl, dodecyl, cetyl, ethylhexyl, triacontyl, etc., or petroleum hydrocarbons such as liquid paraffin, wax, and olefin polymers (polyethylene, polypropylene, polybutene, etc.) The phenols having groups can be used alone or as a mixture thereof.
It is desirable that it can become liquid at a temperature of usually about 130°C, preferably about 120°C. As the alkaline earth metal reagent, oxides or hydroxides of alkaline earth metals, such as oxides or hydroxides of calcium, barium, strontium, magnesium, etc., are used. The amount of alkaline earth metal reagent used relative to the phenols can vary widely; for example, the amount of alkaline earth metal reagent used per gram of phenol stream used may vary widely.
It is preferred to use amounts of 0.01 to 20 gram equivalents, more preferably about 0.05 to 6 gram equivalents. A particularly preferred ratio of alkaline earth metal reagent to phenols is 0.05 to 0.99 gram equivalent/gram equivalent, especially 0.20 to 0.80 gram equivalent/gram equivalent, most preferably 0.30 to 0.70 gram equivalent/gram equivalent. If the amount of one of the phenols and alkaline earth metal reagent used is too large, it will be wasted, and it will be disadvantageous, such as increasing the cost of recovering unreacted raw materials. Next, as the dihydric alcohol, one that has a relatively low boiling point, low viscosity, and high reactivity is used. The dihydric alcohol preferably has 2 to 6 carbon atoms, with ethylene glycol and propylene glycol being particularly preferred. The amount of dihydric alcohol used is approximately 0.15 to 1.5 per gram of alkaline earth metal reagent.
Moles, especially about 0.3 to 1.4 moles are preferred. Dihydric alcohol helps convert phenols into oil-soluble substances through the reaction with alkaline earth metal reagents, stabilizes them, and a portion is incorporated into the product phenate to form multi-equivalent phenate. . In conventional methods, it has been necessary to use dihydric alcohol in large excess over the amount actually incorporated into the product phenate type detergent. That is, in the conventional method, if the amount of dihydric alcohol used is too small, the product conversion rate of the reaction raw material, especially the alkaline earth metal reagent, decreases. However, in the above-mentioned method for producing a phenate-type detergent by the present inventors (Japanese Patent Application No. 142393/1983), the amount of dihydric alcohol used in the product phenate-type detergent can be reduced by adding water as a reaction accelerator. It has now become possible to reduce the amount taken up to the amount that is incorporated into the plant or to the amount that is only slightly in excess of that amount. If the amount of dihydric alcohol used is too large, the metal addition reaction to phenols will proceed smoothly, but the time and utility for distilling off the excess dihydric alcohol from the reaction product will become excessively long. Sulfur (elementary sulfur) can be used in a wide range of amounts from a very small amount to a large amount in the present invention. The amount usually used is less than about 4.0 grams per gram of alkaline earth metal reagent, preferably from about 0.05 to 3.0 grams. If the amount of sulfur used is too large, it becomes difficult to obtain a basic phenate type detergent. The reaction may also be carried out without using sulfur. If too much sulfur is used, the color of the product will become darker. The water added to the reaction system to promote the reaction in the metal addition reaction process of alkaline earth metal reagents to phenols can be distilled water, canned water, industrial water, water produced in the metal addition reaction, etc. There are no particular restrictions on its quality, and water in any state such as cold water, hot water, steam, etc. can be used. Water may be added to the reactor alone, or part or all of water may be added as a mixture with other raw materials such as alkylphenols, dihydric alcohols, and higher alcohols. The timing of adding water to the reactor is not particularly limited, and may be added before or after all reaction materials other than water are mixed, but it is preferably added within about 1 hour after all reaction materials are mixed. The amount of water added to the reaction system is approximately per gram of alkaline earth metal reagent used.
