CN100513380C - Process for producing ester used for lubricating oil - Google Patents
Process for producing ester used for lubricating oil Download PDFInfo
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- CN100513380C CN100513380C CNB200410100604XA CN200410100604A CN100513380C CN 100513380 C CN100513380 C CN 100513380C CN B200410100604X A CNB200410100604X A CN B200410100604XA CN 200410100604 A CN200410100604 A CN 200410100604A CN 100513380 C CN100513380 C CN 100513380C
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- ester
- saturated aliphatic
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- 150000002148 esters Chemical class 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims description 34
- 239000010687 lubricating oil Substances 0.000 title abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 43
- 239000002594 sorbent Substances 0.000 claims abstract description 25
- -1 saturated aliphatic monocarboxylic acid Chemical class 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 46
- 239000000314 lubricant Substances 0.000 claims description 7
- 229920005862 polyol Polymers 0.000 claims description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 abstract 4
- 230000008030 elimination Effects 0.000 abstract 4
- 238000003379 elimination reaction Methods 0.000 abstract 4
- 150000005846 sugar alcohols Polymers 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 229940059574 pentaerithrityl Drugs 0.000 description 12
- 239000002671 adjuvant Substances 0.000 description 11
- 238000001914 filtration Methods 0.000 description 11
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 150000001735 carboxylic acids Chemical class 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 239000002199 base oil Substances 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000005057 refrigeration Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000006837 decompression Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 150000002632 lipids Chemical class 0.000 description 4
- 238000010186 staining Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical compound [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000001298 alcohols 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
- 238000010438 heat treatment Methods 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-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
- NKBWMBRPILTCRD-UHFFFAOYSA-N 2-Methylheptanoic acid Chemical compound CCCCCC(C)C(O)=O NKBWMBRPILTCRD-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
- CVKMFSAVYPAZTQ-UHFFFAOYSA-N 2-methylhexanoic acid Chemical compound CCCCC(C)C(O)=O CVKMFSAVYPAZTQ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- 241001550224 Apha Species 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000000654 additive Substances 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
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 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
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- 229940033355 lauric acid Drugs 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Lubricants (AREA)
Abstract
The invention provides a simple manufacturing method of an ester for lubricating oils which achieves satisfactory acid elimination and decoloring even if a sorbent is used in a reduced amount. The manufacturing method of the ester for lubricating oils comprises the step (1) wherein an aliphatic polyhydric alcohol (A) and a saturated aliphatic monocarboxylic acid (B) are reacted to obtain reaction products including esters; the first acid elimination step (2) wherein the unreacted saturated aliphatic monocarboxylic acid is removed from the reaction products obtained in the step (1); the step (3) wherein the reaction products that have undergone the acid elimination through the step (2) is decolored; and the second acid elimination step (4) wherein the unreacted saturated aliphatic monocaboxylic acid is removed from the reaction products decolored by the step (3).
Description
Technical field
The present invention relates to as the manufacture method of lubricating oil with the ester of base oil use.
Background technology
In the past, the mineral oil that obtains easily with general use in the base oil of lubricating oil.But in recent years, requirement to lubricants performance is more and more higher, harsh day by day as working conditions, adapt to the increase of machinery of energy-conservation requirement and the influence when further being reduced in the environment diffusion etc., make the performances such as oilness, thermotolerance, oxidative stability, low-temperature fluidity, biological degradability of mineral oil seem abundant inadequately.For this reason, substitute as mineral oil, the alcohol esters that are obstructed such as neopentyl glycol, TriMethylolPropane(TMP), tetramethylolmethane that are called POE system (polyol ester), its oilness, thermotolerance, oxidative stability, low-temperature fluidity, biological degradability are good, have been applied in lubricating oil already with in the base oil.
Wherein, along with the refrigeration agent of refrigerator to the transition of not chloride and hydrogenous fluorine carbon refrigeration agent, refrigerator oil requires to adapt to above-mentioned refrigeration agent with lubricating oil.For example disclosing among the JP-A3-128992 with carbonatoms 15 or following, ternary or above polyvalent alcohol and 1 yuan of lipid acid of carbonatoms 2～18 etc. is that ester that raw material obtains is that the hydrogeneous fluorine carbon refrigeration agent of main component is with lubricating oil, HFC refrigeration oil.
