CN1333054C - Lubricating oil composite stabilizer and stable hydrogenation lubricating oil composition - Google Patents
Lubricating oil composite stabilizer and stable hydrogenation lubricating oil composition Download PDFInfo
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- CN1333054C CN1333054C CNB2004100483605A CN200410048360A CN1333054C CN 1333054 C CN1333054 C CN 1333054C CN B2004100483605 A CNB2004100483605 A CN B2004100483605A CN 200410048360 A CN200410048360 A CN 200410048360A CN 1333054 C CN1333054 C CN 1333054C
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- 239000000203 mixture Substances 0.000 title claims abstract description 74
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 35
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 24
- 239000006084 composite stabilizer Substances 0.000 title 1
- 239000003381 stabilizer Substances 0.000 claims abstract description 35
- -1 phenol ester Chemical class 0.000 claims abstract description 30
- 239000004611 light stabiliser Substances 0.000 claims abstract description 20
- 150000001412 amines Chemical class 0.000 claims abstract description 14
- 239000002184 metal Chemical class 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- 239000000314 lubricant Substances 0.000 claims description 19
- 239000002131 composite material Substances 0.000 claims description 15
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical class C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 14
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 13
- 239000012964 benzotriazole Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- 239000006096 absorbing agent Substances 0.000 claims description 10
- 239000003112 inhibitor Substances 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 8
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 claims description 8
- 239000012965 benzophenone Substances 0.000 claims description 7
- 239000003352 sequestering agent Substances 0.000 claims description 7
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical group CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 5
- 229960000969 phenyl salicylate Drugs 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 claims description 4
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- GBRSPKXOFRTAHS-UHFFFAOYSA-N 5-(4-nitrophenyl)-1,2-oxazole-3-carboxylic acid Chemical compound O1N=C(C(=O)O)C=C1C1=CC=C([N+]([O-])=O)C=C1 GBRSPKXOFRTAHS-UHFFFAOYSA-N 0.000 claims description 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 3
- BLBVLMPUSLFQNF-UHFFFAOYSA-N S.P(O)(O)(O)=O Chemical compound S.P(O)(O)(O)=O BLBVLMPUSLFQNF-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 claims description 3
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 3
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- 150000003558 thiocarbamic acid derivatives Chemical class 0.000 claims description 3
- DBOSBRHMHBENLP-UHFFFAOYSA-N 4-tert-Butylphenyl Salicylate Chemical compound C1=CC(C(C)(C)C)=CC=C1OC(=O)C1=CC=CC=C1O DBOSBRHMHBENLP-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 2
- RQVGZVZFVNMBGS-UHFFFAOYSA-N n-octyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(CCCCCCCC)C1=CC=CC=C1 RQVGZVZFVNMBGS-UHFFFAOYSA-N 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 150000003902 salicylic acid esters Chemical class 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000002199 base oil Substances 0.000 abstract description 28
- 239000003963 antioxidant agent Substances 0.000 abstract description 7
- 230000003078 antioxidant effect Effects 0.000 abstract description 7
- 239000002250 absorbent Substances 0.000 abstract 3
- 230000002745 absorbent Effects 0.000 abstract 3
- 239000002738 chelating agent Substances 0.000 abstract 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical class OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract 1
- LICUQAFOHXHWQC-UHFFFAOYSA-N [S].OP(O)(O)=O Chemical compound [S].OP(O)(O)=O LICUQAFOHXHWQC-UHFFFAOYSA-N 0.000 abstract 1
- VCAFTIGPOYBOIC-UHFFFAOYSA-N phenyl dihydrogen phosphite Chemical compound OP(O)OC1=CC=CC=C1 VCAFTIGPOYBOIC-UHFFFAOYSA-N 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 47
- 239000000654 additive Substances 0.000 description 36
- 230000000996 additive effect Effects 0.000 description 33
- 239000007788 liquid Substances 0.000 description 22
- 238000003756 stirring Methods 0.000 description 22
- 239000000463 material Substances 0.000 description 9
- 239000011521 glass Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000002195 synergetic effect Effects 0.000 description 5
- 235000006708 antioxidants Nutrition 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- PJZLSMMERMMQBJ-UHFFFAOYSA-N 3,5-ditert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC(O)=C(O)C(C(C)(C)C)=C1 PJZLSMMERMMQBJ-UHFFFAOYSA-N 0.000 description 1