A formula weight of 0.01 to 10 grams, preferably a formula weight of 0.1 to 2.0 grams. When a metal addition reaction is carried out by adding water into the reaction system from the outside, the reaction proceeds more smoothly than when the reaction is carried out under the same conditions except for the addition of water, and the reaction raw materials, especially alkaline earth metals, are Product conversion of reagents is higher. In the present invention, a diluent or solvent (hereinafter referred to as diluent) having an appropriate viscosity can be added to facilitate handling of reactants, reaction intermediates, products, etc. For example, when recovering excess unreacted phenols from the reaction product after a metal addition reaction step or carbon dioxide treatment, distillation is performed at a high boiling point and in the presence of a diluent with an appropriate viscosity. By carrying out this process, the product (bottom product) can be obtained in the desired liquid state. Note that, along with the distillation of unreacted phenols, a portion of the diluent is also usually distilled out. Therefore, when the recovered phenols are repeatedly used for reaction, it is preferable to use a diluent that does not have a direct adverse effect on the reaction. The reaction may also be carried out in the presence of a diluent. Examples of preferred diluents include petroleum fractions of suitable viscosity, such as paraffinic, naphthenic, aromatic, or mixed base oils, such as boiling points of about 220 to 550°C and viscosities of about 2 to 40 cSt at 100°C.
lubricating oil fractions. Other organic solvents can also be used as diluents if they exhibit hydrophobicity and lipophilicity and are harmless in terms of reaction and product usage. For example, higher alcohols having 8 to 24 carbon atoms can also be used. The main manufacturing process and operating conditions of the basic phenate type detergent in the present invention are as follows. (b) Metal addition or sulfurization - metal addition process The metal addition reaction process involves adding water or sulfur to the reaction raw materials of phenols, dihydric alcohols, and alkaline earth metal reagents before or during the reaction. Perform the reaction. Reaction temperature approx.
The reaction is carried out at a temperature of 60 to 200°C, preferably about 90 to 190°C. The reaction can be carried out under normal pressure, but in order to keep the water added to promote the reaction in the liquid phase in the system, it is preferably carried out under pressure of 0.
It may be carried out under pressure of ~10 atmG. Furthermore, the order in which the raw materials are charged into the reaction vessel is most preferably carried out in the following order in order to allow the reaction to proceed smoothly. The alkaline earth metal reagent is added after the phenols, and the dihydric alcohol and water are added last. The dihydric alcohol and water may be added at the same time or separately, and either one may come first. ) can be added.
When sulfur is used, the metal addition reaction and sulfurization reaction of phenols occur simultaneously, and hydrogen sulfide is generated during the reaction, but it is desirable to remove it from the reaction system during the reaction. This reaction usually completes within about 1 to 9 hours. In the subsequent distillation step, substantially all of the free water consisting of the water added to the reaction system and the water produced by the reaction, and at least a portion of the water that has been added to or reacted with the reaction product (non-free water) are removed. Desorption/distillation from the reaction mixture is essential for the production of basic alkaline earth metal phenolic detergents with good permeability.
Removal of free water can be accomplished by conventional distillation methods, for example in batch distillation, most of the water is distilled off, then the temperature of the overhead distillate is reduced, and the overhead distillate is Distillation may be continued until the temperature rises again to the point of volatility corresponding to about 80° C. and 25 mm Hg. Even in the case of continuous distillation, distillation may be carried out so that free water in batch distillation is distilled out. To remove non-free water, the fraction containing the dihydric alcohol is refluxed for at least about 10 minutes by heating under reduced pressure under conditions where the dihydric alcohol boils, during which time at least part of the water generated in the system is removed. This can be done by removing . The preferred temperature for this operation is about 80-120°C and the time is about 10 minutes to 2 hours. The water generated during the reflux of the dihydric alcohol may be removed by phase separation of the distillate during this operation and the water-rich layer removed from the system, or the water may be distilled off after this operation. . Removal of non-free water can also be achieved by adding at least about 0.2 moles or more of a dihydric alcohol, particularly ethylene glycol, to the system per gram of alkaline earth metal reagent used and redistilling the entire amount. can be removed at the same time. The preferred temperature for this operation is about 80~
At 120°C, the preferred amount of dihydric alcohol added is approximately
It is 0.2 to 1 mole. It is preferable to continue these non-free water removal operations until water is no longer produced to remove all of the non-free water, but only a portion of the non-free water, for example about 5 to 80% of the non-free water, is removed.