On the other hand, it is colored making the polyvalent alcohol of technical grade and the resulting alcohol ester that is obstructed of carboxylic acid reaction, and the acid of using in the reaction has residually, therefore need decolour, depickling handles.In the past from contain the resultant of reaction that makes polyvalent alcohol and the resulting ester of carboxylic acid reaction, utilize method depickling such as decompression after, add the sorbent material that is used to decolour again together and be used for the sorbent material of depickling, decolour, the depickling processing.Proposed a kind of scheme among the JP-A2001-107067,, used the high tetramethylolmethane of monopentaerythritol content, and disclose the Production Example and the adsorption treatment example of pentaerythritol ester in order to obtain the low refrigerator oil base oil of degree of staining.
Summary of the invention
The present invention relates to the manufacture method of lubricant ester, this method comprises:
(1) makes the reaction of aliphatic polyol (A) and representative examples of saturated aliphatic monocarboxylic acid (B) and obtain containing the operation [to call operation (1) in the following text] of the resultant of reaction of ester;
(2) from the resultant of reaction that utilizes operation (1) to obtain, remove monocarboxylic first deacidification process of unreacted representative examples of saturated aliphatic [to call operation (2) in the following text];
(3) operation that the resultant of reaction that utilizes operation (2) depickling is decoloured [to call operation (3) in the following text];
(4) from the resultant of reaction that utilizes operation (3) decolouring, remove monocarboxylic second deacidification process of unreacted representative examples of saturated aliphatic [to call operation (4) in the following text].
Embodiment
In existing method,, thereby be difficult to reduce cost because decolorizing effect, deacidification effect are significantly low.Although disclose the HFC refrigeration oil among the JP-A3-128992, do not mention concrete depickling or decolouring.Although the method for JP-A2001-107067 has satisfied the requirement of decolouring to a certain degree, the reduction of depickling and acid number is not specifically related to.
The invention reside in the manufacture method that a kind of easy lubricant ester is provided, also can realize sufficient depickling and decolouring even this method reduces the usage quantity of sorbent material.Divide decolouring and 2 stages of further adsorbing depickling to handle.The yield that generates ester improves, and treatment effect improves.
Utilize manufacture method of the present invention, can decolour fully and depickling, reduced sorbent material, particularly depickling consumption significantly, improved utilization ratio of raw materials with sorbent material.
Operation (1)
Operation (1) is aliphatic polyol (A) (below be called (A) composition) and representative examples of saturated aliphatic monocarboxylic acid (B) (below be called (B) composition) to be reacted and the operation that obtains containing the resultant of reaction of ester, can carry out according to existing method.
As (A) composition, that can specifically enumerate has: neopentyl glycol, 2-ethyl-2-methyl-1, ammediol, 2-sec.-propyl-2-methyl-1, ammediol, 2,2-diethyl-1, ammediol, 2-normal-butyl-2-ethyl-1, ammediol, two (3-hydroxyls-2,2-dimethyl propyl) ether, trimethylolethane, TriMethylolPropane(TMP), tetramethylolmethane, two trimethylolethanes, two TriMethylolPropane(TMP)s, the polyvalent alcohol that is obstructed such as Dipentaerythritol, perhaps ethylene glycol, Diethylene Glycol, triethylene glycol, TEG, five ethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3 propylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol, glycerine, Glycerol dimer, polyvalent alcohols such as triglycerin.The carbonatoms of these aliphatic polyols is considered to be preferably 2～12 from the viewpoint of the viscosity that generates ester, and more preferably 2～7.In addition, utilize the hydroxyl in the molecule also can adjust the viscosity that generates ester, consider to contain the preferred molecule 2～6 hydroxyls from this viewpoint.And from stable on heating viewpoint consideration, the polyvalent alcohol that is obstructed is outstanding, preferred especially neopentyl glycol, TriMethylolPropane(TMP), tetramethylolmethane.(A) composition also can mix use two kinds or more than.
In addition, as (B) composition, that can specifically enumerate has: straight chain representative examples of saturated aliphatic monocarboxylic acid such as butyric acid, valeric acid (acid of バ レ リ Application), caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, laurostearic acid, isopropylformic acid, isovaleric acid, trimethylacetic acid, 2-ethyl valeric acid, 2-methylhexanoic acid, 2-thylhexoic acid, 3-thylhexoic acid, 2-methyl enanthic acid, cyclohexyl acetic acid, 3, side chain such as 5,5-tri-methyl hexanoic acid, 2-methyloctanoic acid representative examples of saturated aliphatic monocarboxylic acid.Consider that from the low-temperature fluidity of generation ester with to the viewpoint of corrosion of metal preferred carbonatoms is 4～12, further preferred carbonatoms is 5～10.Consider preferably on the α position of carbonyls such as 2-thylhexoic acid, have the carboxylic acid of side chain from the viewpoint of hydrolytic resistance.(B) composition also can mix use two kinds or more than.
