CN105330543A - Refining processing method of polyol esters - Google Patents
Refining processing method of polyol esters Download PDFInfo
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- CN105330543A CN105330543A CN201510679393.8A CN201510679393A CN105330543A CN 105330543 A CN105330543 A CN 105330543A CN 201510679393 A CN201510679393 A CN 201510679393A CN 105330543 A CN105330543 A CN 105330543A
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- acid
- ester
- polyol ester
- polyol
- refining
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- -1 polyol esters Chemical class 0.000 title claims abstract description 133
- 229920005862 polyol Polymers 0.000 title claims abstract description 95
- 238000007670 refining Methods 0.000 title claims abstract description 38
- 238000003672 processing method Methods 0.000 title abstract 5
- 238000000034 method Methods 0.000 claims abstract description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000012043 crude product Substances 0.000 claims abstract description 24
- 238000001914 filtration Methods 0.000 claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004927 clay Substances 0.000 claims abstract description 12
- 239000000741 silica gel Substances 0.000 claims abstract description 6
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims description 85
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 239000003463 adsorbent Substances 0.000 claims description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 25
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 20
- 150000007519 polyprotic acids Polymers 0.000 claims description 19
- 238000006386 neutralization reaction Methods 0.000 claims description 18
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 16
- 150000003077 polyols Chemical class 0.000 claims description 14
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 12
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 11
- 150000002148 esters Chemical class 0.000 claims description 11
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 claims description 10
- 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 claims description 10
- 239000002585 base Substances 0.000 claims description 10
- 150000005846 sugar alcohols Polymers 0.000 claims description 10
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 9
- 150000008065 acid anhydrides Chemical class 0.000 claims description 9
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical group CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 9
- 239000001361 adipic acid Substances 0.000 claims description 8
- 235000011037 adipic acid Nutrition 0.000 claims description 8
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 7
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 5
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 5
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 abstract description 22
- 238000007254 oxidation reaction Methods 0.000 abstract description 22
- 238000001179 sorption measurement Methods 0.000 abstract description 17
- 239000000047 product Substances 0.000 abstract description 15
- 239000000203 mixture Substances 0.000 abstract description 14
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 239000004615 ingredient Substances 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 description 54
- 230000007797 corrosion Effects 0.000 description 54
- 235000014113 dietary fatty acids Nutrition 0.000 description 36
- 239000000194 fatty acid Substances 0.000 description 36
- 229930195729 fatty acid Natural products 0.000 description 36
- 150000004665 fatty acids Chemical class 0.000 description 30
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 20
- 239000011573 trace mineral Substances 0.000 description 20
- 235000013619 trace mineral Nutrition 0.000 description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 18
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 16
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 16
- 239000003921 oil Substances 0.000 description 16
- 239000011574 phosphorus Substances 0.000 description 16
- 229910052698 phosphorus Inorganic materials 0.000 description 16
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 15
- 229910052708 sodium Inorganic materials 0.000 description 15
- 239000011734 sodium Substances 0.000 description 15
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 12
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 10
- 229960002446 octanoic acid Drugs 0.000 description 10
- 239000011135 tin Substances 0.000 description 10
- 229910052718 tin Inorganic materials 0.000 description 10
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 10
- 229910000838 Al alloy Inorganic materials 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
- 230000007774 longterm Effects 0.000 description 9
- 229910052709 silver Inorganic materials 0.000 description 9
- 239000004332 silver Substances 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 6
- 229940116351 sebacate Drugs 0.000 description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 6
- 229940005605 valeric acid Drugs 0.000 description 5
- AWQSAIIDOMEEOD-UHFFFAOYSA-N 5,5-Dimethyl-4-(3-oxobutyl)dihydro-2(3H)-furanone Chemical compound CC(=O)CCC1CC(=O)OC1(C)C AWQSAIIDOMEEOD-UHFFFAOYSA-N 0.000 description 4
- 239000002199 base oil Substances 0.000 description 4
- 239000003925 fat Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- IFNWFYYVXOVTBU-UHFFFAOYSA-N 2-(11-methyldodecoxycarbonyl)benzoic acid Chemical compound CC(C)CCCCCCCCCCOC(=O)C1=CC=CC=C1C(O)=O IFNWFYYVXOVTBU-UHFFFAOYSA-N 0.000 description 3
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NNULWMXRAWTDMT-UHFFFAOYSA-N 10-(11-methyldodecoxy)-10-oxodecanoic acid Chemical compound CC(C)CCCCCCCCCCOC(=O)CCCCCCCCC(=O)O NNULWMXRAWTDMT-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012208 gear oil Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Lubricants (AREA)
Abstract
The invention provides a refining processing method of polyol esters. According to the refining processing method, polyol ester crude products are mixed with an adsorbing agent, and an obtained mixture is filtered so as to obtain refined polyol esters; and the adsorbing agent is one or a mixture of a plurality of ingredients selected for diatomite, alkaline white clay, silica gel, and active carbon. Refining of polyol esters is realized via adsorption and filtering of the polyol esters. The refining processing method is simple; and influence on oil product performance is not caused by processing processes. The polyol esters obtained via the refining processing method possess excellent storage stability and oxidation resistance.
Description
Technical Field
The invention belongs to the technical field of synthetic base oil, and particularly relates to a refining treatment method of polyol ester.
