JP2007277169A - Ester production method - Google Patents
Ester production method Download PDFInfo
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- JP2007277169A JP2007277169A JP2006106034A JP2006106034A JP2007277169A JP 2007277169 A JP2007277169 A JP 2007277169A JP 2006106034 A JP2006106034 A JP 2006106034A JP 2006106034 A JP2006106034 A JP 2006106034A JP 2007277169 A JP2007277169 A JP 2007277169A
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- 150000002148 esters Chemical class 0.000 title claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 238000005886 esterification reaction Methods 0.000 claims abstract description 52
- 230000032050 esterification Effects 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 9
- 230000009467 reduction Effects 0.000 claims description 23
- -1 saturated aliphatic monocarboxylic acid Chemical class 0.000 claims description 12
- 239000010687 lubricating oil Substances 0.000 claims description 11
- 239000002199 base oil Substances 0.000 claims description 9
- 230000008859 change Effects 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 abstract description 6
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 abstract 1
- 229920006395 saturated elastomer Polymers 0.000 abstract 1
- 238000004904 shortening Methods 0.000 abstract 1
- 229940059574 pentaerithrityl Drugs 0.000 description 18
- 239000002253 acid Substances 0.000 description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 16
- 239000003463 adsorbent Substances 0.000 description 14
- 239000007795 chemical reaction product Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- 239000002994 raw material Substances 0.000 description 10
- 238000007664 blowing Methods 0.000 description 9
- 235000014113 dietary fatty acids Nutrition 0.000 description 9
- 229930195729 fatty acid Natural products 0.000 description 9
- 239000000194 fatty acid Substances 0.000 description 9
- 150000004665 fatty acids Chemical class 0.000 description 8
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 7
- OILUAKBAMVLXGF-UHFFFAOYSA-N 3,5,5-trimethyl-hexanoic acid Chemical compound OC(=O)CC(C)CC(C)(C)C OILUAKBAMVLXGF-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 4
- 239000003507 refrigerant Substances 0.000 description 4
- 238000005057 refrigeration Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 238000004042 decolorization Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 229940005605 valeric acid Drugs 0.000 description 3
- NKBWMBRPILTCRD-UHFFFAOYSA-N 2-Methylheptanoic acid Chemical compound CCCCCC(C)C(O)=O NKBWMBRPILTCRD-UHFFFAOYSA-N 0.000 description 2
- YSEQNZOXHCKLOG-UHFFFAOYSA-N 2-methyl-octanoic acid Chemical compound CCCCCCC(C)C(O)=O YSEQNZOXHCKLOG-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- LJOODBDWMQKMFB-UHFFFAOYSA-N cyclohexylacetic acid Chemical compound OC(=O)CC1CCCCC1 LJOODBDWMQKMFB-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- YYVJAABUJYRQJO-UHFFFAOYSA-N isomyristic acid Chemical compound CC(C)CCCCCCCCCCC(O)=O YYVJAABUJYRQJO-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000010721 machine oil Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- ZONJATNKKGGVSU-UHFFFAOYSA-N 14-methylpentadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCC(O)=O ZONJATNKKGGVSU-UHFFFAOYSA-N 0.000 description 1
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 1
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- OARDBPIZDHVTCK-UHFFFAOYSA-N 2-butyloctanoic acid Chemical compound CCCCCCC(C(O)=O)CCCC OARDBPIZDHVTCK-UHFFFAOYSA-N 0.000 description 1
- VNAWKNVDKFZFSU-UHFFFAOYSA-N 2-ethyl-2-methylpropane-1,3-diol Chemical compound CCC(C)(CO)CO VNAWKNVDKFZFSU-UHFFFAOYSA-N 0.000 description 1
- NJHQOQAEEYIWOB-UHFFFAOYSA-N 2-methyl-2-propan-2-ylpropane-1,3-diol Chemical compound CC(C)C(C)(CO)CO NJHQOQAEEYIWOB-UHFFFAOYSA-N 0.000 description 1
- CVKMFSAVYPAZTQ-UHFFFAOYSA-N 2-methylhexanoic acid Chemical compound CCCCC(C)C(O)=O CVKMFSAVYPAZTQ-UHFFFAOYSA-N 0.000 description 1
- GRFUBKQMUNOERA-UHFFFAOYSA-N 3-(3-hydroxy-2,2-dimethylpropoxy)-2,2-dimethylpropan-1-ol Chemical compound OCC(C)(C)COCC(C)(C)CO GRFUBKQMUNOERA-UHFFFAOYSA-N 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- UWWDUVVCVCAPNU-UHFFFAOYSA-N 3-ethylhexanoic acid Chemical compound CCCC(CC)CC(O)=O UWWDUVVCVCAPNU-UHFFFAOYSA-N 0.000 description 1
- FJNCXZZQNBKEJT-UHFFFAOYSA-N 8beta-hydroxymarrubiin Natural products O1C(=O)C2(C)CCCC3(C)C2C1CC(C)(O)C3(O)CCC=1C=COC=1 FJNCXZZQNBKEJT-UHFFFAOYSA-N 0.000 description 1
- 241001550224 Apha Species 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004386 Erythritol Substances 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000005643 Pelargonic acid Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- BAZMYXGARXYAEQ-UHFFFAOYSA-N alpha-ethyl valeric acid Chemical compound CCCC(CC)C(O)=O BAZMYXGARXYAEQ-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000010720 hydraulic oil Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- XRVCFZPJAHWYTB-UHFFFAOYSA-N prenderol Chemical compound CCC(CC)(CO)CO XRVCFZPJAHWYTB-UHFFFAOYSA-N 0.000 description 1
- 229950006800 prenderol Drugs 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Lubricants (AREA)
Abstract
Description
本発明は、エステルの製造方法に関する。 The present invention relates to a method for producing an ester.
従来、潤滑油用基油には入手が容易な鉱物油が用いられていた。しかし、近年、使用条件の過酷化や省エネルギー対応機器の増加、さらには環境中に拡散された場合の影響低減などの潤滑油への要求性能の高度化に対し、鉱物油は潤滑性・耐熱性・酸化安定性・低温流動性・生分解性などの性能が不十分となってきた。そのため鉱物油の代替品として、潤滑性・耐熱性・酸化安定性・低温流動性・生分解性に優れたPOE系(ポリオールエステル)と呼ばれるネオペンチルグリコール、トリメチロールプロパン、ペンタエリスリトール等のヒンダードアルコールエステルが潤滑油用基油に用いられるようになった。 Conventionally, mineral oil, which is easily available, has been used as a base oil for lubricating oil. However, in recent years, mineral oils have improved lubricity and heat resistance in response to increasingly demanding conditions for lubricants, such as severer use conditions, increased energy-saving equipment, and reduced impact when diffused into the environment.・ Performance such as oxidation stability, low-temperature fluidity and biodegradability has become insufficient. Therefore, as a substitute for mineral oil, hindered materials such as neopentyl glycol, trimethylol propane and pentaerythritol, which are called POE (polyol ester), which are excellent in lubricity, heat resistance, oxidation stability, low-temperature fluidity and biodegradability Alcohol esters have been used in lubricating base oils.