In operation (1), (A) composition and (B) reaction of composition preferably under the condition of (B) composition surplus, carry out.Specifically, consider from the viewpoint that improves esterification speed, preferably with the equivalence ratio of (B)/(A)=1.05～1.4, more preferably make (A) and (B) react with 1.1～1.3 equivalence ratio.In addition, this equivalence ratio is the ratio of the hydroxyl of per 1 (A) composition (use under two kinds or the above situation and be all (A) compositions) with respect to the number of the carboxyl of (B) composition (using under two kinds or the above situation to owning (B) compositions).By so excessively using (B) composition, as the back will speak of like that, when (B) composition circulation that operation (2) is removed is used as (B) composition in the operation (1), be favourable.
If (A) composition in the operation of exemplifying (1) and (B) example reacting of composition, then when (A) composition with (B) when the equivalence ratio of composition is above-mentioned scope, temperature of reaction is 200～260 ℃, and the reaction times is 5～12 hours, and reaction pressure is 13～101kPa.For example, when (A) composition is tetramethylolmethane, under nitrogen gas stream and normal pressure, make its reaction 5～12 hours in 230～260 ℃, can make reaction proceed to hydroxyl value and reach 5mgKOH/g or following.
The end of esterification can be a standard with the hydroxyl value in the resultant of reaction in the operation (1), and the hydroxyl value that preferably makes reaction proceed to resultant of reaction reaches 5mgKOH/g or following.
Operation (2)
Operation (2) is from the resultant of reaction that operation (1) obtains, and removes unreacted (B) composition.Concrete example has: resultant of reaction is carried out reduced pressure treatment, remove (B) composition from react biology.(B) composition of removing reclaims, and the reaction raw materials that can be used as operation (1) utilizes again.In addition, also can utilize the sorbent material that can adsorb (B) composition to remove (B) composition, but consider to remove efficient and (B) utilization again of composition, preferably utilize the method for reduced pressure treatment.
Remove unreacted (B) composition that comes from resultant of reaction by operation (2), can be that standard is carried out with the acid number in the resultant of reaction, the acid number that preferably makes depickling proceed to resultant of reaction is 0.3mgKOH/g or following, 0.2mgKOH/g or following more preferably, more preferably 0.1mgKOH/g or following preferably carries out with the method for reduced pressure treatment.
Operation 3
Operation (3) makes the resultant of reaction decolouring that utilizes operation (2) depickling.The preferred following mode of decolouring is carried out, that is: sorbent material with pigment adsorptive power (below be called decolorizing adsorbent) and resultant of reaction are contacted.
As decolorizing adsorbent, can enumerate gac, atlapulgite etc.These decolorizing adsorbents use 0.1～1.5 weight % according to the preferred relative response resultant of the degree of staining of resultant of reaction, more preferably use 0.1～1.0 weight %.
In addition, the degree of staining of resultant of reaction preferably proceeds to APHA100 or following, more preferably proceeds to APHA50 or following.This APHA can measure (down together) according to JIS K-0071-1.
Operation 4
Operation (4) is from the resultant of reaction that utilizes operation (3) decolouring, removes second deacidification process of unreacted (B) composition.Second deacidification process is preferably by making the sorbent material that can adsorb (B) composition (below be called sour sorbent material) contact with resultant of reaction, thereby removes (B) composition.Although also can utilize reduced pressure treatment from resultant of reaction, to remove (B) composition, because before in operation (4), the concentration of (B) composition in the reactant is reduced significantly, so consider and remove efficient, compare with reduced pressure treatment, more preferably use sour sorbent material.
As sour sorbent material, adducible have: activated alumina, atlapulgite, aluminium hydroxide, the synthetic zeolite that the anionresin sorptive power is arranged or ion exchange resin or hydrotalcite etc.Acid sorbent material relative response resultant preferably uses the ratio of 0.1～0.6 weight %.As common manufacture method, when sour sorbent material and deacidification adsorbent being added together when using, sour sorbent material is used with the ratio of 0.6～2.0 weight % with respect to resultant of reaction, thereby, can reduce the usage quantity of sour sorbent material significantly according to the present invention.Therefore, resultant of reaction also reduces the adsorptive capacity of sour sorbent material, is expected to further improve raw material availability.Particularly industrial, the raising of the yield of final ester brings bigger influence to economy, considers that from this some method of the present invention also is very useful.