Background
The polyol ester serving as a synthetic base oil with excellent performance has good oxidation stability, thermal stability, low-temperature fluidity, viscosity-temperature performance and the like, and is widely applied to the fields of aircraft engine lubricating oil, precision instrument oil, gear oil and the like. Mainly along with the development of aircraft engines, the performance requirements and specification standards of the engines on lubricating oil are continuously improved, and the performance requirements on polyol ester base oil are higher and higher. Although the excellent performance of the polyol ester is closely related to the early reaction structure of the polyol ester, the performance of the polyol ester cannot be improved or enhanced by leaving the later refining process.
The prior polyol ester refining treatment process in China mainly comprises filtration, alkali water washing and distillation, and aims to remove excessive acid and alcohol contained in crude polyol ester and half ester or partial ester which is not completely reacted; meanwhile, the catalyst remained in the crude ester also needs to be removed by post-treatment refining, so that the high-temperature and low-temperature performance of the oil product is fully guaranteed. The existing refining treatment procedures in China are complicated, multiple in steps, long in time and laggard in equipment, and the performance of the oil product is reduced and the risk of the oil product in use is increased in the process of repeatedly refining the crude ester.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a method for refining polyol ester, which is simple and does not affect the performance of oil products during the treatment process.
The invention provides a refining treatment method of polyol ester, which comprises the following steps:
mixing the polyol ester crude product with an adsorbent and then filtering to obtain refined polyol ester; the adsorbent is selected from one or more of diatomite, alkaline clay, silica gel and activated carbon.
Preferably, the mixing temperature is 100-120 ℃, and the mixing time is 1-2 h.
Preferably, the mass ratio of the crude polyol ester to the adsorbent is 1: (0.005-0.02).
Preferably, the polyol ester is selected from one or more of trimethylolpropane ester, neopentyl glycol ester, pentaerythritol ester and polypentaerythritol ester.
Preferably, the method further comprises the step of subjecting the crude polyol ester to acid value treatment before mixing the crude polyol ester with the adsorbent.
Preferably, the acid value treatment is to perform vacuum deacidification on the polyol ester crude product and then neutralize the polyol ester crude product with alkali liquor.
Preferably, the vacuum degree of the vacuum deacidification is-0.093 to-0.1 MPa, and the vacuum deacidification time is 0.5 to 1 hour.
Preferably, the polyol ester is prepared as follows:
mixing polybasic acid and polyalcohol in the presence of a catalyst to perform acid-base neutralization reaction to obtain polyalcohol ester;
or,
in the presence of a catalyst, acid anhydride and polyol are mixed for acid-base neutralization reaction to obtain polyol ester.
Preferably, the method is characterized in that,
the polybasic acid is selected from one or more of monocarbonic acid with 5-10 carbon atoms, sebacic acid, phthalic anhydride, adipic acid and oleic acid;
the polybasic acid anhydride is selected from phthalic anhydride;
the polyhydric alcohol is selected from one or more of isooctanol, isotridecanol, pentaerythritol, trimethylolpropane and dipentaerythritol;
the catalyst is selected from concentrated sulfuric acid, sodium hydroxide solution, sodium bisulfate, tetra-n-butyl titanate or stannous oxalate.
Preferably, the temperature of the neutralization reaction is 15-250 ℃, and the vacuum degree of the neutralization reaction is-0.06-0.1 MPa.
Compared with the prior art, the invention provides a refining treatment method of polyol ester, which comprises the following steps: mixing the polyol ester crude product with an adsorbent and then filtering to obtain refined polyol ester; the adsorbent is selected from one or more of diatomite, alkaline clay, silica gel and activated carbon. The invention realizes the refining of the polyol ester by carrying out adsorption and filtration treatment on the polyol ester. The treatment method provided by the invention is simple, and the treatment process does not affect the performance of the oil product. And the polyol ester treated by the method has good storage stability and oxidation resistance.
The results show that the elements such as sodium, magnesium, sulfur, phosphorus and the like are not detected after the polyol ester is refined. The acid value of the refined polyol ester is less than or equal to 0.05mgKOH/g, the hydroxyl value is less than or equal to 1.1mgKOH/g, and the kinematic viscosity at 40 ℃ is less than or equal to 80mm2The kinematic viscosity at minus 40 ℃ is less than or equal to 7000mm2And/s, the acid value after oxidation is less than or equal to 0.36mgKOH/g, the change of the kinematic viscosity (40 ℃) is 0.45 percent, the corrosion of LY12 hard aluminum alloy sheet is less than or equal to 0.01, the corrosion of No. 1 silver sheet is less than or equal to 0.03, the corrosion of copper sheet is less than or equal to 0.03, the corrosion of No. 15 low-carbon steel sheet is 0, and the corrosion of MB2 magnesium sheet is less than or equal to 0.01, which are measured by GJB563 corrosion and oxidation stability (200 ℃, 48h, 83 mL/min). In a long-term storage stability experiment, the acid value is less than or equal to 0.06mgKOH/g in 90 days, less than or equal to 0.06mgKOH/g in 180 days, less than or equal to 0.07mgKOH/g in 360 days, and the change of the acid value is not more than 0.1 mgKOH/g.
Detailed Description
The invention provides a refining treatment method of polyol ester, which comprises the following steps:
mixing the polyol ester crude product with an adsorbent and then filtering to obtain refined polyol ester; the adsorbent is selected from one or more of diatomite, alkaline clay, silica gel and activated carbon.