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 230000003351 photoxidation Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000036561 sun exposure Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- ZNCAMSISVWKWHL-UHFFFAOYSA-L zinc;butoxy-butylsulfanyl-oxido-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CCCCOP([O-])(=S)SCCCC.CCCCOP([O-])(=S)SCCCC ZNCAMSISVWKWHL-UHFFFAOYSA-L 0.000 description 1
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Abstract
The present invention relates to a complex stabilizer for lubricating oil, which comprises an ultraviolet light absorbent, a hindered amine light stabilizer, an antioxidant and a chelating agent made from phosphorous acid phenyl ester by using the total weight of the complex stabilizer as a reference, wherein the weight ratio of the ultraviolet light absorbent to the hindered amine light stabilizer is 1: 1 to 5: 1, and the total weight content of the ultraviolet light absorbent to the hindered amine light stabilizer in a composition is from 40% to 80%; 2, the antioxidant is selected from shielded phenol, aryl amine, phenol ester, metal salt containing sulfur phosphoric acid and thiocarbamic acid ester, and the weight content of the antioxidant is from 15% to 45%; 3, the weight content of the chelating agent is from 3% to 18%. The complex stabilizer for lubricating oil is added into the base oil of the lubricating oil with hydrogenation in the dose of 0.01% to 2.0%, and can obviously improve the light stability of the lubricating oil with hydrogenation.
Description
Technical field
The present invention relates to a kind of one package stabilizer that is used to improve the lube base oil-proofness of hydrotreatment, and the hydrogenation lubricating oil composition.
Technical background
The lubricant base of hydrotreatment compare with the lubricant base of " old three cover " explained hereafter have that colourity is good, sulphur and nitrogen content is low, volatility is low, to the additive response advantages of much giving prominence to such as good.But the light stability of most hydrogenated oil is relatively poor, under the irradiation of daylight or UV-light, variable color, muddiness can take place, even sedimentary phenomenon occurs.The existence of the polycyclic aromatic hydrocarbons of partial hydrogenation may be the major cause that influences its light stability in the hydrogenated oil.
At present, the method that solves hydrotreatment lubricant base light stability difference has two kinds, promptly improves processing condition and adds additive.Before a kind of method not only will further increase investment, and operational difficulty, expense are very high.A kind of method in back is simple to operate, and economical convenient, instant effect.Usually, with the recombiner that the additive compound of number of different types gets up to obtain, the result of use of any additive will improve much i.e. synergism to its result of use than using wherein separately.So, the additive of light stabilizer and other kinds is compound, can obtain synergistic effect preferably, thereby improve the stability of hydrotreatment lubricant base.
US 4,427,563 and US 4,498,998 reports, contain in the oil product of dihydric compound hydrotreatment, UV-light is had restraining effect, as: dihydroxyl diphenyl compounds 4 contained, 4 '-two (2, the 6-di-tert-butylphenol), 3,5-di-t-butyl pyrocatechol, 4,6-di-tert-butyl resorcin.It adds dosage is 0.01%～1.0%.
US 4,306, and 985 introduce the compound photodegradation that can suppress oil product significantly of arylamine and alkylphenol.
Summary of the invention
The invention provides a kind of one package stabilizer of the stability that is used to improve the hydrogenation lubricant base, especially light stability.
The present invention also provides the hydrogenation that comprises above-mentioned one package stabilizer lubricating oil composition.
Composite lubricating oil stabilizer provided by the invention comprises following composition: with the one package stabilizer gross weight is benchmark,
(I) weight ratio is 1: 1～5: 1 ultraviolet absorbers and a hindered amine light stabilizer, and the two gross weight content in composition is 40%～80%, preferred 45%～72%;
(II) be selected from the oxidation inhibitor that shields phenols, arylamine class, phenolic ester class, sulphur phosphate metal salt and thiocarbamates, weight content is 15%～45%, preferred 18%～42%;
(III) phenyl-phosphite class sequestrant, weight content are 3%～18%, preferred 5%～15%.
One package stabilizer component of the present invention (I) comprises two types of photostabilizers: ultraviolet absorbers and hindered amine as light stabilizer.Most photostabilizers are applicable in the high molecular polymer that as plastics, fiber, natural or synthetical glue, various kinds of resin etc., their oil solubles in oil product are relatively poor, and price is more expensive, so consumption is less.By contrast, ultraviolet absorbers wherein and hindered amine as light stabilizer are applicable in the oil product.