なかでも、冷凍機油用潤滑油は、冷凍機の冷媒が塩素を含まない水素含有フロン冷媒に移行していることに伴い、このような冷媒に対応できるものが要望されている。例えば、特許文献1には、炭素数15以下、3価以上の多価アルコールと炭素数2〜18の1価脂肪酸等とを原料として得たエステルを主成分とする水素含有フロン冷媒用潤滑油が開示されている。また、特許文献2には、着色度の低い冷凍機油用基油を得るために、原料としてモノペンタエリスリトール含有量の高いペンタエリスリトールを用いる方法が提案されている。更に、特許文献3には、吸着剤の使用量を低減しても吸着剤の使用量を低減しても十分な脱酸、脱色が達成される簡易な潤滑油用エステルの製造方法として、特定の工程(1)〜(4)を含む製造方法が開示されている。
こうしたエステルを製造するにあたり、製造工程を短縮して製造効率を高めることは工業上有意義であるが、単に反応時間を短縮しただけでは品質を維持しつつエステルを製造することは困難となる。 In producing such an ester, it is industrially significant to shorten the production process and increase the production efficiency, but it is difficult to produce the ester while maintaining the quality simply by reducing the reaction time.
本発明の課題は、品質を維持しつつ、反応時間を短縮して製造効率を高めることができるエステルの製造方法を提供することにある。 The subject of this invention is providing the manufacturing method of ester which shortens reaction time and can improve manufacturing efficiency, maintaining quality.
本発明は、多価アルコールと飽和脂肪族モノカルボン酸又はその誘導体とを、190℃以上の温度で反応させる工程(以下、エステル化工程という)を有するエステルの製造方法であって、エステル化工程の終了時に反応系の水分量が、反応系1kgあたり200mg以下となるように水分を低減することを行う、エステルの製造方法に関する。 The present invention is a method for producing an ester comprising a step of reacting a polyhydric alcohol with a saturated aliphatic monocarboxylic acid or a derivative thereof at a temperature of 190 ° C. or higher (hereinafter referred to as an esterification step). It is related with the manufacturing method of ester which performs a water | moisture content reduction so that it may become 200 mg or less per kg of reaction systems at the time of completion | finish of this.
本発明によれば、品質を維持しつつ、反応時間を短縮して製造効率を高めることができるエステルの製造方法を提供される。本発明の製造方法により得られるエステルは、潤滑油用基油、特に、冷凍機油用潤滑油として好適である。 ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of ester which can shorten reaction time and can improve manufacturing efficiency is provided, maintaining quality. The ester obtained by the production method of the present invention is suitable as a base oil for lubricating oil, particularly as a lubricating oil for refrigerator oil.
本発明では、多価アルコール〔以下、(A)成分という〕と飽和脂肪族モノカルボン酸又はその誘導体〔以下、(B)成分という〕とを反応させてエステルを含む反応生成物を得る。 In the present invention, a reaction product containing an ester is obtained by reacting a polyhydric alcohol [hereinafter referred to as component (A)] with a saturated aliphatic monocarboxylic acid or a derivative thereof (hereinafter referred to as component (B)).
(A)成分としては、具体的には、ネオペンチルグリコール、2−エチル−2−メチル−1,3−プロパンジオール、2−イソプロピル−2−メチル−1,3−プロパンジオール、2,2−ジエチル−1,3−プロパンジオール、2−n−ブチル−2−エチル−1,3−プロパンジオール、ジ(3-ヒドロキシ-2,2-ジメチルプロピル)エーテル、トリメチロールエタン、トリメチロールプロパン、ペンタエリスリトール、ジトリメチロールエタン、ジトリメチロールプロパン、ジペンタエリスリトール、トリトリメチロールエタン、トリトリメチロールプロパン、トリペンタエリスリトール等のヒンダード多価アルコール、あるいは、エチレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ペンタエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、1,3−プロパンジオール、1,4−ブタンジオール、1,6−ヘキサンジオール、グリセリン、ジグリセリン、トリグリセリン等の多価アルコールが挙げられる。これらの多価アルコールの炭素原子数は、生成エステルの粘度の観点から2〜18が好ましく、2〜7がさらに好ましい。また、分子中のヒドロキシ基によっても生成エステルの粘度を調整でき、この観点から分子中にヒドロキシ基を2〜8個含むことが好ましい。さらに、耐熱性の観点からはヒンダード多価アルコールが優れており、とくに、ネオペンチルグリコール、トリメチロールプロパン、ペンタエリスリトールが好ましい。(A)成分は、2種以上を併用することもできる。 As the component (A), specifically, neopentyl glycol, 2-ethyl-2-methyl-1,3-propanediol, 2-isopropyl-2-methyl-1,3-propanediol, 2,2- Diethyl-1,3-propanediol, 2-n-butyl-2-ethyl-1,3-propanediol, di (3-hydroxy-2,2-dimethylpropyl) ether, trimethylolethane, trimethylolpropane, penta Hindered polyhydric alcohols such as erythritol, ditrimethylolethane, ditrimethylolpropane, dipentaerythritol, tritrimethylolethane, tritrimethylolpropane, tripentaerythritol, or ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol ,propylene Recall, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, glycerin, diglycerin, and polyhydric alcohols and triglycerin. The number of carbon atoms of these polyhydric alcohols is preferably 2 to 18 and more preferably 2 to 7 from the viewpoint of the viscosity of the produced ester. Moreover, the viscosity of the produced ester can be adjusted also by the hydroxy group in the molecule. From this viewpoint, it is preferable that the molecule contains 2 to 8 hydroxy groups. Further, from the viewpoint of heat resistance, hindered polyhydric alcohols are excellent, and neopentyl glycol, trimethylolpropane, and pentaerythritol are particularly preferable. (A) 2 or more types can also be used together for a component.