The invention takes crude product of polyol ester as raw material. The kind of the polyol ester is not particularly limited, and the polyol ester known to those skilled in the art can be used for synthesizing the base oil, and is preferably one or more of trimethylolpropane ester, neopentyl glycol ester, pentaerythritol ester and polypentaerythritol ester.
The source of the crude polyol ester is not particularly limited, and the crude polyol ester can be generally sold in the market or prepared by self. In the present invention, the polyol ester is preferably prepared as follows:
mixing polybasic acid and polyalcohol in the presence of a catalyst to perform acid-base neutralization reaction to obtain polyalcohol ester;
or,
in the presence of a catalyst, acid anhydride and polyol are mixed for acid-base neutralization reaction to obtain polyol ester.
When the preparation of the polyol ester is carried out, firstly, the polybasic acid and the polyol are mixed and placed in a reaction kettle, and the polybasic acid and the polyol carry out acid-base neutralization reaction under the action of a catalyst to obtain the polyol ester.
Wherein the polybasic acid is preferably one or more of monocarbonic acid, sebacic acid, phthalic anhydride, adipic acid and oleic acid with 5-10 carbon atoms, and is preferably one or more of monocarbonic acid, adipic acid, sebacic acid and phthalic anhydride with 5-9 carbon atoms; in some embodiments of the present invention, the polybasic acid is a mixed fatty acid with 7, 8 and 9 carbon atoms respectively, wherein the mass ratio of the fatty acid with 7 carbon atoms, the fatty acid with 8 carbon atoms and the fatty acid with 9 carbon atoms is preferably (25-35): (35-40): (40-25); in other embodiments of the present invention, the polybasic acid is a mixed fatty acid having 5, 6, 7 and 8 carbon atoms, wherein the mass ratio of the fatty acid having 5 carbon atoms, the fatty acid having 6 carbon atoms, the fatty acid having 7 carbon atoms and the fatty acid having 8 carbon atoms is preferably (15-22): (25-35): (35-20): (25-23); in other specific embodiments of the present invention, the polybasic acid is a mixed acid of a mixed fatty acid having 5, 6, 7, 8 and 9 carbon atoms and adipic acid, wherein the mass ratio of the fatty acid having 5 carbon atoms, the fatty acid having 6 carbon atoms, the fatty acid having 7 carbon atoms, the fatty acid having 8 carbon atoms and the fatty acid having 9 carbon atoms is preferably (5 to 10): (17-20): (26-30): (30-25): (22-15), the mass ratio of the mixed fatty acid to the adipic acid is preferably 4: 1; in other specific embodiments of the present invention, the polybasic acid is a mixed acid of a mixed fatty acid having 5, 6, 7, 8 and 9 carbon atoms and sebacic acid, wherein the mass ratio of the fatty acid having 5 carbon atoms, the fatty acid having 6 carbon atoms, the fatty acid having 7 carbon atoms, the fatty acid having 8 carbon atoms and the fatty acid having 9 carbon atoms is preferably (5 to 10): (17-20): (26-30): (30-25): (22-15), the mass ratio of the mixed fatty acid to the sebacic acid is preferably 10: 1; in other embodiments of the present invention, the polyacid is sebacic acid; in other embodiments of the present invention, the polybasic acid is phthalic anhydride.
The polyhydric alcohol is preferably one or more of isooctanol, isotridecanol, pentaerythritol, trimethylolpropane and dipentaerythritol, and more preferably one or more of pentaerythritol, trimethylolpropane, isooctanol and isotridecanol; in some embodiments of the present invention, the polyol is selected from pentaerythritol; in other embodiments of the present invention, the polyol is selected from isotridecanol; in other embodiments of the present invention, the polyol is selected from the group consisting of mixed alcohols of isooctyl alcohol and isotridecyl alcohol; in other embodiments of the present invention, the polyol is selected from trimethylolpropane.
In the present invention, the catalyst is preferably one of concentrated sulfuric acid, sodium hydroxide solution, sodium bisulfate, tetra-n-butyl titanate, or stannous oxalate.
In the preparation process of the polyol ester, the ratio of the mole number of carboxyl groups in the polybasic acid to the mole number of hydroxyl groups in the polyhydric alcohol is preferably (05-5): 1, and more preferably 1: 1. The amount of catalyst added is preferably from 0.1 to 5% by weight, based on the weight of the final theoretical product.
The temperature of the acid-base neutralization reaction is preferably 15-250 ℃, more preferably 100-240 ℃, and most preferably 180-230 ℃; the vacuum degree of the neutralization reaction is-0.06-0.093 MPa.
When the preparation of the polyol ester is carried out, the method can also mix polybasic acid anhydride and the polyol in the presence of a catalyst to carry out acid-base neutralization reaction to obtain the polyol ester.
In the present invention, the method of mixing the acid anhydride with the polyol to perform the neutralization reaction is the same as the method of mixing the polybasic acid with the polyol to perform the neutralization reaction, and the polybasic acid in the method may be replaced by the acid anhydride.
In the present invention, the acid anhydride is preferably phthalic anhydride. The ratio of the number of moles of carboxyl groups in the corresponding polyacid to the number of moles of hydroxyl groups in the polyol before dehydration of the anhydride is preferably 1: 1.