You can just remove it. Furthermore, even if the reaction product is directly subjected to the non-free water removal operation described above without performing the above-mentioned ordinary distillation operation for removing free water, substantially all of the free water is removed along with at least a portion of the non-free water. However, the processing time becomes longer and the amount of dihydric alcohol added increases. In the region where the ratio of dihydric alcohol to alkaline earth metal reagent incorporated into the intermediate product after these water removal operations is small, the alkali value and metal addition equivalent ratio of the final product will be small, so the above ratio is approximately 0.2. ~0.6, especially around 0.45-0.60
A mole/gram formula weight range is preferred. (b) Carbon dioxide treatment process In order to further increase the stability and oil solubility of the product, the liquid distillation residue that has undergone the sulfurization-metal addition reaction process is placed in an autoclave, and the reaction temperature is approximately 50-230°C, preferably is about 80~200℃,
Reaction pressure: about 0 to 50 atmG, preferably about 0 to 50 atmG
React with carbon dioxide under 20 amG conditions. If necessary, this product is further heated under a carbon dioxide atmosphere, preferably under pressure (0 to 50 atmG, preferably 0 to 20 atmG), at about 100 to 230°C for several minutes to more than ten hours, preferably about 0.5 to 10 hours. Hold time. In the carbon dioxide treatment step, carbon dioxide is reacted and introduced into the side chains of phenols and the phenolic aromatic nucleus. Analysis of the reaction products revealed salicylate bone cores in addition to phenate bone cores. Carbon dioxide treatment further improves the performance of the product as a lubricating oil additive and a fuel oil additive (in particular, the cleanliness and stability of engine oil when added to engine oil). If necessary, the series of operations of adding an alkaline earth metal reagent and a dihydric alcohol to the reaction product after carbon dioxide treatment, carrying out the metal addition reaction as described above again, and then treating with carbon dioxide may be repeated. It is also possible to further add metal by repeating the process several times or more. For economical reasons, it is preferable to recover some or most of the unreacted phenols in the reaction product after carbon dioxide treatment, and it is also possible to reuse the recovered phenols as raw materials. can. Moreover, the dihydric alcohol which becomes surplus in the metal addition or sulfurization-metal addition step may be recovered together with unreacted phenols etc. after the carbon dioxide treatment step. The amount of dihydric alcohol recovered before and after carbon dioxide treatment is such that the ratio of dihydric alcohol to alkaline earth metal reagent incorporated in the final product is less than or equal to about 0.50 mole/gram formula weight, particularly about 0.45 mole. /gram formula weight or less is preferable in terms of effectiveness as an additive. If the unreacted phenols are distilled in the presence of a lubricating oil base oil, which is a common diluent for phenate type detergents, the distillation residue can be obtained in a preferred liquid state. A small amount of remaining insoluble substances can be removed by an operation such as filtration or centrifugation before or after recovery of the phenols. Although the details of the exact structure of the reaction product of the method of the present invention are unknown, salicylic acids and phenols are contained in the oil layer obtained by hydrolyzing the reaction product and extracting the hydrolyzate with a solvent such as hexane. Since both were detected, it is considered that part of the raw material phenols was converted into salicylate by reaction with carbon dioxide. In addition, since the reaction product contains more than the theoretical amount of alkaline earth metal element per gram equivalent of the total of phenols and salicylic acids, the product is a basic alkaline earth metal salicylate or a basic sulfurized alkaline earth metal salicylate and a base. It is thought to contain a bone core of a basic alkaline earth metal phenate or a basic sulfurized alkaline earth metal phenate. On the other hand, whether the reaction product is a mixture of a molecule consisting only of salicylate bone cores and a molecule consisting only of phenate bone cores, or a compound containing both salicylate bone cores and phenate bone cores in one molecule, The details of the bonding mode between the core and the phenate bone core, the alkaline earth metal element, the reacted sulfur, and the reacted dihydric alcohol are unknown, and furthermore, the amount of carbon dioxide other than that used for conversion to salicylate among the reacted carbon dioxide is unknown. The bonding mode of carbon in the product is unclear, and the reaction product of the present invention is a basic sulfurized alkaline earth metal salicylate, or a basic alkaline earth metal salicylate and a basic alkaline earth metal phenate, or a basic alkali sulfide. It can also be called a complex with earth metal phenates.