(B)成分としては、具体的には、酪酸、バレリン酸、カプロン酸、エナント酸、カプリル酸、ペラルゴン酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸等の直鎖飽和脂肪族モノカルボン酸や、イソ酪酸、イソバレリン酸、ピバリン酸、2−エチルペンタン酸、2−メチルヘキサン酸、2−エチルヘキサン酸、3−エチルヘキサン酸、2−メチルヘプタン酸、シクロヘキシル酢酸、3,5,5−トリメチルヘキサン酸、2−メチルオクタン酸、イソミリスチン酸、イソパルミチン酸、イソステアリン酸等の分岐鎖飽和脂肪族モノカルボン酸が挙げられ、これらの誘導体としては、該脂肪酸のネオペンチルグリコールモノエステル、該脂肪酸のネオペンチルグリコールジエステル、該脂肪酸のトリメチロールプロパンモノエステル、該脂肪酸のトリメチロールプロパンジエステル、該脂肪酸のトリメチロールプロパントリエステル、該脂肪酸のペンタエリスリトールモノエステル、該脂肪酸のペンタエリスリトールジエステル、該脂肪酸のペンタエリスリトールトリエステル、該脂肪酸のペンタエリスリトールテトラエステル等が挙げられる。生成エステルの低温流動性と金属に対する腐食性の観点から、炭素原子数は4〜12のものが好ましく、5〜10のものが更に好ましい。耐加水分解性の観点からは2−エチルヘキサン酸等のカルボニル基のα位に分岐鎖を持つカルボン酸が好ましい。(B)成分は2種以上を併用することもできる。(B)成分の沸点は、180〜380℃が好ましい。 Specific examples of the component (B) include linear saturated aliphatic acids such as butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and the like. Monocarboxylic acid, isobutyric acid, isovaleric acid, pivalic acid, 2-ethylpentanoic acid, 2-methylhexanoic acid, 2-ethylhexanoic acid, 3-ethylhexanoic acid, 2-methylheptanoic acid, cyclohexylacetic acid, 3,5 Branched-chain saturated aliphatic monocarboxylic acids such as 1,5-trimethylhexanoic acid, 2-methyloctanoic acid, isomyristic acid, isopalmitic acid, and isostearic acid, and these derivatives include neopentyl glycol mono Ester, neopentyl glycol diester of the fatty acid, trimethylolpropane monoester of the fatty acid Trimethylolpropane diester of the fatty acid, trimethylolpropane triester of the fatty acid, pentaerythritol monoester of the fatty acid, pentaerythritol diester of the fatty acid, pentaerythritol triester of the fatty acid, pentaerythritol tetraester of the fatty acid, etc. It is done. From the viewpoint of the low temperature fluidity of the resulting ester and the corrosiveness to metals, the number of carbon atoms is preferably 4 to 12, and more preferably 5 to 10. From the viewpoint of hydrolysis resistance, a carboxylic acid having a branched chain at the α-position of the carbonyl group such as 2-ethylhexanoic acid is preferable. (B) 2 or more types can also be used together. (B) As for the boiling point of a component, 180-380 degreeC is preferable.
本発明では、エステル化工程での(A)成分と(B)成分の反応は、(B)成分が(A)成分に対して過剰となる条件で行うことが好ましく、具体的には、(A)と(B)とを、(B)/(A)=1.05〜1.4、更に1.1〜1.3の当量比で反応させることが、エステル化の反応速度を上げる観点から好ましい。なお、この当量比は、(A)成分〔複数の場合、全(A)成分〕の水酸基1個あたりの(B)成分〔複数の場合、全(B)成分〕のカルボキシル基の個数である。このように(B)成分を過剰に用いることで、(B)成分を循環使用する際に有利となる。 In the present invention, the reaction between the component (A) and the component (B) in the esterification step is preferably performed under the condition that the component (B) is excessive with respect to the component (A). From the viewpoint of increasing the reaction rate of esterification by reacting A) and (B) at an equivalent ratio of (B) / (A) = 1.05 to 1.4, and further 1.1 to 1.3 To preferred. In addition, this equivalence ratio is the number of the carboxyl groups of the (B) component [all the (B) component in plural]] per one hydroxyl group of the (A) component [when plural, all (A) component]. . Thus, by using the component (B) excessively, it becomes advantageous when the component (B) is recycled.
本発明では、(A)成分と(B)成分とを、190℃以上の温度で、好ましくは2〜10時間反応させるエステル化工程を行う。エステル化工程の反応時間は2〜6時間の範囲から選択されることが、より好ましい。 In the present invention, an esterification step is performed in which the component (A) and the component (B) are reacted at a temperature of 190 ° C. or higher, preferably for 2 to 10 hours. The reaction time in the esterification step is more preferably selected from the range of 2 to 6 hours.
エステル化工程は190℃以上で行われるが、本発明では、一定温度で一定時間、(A)成分と(B)成分とを反応させることが好ましいので、(A)成分、(B)成分の種類や仕込み比率などを考慮して決定された設定温度Xからの温度変動が少ないことが好ましい。設定温度Xは、190〜270℃の範囲から選択されることが好ましい。 The esterification step is performed at 190 ° C. or higher. In the present invention, it is preferable to react the component (A) and the component (B) at a constant temperature for a certain time. It is preferable that the temperature fluctuation from the set temperature X determined in consideration of the type and the charging ratio is small. The set temperature X is preferably selected from a range of 190 to 270 ° C.
本発明では、特に、エステル工程において、温度勾配0〜10℃の期間(以下、フラット期間という)が存在すること好適である。ここで、温度勾配は、ある時点の反応系の温度をT(℃)とし、その時点から1時間後の反応系の温度がT’(℃)であるとき、T−T’で求まる温度差ΔTの絶対値(|ΔT|)として算出される。本発明では、反応系の温度が190℃以上となったエステル化工程において、この範囲の温度勾配を満たす期間が存在することが好ましい。なお、任意の時点からのエステル化工程の残り時間が1時間未満の場合は、その間の温度変化が0〜10℃であれば、この温度勾配を満たすものとする。通常、反応に供する原料化合物の特性に応じて適宜設定される190℃以上の設定温度Xに最初に到達した時点を基準にして、その時点からの温度勾配が0〜10℃になるように制御される。一方、設定される温度に最初に到達する前の昇温時には、この温度勾配は10℃を超える。本発明では、エステル化工程の少なくとも一部にこのようなフラット期間が存在することが好ましいが、フラット期間がエステル化工程の終了まで継続することが、より好ましい。また、最初のフラット期間が開始する時点Y1での反応系の温度をX1としたときに、設定温度Xと温度X1とが一致することが好ましい。 In the present invention, it is particularly preferable that a period with a temperature gradient of 0 to 10 ° C. (hereinafter referred to as a flat period) exists in the ester process. Here, the temperature gradient is a temperature difference obtained by TT ′ when the temperature of the reaction system at a certain time is T (° C.) and the temperature of the reaction system one hour after that time is T ′ (° C.). Calculated as the absolute value of ΔT (| ΔT |). In the present invention, it is preferable that a period satisfying the temperature gradient in this range exists in the esterification step in which the temperature of the reaction system becomes 190 ° C. or higher. In addition, when the remaining time of the esterification process from arbitrary time is less than 1 hour, if the temperature change in the meantime is 0-10 degreeC, this temperature gradient shall be satisfy | filled. Usually, control is performed so that the temperature gradient from 0 to 10 ° C. is reached with reference to the time point when the set temperature X is first set to 190 ° C. or higher, which is appropriately set according to the characteristics of the raw material compound to be subjected to the reaction. Is done. On the other hand, when the temperature rises before reaching the set temperature for the first time, this temperature gradient exceeds 10 ° C. In the present invention, it is preferable that such a flat period exists in at least a part of the esterification process, but it is more preferable that the flat period continues until the end of the esterification process. Moreover, when the temperature of the reaction system at the time point Y1 when the first flat period starts is X1, it is preferable that the set temperature X and the temperature X1 coincide.