And after the acid-base neutralization reaction is finished, obtaining a crude product of the polyol ester. The method also comprises the step of carrying out acid value treatment on the crude polyol ester before mixing the crude polyol ester with the adsorbent. The specific method of acid value treatment is not particularly limited in the present invention, and any method known to those skilled in the art for acid value treatment of oils may be used. In the present invention, the acid value treatment is preferably:
and neutralizing the crude product of the polyol ester by using alkali liquor after vacuum deacidification. The vacuum degree of the vacuum deacidification is preferably-0.06 to-0.1 MPa, and the vacuum deacidification time is preferably 0.5 to 1 hour.
In the present invention, the vacuum deacidification process is performed simultaneously with the polyol ester preparation process. Namely, vacuum conditions are provided for the prepared polyol ester during the preparation of the polyol ester, and a vacuum deacidification process is also carried out during the preparation of the crude polyol ester.
The alkali liquor is preferably sodium hydroxide solution, more preferably industrial sodium hydroxide, and the mass concentration is preferably 10-20 wt%.
The method mixes the polyol ester crude product subjected to acid value treatment with an adsorbent to perform adsorption reaction. Wherein the adsorbent is selected from one or more of diatomite, alkaline clay, silica gel and activated carbon. The specific source of the adsorbent is not particularly limited in the present invention, and the adsorbent is generally commercially available. In the present invention, the activated carbon is preferably 120 mesh activated carbon. In some embodiments of the invention, the adsorbent is selected from activated carbon; in other embodiments of the present invention, the adsorbent is selected from the group consisting of alkaline clays; in other embodiments of the present invention, the adsorbent is selected from mixed adsorbents of activated carbon and diatomaceous earth, preferably in a 2:1 mass ratio; in other embodiments of the present invention, the adsorbent is selected from mixed adsorbents of alkaline clay and diatomaceous earth, preferably in a mass ratio of 1: 2; in other embodiments of the present invention, the adsorbent is selected from mixed adsorbents of alkaline clay and activated carbon, preferably in a 2:1 ratio by mass of alkaline clay to activated carbon.
In the invention, the mixing temperature of the polyol ester crude product and the adsorbent is preferably 100-120 ℃, and more preferably 110 ℃; the mixing time is 1-2 h.
The mass ratio of the polyol ester crude product to the adsorbent is preferably 1: (0.005-0.02), in some embodiments, the mass ratio of the crude polyol to the adsorbent is 1:0.01, and in other embodiments, the mass ratio of the crude polyol ester to the adsorbent is 1: 0.015.
And (3) filtering after the polyol ester crude product and the adsorbent are mixed and adsorbed to react to obtain the refined polyol ester. The method of filtration is not particularly limited in the present invention, and a filtration method known to those skilled in the art may be used.
The invention realizes the refining of the polyol ester by carrying out adsorption and filtration treatment on the polyol ester. The treatment method provided by the invention is simple, and the treatment process does not affect the performance of the oil product. And the polyol ester treated by the method has more excellent storage stability and oxidation resistance.
The results show that the elements such as sodium, magnesium, sulfur, phosphorus and the like are not detected after the polyol ester is refined. The acid value of the refined polyol ester is less than or equal to 0.05mgKOH/g,hydroxyl value is less than or equal to 1.1mgKOH/g, kinematic viscosity at 40 ℃ is less than or equal to 80mm2The kinematic viscosity at minus 40 ℃ is less than or equal to 7000mm2And/s, the acid value after oxidation is less than or equal to 0.36mgKOH/g, the change of the kinematic viscosity (40 ℃) is 0.45 percent, the corrosion of LY12 hard aluminum alloy sheet is less than or equal to 0.01, the corrosion of No. 1 silver sheet is less than or equal to 0.03, the corrosion of copper sheet is less than or equal to 0.03, the corrosion of No. 15 low-carbon steel sheet is 0, and the corrosion of MB2 magnesium sheet is less than or equal to 0.01, which are measured by GJB563 corrosion and oxidation stability (200 ℃, 48h, 83 mL/min). In a long-term storage stability experiment, the acid value is less than or equal to 0.06mgKOH/g in 90 days, less than or equal to 0.06mgKOH/g in 180 days, less than or equal to 0.07mgKOH/g in 360 days, and the change of the acid value is not more than 0.1 mgKOH/g.
For further understanding of the present invention, the method for refining polyol ester provided by the present invention is illustrated below with reference to the following examples, and the scope of the present invention is not limited by the following examples.
EXAMPLE 1 refining treatment of Mixed fatty acid pentaerythritol ester
Mixing valeric acid, caproic acid, heptanoic acid and caprylic acid according to the mass ratio of 20: 30: 37: 13 and pentaerythritol in a molar ratio of 4:1, adding the mixed acid into a reaction kettle, and reacting for 6-8 hours at 220 ℃ under the action of 0.5 wt% of catalyst stannous oxalate to generate the mixed acid pentaerythritol ester. Valeric acid, caproic acid and heptanoic acid are purchased from chemical industry Limited, China city, N.C. of the Chachentai city, Hebei, at industrial level; octanoic acid is imported from Natoleo, a natural oil company of Malaysia, technical grade. Pentaerythritol was purchased from industrialized, Hubei, chemical industries, Inc.
The acid value of the pentaerythritol ester as the mixed acid was measured to be 5mgKOH/g and the hydroxyl value was measured to be 1 mgKOHg. Adding 10-20 wt% of sodium hydroxide alkali liquor to treat the mixed acid pentaerythritol ester to obtain a crude product of the mixed acid pentaerythritol ester. The content of the trace elements is measured as follows: 10ppm of sodium, 300ppm of tin, 6ppm of sulfur and 8ppm of phosphorus.