Said ultraviolet absorbers can be selected from benzotriazole category, benzophenone and salicylate class, for example: 2-(2 '-hydroxyl-3 ', 5 '-di-t-butyl) benzotriazole, 2-(2 '-hydroxyl-3 '-tertiary butyl-5 '-aminomethyl phenyl)-the 5-chlorinated benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-the 5-chlorinated benzotriazole, 2-(2 '-hydroxyl-5 '-the Te octyl phenyl) benzotriazole, 2-hydroxyl-4-n-octyloxy-benzophenone, 2, the 4-dihydroxy benaophenonel, 2-hydroxyl-4-methoxyl group-benzophenone, 2-hydroxyl-4-(2 '-second for hexyloxy)-benzophenone, salol, 4,4 '-isopropylidene two (phenol salicylate), the mixture of one or more in the p-t-butylphenyl salicylate.
Said hindered amine as light stabilizer can be selected from: two (2,2,6, the 6-tetramethyl-piperidyl) sebate, ethyl two (2,2,6,6-tetramethyl-piperazine ketone), N-nitrilotriacetic (2,2,6,6-tetramethyl--4-piperidyl) ester, N-nitrilotriacetic (1,2,2,6,6-pentamethyl--4-piperidyl) ester, two (1,2,2,6,6-pentamethyl--4-piperidyl) mixture of one or more in the sebate.
When using ultraviolet absorbers or hindered amine light stabilizer separately, though the variation of oil product colourity is less, their oil soluble is all relatively poor, and hindered amine light stabilizer is prone to precipitation after placing.Therefore, they are more suitable for being applied in the macromolecular material, and adding dosage and should suitably reduce in oil product.This photostabilizer of two types is composite, can bring into play the synergistic effect between them.The weight ratio of ultraviolet absorbers and hindered amine light stabilizer is 1: 1～5: 1, preferred 1: 1～3: 1.
The component of one package stabilizer of the present invention (II) is the oxidation inhibitor that is selected from shielding phenols, arylamine class, phenolic ester class, sulphur phosphate metal salt, thiocarbamates, for example: 2,6 ditertiary butyl p cresol, C
4-C
20Zinc dialkyl dithiophosphate, C
4-C
20Dialkyl dithio amino formate, octyl group, butyl or fourth octyl diphenylamine, 3, the mixture of one or more in the 5-di-tert-butyl-hydroxy phenyl Isooctyl acrylate monomer.
The component of one package stabilizer of the present invention (III) is a phenyl-phosphite class sequestrant, for example: the mixture of one or more in triphenyl phosphite, diisooctyl phenyl phosphite, trisnonyl phenyl phosphite, two (to nonylphenol) phenol phosphorous acid ester, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester.
One package stabilizer of the present invention optionally contains metal passivator, to eliminate the effect of the photooxidation reaction that relict catalyst was caused.Metal passivator is a nitrogen-containing heterocycle compound, can be selected from 124 Triazole-aldehyde-amine condenses, 124 Triazole, 2,6-two (alkyl dithio) thiadiazoles etc.Gross weight with one package stabilizer is a benchmark, and the weight content of metal passivator is 5%～15%, preferred 8%～13%.
One package stabilizer provided by the invention can prepare by the following method: under 40～90 ℃, various additives are mixed, fully stir, make mixing of materials even, promptly get one package stabilizer.
Stable hydrogenation lubricating oil composition provided by the invention is a benchmark with the composition gross weight, comprising:
(3) one package stabilizer 0.01%～2.0% provided by the invention, preferred 0.05%～1.5%;
(4) the hydrogenation lubricant base of surplus.
Said hydrogenation lubricant base is the lubricating oil of producing through technological processs such as low-voltage hydrogenation, solvent treatment, medium-pressure hydrocracking are refining, the lubricant base of hydrotreatment is compared with the lubricant base of " old three covers " explained hereafter, aromaticity content is low, sulphur content is low, wherein aromaticity content is 1%～10%, and sulphur content is less than 100ppm.Wherein, the existence of the polycyclic aromatic hydrocarbons of partial hydrogenation may be the major cause that influences its light stability in the hydrogenated oil.