また、フラット期間の長さはエステル化工程の50〜85%(時間基準)を占めることが好ましく、具体的にはフラット期間の時間は2〜10時間、更に2〜6時間の範囲から選択されることが好ましい。なお、本発明では、エステルの製造工程の全域にわたる温度挙動を監視して、190℃以上において温度勾配が0〜10℃となる期間をフラット期間としてもよい。その場合、最初に温度勾配が0〜10℃となる時点での温度をX1とできる。 Further, the length of the flat period preferably occupies 50 to 85% (time basis) of the esterification step. Specifically, the time of the flat period is selected from the range of 2 to 10 hours, and further 2 to 6 hours. It is preferable. In the present invention, the temperature behavior over the entire production process of the ester is monitored, and the period during which the temperature gradient is 0 to 10 ° C. at 190 ° C. or higher may be set as the flat period. In that case, the temperature when the temperature gradient first becomes 0 to 10 ° C. can be X1.
温度勾配の測定は、複数回行うことが好ましく、0.5〜1時間から選ばれる一定時間ごとに測定を行うことが好ましい。通常、エステル化反応の設定温度Xは、反応に供する原料化合物の特性に応じて適宜設定されるので、反応槽に熱電対等の温度センサーを設置し、温度を連続的に測定し、エステル化工程において温度勾配が好ましくは0℃〜10℃となるフラット期間が存在するように制御される。フラット期間における温度勾配は、0℃〜5℃、更に0℃〜2℃が好ましい。 The measurement of the temperature gradient is preferably performed a plurality of times, and is preferably performed at regular intervals selected from 0.5 to 1 hour. Usually, the set temperature X of the esterification reaction is appropriately set according to the characteristics of the raw material compound to be subjected to the reaction. Therefore, a temperature sensor such as a thermocouple is installed in the reaction tank, and the temperature is continuously measured. The temperature gradient is controlled so that a flat period in which the temperature gradient is preferably 0 ° C. to 10 ° C. exists. The temperature gradient in the flat period is preferably 0 ° C to 5 ° C, more preferably 0 ° C to 2 ° C.
また、本発明では、エステル化工程のフラット期間における反応温度の変化量が10℃以内であること、すなわち、フラット期間が開始する時点Y1での温度X1に対して、フラット期間が終了するまでX1±10℃の温度範囲である(ただし、X1±10℃は190℃以上である)ことが好ましい。 Further, in the present invention, the amount of change in the reaction temperature during the flat period of the esterification step is within 10 ° C., that is, the temperature X1 at the time point Y1 when the flat period starts until the flat period ends. It is preferable that the temperature range is ± 10 ° C. (where X1 ± 10 ° C. is 190 ° C. or higher).
エステル化工程において、最初のフラット期間が開始する時点Y1での反応系中の水分量W1としては、反応系1kgあたり1000mg以下、更に700mg以下、更に500mg以下、更に400mg以下、更に300mg以下、更に好ましくは200mg以下とすることができる。また、W1が、反応系1kgあたり250〜1000mgである場合は、後述するように、フラット期間において反応系からの水分の単位時間当たりの低減量を少なくとも1回増加させることが、エステル化工程の終了時の反応系中の水分量を反応系1kg当たり200mg以下にする上で有効である。W1は、仕込み温度から温度X1に最初に到達するまでに水分を除去することで調整できる。 In the esterification step, the water content W1 in the reaction system at the time point Y1 when the first flat period starts is 1000 mg or less, further 700 mg or less, further 500 mg or less, further 400 mg or less, further 300 mg or less, Preferably it can be 200 mg or less. Further, when W1 is 250 to 1000 mg per kg of the reaction system, as will be described later, it is possible to increase the amount of reduction of water from the reaction system per unit time at least once in the flat period. This is effective in reducing the amount of water in the reaction system at the end to 200 mg or less per kg of the reaction system. W1 can be adjusted by removing moisture from the preparation temperature until the temperature X1 is first reached.
本発明では、エステル化反応が実質的に進行しなくなったときをエステル化工程の終了時とする。例えば、エステル化反応を、水酸基価を指標にして監視する場合は、目標とする水酸基価に到達した後、その水酸基価が一定になるように反応系の条件を設定したときは、エステル化反応が実質的に進行しなくなるため、この時点でエステル化工程が終了したとすることができる。潤滑油用基油のような高純度を要求されるエステルの製造においては、エステルの水酸基価が好ましくは15mgKOH、より好ましくは10mgKOH、更に好ましくは5mgKOHに到達したときをエステル化工程の終了時としてよい。 In the present invention, the time when the esterification reaction does not substantially proceed is regarded as the end of the esterification step. For example, when the esterification reaction is monitored using the hydroxyl value as an index, after reaching the target hydroxyl value, the reaction system conditions are set so that the hydroxyl value becomes constant. Can be considered to have ended at this point. In the production of esters that require high purity, such as base oils for lubricating oils, the end of the esterification step is when the hydroxyl value of the ester has preferably reached 15 mgKOH, more preferably 10 mgKOH, and even more preferably 5 mgKOH. Good.
本発明では、好ましくはエステル化工程、より好ましくはフラット期間で反応系の水分量が、反応系1kgあたり200mg以下、好ましくは150mg以下、より好ましくは100mg以下、更に好ましくは70mg以下、特に好ましくは50mg以下になるように水分を低減することを行う。反応系の水分量の低減は、エステル化工程、好ましくはフラット期間において行うことができる。また、エステル化工程の前、又は後に行うこともできる。例えば、エステル化工程の前に反応系の水分量の低減を行う場合、設定温度に到達するまでの昇温速度を変える、反応系内への不活性気体の導入量を変える、設定温度を高く設定する、などにより行うことができる。また、エステル化工程の後に反応系の水分量の低減を行う場合、設定温度よりも高い温度で熟成工程を行う、反応槽内を減圧する、反応系内への不活性気体の導入量を更に増加する、などにより行うことができる。 In the present invention, the water content of the reaction system is preferably 200 mg or less, preferably 150 mg or less, more preferably 100 mg or less, still more preferably 70 mg or less, particularly preferably 70 mg or less, particularly preferably in the esterification step, more preferably in the flat period. Moisture is reduced to 50 mg or less. The water content in the reaction system can be reduced in the esterification step, preferably in the flat period. Moreover, it can also carry out before or after an esterification process. For example, when the water content of the reaction system is reduced before the esterification step, the rate of temperature rise until the set temperature is reached, the amount of inert gas introduced into the reaction system is changed, or the set temperature is increased. This can be done by setting. In addition, when the water content of the reaction system is reduced after the esterification process, the aging process is performed at a temperature higher than the set temperature, the reaction tank is depressurized, and the amount of inert gas introduced into the reaction system is further increased. It can be done by increasing.