As described above, the detailed structure of the reaction product of the present invention is unknown, but basic alkaline earth metal salicylate bone core or basic sulfurized alkaline earth metal salicylate bone core and a relatively large proportion of basic alkaline earth metal sulfide The reaction product is herein described as a basic alkaline earth metal phenate type detergent because it has a metalloid phenate core or a basic alkaline earth metal phenate core. However, as mentioned above, this name does not describe the exact name of the chemical product, and the present invention is not bound by the above-mentioned assumption or theory, but simply uses the above name for convenience of understanding. As described above, according to the present invention, it is possible to produce a basic alkaline earth metal phenate-type detergent with good filtration and a large amount of alkaline earth metal added per phenol in a good yield (high product conversion rate) with respect to the metal used. I can do it. The present invention will be explained below with reference to Examples. Example 1 Nonylphenol with a purity of 89.3 wt% (from p-nonylphenol 55.4%, o-nonylphenol 33.9% and mineral oil 10.7%) was placed in a stainless steel autoclave equipped with a stirrer, a dropping funnel, a nitrogen gas inlet tube and a thermometer. Nonylphenol content: 3.0 mol), 1.0 gram formula amount of calcium oxide, and 0.7 gram formula amount (22.47 g) of sulfur, and to this suspension with stirring, 0.55 mol ethylene glycol (34.2 g) and 0.8 gram water. The mixture with the formula weight was added at 125℃ under a pressure of 1atmG in a nitrogen stream for 30 minutes, and the contents were heated and stirred at 130℃ and 2atmG for 5 hours to perform a sulfide-metal addition reaction while removing hydrogen sulfide. Summer. After the reaction was completed, the dropping funnel was replaced with a cooling tube, and the pressure inside the reaction system was gradually reduced to distill off the added water and the water produced in the reaction. The final distillation temperature at this time was 48.5°C (10mmHg). After the distillation of this free water was finished, the autoclave was continued to be heated until the bottom temperature reached 175℃ (30mmHg).
(under boiling conditions of ethylene glycol)
When heat treatment was performed while applying total reflux, it was observed that a small amount of water (non-free water) was newly generated from within the system. After continuing the heat treatment for 1.5 hours, water and a small amount of ethylene glycol generated during the treatment were distilled off. The obtained above distillation residue was heated under pressure (0 to
Carbon dioxide was absorbed for 30 minutes at a temperature of 120°C (5atmG, maximum 5atmG). The mixture was then maintained at 175° C. for 2 hours under pressure (5 atmG) using carbon dioxide to obtain a reaction product solution. This reaction product solution was diluted with 242.3 g of diluent 150 neutral oil (paraffinic lubricating oil with a viscosity of 5.39 cS (99°C)), and the resulting mixture was filtered to remove a very small amount of undissolved matter (1.18 g). I got it. When the product mixture was filtered, the clogging index (SI value), which is an index indicating the difficulty of filtering, was measured and found to be 6.4. Pour this liquid into a 2-necked pear-shaped flask and distill it under reduced pressure to remove most of the unreacted ethylene glycol and nonylphenol mixed in the liquid, leaving the distillation residue as the final product.
536.8g was obtained. The final distillate temperature at that time was 158℃
(1 mmHg). Table 1 shows the conversion rate of the raw materials and the properties of the final product (the reaction CO 2 content was calculated from the material balance of the raw materials) for the final basic alkaline earth metal phenate type detergent.
In Table 1, the product conversion rate of raw materials refers to the proportion of raw materials incorporated into the final product, and the metal addition equivalent ratio refers to the alkaline earth metal reagent phenols (excluding free phenols) incorporated into the final product. The gram equivalent ratio of A part of the final product having the properties shown in Table 1 was subjected to column chromatography using silica gel as an adsorbent and n-hexane as a displacing agent to isolate the active ingredient. Excess amount of active ingredient in isolated pale yellow powder
Hydrolysis was performed using a 1NH 2 SO 4 aqueous solution, and the resulting oil layer was analyzed by liquid chromatography.