Hydrogenation lubricating oil composition provided by the invention can prepare by following two kinds of methods: (1) joins one package stabilizer provided by the invention in the hydrogenation lubricant base with described ratio, at 50～60 ℃ of following stir about 10-30 minutes, can get the hydrogenation lubricating oil composition; Or (2) join several additives respectively in the hydrogenation lubricant base in ratio separately, stirred miscible 30～40 minutes down in 70～80 ℃, can get the hydrogenation lubricating oil composition.
In oil product or polymkeric substance weathering process, photoxidation and thermooxidizing often take place simultaneously, and therefore, light stabilization method must have anti-oxidant measure simultaneously efficiently.Experiment showed, independent use photostabilizer or oxidation inhibitor, little to the stabilizing effect of the lubricant base that improves hydrotreatment, obvious synergistic effect then arranged with photostabilizer and oxidation inhibitor are composite, be equipped with sequestrant again the stability of oil product is increased.Therefore, one package stabilizer provided by the invention, after the composite use of photostabilizer, oxidation inhibitor and sequestrant, its protection effect can surpass adding of the independent effect of each composition and, have outstanding synergistic effect.
One package stabilizer provided by the invention has not only improved the light stability of hydrogenated oil, has also improved the heat-resistant quality of hydrogenated oil simultaneously, has prolonged the usage period of oil product greatly.Though hydrogenated oil is good than the thermal oxidation stability of the base oil of " old three covers " explained hereafter, but oxidation stain significantly at high temperature still can take place in it, color is by the original colourless deep yellow that becomes, and after having added one package stabilizer of the present invention, the colourity of oil product is changed significantly and alleviates, and only is little yellow or faint yellow.One package stabilizer of the present invention has reduced the total consumption of additive in oil product owing to the synergistic effect of having utilized between the multiple additives, has improved the economy and the practicality of one package stabilizer.
Embodiment
Comparative example's 1 composite antioxidant
In the 100ml beaker, add 2,6-ditertbutylparacresol 20.0g, 3,5-di-tert-butyl-hydroxy phenyl Isooctyl acrylate monomer 20.0g, dibutyl dithiocaarbamate ester 20.0g are put on the well heater and heat, and stir with glass stick and mix, 80 ± 5 ℃ of controlled temperature, keep 30min., make material even, obtain a transparent light yellow liquid.
Comparative example's 2 composite light stabilizers
In the 100ml beaker, adding 2-(2 '-hydroxyl-3 ', 5 '-di-t-butyl) benzotriazole 20.0g, two (2,2,6, the 6-tetramethyl-piperidyl) sebate 20.0g, 2,4-dihydroxy benaophenonel 20.0g, be put on the well heater and heat, stir with glass stick and mix 80 ± 5 ℃ of controlled temperature, keep 30min., make material even, obtain a transparent light yellow liquid, the cooling back is the paste solid.Therefore, this composite light stabilizer preferably directly is formulated in the base oil.
Embodiment 3 one package stabilizers-1
In the 100ml beaker, add zinc dibutyldithiophosphate 8.5g, octyl group/butyl alkylated diphenylamine 7.0g, 3,5-di-tert-butyl-hydroxy phenyl Isooctyl acrylate monomer 8.5g, 2-(2 '-hydroxyl-3 ', 5 '-di-t-butyl) benzotriazole 15.5g, two (2,2,6, the 6-tetramethyl-piperidyl) sebate 15.5g, trisnonyl phenyl phosphite 6.0g, be put on the well heater and heat, stir mixing with glass stick, 80 ± 5 ℃ of controlled temperature are kept 30min., make material even, obtain a transparent light yellow liquid.
Embodiment 4 one package stabilizers-2
In the 100ml beaker, add 2,6-ditertbutylparacresol 9.0g, 3,5-di-tert-butyl-hydroxy phenyl Isooctyl acrylate monomer 12.0g, 2-(2 '-hydroxyl-3 ', 5 '-di-t-butyl) benzotriazole 21.3g, ethyl two (2,2,6,6-tetramethyl-piperazine ketone) 5.8g, N-nitrilotriacetic (2,2,6,6-tetramethyl--4-piperidyl) ester 7.7g, trisnonyl phenyl phosphite 4.2g, be put on the well heater and heat, stir mixing with glass stick, 80 ± 5 ℃ of controlled temperature are kept 30min., make material even, obtain a transparent light yellow liquid.