フラット期間において水分を低減する場合は、反応系からの水分の単位時間当りの低減量を少なくとも1回増加させることが好ましい。その場合、反応系からの水分の単位時間当りの低減量を連続的に増加させてもよいし、段階的に増加あせてもよいが、段階的に増加することが好ましい。すなわち、反応系の温度をより高くする、反応系への不活性ガスの導入量を増加する、(B)成分の循環量を増加する等の、水分をより低減する操作を複数行い、水分の単位時間当りの低減量が、連続的及び/又は段階的に増加する(反応系中の水分量が連続的及び/又は段階的に減少する)ようにすることが好ましい。 In the case of reducing moisture during the flat period, it is preferable to increase the amount of reduction of moisture from the reaction system per unit time at least once. In this case, the amount of moisture per unit time from the reaction system may be continuously increased or increased stepwise, but it is preferable to increase stepwise. That is, by performing a plurality of operations for further reducing moisture, such as raising the temperature of the reaction system, increasing the amount of inert gas introduced into the reaction system, and increasing the amount of component (B) circulated, It is preferable that the reduction amount per unit time increases continuously and / or stepwise (the amount of water in the reaction system decreases continuously and / or stepwise).
フラット期間において水分を低減する場合は、反応系からの水分の単位時間当りの低減量を少なくとも1回増加させる場合、最初に温度X1に到達した時点から、Yt×T〔Ytはフラット期間の時間、Tは0超0.9以下〕時間以内に、前記低減量の最初の増加を行うことができる。前記低減量の最初の増加を行う時点Y2での水分量W2が、反応系1kgあたり250〜1000mgであることが好ましい。 When reducing the moisture in the flat period, when increasing the amount of moisture per unit time from the reaction system at least once, Yt × T [Yt is the time of the flat period from the time when the temperature X1 is first reached. , T is greater than 0 and less than or equal to 0.9] within a period of time, an initial increase in the reduction can be made. It is preferable that the water content W2 at the time point Y2 when the first reduction amount is increased is 250 to 1000 mg per 1 kg of the reaction system.
反応系からの水分の単位時間当りの低減量を段階的に増加する場合、前記低減量の最初の増加を行った時点Y2からエステル化工程の残り時間が1時間以上ある場合、該Y2から1時間後の、下記式で定義される水分低減率が10%以上であることが好ましい。
水分低減率(%)=〔(W2−W3)/W2〕×100
W2:低減量の最初の増加を行う時点Y2での水分量
W3:低減量の最初の増加を行った時点Y2から1時間後の反応系1kgあたりの水分量
When the reduction amount of water from the reaction system per unit time is increased stepwise, when the remaining time of the esterification process is 1 hour or more from the time point Y2 at which the reduction amount is first increased, the Y2 to 1 It is preferable that the moisture reduction rate defined by the following formula after time is 10% or more.
Moisture reduction rate (%) = [(W2-W3) / W2] × 100
W2: Moisture amount at the time point Y2 when the first reduction amount is increased W3: Water amount per kg of the reaction system one hour after the first time point when the reduction amount is increased Y2
なお、Y2からのエステル化工程の残り時間が1時間未満である場合は、上記のW3を「エステル化工程終了時点での反応系1kgあたりの水分量」と置き換えて水分低減率を算出するものとする。 When the remaining time of the esterification step from Y2 is less than 1 hour, the water reduction rate is calculated by replacing the above W3 with “the amount of water per kg of the reaction system at the end of the esterification step” And
フラット期間での水分の低減は、反応系中の水分の低減に寄与する条件(以下、減水条件という)を、より低減量が大きくなるよう変化させることで行うことが好ましい。ここで、反応系中の水分の低減に寄与する条件としては、反応圧力、反応成分の接触状態などが挙げられ、具体的には、反応系を減圧する、不活性ガスを反応系(反応液)中に導入する、等の方法により、減水条件を、より低減量が大きくなるよう変化させることができる。なお、フラット期間で減水条件を変化させたことにより、水分の低減以外の効果が得られることがあってもよい。 It is preferable to reduce the moisture during the flat period by changing the conditions that contribute to the reduction of moisture in the reaction system (hereinafter referred to as water reduction conditions) so that the amount of reduction becomes larger. Here, the conditions contributing to the reduction of moisture in the reaction system include reaction pressure, contact state of reaction components, and the like. Specifically, the reaction system is depressurized, and an inert gas is reacted with the reaction system (reaction liquid). ) Can be changed so that the amount of reduction becomes larger. In addition, effects other than the reduction of moisture may be obtained by changing the water reduction condition in the flat period.
本発明の製造方法により得られるエステルの水酸基価は、耐吸湿性と潤滑剤としての耐摩耗性の観点から、好ましくは15mgKOH/g以下、より好ましくは10mgKOH/g以下、とくに好ましくは5mgKOH/g以下である。該水酸基価は、JIS K0070 7.2に基づいて測定することができる。エステルの水酸基価を低減するには、エステル化工程、好ましくはフラット期間において、温度を上げる、窒素置換量を増大する、反応時間を延ばす等により、エステル化工程の終了時の反応生成物(エステル)の水酸基価が20mgKOH/g以下、更に15mgKOH/g以下、更に10mgKOH/g以下、更に5mgKOH/g以下、更に4mgKOH/g以下とすることが好ましい。エステル化工程の終了をこのような反応生成物の水酸基価を指標にして決めてもよい。エステル反応終了後では、酸吸着剤による吸着処理の後でカチオン吸着剤による吸着処理を行うことで調整できる。 The hydroxyl value of the ester obtained by the production method of the present invention is preferably 15 mgKOH / g or less, more preferably 10 mgKOH / g or less, particularly preferably 5 mgKOH / g, from the viewpoint of moisture absorption resistance and wear resistance as a lubricant. It is as follows. The hydroxyl value can be measured based on JIS K0070 7.2. In order to reduce the hydroxyl value of the ester, the reaction product (ester) at the end of the esterification step is increased by increasing the temperature, increasing the amount of nitrogen substitution, extending the reaction time, etc. in the esterification step, preferably in the flat period. ) Is preferably 20 mgKOH / g or less, more preferably 15 mgKOH / g or less, further 10 mgKOH / g or less, further 5 mgKOH / g or less, and further preferably 4 mgKOH / g or less. The end of the esterification step may be determined using the hydroxyl value of such a reaction product as an index. After completion of the ester reaction, adjustment can be performed by performing adsorption treatment with a cationic adsorbent after adsorption treatment with an acid adsorbent.