It was found that 10.8 mol% was nonyl salicylic acid. Example 2 A reaction similar to Example 1 was carried out. After completion of the metal addition and sulfurization reactions, the added water and produced water were distilled off while reducing the pressure. After that, ethylene glycol was added to the system in an amount of 0.3 mol/gram of CaO, and the autoclave was maintained under heating and reduced pressure conditions while stirring to distill out an amount of ethylene glycol corresponding to the added ethylene glycol again. It was observed that water was newly generated and simultaneously distilled off. The final distillation conditions were a top temperature of 74°C (5 mmHg). After carbonation reaction under the same conditions as Example 1, diluent
After adding 242.3g of 150 neutral oil, the SI of the liquid
When the value was measured, it was 4.4. The properties of the final product were as shown in Table 1. In addition, nonylphenol, which constitutes the active ingredient,
105% was converted to nonyl salicylate. Example 3 2.0 mol of nonylphenol was used instead of 3.0 mol, 0.5 mol of ethylene glycol was added instead of 0.3 mol per gram of calcium oxide after distillation of free water, and the blowing temperature of carbon dioxide was set to 120 mol. ℃
Sulfurization-metal addition, distillation, carbonation treatment,
A basic alkaline earth metal phenate type detergent was prepared by filtration and distillation. After adding 242.3 g of carbonation reaction diluent 150 neutral oil, the SI value of the resulting liquid was measured and found to be 5.3. The properties of the final product were as shown in Table 1. Comparative Example 1 The same reaction as in Example 1 was carried out. The traces of the completion of the metal addition and sulfurization reactions, the added water, the water produced in the reaction, and a very small amount of ethylene glycol were distilled off while gradually reducing the pressure in the reaction system. The final distillation temperature at this time was 48.0°C (10 mmHg). The obtained liquid distillation residue was not subjected to any further treatment, but was immediately subjected to a carbonation reaction under the same conditions as in Example 1, and the reaction product solution was diluted with a diluent of 150
It was diluted with 242.3 g of neutral oil and the SI value of the solution was measured and found to be 131. The overstep was significantly more difficult than in Examples 1-3. The properties of the final product were as shown in Table 1.
【表】【table】
【表】
実施例 ４
硫黄を使用しなかつた以外は実施例１と全く同
様にして塩基性アルカリ土類金属フエネート型清
浄剤を製造した。製品が硫黄分を含まないことと
かなりサリチレート含有率を示したこと以外は実
施例１と同様の結果が得られた。[Table] Example 4 A basic alkaline earth metal phenate type detergent was produced in exactly the same manner as in Example 1 except that sulfur was not used. Similar results were obtained as in Example 1, except that the product was sulfur-free and had a significant salicylate content.
Claims (1)
カリ土類金属酸化物および／または水酸化物から
なるアルカリ土類金属試薬よりなる出発原料混合
物に水を添加し反応させてフエノール類の金属付
加を、またはこれらに硫黄を加えたものを反応さ
せて金属付加と硫化とを同時に行なわせ、反応生
成物をその後二酸化炭素で処理することよりなる
塩基性アルカリ土類金属フエネート型清浄剤の製
法において、金属付加もしくは硫化−金属付加工
程後二酸化炭素処理工程前に系内の遊離水の実質
上全部、および生成物に付加もしくは反応してい
る水の少なくとも一部を除去することを特徴とす
る塩基性アルカリ土類金属フエネート型清浄剤の
製法。1 Water is added to a starting material mixture consisting of phenols, dihydric alcohols, and alkaline earth metal reagents consisting of alkaline earth metal oxides and/or hydroxides to react, thereby metal addition of phenols or In the method for producing a basic alkaline earth metal phenate type detergent, which involves reacting sulfur with sulfur to simultaneously perform metal addition and sulfurization, and then treating the reaction product with carbon dioxide, the metal addition or A basic alkaline earth compound characterized by removing substantially all of the free water in the system after the sulfidation-metal addition step and before the carbon dioxide treatment step, and at least a portion of the water that has been added to or reacted with the product. Method for manufacturing metal phenate type detergent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2488284A JPS60168794A (en) | 1984-02-13 | 1984-02-13 | Production of basic alkaline earth metal phenate detergent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2488284A JPS60168794A (en) | 1984-02-13 | 1984-02-13 | Production of basic alkaline earth metal phenate detergent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60168794A JPS60168794A (en) | 1985-09-02 |
| JPH0460159B2 true JPH0460159B2 (en) | 1992-09-25 |
Family
ID=12150554
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2488284A Granted JPS60168794A (en) | 1984-02-13 | 1984-02-13 | Production of basic alkaline earth metal phenate detergent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60168794A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8621343D0 (en) * | 1986-09-04 | 1986-10-15 | Exxon Chemical Patents Inc | Overbased alkali metal additives |
| US5292968A (en) * | 1992-02-26 | 1994-03-08 | Cosmo Research Institute | Process for producing over-based alkaline earth metal phenate |
-
1984
- 1984-02-13 JP JP2488284A patent/JPS60168794A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60168794A (en) | 1985-09-02 |
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