Embodiment 5 one package stabilizers-3
In the 100ml beaker, add octyl group/butyl alkylated diphenylamine 6.0g, di-isooctyl dithio zinc phosphate 6.0g, 2,6-ditertbutylparacresol 6.8g, 2-(2 '-hydroxyl-3 ', 5 '-di-t-butyl) benzotriazole 15.0g, 2-hydroxyl-4-n-octyloxy-benzophenone 9.4g, two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate 12.2g, triphenyl phosphite 5.4g are put on the well heater and heat, and stir with glass stick and mix, 60 ± 5 ℃ of controlled temperature, keep 30min., make material even, obtain a transparent light yellow liquid.
Embodiment 6 one package stabilizers-4
In the 100ml beaker, add dialkyl dithio amino formate 7.5g, 3,5-di-tert-butyl-hydroxy phenyl Isooctyl acrylate monomer 7.5g, 2-(2 '-hydroxyl-3 ', 5 '-di-t-butyl) benzotriazole 20.0g, salol 7.5g, two (2,2,6, the 6-tetramethyl-piperidyl) sebate 10.5g, diisooctyl phenyl phosphite 3.6g, two-(to nonylphenol) phenol phosphorous acid ester 3.0g, be put on the well heater and heat, stir mixing with glass stick, 80 ± 5 ℃ of controlled temperature are kept 30min., make material even, obtain a transparent light yellow liquid.
Embodiment 7 one package stabilizers-5
In the 100ml beaker, add 3,5-di-tert-butyl-hydroxy phenyl Isooctyl acrylate monomer 13.2g, 2-(2 '-hydroxyl-3 ', 5 '-di-t-butyl) benzotriazole 22.5g, 2-hydroxyl-4-(2 '-second for hexyloxy)-benzophenone 9.0g, two (2,2,6, the 6-tetramethyl-piperidyl) sebate 10.5g, trisnonyl phenyl phosphite 4.8g, 124 Triazole-aldehyde-amine condenses 3.0g is put on the well heater and heats, and stirs with glass stick and mixes, 80 ± 5 ℃ of controlled temperature, keep 30min., make material even, obtain a transparent light yellow liquid.
The hydrogenated oil composition-1 of embodiment 8 stable compositions
Base oil: the lubricating oil of the hydrotreatment that the Kelamayi refinery is produced, physicochemical property is as shown in table 1.
Additive: 0.20% (quality percentage composition, as follows) composite antioxidant
With above-mentioned percentage composition additive and above-mentioned base oil, at 50～60 ℃ of stirring and dissolving 20min., obtain a transparent nearly colourless liquid, performance is as shown in table 2.
The hydrogenated oil composition-2 of embodiment 9 stable compositions
Base oil: the lubricating oil of the hydrotreatment that Jingmen refinery is produced, physicochemical property is as shown in table 1.
Additive: 0.30% (quality percentage composition, as follows) composite antioxidant
With above-mentioned percentage composition additive and above-mentioned base oil, at 50～60 ℃ of stirring and dissolving 20min., obtain a transparent nearly colourless liquid, performance is as shown in table 2.
The hydrogenated oil composition-3 of embodiment 10 stable compositions
Base oil: the lubricating oil of the hydrotreatment that the Kelamayi refinery is produced.
Additive: 0.20% (quality percentage composition, as follows) composite light stabilizer
Because composite light stabilizer normal temperature is down the paste solid, so the preparation of the hydrogenated oil composition-3 of stable composition is except the method that can adopt embodiment 9, also can adopt the second method of preparation hydrogenation lubricating oil composition provided by the present invention, in the 150ml beaker, adding 2-(2 '-hydroxyl-3 ', 5 '-di-t-butyl) benzotriazole 0.067g, two (2,2,6, the 6-tetramethyl-piperidyl) sebate 0.067g, 2,4 dihydroxyl benzophenone 0.067g, the lubricating oil 99.8g of the hydrotreatment that the Kelamayi refinery is produced, be put on the well heater and heat, under 70～80 ℃, stir miscible 30～40min., obtain a transparent nearly colourless liquid.Its performance is as shown in table 2.
The hydrogenated oil composition-4 of embodiment 11 stable compositions
Base oil: the lubricating oil of the hydrotreatment that Jingmen refinery is produced.
