CN105779078A - Refrigerating machine oil composition and preparation method thereof - Google Patents
Refrigerating machine oil composition and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a refrigerating machine oil composition and a preparation method thereof.Naphthenic base light ends and paraffin base light ends obtained through petroleum fraction are adopted as base oil, wherein the naphthenic base light ends account for 20-40% of the base oil by mass, and the paraffin base light ends account for 60-80% of the base oil by mass.The refrigerating machine oil has the excellent thermal stability and lubrication performance, the refrigeration efficiency of a refrigeration compressor can be improved due to the high lubrication performance and high flash points in a refrigeration cycle, and long-term stable operation is ensured.According to the refrigerating machine oil composition, traditional mineral oil is adopted as the base oil, the technological processes are simple, the refrigerating machine oil composition is environmentally friendly and high in yield, and the composition can achieve the same performance as other similar synthetic type refrigerating machine oil, is easier to prepare and higher in economic value compared with synthetic oil, and achieves industrial scale production easily.
Description
Technical field
The invention provides a kind of suitable in compression-type refrigerating system refrigerated machine oil composition.
Background technology
In compression-type refrigerating system, generally adopt the chloride or not chloride fluorinated hydrocarbons such as CFCs (fluorochlorohydrocarbon), HCFCs (hydrogen fluorochlorohydrocarbon), HFCs (hydrogen fluorohydrocarbon) as cold-producing medium, and adopt various types of mineral oil, artificial oil as lubricating oil.But, these fluorinated hydrocarbons cold-producing mediums are at the severe attrition causing earth atmosphere ozone layer, while the interior dynamic equilibrium that damages the ozone layer, also increased the weight of the disadvantageous greenhouse effect of global environment.In the face of Ozone depletion and this world-famous puzzle of climate warming; international community is from early 1990s; under the coordination of United Nations Environment Programme, in succession formulate a series of Ozonosphere protection international convention, it is stipulated that the kind of controlled substance, control the benchmark of limit, control time etc..Certainly, the restraint that fluorinated hydrocarbons cold-producing medium is taked by international community, also accelerate the applied research of Hydrocarbon R600a.
Low molecular hydrocarbons R600a cold-producing medium, does not damage the ozone layer because it has, greenhouse effect index is little, Energy Efficiency Ratio is high and will not produce again the advantage of environmental problem and enjoy favor, current R600a to become the floride-free domestic refrigerating appts cold-producing medium that the world today commonly uses.The domestic refrigerating appts such as present stage refrigerator, refrigerator, water dispenser, ice machine day by day tend to new material, new technique, efficiently, the green manufacturing of energy-saving and environmental protection.This change and progress has promoted exploitation and the production of Novel freezing machine oil, also its performance and quality is had higher requirement simultaneously.
Refrigerator oil is the vital ingredient determining and affecting refrigerating plant function and effect in refrigeration system.During compressor operating, refrigerator oil directly contacts in refrigeration compression system with cold-producing medium, and participate in freeze cycle, its operating temperature range is very wide and life-span same with compressor, therefore for refrigerator oil, except playing sealing, cooling effect in refrigeration compressor, lubrication is particularly important with stability.
Refrigerator oil is made up of base oil and the various additive for improving other performance of refrigerator oil, and its main performance such as viscosity temperature characteristic, flash-point, low temperature flow pour point and the intersolubility etc. with cold-producing medium are all determined by basis oil properties.Therefore, the selection of refrigerator oil is concentrated mainly in the selection of base oil.
As refrigerator oil matching used with R600a cold-producing medium, its viscosity grade being suitable for is generally 40 DEG C of kinematic viscosity 7～15mm2/ s, and have the trend of reduction further." cycloalkyl refrigerator oil and cold-producing medium " literary composition of domestic periodical " lubricating oil " illustrates the part typical data of the Kunlun board cycloalkyl refrigerator oil KRD series (being applicable to Hydrocarbon R600a cold-producing medium) the totally-enclosed refrigerator oil of KRD8, KRD10, KRD15.The development standard of two kinds of totally-enclosed refrigerator oils of KRD10, KRD15 and production process route disclosed in " development of novel totally-enclosed refrigerator oil " literary composition of domestic periodical " lubricating oil ".Three sections of articles of domestic periodical " petroleum refining and chemical industry " and " lubricating oil " individually disclose development standard and the production process route of the totally-enclosed refrigerator oil of L-DRB/A8, L-DRB/A10, L-DRB/A15.Feedack current domestic industry market, it is adaptable to the refrigerator oil of R600a cold-producing medium be mainly 40 DEG C of kinematic viscositys be 8,10,12,15mm2The product of these four viscosity grades of/s, in particular by conventional mineral oil lube cut produce product, their base oil manufacturing process all comparative maturities, product quality be all more stable.