Second deacidification process through operation (4) can obtain lubricant ester, and the acid number of this ester is preferably 0.02mg KOH/g or following, more preferably 0.01mg KOH/g or following.
The ester that utilizes manufacture method of the present invention to obtain, its degree of staining and acid number are low, can be suitable for use as the lubricating oil base oil.For example can be used as the base oil that refrigerator oil, lubricating oil, hydraulic efficiency oil, engine wet goods lubricating oil are used, be especially suitable for use as refrigerator oil.In this ester as base oil, suitably cooperate additives such as oxidation inhibitor, rust-preventive agent, can make lubricating oil, particularly refrigerator oil.
Embodiment
The following describes embodiment 1～3, comparative example 1,2, following embodiment is used to illustrate the present invention, the invention is not restricted to this.
Embodiment 1
In being provided with 2 liters of four-hole boiling flasks of wet separator that stirring rod, nitrogen be blown into pipe, thermometer and band water cooler, add tetramethylolmethane 272g (2.0 moles), 2-thylhexoic acid 1382.4g (9.6 moles) (hydroxyl of relative 1 normal tetramethylolmethane, the carboxyl of aforementioned 2-thylhexoic acid are 1.20 equivalents).
Then, under agitation be blown into the nitrogen limit and make its 10 hours [operation (1)] of reaction, remove the water that distills out at 250 ℃ to the flask inner edge.After reaction finished, decompression was at leisure finally distilled 1 hour under 0.2kPa, heated up in a steamer superfluous carboxylic acid, carried out decatize again under the decompression of 1kPa 1 hour [operation (2)].Heating up in a steamer the 2-thylhexoic acid that reclaims is 223g, and after lipid acid heated up in a steamer, the acid number that generates ester mixture was 0.06mgKOH/g, and form and aspect are APHA300.Then, gac (military field medicine カ Le ボ ラ Off イ Application) 6g and filtration adjuvant 2g (clear and chemical system ラ ジ オ ラ イ ト #900) are put into this generation ester mixture, in 1.3kPa, 1 hour [operation (3)] of 80 ℃ of following stirrings, then utilize Japan's filter paper system No2 filter paper to remove gac and filtration adjuvant.Filtrate is that the acid number of ester mixture is 0.06mgKOH/g, and form and aspect are APHA15.Then this filtrate placing is provided with 2 liters the four-hole boiling flask that stirring rod, nitrogen are blown into pipe and thermometer, add sour sorbent material 6g (consonance chemical industry (strain) system, trade(brand)name: キ ヨ-ワ-De 500SH) with filtration adjuvant (with preceding identical) 2g, after 1.3kPa, 80 ℃ stir 1 hour [operation (4)] down, filter with above-mentioned the samely.The acid number of the ester that obtains is that 0.004mgKOH/g, form and aspect are that APHA15, kinematic viscosity are 44.34mm
2/ s) (40 ℃).
Embodiment 2
In being provided with 2 liters of four-hole boiling flasks of wet separator that stirring rod, nitrogen be blown into pipe, thermometer and band water cooler, add tetramethylolmethane 272g (2.0 moles), 2-thylhexoic acid 691.2g (4.8 moles), 3,5,5-tri-methyl hexanoic acid 758.4g (4.8 moles) is (with respect to the hydroxyl of 1 normal tetramethylolmethane, aforementioned 2-thylhexoic acid and 3, the carboxyl of 5,5-tri-methyl hexanoic acid adds up to 1.20 equivalents).
Then, under agitation be blown into the nitrogen limit and make its 10 hours [operation (1)] of reaction, remove the water that distills out at 250 ℃ to the flask inner edge.After reaction finished, decompression was at leisure finally distilled 1 hour under 0.2kPa, heated up in a steamer superfluous carboxylic acid, carried out decatize again under the decompression of 1kPa 1 hour [operation (2)].Heat up in a steamer the 2-thylhexoic acid and 3,5 that reclaims, 5-tri-methyl hexanoic acid adds up to 230g, and after these lipid acid heated up in a steamer, the acid number that generates ester mixture was 0.10mgKOH/g, and form and aspect are APHA200.Then, gac (identical with embodiment 1) 6g is put into this generation ester mixture with filtration adjuvant (identical with embodiment 1) 2g, in 1.3kPa, 1 hour [operation (3)] of 80 ℃ of following stirrings, then, utilize Japan's filter paper system No2 filter paper to remove gac and filtration adjuvant.Filtrate is that the acid number of ester mixture is 0.10mgKOH/g, and form and aspect are APHA25.Then, this filtrate placing is provided with 2 liters of four-hole boiling flasks that stirring rod, nitrogen are blown into pipe and thermometer, add sour sorbent material (identical) 6g and filtration adjuvant (identical) 2g with embodiment 1 with embodiment 1, after 1.3kPa, 80 ℃ stir 1 hour [operation (4)] down, filter with above-mentioned the samely.The acid number of the ester that obtains is that 0.007mgKOH/g, form and aspect are that APHA15, kinematic viscosity are 67.36mm
2/ s) (40 ℃).