And adding 1 wt% of activated carbon with the particle size of 120 meshes into the mixed acid pentaerythritol ester crude product, mixing, performing adsorption treatment for 1-2 hours, and filtering to obtain the refined mixed acid pentaerythritol ester.
And (3) measuring the trace elements in the refined mixed acid pentaerythritol ester, wherein the result shows that the trace elements of sodium, tin, sulfur and phosphorus are not detected.
The performance of the refined mixed acid pentaerythritol ester is detected, and the result is as follows: the acid value is 0.02mgKOH/g, the hydroxyl value is 0.8mgKOHg, and the kinematic viscosity at 40 ℃ is 23mm2(s) kinematic viscosity at-40 ℃ of 5000mm2And/s, the acid value after oxidation is 0.34mgKOH/g, the change of kinematic viscosity (40 ℃) is 3%, the corrosion of LY12 hard aluminum alloy sheet is 0.01, the corrosion of No. 1 silver sheet is 0, the corrosion of copper sheet is 0.02, the corrosion of No. 15 low-carbon steel sheet is 0, and the corrosion of MB2 magnesium sheet is 0.01, which are measured by GJB563 corrosion and oxidation stability (200 ℃, 48h, 83 mL/min). By long-term storage stability experiments of GJB135A-98, the acid value was 0.03mgKOH/g in 90 days, 0.03mgKOH/g in 180 days, 0.04mgKOH/g in 360 days, and the change in acid value was not more than 0.1 mgKOH/g.
Example 2: refining treatment of mixed fatty acid trimethylolpropane ester
Mixing heptanoic acid, octanoic acid and nonanoic acid according to the mass ratio of 30: 40: after 30 times of reaction, and trimethylolpropane according to the molar ratio of 3: 1, adding the mixture into a reaction kettle, and reacting for 5-7 hours at 210 ℃ under the action of 3 wt% of catalyst sodium bisulfate to obtain the mixed acid trimethylolpropane ester. Heptanoic acid was purchased from the chemical company Limited, Chongqing, south China, from the chentai city, Hebei, at industrial level; octanoic acid and nonanoic acid are imported from Natoleo, a natural oil and fat company of Malaysia, and are of industrial grade. Trimethylolpropane is imported from Bayer, germany, technical grade.
The acid value of the mixed acid trimethylolpropane ester was measured to be 4mgKOH/g, and the hydroxyl value was measured to be 0.8 mgKOHg. Adding 10-20 wt% of sodium hydroxide alkali liquor to treat the mixture to obtain a crude product of the mixed acid trimethylolpropane ester. The content of the trace elements is measured as follows: 12ppm of sodium, 300ppm of tin, 6ppm of silicon and 8ppm of phosphorus.
And adding 1.5 wt% of alkaline clay into the crude product of the mixed acid trimethylolpropane ester to perform adsorption treatment for 1-2 hours, and filtering to obtain the refined mixed acid trimethylolpropane ester.
The trace elements in the refined trimethylolpropane ester mixed acid are measured, and the result is that: trace elements sodium, tin, silicon and phosphorus were not detected.
The oil product has detected acid value of 0.02mgKOH/g, hydroxyl value of 0.3mgKOHg, flash point of 245 deg.C, kinematic viscosity of 19mm at 40 deg.C2Has a kinematic viscosity of 4000mm at-40 DEG C2And/s, the acid value after oxidation is 0.36mgKOH/g, the change of kinematic viscosity (40 ℃) is 2.1%, the corrosion of LY12 hard aluminum alloy sheet is 0, the corrosion of No. 1 silver sheet is 0.01, the corrosion of copper sheet is 0.03, the corrosion of No. 15 low-carbon steel sheet is 0, and the corrosion of MB2 magnesium sheet is 0, which are measured by GJB563 corrosion and oxidation stability (200 ℃, 48h, 83 mL/min). By long-term storage stability experiments of GJB135A-98, the acid value was 0.02mgKOH/g in 90 days, 0.02mgKOH/g in 180 days, 0.03mgKOH/g in 360 days, and the change in acid value was not more than 0.1 mgKOH/g.
Example 3: refining treatment of iso-octyl alcohol iso-tridecyl ester sebacate
Sebacic acid, isooctanol and isotridecanol are mixed according to a molar ratio of 1: 1.2: 1.2 adding the mixture into a reaction kettle, and reacting for 5-7 hours at 200 ℃ under the action of 1 wt% of tetra-n-butyl titanate serving as a catalyst to obtain isooctyl alcohol isotridecyl sebacate. Sebacic acid was purchased at industrial level from Tonglio chemical Co. Isooctanol was purchased from daqing petrochemical company, industrial grade. Isotridecanol is available from Shanghai Noita chemical Co., Ltd, technical grade.
The acid value of the isooctanol iso-tridecanol sebacate was determined to be 0.6mgKOH/g and the hydroxyl value was determined to be 1.2 mgKOHg. Adding 10-20 wt% of sodium hydroxide alkali liquor to treat the mixture to obtain a crude iso-octyl sebacate iso-tridecyl alcohol ester product. The content of the trace elements is measured as follows: 14ppm of sodium, 120ppm of magnesium, 20ppm of sulfur and 12ppm of phosphorus.
Adding 1 wt% of 120-mesh active carbon and 0.5 wt% of diatomite into the crude isooctanol iso-tridecanol sebacate product for adsorption treatment for 1-2 hours, and filtering to obtain refined isooctanol iso-tridecanol sebacate.