Additive: 0.20% (quality percentage composition, as follows) composite light stabilizer
With above-mentioned percentage composition additive and above-mentioned base oil,, obtain a transparent nearly colourless liquid at 50～60 ℃ of stirring and dissolving 20min..Its performance is as shown in table 2.
The hydrogenated oil composition-5 of embodiment 12 stable compositions
Base oil: the lubricating oil of the hydrotreatment that Jingmen refinery is produced.
Additive: 0.15% (quality percentage composition, as follows) one package stabilizer-1
With above-mentioned percentage composition additive and above-mentioned base oil,, obtain a transparent nearly colourless liquid at 50～60 ℃ of stirring and dissolving 20min..Its performance is as shown in table 2.
The hydrogenated oil composition-6 of embodiment 13 stable compositions
Base oil: the lubricating oil of the hydrotreatment that the Kelamayi refinery is produced.
Additive: 0.05% (quality percentage composition, as follows) one package stabilizer-1
With above-mentioned percentage composition additive and above-mentioned base oil,, obtain a transparent nearly colourless liquid at 50～60 ℃ of stirring and dissolving 20min..Its performance is as shown in table 2.
The hydrogenated oil composition-7 of embodiment 14 stable compositions
Base oil: the lubricating oil of the hydrotreatment that Jingmen refinery is produced.
Additive: 0.30% (quality percentage composition, as follows) one package stabilizer-2
With above-mentioned percentage composition additive and above-mentioned base oil,, obtain a transparent nearly colourless liquid at 50～60 ℃ of stirring and dissolving 20min..Its performance is as shown in table 2.
The hydrogenated oil composition-8 of embodiment 15 stable compositions
Base oil: the lubricating oil of the hydrotreatment that the Kelamayi refinery is produced.
Additive: 0.30% (quality percentage composition, as follows) one package stabilizer-2
With above-mentioned percentage composition additive and above-mentioned base oil,, obtain a transparent nearly colourless liquid at 50～60 ℃ of stirring and dissolving 20min..Its performance is as shown in table 2.
The hydrogenated oil composition-9 of embodiment 16 stable compositions
Base oil: the lubricating oil of the hydrotreatment that the Kelamayi refinery is produced.
Additive: 0.40% (quality percentage composition, as follows) one package stabilizer-3
With above-mentioned percentage composition additive and above-mentioned base oil,, obtain a transparent nearly colourless liquid at 50～60 ℃ of stirring and dissolving 20min..Its performance is as shown in table 2.
The hydrogenated oil composition-10 of embodiment 17 stable compositions
Base oil: the lubricating oil of the hydrotreatment that the Kelamayi refinery is produced.
Additive: 0.45% (quality percentage composition, as follows) one package stabilizer-4
With above-mentioned percentage composition additive and above-mentioned base oil,, obtain a transparent nearly colourless liquid at 50～60 ℃ of stirring and dissolving 20min..Its performance is as shown in table 2.
The hydrogenated oil composition-11 of embodiment 18 stable compositions
Base oil: the lubricating oil of the hydrotreatment that Jingmen refinery is produced.
Additive: 0.60% (quality percentage composition, as follows) one package stabilizer-5
With above-mentioned percentage composition additive and above-mentioned base oil,, obtain a transparent nearly colourless liquid at 50～60 ℃ of stirring and dissolving 20min..Its performance is as shown in table 2.
The hydrogenated oil composition-11 of embodiment 19 stable compositions
Base oil: the lubricating oil of the hydrotreatment that the Kelamayi refinery is produced.
Additive: 1.5% (quality percentage composition, as follows) one package stabilizer-5
With above-mentioned percentage composition additive and above-mentioned base oil,, obtain a transparent nearly colourless liquid at 50～60 ℃ of stirring and dissolving 20min..Its performance is as shown in table 2.
The hydrogenated oil composition-11 of embodiment 20 stable compositions
Base oil: the lubricating oil of the hydrotreatment that Jingmen refinery is produced.
Additive: 1.5% (quality percentage composition, as follows) one package stabilizer-4
With above-mentioned percentage composition additive and above-mentioned base oil,, obtain a transparent nearly colourless liquid at 50～60 ℃ of stirring and dissolving 20min..Its performance is as shown in table 2.