Comparative example 1
With embodiment 1 the same ground building-up reactions thing, heat up in a steamer superfluous carboxylic acid afterwards.After carboxylic acid heated up in a steamer, the acid number that generates ester mixture was 0.06mgKOH/g, and form and aspect are APHA250.
Then, with gac (identical) 6g, sour sorbent material (identical) 11g with embodiment 1 with embodiment 1, and filtration adjuvant (identical) 2g with embodiment 1 put into this generation ester mixture, 1.3kPa, 80 ℃ of following stirrings 1 hour, then, utilize Japan's filter paper system No2 filter paper to remove activated carbon of sorbent, sour sorbent material and filtration adjuvant.Filtrate is that the acid number of ester mixture is 0.01mgKOH/g, and form and aspect are that APHA20, kinematic viscosity are 44.51mm
2/ s) (40 ℃).
Comparative example 2
With embodiment 1 the same ground building-up reactions thing, heat up in a steamer superfluous carboxylic acid afterwards.After carboxylic acid heated up in a steamer, the acid number that generates ester mixture was 0.06mgKOH/g, and form and aspect are APHA350.
Then, sour sorbent material (identical with embodiment 1) 10g and filtration adjuvant (identical with embodiment 1) 2g are put into this generation ester mixture,, then, utilize Japan filter paper system No2 filter paper to remove disacidify sorbent material and filtration adjuvant 1.3kPa, 80 ℃ of following stirrings 1 hour.Filtrate is that the acid number of ester mixture is 0.02mgKOH/g, and form and aspect are APHA200.Then, in this filtrate, put into gac (identical) 6g and filtration adjuvant (identical) 2g,, filter with above-mentioned afterwards the samely 1.3kPa, 80 ℃ of following stirrings 1 hour with embodiment 1 with embodiment 1.The acid number of the ester that obtains is 0.018mgKOH/g, and form and aspect are that APHA80, kinematic viscosity are 44.53mm
2/ s) (40 ℃).This example operation among the embodiment 1 (3) and operation (4) are reversed [before just operation (4) being placed, carrying out operation (3) thereafter] carry out.
Embodiment 3
Except that the 2-thylhexoic acid 223g (1.5 moles) that uses tetramethylolmethane 272g (2.0 moles), 2-thylhexoic acid 1152g (8.0 moles) and embodiment 1 to reclaim, other carries out esterification with embodiment 1 the samely, heat up in a steamer superfluous lipid acid, decolouring in order obtains ester with deacidification process.Behind the deacidification process through operation (2), the acid number that generates ester mixture is that 0.08mgKOH/g, form and aspect are APHA300.In addition, after operation (4), the acid number of final ester is that 0.005mgKOH/g, form and aspect are that APHA10, kinematic viscosity are 44.28mm
2/ s) (40 ℃).Obtain the ester identical with the situation of using new raw material.
Claims (7)
1, a kind of manufacture method of lubricant ester, this method comprises: operation (1): make the reaction of aliphatic polyol (A) and representative examples of saturated aliphatic monocarboxylic acid (B) and obtain containing the operation of the resultant of reaction of ester; Operation (2): from the resultant of reaction that utilizes operation (1) to obtain, remove monocarboxylic first deacidification process of unreacted representative examples of saturated aliphatic; Operation (3): the operation that the resultant of reaction that utilizes operation (2) depickling is decoloured; Operation (4): from the resultant of reaction that utilizes operation (3) decolouring, remove monocarboxylic second deacidification process of unreacted representative examples of saturated aliphatic.
2, manufacture method as claimed in claim 1, wherein, utilizing the acid number of the resultant of reaction of operation (2) depickling is 0.3mgKOH/g or following.