Determining the trace elements in the refined isooctyl alcohol isotridecyl sebacate, and obtaining the following results: the trace elements of sodium, magnesium, sulfur and phosphorus are not detected after the adsorption treatment.
The oil product has an acid value of 0.03mgKOH/g, a hydroxyl value of 1.1mgKOHg and a kinematic viscosity of 17mm at 40 DEG C2The kinematic viscosity at-40 ℃ is 3200mm2And/s, the acid value after oxidation is 0.32mgKOH/g, the change of kinematic viscosity (40 ℃) is 1.8%, the corrosion of LY12 hard aluminum alloy sheet is 0, the corrosion of No. 1 silver sheet is 0.02, the corrosion of copper sheet is 0.02, the corrosion of No. 15 low-carbon steel sheet is 0, and the corrosion of MB2 magnesium sheet is 0.01, which are measured by GJB563 corrosion and oxidation stability (175 ℃, 96h, 83 mL/min). By long-term storage stability experiments of GJB135A-98, the acid value is 0.04mgKOH/g in 90 days, 0.05mgKOH/g in 180 days, 0.05mgKOH/g in 360 days, and the change of the acid value is not more than 0.1 mgKOH/g.
Example 4: refining treatment of isotridecyl phthalate
Phthalic anhydride and isotridecanol are mixed according to a molar ratio of 1:2, adding the mixture into a reaction kettle, and reacting for 6-8 hours at 180 ℃ under the action of 3% of catalyst concentrated sulfuric acid to obtain the isotridecyl phthalate. Phthalic anhydride was purchased from sunshine Cantonese chemical technology, Inc., technical grade. Isotridecanol is available from Shanghai Noita chemical Co., Ltd, technical grade.
The isotridecyl phthalate was determined to have an acid value of 1.2mgKOH/g and a hydroxyl value of 1.1 mgKOHg. Adding 10-20 wt% of sodium hydroxide alkali liquor to treat the solution to obtain a crude isotridecanol phthalate product. The content of the trace elements is measured as follows: 12ppm of sodium, 10ppm of sulfur, 10ppm of silicon and 13ppm of phosphorus.
And adding 0.5% of alkaline clay and 1% of diatomite into the isotridecanol phthalate crude product, performing adsorption treatment for 1-2 hours, and filtering to obtain refined isotridecanol phthalate.
The trace elements in the refined isotridecanol phthalate were measured and the results were: the original trace elements such as sodium 12ppm, sulfur 10ppm, silicon 10ppm, phosphorus 13ppm and the like before adsorption were not detected after adsorption treatment.
The refined isotridecanol phthalate is detected to have an acid value of 0.05mgKOH/g, a hydroxyl value of 1.0mgKOHg and a kinematic viscosity of 80mm at 40 DEG C2Has a kinematic viscosity of 4000mm at-40 DEG C2And/s, the acid value after oxidation is 0.45mgKOH/g, the change of kinematic viscosity (40 ℃) is 1.8%, the corrosion of LY12 hard aluminum alloy sheet is 0, the corrosion of No. 1 silver sheet is 0.03, the corrosion of copper sheet is 0.02, the corrosion of No. 15 low-carbon steel sheet is 0, and the corrosion of MB2 magnesium sheet is 0, which are measured by GJB563 corrosion and oxidation stability (175 ℃, 96h, 83 mL/min). By long-term storage stability experiments of GJB135A-98, the acid value was 0.06mgKOH/g in 90 days, 0.06mgKOH/g in 180 days, 0.07mgKOH/g in 360 days, and the change in acid value was not more than 0.1 mgKOH/g.
Example 5: refining treatment of mixed fatty acid dipentaerythritol sebacate
Mixing valeric acid, caproic acid, heptanoic acid, caprylic acid and nonanoic acid in a mass ratio of 5: 19: 28: 30: 18, and sebacic acid and dipentaerythritol according to a molar ratio of 10: 1:2, adding the mixture into a reaction kettle, and reacting for 10-12 hours at 230 ℃ under the action of 1 wt% of catalyst tetra-n-butyl titanate to obtain the mixed fatty acid sebacic acid dipentaerythritol ester. 5, the fatty acid, the caproic acid and the enanthic acid are purchased from the chemical industry Limited company of Chongqing, Xinchentai, Hebei, and the south China; octanoic acid and nonanoic acid are imported from Natoleo, a crude oil and fat company, Malaysia, technical grade. Sebacic acid was purchased at industrial level from Tonglio chemical Co. Dipentaerythritol is available from industrialized, Hubei chemical industries, Ltd.
The acid value of the mixed fatty acid dipentaerythritol sebacate was determined to be 6mgKOH/g, and the hydroxyl value was determined to be 1.5 mgKOHg. Adding 10-20 wt% of sodium hydroxide alkali liquor to treat the mixture to obtain a mixed fatty acid dipentaerythritol sebacate crude product. The content of the trace elements is measured as follows: 15ppm, 260ppm tin, 10ppm sulphur and 9ppm phosphorus.
And adding 1.5 wt% of active carbon with the particle size of 120 meshes into the mixed fatty acid dipentaerythritol sebacate crude product, carrying out adsorption treatment for 1-2 hours, and filtering to obtain the refined mixed fatty acid dipentaerythritol sebacate.
The determination of the trace elements in the refined mixed fatty acid sebacic acid dipentaerythritol ester results in that: the original trace elements such as sodium 15ppm, tin 260ppm, sulfur 10ppm, phosphorus 9ppm before adsorption were not detected after adsorption treatment.