エステル化工程における(A)成分と(B)成分の反応の一例を挙げれば、(A)成分と(B)成分の当量比が上記範囲である場合に、反応温度(設定温度)200〜260℃、反応時間2〜6時間、反応圧力13〜101kPaであり、該温度を基準として温度勾配が0〜10℃の期間が存在することである。例えば、(A)成分がペンタエリスリトールの場合、窒素気流下、常圧で230〜260℃で2〜4時間反応させ、水酸基価が4mgKOH/g以下となるまで反応を行うことが挙げられる。 If an example of reaction of (A) component and (B) component in an esterification process is given, when the equivalent ratio of (A) component and (B) component is the said range, reaction temperature (set temperature) 200-260 The reaction pressure is 13 to 101 kPa, and the temperature gradient is 0 to 10 ° C. on the basis of the temperature. For example, in the case where the component (A) is pentaerythritol, the reaction is performed at 230 to 260 ° C. for 2 to 4 hours under a nitrogen stream, and the reaction is performed until the hydroxyl value becomes 4 mgKOH / g or less.
エステル化工程の後、脱酸、水洗、及び吸着(脱色)処理などの一般の精製工程により該エステルを精製することができる。着色度をさらに下げたい場合は、例えば活性白土吸着剤及び濾過助剤などの吸着剤を目的の水準に応じてエステルに加えて混合、濾過することが可能である。 After the esterification step, the ester can be purified by a general purification step such as deoxidation, washing with water, and adsorption (decolorization) treatment. In order to further reduce the degree of coloring, it is possible to add adsorbents such as activated clay adsorbent and filter aid to the ester according to the target level, and mix and filter.
本発明では、エステル化工程により得られた反応生成物から、未反応の(B)成分を除去することが好ましい。具体的には、反応生成物を減圧処理して(B)成分を反応生成物から除去することが挙げられる。除去した(B)成分は、回収してエステル化工程の反応原料として再利用することができる。なお、(B)成分を吸着し得る吸着剤により(B)成分を除去してもよいが、減圧処理の方が除去効率や(B)成分の再利用の点で好ましい。 In the present invention, it is preferable to remove the unreacted component (B) from the reaction product obtained by the esterification step. Specifically, the reaction product is treated under reduced pressure to remove the component (B) from the reaction product. The removed component (B) can be recovered and reused as a reaction raw material in the esterification step. In addition, although (B) component may be removed with the adsorbent which can adsorb | suck (B) component, the decompression process is more preferable at the point of removal efficiency and reuse of (B) component.
反応生成物からの未反応の(B)成分の除去は、反応生成物中の酸価を目安に行うことができ、好ましくは反応生成物の酸価が0.3mgKOH/g以下、より好ましくは0.2mgKOH/g以下、更に好ましくは0.1mgKOH/g以下となるまで脱酸、好ましくは減圧処理を行うことである。 Removal of the unreacted component (B) from the reaction product can be performed based on the acid value in the reaction product, preferably the acid value of the reaction product is 0.3 mg KOH / g or less, more preferably Deoxidation, preferably reduced pressure treatment is performed until the concentration is 0.2 mgKOH / g or less, more preferably 0.1 mgKOH / g or less.
また、本発明では、上記エステル化工程の後、未反応の(B)成分を除去された反応生成物を脱色することが好ましい。脱色は、色素の吸着能を有する吸着剤(以下、脱色吸着剤という)を反応生成物と接触させることにより行うのが好ましい。 Moreover, in this invention, it is preferable to decolorize the reaction product from which the unreacted (B) component was removed after the said esterification process. Decolorization is preferably performed by bringing an adsorbent having an ability to adsorb a dye (hereinafter referred to as a decolorizing adsorbent) into contact with a reaction product.
脱色吸着剤としては、活性炭、活性白土等が挙げられる。これら脱色吸着剤は、反応生成物の着色度に応じて、反応生成物に対して0.1〜1.5重量%使用されるのが好ましい。 Examples of the decolorizing adsorbent include activated carbon and activated clay. These decolorizing adsorbents are preferably used in an amount of 0.1 to 1.5% by weight based on the reaction product, depending on the degree of coloration of the reaction product.
また、脱色は、反応生成物であるエステルの着色度がAPHA100以下となるまで行うことが好ましい。このAPHAは、JIS K−0071−1に基づいて測定することができる。 Moreover, it is preferable to perform decoloring until the coloring degree of ester which is a reaction product becomes APHA100 or less. This APHA can be measured based on JIS K-0071-1.
本発明の製造方法により得られるエステルの酸価は、金属への腐食防止の観点から低い程良く、好ましくは0.1mgKOH/g以下、更に好ましくは0.05mgKOH/g以下、特に好ましくは0.03mgKOH/g以下である。エステル化反応後、過剰の酸を減圧下除去し、更に吸着剤で吸着除去し、酸価を下げることができる。該酸価は、JIS K0070 3.1に基づいて測定することができる。エステルの酸価は、例えば酸吸着剤の使用量を既エステルに対し0.01〜5重量%に制御することで調整できる。また、酸吸着剤量による吸着処理の実施回数を1回〜5回行うことでも調整できる。 The acid value of the ester obtained by the production method of the present invention is preferably as low as possible from the viewpoint of preventing corrosion to metals, preferably 0.1 mgKOH / g or less, more preferably 0.05 mgKOH / g or less, particularly preferably 0.8. 03 mgKOH / g or less. After the esterification reaction, excess acid can be removed under reduced pressure and further adsorbed and removed with an adsorbent to lower the acid value. The acid value can be measured based on JIS K0070 3.1. The acid value of the ester can be adjusted, for example, by controlling the amount of the acid adsorbent used to 0.01 to 5% by weight based on the existing ester. Moreover, it can also adjust by performing the frequency | count of implementation of the adsorption process by the amount of acid adsorbents 1-5 times.
本発明の製造方法により得られるエステルは、潤滑油用基油として好適に使用することができる。たとえば、冷凍機油、グリース油、作動油油、エンジン油などの潤滑油用の基油として用いることができ、とくに冷凍機油に適する。基油としての該エステルに、酸化防止剤、防錆剤等の添加剤を適宜配合することにより、潤滑油、特に冷凍機油を製造することができる。 The ester obtained by the production method of the present invention can be suitably used as a base oil for lubricating oil. For example, it can be used as a base oil for lubricating oil such as refrigeration oil, grease oil, hydraulic oil, and engine oil, and is particularly suitable for refrigeration oil. Lubricating oils, in particular, refrigerating machine oils can be produced by appropriately blending additives such as antioxidants and rust inhibitors with the esters as base oils.
以下の実施例及び比較例では、設定温度Xにおける温度勾配(温度Xに達してから1時間後の温度の変化)は、3.0℃以下であった。また、何れも、エステル化工程の終了までフラット期間は継続していた。 In the following examples and comparative examples, the temperature gradient at the set temperature X (change in temperature one hour after reaching the temperature X) was 3.0 ° C. or less. In all cases, the flat period continued until the end of the esterification step.