3, manufacture method as claimed in claim 1 or 2 wherein, makes (A) and (B) reacts according to the equivalence ratio of (B)/(A)=1.05～1.4.
4, manufacture method as claimed in claim 1 or 2, wherein, the acid number of lubricant ester is 0.02mgKOH/g or following.
5, manufacture method as claimed in claim 1 or 2 wherein, reclaims the representative examples of saturated aliphatic monocarboxylic acid in operation (2), it is re-used as (B) in the operation (1).
6, manufacture method as claimed in claim 1 or 2, wherein, removing unreacted representative examples of saturated aliphatic monocarboxylic acid by operation (2) is to be undertaken by the mode that resultant of reaction is exposed under the reduced atmosphere.
7, manufacture method as claimed in claim 1 or 2, wherein, removing unreacted representative examples of saturated aliphatic monocarboxylic acid by operation (4) is to utilize the sour sorbent material that can adsorb this carboxylic acid to carry out.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP409817/2003 | 2003-12-09 | ||
| JP2003409817A JP4545422B2 (en) | 2003-12-09 | 2003-12-09 | Method for producing ester for lubricating oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1636960A CN1636960A (en) | 2005-07-13 |
| CN100513380C true CN100513380C (en) | 2009-07-15 |
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| CNB200410100604XA Expired - Fee Related CN100513380C (en) | 2003-12-09 | 2004-12-09 | Process for producing ester used for lubricating oil |
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| JP (1) | JP4545422B2 (en) |
| CN (1) | CN100513380C (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4160081B2 (en) * | 2006-04-07 | 2008-10-01 | 花王株式会社 | Method for producing ester |
| JP4786594B2 (en) * | 2006-05-17 | 2011-10-05 | 花王株式会社 | Method for producing ester for lubricating oil |
| JP4633765B2 (en) * | 2006-06-07 | 2011-02-16 | 花王株式会社 | Method for producing ester |
| JP5375227B2 (en) * | 2009-03-16 | 2013-12-25 | 日油株式会社 | Method for producing ester lubricating oil for refrigerator |
| DE102009048772A1 (en) * | 2009-10-08 | 2011-04-21 | Oxea Deutschland Gmbh | Process for the preparation of polyol esters |
| CN106008215A (en) * | 2011-07-13 | 2016-10-12 | Kh新化株式会社 | Tetraester of pentaerythritol |
| JP2014152127A (en) * | 2013-02-06 | 2014-08-25 | Tokuyama Corp | Production method of olmesartan medoxomil |
| JP6159373B2 (en) | 2015-10-07 | 2017-07-05 | 出光興産株式会社 | Refrigerator oil, composition for refrigerator, refrigerator and method for selecting refrigerator oil |
| JP6801929B2 (en) * | 2017-04-25 | 2020-12-16 | 出光興産株式会社 | Selection method of refrigerating machine oil, composition for refrigerating machine, refrigerating machine and refrigerating machine oil |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1347867A (en) * | 2000-10-16 | 2002-05-08 | 日本油脂株式会社 | Process for producing ester |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56131548A (en) * | 1980-03-18 | 1981-10-15 | Nippon Oil & Fats Co Ltd | Neopentylpolyol ester, and flon-resistant oil containing said ester as base oil |
| JP2571100B2 (en) * | 1988-05-30 | 1997-01-16 | 日清製油株式会社 | Lubricant |
| JPH1180766A (en) * | 1997-09-02 | 1999-03-26 | Kao Corp | Grease base oil |
| JP4393625B2 (en) * | 1999-06-18 | 2010-01-06 | 花王株式会社 | Synthetic lubricant base oil |
| JP3622896B2 (en) * | 1999-10-08 | 2005-02-23 | 花王株式会社 | Refrigerator oil base oil |
| JP4929555B2 (en) * | 2000-10-16 | 2012-05-09 | 日油株式会社 | Method for producing ester |
| JP4876331B2 (en) * | 2001-05-29 | 2012-02-15 | 日油株式会社 | Refrigerator lubricating oil composition and refrigerator working fluid composition |
-
2003
- 2003-12-09 JP JP2003409817A patent/JP4545422B2/en not_active Expired - Fee Related
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2004
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1347867A (en) * | 2000-10-16 | 2002-05-08 | 日本油脂株式会社 | Process for producing ester |
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| Publication number | Publication date |
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| CN1636960A (en) | 2005-07-13 |
| JP2005170998A (en) | 2005-06-30 |
| JP4545422B2 (en) | 2010-09-15 |
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