The refined mixed fatty acid sebacic acid dipentaerythritol ester has the acid value of 0.03mgKOH/g, the hydroxyl value of 1.0mgKOHg and the kinematic viscosity of 45mm at 40 ℃ through detection2And/s, the acid value after oxidation is 0.21mgKOH/g, the change of kinematic viscosity (40 ℃) is 1.8%, the corrosion of LY12 hard aluminum alloy sheet is 0, the corrosion of No. 1 silver sheet is 0.02, the corrosion of copper sheet is 0.02, the corrosion of No. 15 low-carbon steel sheet is 0, and the corrosion of MB2 magnesium sheet is 0.01, which are measured by GJB563 corrosion and oxidation stability (200 ℃, 48h, 83 mL/min). By long-term storage stability experiments of GJB135A-98, the acid value is 0.04mgKOH/g in 90 days, 0.04mgKOH/g in 180 days, 0.05mgKOH/g in 360 days, and the change of the acid value is not more than 0.1 mgKOH/g.
Example 6: refining treatment of mixed fatty acid adipic acid trimethylolpropane ester
Mixing valeric acid, caproic acid, heptanoic acid, caprylic acid and nonanoic acid in a mass ratio of 9: 18: 28: 27: after 18 times of polymerization, mixing with adipic acid and trimethylolpropane according to the molar ratio of 4: 1:2, adding the mixture into a reaction kettle, and reacting for 5-7 hours at 210 ℃ under the condition that 1 wt% of tetra-n-butyl titanate serving as a catalyst is used to obtain the trimethylolpropane ester of the mixed acid. Valeric acid, caproic acid and heptanoic acid are all produced in the chemical industry of the Ming dynasty city, the Ministry of the Chen Tai, Hebei province, and are in the industrial grade; octanoic acid and nonanoic acid are imported from Natoleo, a natural oil and fat company of Malaysia, and are of industrial grade. Adipic acid is available from petroleum and gas, Inc., China, technical grade. Trimethylolpropane is imported from Bayer, germany, technical grade.
The acid value of the mixed acid trimethylolpropane ester was measured to be 4mgKOH/g, and the hydroxyl value was measured to be 0.8 mgKOHg. Adding 10-20 wt% of sodium hydroxide alkali liquor to treat the mixture to obtain a crude product of the mixed acid trimethylolpropane ester. The content of the trace elements is measured as follows: 12ppm of sodium, 300ppm of tin, 6ppm of silicon and 8ppm of phosphorus.
And adding 1 wt% of alkaline clay and 0.5 wt% of active carbon with the particle size of 120 meshes into the crude skin of the mixed acid trimethylolpropane ester, carrying out adsorption treatment for 1-2 hours, and filtering to obtain the refined mixed acid trimethylolpropane ester.
The trace elements in the refined trimethylolpropane ester mixed acid are measured, and the result is that: the original trace elements of sodium 12PPM, tin 300PPM, silicon 6PPM, phosphorus 8PPM and the like before adsorption are not detected after adsorption treatment.
The refined mixed acid trimethylolpropane ester has the detected acid value of 0.02mgKOH/g, the hydroxyl value of 0.8mgKOHg and the kinematic viscosity of 24mm at 40 DEG C2The kinematic viscosity at-40 ℃ is 7000mm2And/s, the acid value after oxidation is 0.12mgKOH/g, the change of kinematic viscosity (40 ℃) is 1.8%, the corrosion of LY12 hard aluminum alloy sheet is 0, the corrosion of No. 1 silver sheet is 0.02, the corrosion of copper sheet is 0.02, the corrosion of No. 15 low-carbon steel sheet is 0, and the corrosion of MB2 magnesium sheet is 0.01, which are measured by GJB563 corrosion and oxidation stability (200 ℃, 48h, 83 mL/min). By long-term storage stability experiments of GJB135A-98, the acid value was 0.02mgKOH/g in 90 days, 0.03mgKOH/g in 180 days, 0.03mgKOH/g in 360 days, and the change in acid value was not more than 0.1 mgKOH/g.
Comparative example 1 refining treatment of trimethylolpropane ester of Mixed fatty acid
Mixing heptanoic acid, octanoic acid and nonanoic acid in a ratio of 30: 40: after 30 times of reaction, and trimethylolpropane according to the molar ratio of 3: 1, adding the mixture into a reaction kettle, and reacting for 5-7 hours at 210 ℃ under the action of 3% of catalyst sodium bisulfate to obtain the mixed acid trimethylolpropane ester. Heptanoic acid was purchased from the chemical company Limited, Chongqing, south China, from the chentai city, Hebei, at industrial level; octanoic acid and nonanoic acid are imported from Natoleo, Malaysia Natural fats & oils. Trimethylolpropane is imported from Bayer, germany, technical grade.
The acid value of the mixed acid trimethylolpropane ester was measured to be 4mgKOH/g, and the hydroxyl value was measured to be 0.8 mgKOHg. And adding 10-20 wt% of sodium hydroxide alkali liquor to treat the mixture to obtain a crude product of the mixed acid trimethylolpropane ester. The content of the trace elements is measured as follows: 12ppm of sodium, 300ppm of tin, 6ppm of silicon and 8ppm of phosphorus.