実施例1〜3及び比較例1
2L容の四つ口フラスコに攪拌機、温度計、窒素吹込管、および冷却器付きの脱水管を取り付けた。原料のペンタエリスリトール230gと3,5,5−トリメチルヘキサン酸1340gとを前記四つ口フラスコに入れ、0.03NL/m/kgの窒素ガス吹込下、温度Xを250℃と設定し、250℃まで昇温を行い、250℃〜255℃でエステル化反応を行った。次に表1記載の条件で四つ口フラスコ内の水分を低減させながら水酸基価が3mgKOH/g以下となるまでエステル化反応を行った。その後、冷却器付きの脱水管を脱酸管及び受器に付け替え、未反応の3,5,5−トリメチルヘキサン酸を0.7kPaの減圧下で酸価が0.1mgKOH/g以下になるまで脱酸し、ペンタエリスリトールテトラエステルを得た。なお、最初に温度Xに到達してから2.0時間後とそこから1時間後の間では、温度勾配は2.0℃であった。更に、最初に温度Xに到達してから3.0時間後とそこから1時間後の間では、温度勾配は1.0℃であった。その結果、フラット期間が開始する時点での温度X1は250℃であることがわかる。
Examples 1 to 3 and Comparative Example 1
A 2 L four-necked flask was equipped with a stirrer, a thermometer, a nitrogen blowing tube, and a dehydrating tube with a condenser. 230 g of raw material pentaerythritol and 1340 g of 3,5,5-trimethylhexanoic acid were put into the four-necked flask, and the temperature X was set to 250 ° C. under a nitrogen gas blowing of 0.03 NL / m / kg. The temperature was raised to 250.degree. C. to 255.degree. C. to carry out the esterification reaction. Next, the esterification reaction was performed until the hydroxyl value became 3 mgKOH / g or less while reducing the moisture in the four-necked flask under the conditions described in Table 1. Thereafter, the dehydration tube with a cooler is replaced with a deoxidation tube and a receiver, and the unreacted 3,5,5-trimethylhexanoic acid is reduced to 0.7 mg KOH / g or less under a reduced pressure of 0.7 kPa. Deoxidation gave pentaerythritol tetraester. The temperature gradient was 2.0 ° C. between 2.0 hours after reaching the temperature X for the first time and 1 hour after that. Furthermore, the temperature gradient was 1.0 ° C. between 3.0 hours after reaching the temperature X for the first time and 1 hour after that. As a result, it can be seen that the temperature X1 at the start of the flat period is 250 ° C.
実施例4及び比較例2
3L容の四つ口フラスコに攪拌機、温度計、窒素吹き込み管、および冷却器付きの脱水管を取り付けた。原料のペンタエリスリトール470gとノルマル吉草酸1750gとを前記四つ口フラスコに入れ、0.03NL/m/kgの窒素ガス吹込下、温度Xを210℃と設定し、210℃まで昇温を行い、210℃〜215℃でエステル化反応を行った。次に表1記載の条件で四つ口フラスコ内の水分を低減させながら水酸基価が3mgKOH/g以下となるまでエステル化反応を行った。その後、冷却器付きの脱水管を脱酸管及び受器に付け替え、未反応のノルマル吉草酸を0.7kPaの減圧下で酸価が0.1mgKOH/g以下になるまで脱酸し、ペンタエリスリトールテトラエステルを得た。なお、最初に温度Xに到達してから2.0時間後とそこから1時間後の間では、温度勾配は2.5℃であった。更に、最初に温度Xに到達してから4.0時間後とそこから1時間後の間では、温度勾配は1.5℃であった。その結果、フラット期間が開始する時点での温度X1は210℃であることがわかる。
Example 4 and Comparative Example 2
A 3 L four-necked flask was equipped with a stirrer, a thermometer, a nitrogen blowing tube, and a dehydrating tube equipped with a condenser. Put 470 g of raw materials pentaerythritol and 1750 g of normal valeric acid in the four-necked flask, set temperature X to 210 ° C. under nitrogen gas blowing of 0.03 NL / m / kg, and raise the temperature to 210 ° C. The esterification reaction was performed at 210 ° C to 215 ° C. Next, the esterification reaction was performed until the hydroxyl value became 3 mgKOH / g or less while reducing the moisture in the four-necked flask under the conditions described in Table 1. Thereafter, the dehydrating tube with a cooler was replaced with a deoxidizing tube and a receiver, and unreacted normal valeric acid was deoxidized under a reduced pressure of 0.7 kPa until the acid value became 0.1 mgKOH / g or less, and pentaerythritol The tetraester was obtained. The temperature gradient was 2.5 ° C. between 2.0 hours after reaching the temperature X for the first time and 1 hour after that. Furthermore, the temperature gradient was 1.5 ° C. between 4.0 hours after reaching the temperature X for the first time and 1 hour after that. As a result, it can be seen that the temperature X1 at the start of the flat period is 210 ° C.
実施例5〜6及び比較例3
5L容の四つ口フラスコに攪拌機、温度計、窒素吹き込み管、および冷却器付きの脱水管を取り付けた。原料のペンタエリスリトール380gとイソステアリン酸3700gとを前記四つ口フラスコに入れ、0.03NL/m/kgの窒素ガス吹込下、温度Xを260℃と設定し、260℃まで昇温を行い、260℃〜265℃でエステル化反応を行った。次に表1記載の条件で四つ口フラスコ内の水分を低減させながら水酸基価が3mgKOH/g以下となるまでエステル化反応を行った。その後、冷却器付きの脱水管を脱酸管及び受器に付け替え、未反応のイソステアリン酸を0.7kPaの減圧下で酸価が0.1mgKOH/g以下になるまで脱酸し、ペンタエリスリトールテトラエステルを得た。なお、最初に温度Xに到達してから1.0時間後とそこから1時間後の間では、温度勾配は1.5℃であった。更に、最初に温度Xに到達してから2.0時間後とそこから1時間後の間では、温度勾配は1.0℃であった。その結果、フラット期間が開始する時点での温度X1は260℃であることがわかる。
Examples 5 to 6 and Comparative Example 3
A stirrer, a thermometer, a nitrogen blowing tube, and a dehydrating tube with a condenser were attached to a 5-L four-necked flask. Raw material pentaerythritol (380 g) and isostearic acid (3700 g) were put into the four-necked flask, under a nitrogen gas blowing of 0.03 NL / m / kg, the temperature X was set to 260 ° C., and the temperature was raised to 260 ° C. The esterification reaction was carried out at a temperature between deg. Next, the esterification reaction was performed until the hydroxyl value became 3 mgKOH / g or less while reducing the moisture in the four-necked flask under the conditions described in Table 1. Thereafter, the dehydration tube with a cooler was replaced with a deoxidation tube and a receiver, and unreacted isostearic acid was deoxidized under a reduced pressure of 0.7 kPa until the acid value was 0.1 mgKOH / g or less, and pentaerythritol tetra An ester was obtained. The temperature gradient was 1.5 ° C. between 1.0 hour after reaching the temperature X for the first time and 1 hour after that. Further, the temperature gradient was 1.0 ° C. between 2.0 hours after reaching the temperature X for the first time and 1 hour after that. As a result, it can be seen that the temperature X1 at the start of the flat period is 260 ° C.