The lubricants performance data of table 1 hydrotreatment
| Project | Gram refining hydrogenated oil | Jingmen hydrogenated oil | Test method | |
| Product appearance | The white transparent liquid | The white transparent liquid | Range estimation | |
| Kinematic viscosity, 40 ℃, mm 2/s | 184.10 | 96.44 | GB/T265 | |
| Pour point, ℃ ≯ | -18 | -6 | GB/T3535 | |
| Flash-point (opening), ℃ ≮ | 220 | 190 | GB/T3536 | |
| Aniline point/℃ ≯ | 104 | 100 | GB/T262 | |
| Cut hydrocarbon composition % | Paraffinic hydrocarbons | 6.8 | 21.0 | ASTM D2786，D3239 |
| Total naphthenic hydrocarbon | 90.5 | 74.4 | ||
| Alkylbenzene | 2.7 | 0 | ||
| Total aromatic hydrocarbons | 2.7 | 4.6 | ||
Table 2 adds the hydrogenated oil composition salient features of additive
Annotate: 1. sun test condition is normal temperature, normal pressure, remain silent, sun exposure.
When 2. observing the oil product outward appearance, oil product need place the transparent glass cup, and core intersection ≮ 10cm.The oil product color depth is in proper order during range estimation: little yellow＜faint yellow＜light yellow＜yellow＜deep yellow.
3. to investigate the condition of test be 160 ℃, 4h, air velocity 60ml/min. to thermal oxidation stability, and it is that the method for aberration characterizes at the changing value of the transmittance at λ=460nm place that oil product colourity changes then with oxidation front and back oil sample.
After adding additive, the stability of the lubricant base of hydrotreatment all has improvement in various degree.But use oxidation inhibitor separately or use the stabilizing effect bad (embodiment 8, embodiment 9, embodiment 10 and embodiment 11) of photostabilizer separately the lubricant base of raising hydrotreatment.The adding of one package stabilizer has then improved stability, the especially light stability of the lubricant base of hydrotreatment significantly.In addition, the hydrogenated oil that has added one package stabilizer is through after certain Exposure to Sunlight time (about 20～30 days), and its colour-change tends towards stability, and sees Table 3.
The oil product appearance change of the hydrogenated oil composition of table 3 stable composition
| Fate | The oil product outward appearance | Fate | The oil product outward appearance | Fate | The oil product outward appearance | |
| Embodiment 12 | 15 | Little yellow transparent | 25 | Light yellow transparent | 126 | Yellow transparent |
| Embodiment 13 | 20 | Little yellow transparent | 33 | Yellow transparent | 136 | Yellow transparent |
| Embodiment 14 | 15 | Light yellow transparent | 40 | Faint yellow transparent | 143 | Light yellow transparent |
| Embodiment 15 | 14 | Water white transparency | 39 | Faint yellow transparent | 197 | Faint yellow transparent |
| Embodiment 16 | 10 | Water white transparency | 36 | Light yellow transparent | 197 | Light yellow transparent |
| Embodiment 17 | 19 | Water white transparency | 30 | Little yellow transparent | 198 | Little yellow transparent |
| Embodiment 18 | 18 | Water white transparency | 39 | Faint yellow transparent | 143 | Faint yellow transparent |
| Embodiment 19 | 17 | Water white transparency | 41 | Little yellow transparent | 197 | Little yellow transparent |
| Embodiment 20 | 20 | Water white transparency | 43 | Faint yellow transparent | 198 | Faint yellow transparent |
Claims (11)
1. a composite lubricating oil stabilizer is a benchmark with the one package stabilizer gross weight, comprises following composition:
(I) weight ratio is 1: 1～5: 1 the ultraviolet absorbers and the hindered amine light stabilizer that are selected from benzotriazole category, benzophenone and salicylate class, and gross weight content is 40%～80%;
(II) be selected from the oxidation inhibitor that shields phenols, arylamine class, phenolic ester class, sulphur phosphate metal salt and thiocarbamates, weight content is 15%～45%;
(III) phenyl-phosphite class sequestrant, weight content are 3%～18%.