Washing the crude product of the mixed acid trimethylolpropane ester with 10-20 wt% sodium hydroxide alkaline water for 1 time, washing with water for 5 times, carrying out reduced pressure distillation and filtration, and carrying out post-treatment with urea to obtain the refined mixed acid trimethylolpropane ester. The content of the trace elements is measured as follows: 13ppm of sodium, 280ppm of tin, 8ppm of silicon and 10ppm of phosphorus.
The acid value of the oil product is 0.05mgKOH/g, the hydroxyl value is 0.8mgKOHg, the flash point is 230 ℃, the acid value after oxidation is 0.46mgKOH/g, the kinematic viscosity (40 ℃) change is 3.6%, the corrosion of LY12 hard aluminum alloy sheet is 0, the corrosion of No. 1 silver sheet is 0.02, the corrosion of copper sheet is 0.08, the corrosion of No. 15 low-carbon steel sheet is 0, and the corrosion of MB2 magnesium sheet is 0.06, which are determined by GJB563 corrosion and oxidation stability (200 ℃, 48h, 83 mL/min). According to the long-term storage stability experiment of GJB135A-98, the acid value is 0.08mgKOH/g in 90 days, 0.09mgKOH/g in 180 days and 0.15mgKOH/g in 360 days.
According to the results provided in examples 1 to 6, the refining method provided by the present invention can improve the performance of the oil product.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A refining treatment method of polyol ester is characterized by comprising the following steps:
mixing the polyol ester crude product with an adsorbent and then filtering to obtain refined polyol ester; the adsorbent is selected from one or more of diatomite, alkaline clay, silica gel and activated carbon.
2. The refining treatment method according to claim 1, wherein the mixing temperature is 100 to 120 ℃ and the mixing time is 1 to 2 hours.
3. The refining treatment method of claim 1, wherein the mass ratio of the crude polyol ester to the adsorbent is 1: (0.005-0.02).
4. The refining treatment method according to claim 1, wherein the polyol ester is selected from one or more of trimethylolpropane ester, neopentyl glycol ester, pentaerythritol ester and polypentaerythritol ester.
5. The refining process of claim 1, further comprising subjecting the crude polyol ester to an acid number treatment prior to mixing the crude polyol ester with the adsorbent.
6. The refining treatment method according to claim 5, wherein the acid value treatment is vacuum deacidification and neutralization with alkali liquor of crude polyol ester.
7. The refining treatment method according to claim 6, wherein the vacuum degree of vacuum deacidification is-0.093 to-0.1 MPa, and the vacuum deacidification time is 0.5 to 1 hour.
8. The refining process of claim 1, wherein the polyol ester is prepared according to the following process:
mixing polybasic acid and polyalcohol in the presence of a catalyst to perform acid-base neutralization reaction to obtain polyalcohol ester;
or,
in the presence of a catalyst, acid anhydride and polyol are mixed for acid-base neutralization reaction to obtain polyol ester.
9. The refining treatment method according to claim 8,
the polybasic acid is selected from one or more of monocarbonic acid with 5-10 carbon atoms, sebacic acid, adipic acid and oleic acid;
the polybasic acid anhydride is selected from phthalic anhydride;
the polyhydric alcohol is selected from one or more of isooctanol, isotridecanol, pentaerythritol, trimethylolpropane and dipentaerythritol;
the catalyst is selected from concentrated sulfuric acid, sodium hydroxide solution, sodium bisulfate, tetra-n-butyl titanate or stannous oxalate.
10. The refining treatment method according to claim 8, wherein the temperature of the neutralization reaction is 15 to 250 ℃, and the degree of vacuum of the neutralization reaction is-0.06 to-0.1 MPa.
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| CN106975475B (en) * | 2017-04-26 | 2019-12-20 | 中国石油化工股份有限公司 | Catalyst for synthesizing trimethylolpropane ester and preparation method and application thereof |
| CN106986765A (en) * | 2017-04-26 | 2017-07-28 | 中国石油化工股份有限公司 | A kind of high temperature modification pentaerythritol ester and preparation method thereof |
| CN106975475A (en) * | 2017-04-26 | 2017-07-25 | 中国石油化工股份有限公司 | It is a kind of for catalyst of synthesizing trimethylol propane ester and preparation method thereof and application |
| CN106986765B (en) * | 2017-04-26 | 2020-04-10 | 中国石油化工股份有限公司 | High-temperature pentaerythritol ester and preparation method thereof |
| CN108676602A (en) * | 2018-04-26 | 2018-10-19 | 中国科学院青岛生物能源与过程研究所 | A kind of method that castor oil prepares the high-end lubricating oil in esters of low-carbon |
| CN109232241A (en) * | 2018-09-21 | 2019-01-18 | 浙江皇马科技股份有限公司 | A kind of preparation method of trihydroxymethylpropanyl ester |
| CN109293510A (en) * | 2018-09-30 | 2019-02-01 | 浙江皇马科技股份有限公司 | A kind of preparation method of pentaerythritol ester |
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| CN111533657B (en) * | 2020-04-17 | 2023-06-16 | 上海抚佳精细化工有限公司 | Purification method and preparation method of trimethylolpropane oleate |
| CN113801018A (en) * | 2021-10-29 | 2021-12-17 | 中国石油化工股份有限公司 | Dibasic acid isomeric alcohol ester and preparation method thereof |
| CN113801018B (en) * | 2021-10-29 | 2024-05-28 | 中国石油化工股份有限公司 | Dibasic acid isomeric alcohol ester and preparation method thereof |
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