実施例7〜10及び比較例4
5L容の四つ口フラスコに攪拌機、温度計、窒素吹き込み管、および冷却器付きの脱水管を取り付けた。原料のペンタエリスリトール570gと2−エチルヘキサン酸1550gと3,5,5−トリメチルヘキサン酸1610gとを前記四つ口フラスコに入れ、0.03NL/m/kgの窒素ガス吹込下、温度Xを250℃と設定し、250℃まで昇温を行い、250℃〜255℃でエステル化反応を行った。次に表1記載の条件で四つ口フラスコ内の水分を低減させながら水酸基価が3mgKOH/g以下となるまでエステル化反応を行った。その後、冷却器付きの脱水管を脱酸管及び受器に付け替え、未反応の2−ヘチルヘキサン酸と3,5,5−トリメチルヘキサン酸とを0.7kPaの減圧下で酸価が0.1mgKOH/g以下になるまで脱酸し、ペンタエリスリトールテトラエステルを得た。なお、最初に温度Xに到達してから2.0時間後とそこから1時間後の間では、温度勾配は1.5℃であった。更に、最初に温度Xに到達してから4.0時間後とそこから1時間後の間では、温度勾配は1.0℃であった。その結果、フラット期間が開始する時点での温度X1は250℃であることがわかる。
Examples 7 to 10 and Comparative Example 4
A stirrer, a thermometer, a nitrogen blowing tube, and a dehydrating tube with a condenser were attached to a 5-L four-necked flask. The raw material pentaerythritol (570 g), 2-ethylhexanoic acid (1550 g) and 3,5,5-trimethylhexanoic acid (1610 g) were put into the four-necked flask, and the temperature X was 250 under a nitrogen gas blowing of 0.03 NL / m / kg. The temperature was set to 250C, the temperature was raised to 250 ° C, and an esterification reaction was performed at 250 ° C to 255 ° C. Next, the esterification reaction was performed until the hydroxyl value became 3 mgKOH / g or less while reducing the moisture in the four-necked flask under the conditions described in Table 1. Thereafter, the dehydrating tube with a cooler was replaced with a deoxidizing tube and a receiver, and unreacted 2-hexylhexanoic acid and 3,5,5-trimethylhexanoic acid were reduced to 0.7 kPa with an acid value of 0.1 mgKOH. The acid was deoxidized until it became less than / g, and pentaerythritol tetraester was obtained. The temperature gradient was 1.5 ° C. between 2.0 hours after reaching the temperature X for the first time and 1 hour after that. Furthermore, the temperature gradient was 1.0 ° C. between 4.0 hours after reaching the temperature X for the first time and 1 hour after that. As a result, it can be seen that the temperature X1 at the start of the flat period is 250 ° C.
実施例11
エステル化工程を265℃〜268℃で行う以外は、実施例7等と同様にしてペンタエリスリトールテトラエステルを得た。なお、反応原料の仕込み後、温度Xは265℃とし、窒素ガスの吹き込み開始から265℃に到達するまでに要する時間は、実施例7等と同じとした。なお、最初に温度Xに到達してから1.0時間後とそこから1時間後の間では、温度勾配は2.0℃であった。更に、最初に温度Xに到達してから2.0時間後とそこから1時間後の間では、温度勾配は1.0℃であった。その結果、フラット期間が開始する時点での温度X1は265℃であることがわかる。
Example 11
Pentaerythritol tetraester was obtained in the same manner as in Example 7 except that the esterification step was performed at 265 ° C to 268 ° C. The temperature X was 265 ° C. after the reaction raw materials were charged, and the time required to reach 265 ° C. from the start of nitrogen gas blowing was the same as in Example 7 and the like. The temperature gradient was 2.0 ° C. between 1.0 hour after reaching the temperature X for the first time and 1 hour after that. Further, the temperature gradient was 1.0 ° C. between 2.0 hours after reaching the temperature X for the first time and 1 hour after that. As a result, it can be seen that the temperature X1 at the start of the flat period is 265 ° C.
表中の記号は以下の意味である。
・3,5,5TMHA:3,5,5−トリメチルヘキサン酸
・2−EHA:2−ヘチルヘキサン酸
・Y3:エステル化工程終了の時点
・W4:エステル化工程終了時の反応系1kgあたりの水分量
The symbols in the table have the following meanings.
・ 3,5,5TMHA: 3,5,5-trimethylhexanoic acid ・ 2-EHA: 2-hetylhexanoic acid ・ Y3: time of esterification step completion ・ W4: water content per kg of reaction system at the end of esterification step
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JP2006106034A Expired - Fee Related JP4160081B2 (en) | 2006-04-07 | 2006-04-07 | Method for producing ester |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012102046A (en) * | 2010-11-10 | 2012-05-31 | Kao Corp | Ester compound |
JP2014097939A (en) * | 2012-11-13 | 2014-05-29 | Nof Corp | Production method of ester |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102304041B (en) * | 2011-05-12 | 2013-10-30 | 中国科学院新疆理化技术研究所 | Solvent-free esterification-distillation integrated process |
WO2013008487A1 (en) * | 2011-07-13 | 2013-01-17 | Khネオケム株式会社 | Tetraester of pentaerythritol |
WO2013014959A1 (en) * | 2011-07-27 | 2013-01-31 | Khネオケム株式会社 | Tetraester of pentaerythritol |
WO2013027428A1 (en) * | 2011-08-19 | 2013-02-28 | Khネオケム株式会社 | Tetraester of pentaerythritol |
US9523058B2 (en) | 2012-03-23 | 2016-12-20 | Kh Neochem Co., Ltd. | Mixed ester |
JP5975262B2 (en) * | 2012-04-26 | 2016-08-23 | 日油株式会社 | Method for producing ester for refrigerator oil |
CN108689848B (en) * | 2017-04-05 | 2021-07-02 | 中国石油天然气股份有限公司 | Refining method of polyol ester crude product |
CN109880666B (en) * | 2019-03-13 | 2022-04-15 | 上海鸣起能源科技有限公司 | Preparation method and refining method of ester synthetic oil |
Family Cites Families (2)
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US4868329A (en) * | 1986-08-01 | 1989-09-19 | Hoechst Celanese Corp. | Accelerated preparation of carboxylic acid esters |
JP4545422B2 (en) * | 2003-12-09 | 2010-09-15 | 花王株式会社 | Method for producing ester for lubricating oil |
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2006
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012102046A (en) * | 2010-11-10 | 2012-05-31 | Kao Corp | Ester compound |
JP2014097939A (en) * | 2012-11-13 | 2014-05-29 | Nof Corp | Production method of ester |
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CN101050178B (en) | 2013-03-20 |
JP4160081B2 (en) | 2008-10-01 |
CN101050178A (en) | 2007-10-10 |
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