2. according to the described one package stabilizer of claim 1, it is characterized in that, said ultraviolet absorbers be selected from 2-(2 '-hydroxyl-3 ', 5 '-di-t-butyl) benzotriazole, 2-(2 '-hydroxyl-3 '-tertiary butyl-5 '-aminomethyl phenyl)-the 5-chlorinated benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-the 5-chlorinated benzotriazole, 2-(2 '-hydroxyl-5 '-the Te octyl phenyl) benzotriazole, 2-hydroxyl-4-n-octyloxy-benzophenone, 2, the 4-dihydroxy benaophenonel, 2-hydroxyl-4-methoxyl group-benzophenone, 2-hydroxyl-4-(2 '-second for hexyloxy)-benzophenone, salol, 4,4 '-isopropylidene two (phenol salicylate), the mixture of one or more in the p-t-butylphenyl salicylate.
3. according to the described one package stabilizer of claim 1, it is characterized in that said hindered amine as light stabilizer is selected from two (2,2,6,6-tetramethyl-piperidyl) sebate, ethyl two (2,2,6,6-tetramethyl-piperazine ketone), N-nitrilotriacetic (2,2,6,6-tetramethyl--4-piperidyl) ester, N-nitrilotriacetic (1,2,2,6,6-pentamethyl--4-piperidyl) ester, two (1,2,2,6,6-pentamethyl--4-piperidyl) mixture of one or more in the sebate.
4. according to the described one package stabilizer of claim 1, it is characterized in that the weight ratio of ultraviolet absorbers and hindered amine light stabilizer is 1: 1～3: 1.
5. according to the described one package stabilizer of claim 1, it is characterized in that, said oxidation inhibitor is selected from 2,6-ditertbutylparacresol, zinc dialkyl dithiophosphate, dialkyl dithio amino formate, octyl group, butyl or fourth octyl diphenylamine, 3, the mixture of one or more in the 5-di-tert-butyl-hydroxy phenyl Isooctyl acrylate monomer.
6. according to the described one package stabilizer of claim 1, it is characterized in that, said sequestrant is selected from one or more the mixture in triphenyl phosphite, diisooctyl phenyl phosphite, trisnonyl phenyl phosphite, two (to nonylphenol) phenol phosphorous acid ester, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester.
7. according to the described one package stabilizer of claim 1, it is characterized in that the gross weight content of ultraviolet absorbers and hindered amine light stabilizer is 45%～72%, the oxidation inhibitor weight content is 18%～42%, and the sequestrant weight content is 5%～15%.
8. a stable hydrogenation lubricating oil composition is a benchmark with the composition gross weight, comprising:
(1) the described composite lubricating oil stabilizer of claim 1, weight content 0.01～2.0%;
(2) the hydrogenation lubricant base of surplus.
9. according to the described composition of claim 8, it is characterized in that the weight content 0.05%～1.5% of one package stabilizer.
10. according to the described composition of claim 8, it is characterized in that said hydrogenation lubricant base is the lubricating oil of producing through low-voltage hydrogenation, solvent treatment, medium-pressure hydrocracking process for refining process.
11., it is characterized in that aromaticity content is 1%～10% in the said hydrogenation lubricant base according to the described composition of claim 8, sulphur content is less than 100ppm.
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| CNB2004100483605A CN1333054C (en) | 2004-06-29 | 2004-06-29 | Lubricating oil composite stabilizer and stable hydrogenation lubricating oil composition |
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| CNB2004100483605A CN1333054C (en) | 2004-06-29 | 2004-06-29 | Lubricating oil composite stabilizer and stable hydrogenation lubricating oil composition |
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| CN102260579A (en) * | 2010-06-07 | 2011-11-30 | 江苏双江石化制品有限公司 | Composite light stabilizer for hydrogenated lubricating base oil |
| CN102260574A (en) * | 2010-06-07 | 2011-11-30 | 江苏双江石化制品有限公司 | Processing technology for improving oxidation stability of transformer oil |
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| CN102627994B (en) * | 2012-03-21 | 2013-10-16 | 上海应用技术学院 | High pressure hydrogenation naphthenic lubricating oil light stabilizer composition and application thereof |
| CN102690704B (en) * | 2012-04-23 | 2013-12-04 | 上海应用技术学院 | Heat stabilizer composition of high-pressure hydrogenated cycloalkyl lubricating oil, preparation method thereof, and application thereof |
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| CN112625781B (en) * | 2020-12-21 | 2022-09-06 | 山东恒利热载体工程技术有限公司 | Production process of oil product light stabilizer |
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