From the viewpoint of economize on electricity, also use the refrigerator oil of more low-viscosity at some special occasions, for instance viscosity grade is 5mm2The refrigerator oil of/s (40 DEG C of kinematic viscositys).In current domestic industry market, this series products of circulation is mainly synthesis type oil.
Disclosed relevant in the patent of refrigerated machine oil composition at home, disclosed in CN101233217A, one 40 DEG C of kinematic viscositys are 1～8mm2The refrigerated machine oil composition of/s, involved base oil, it is mainly selected from the hydride of low viscous alpha-olefin low polymers.Disclosed in CN101248163A, a kind of 40 DEG C of kinematic viscositys are 1～8mm2The refrigerated machine oil composition of/s, involved base oil mainly contains polyvinylether and/or polyoxyalkylene glycol derivant.It is 1～8mm that CN101305084A provides a kind of 40 DEG C of kinematic viscositys2The refrigerated machine oil composition of/s, its base oil contains at least one in the polyether polyols bis ether that averaged repeating numbers is less than 2 of monoether compounds, aklylene glycol bis ether and oxyalkylene as main component.The refrigerated machine oil composition of above patent disclosure has the purpose that viscosity is low, sealing is good, lubricity is excellent and reaches to improve energy saving.Its involved base oil is all become by synthesis type line of oils.
It is 1～8mm that CN101305083A provides a kind of 40 DEG C of kinematic viscositys2The refrigerated machine oil composition of/s, its base oil is mainly selected from least one of mineral oil, synthetic fat ring type hydrocarbon compound and synthesis aromatic hydrocarbon compound as main component.It can be seen that adopt the refrigerator oil of oil based on mineral oil from patent Example, although the kinematic viscosity when 40 DEG C can be less than equal to 5mm2The low viscosity of/s, but, due to its flash-point (more than 120 DEG C), poor stability, it is difficult to the requirement reaching refrigeration compressor to refrigerator oil minimum flash point (more than 130 DEG C), additionally the viscosity index (VI) of this oil product is low, lubricity is slightly worse, it is impossible to meet the instructions for use of conventional compact refrigeration system.
Disclosed in CN101177643A, a kind of 40 DEG C of kinematic viscositys are 3～6mm2The refrigerated machine oil composition of/s, this refrigerated machine oil composition contain based on oil mixedαolefin godied oil and additive.Wherein, described mixedαolefin polymer is C15-C22Mixing isomeric olefine, C15-C22Mixing isoparaffin or C15-C22Mixing isomeric olefine and C15-C22The mixture of mixing isoparaffin.Said composition can meet energy-conservation requirement, can meet again refrigerator oil to safety, low temperature flow and the requirement good with the intermiscibility of R600a.But based on loaded down with trivial details, the complicated preparation technology of mixedαolefin godied oil of oil, the production cost causing said composition is higher.
Mostly the refrigerated machine oil composition that invention disclosed above relates to is alpha-olefin polymerization oil, alkylbenzene, ether oil, Esters oil and fluorocarbon oil composition, or with conventional mineral oil for key component, add appropriate synthetic hydrocarbon compounds or modifying agent is used as refrigerator oil matched with R600a cold-producing medium.
In PetroChina Company Ltd. patent CN102295956A, disclose a kind of naphthene crude oils fraction that adopts, the preparation method that hydrogenated process-clay finishing group technology produces the low viscosity refrigerator oil base oil with cycloalkyl characteristic.The refrigerator oil base oil produced in the method has suitable arene content, excellent cryogenic property, although its minimum flash point can reach the requirement of (more than 120 DEG C), but compared with special oil alkylbenzene in the market, its flash-point still can not meet the instructions for use of special compression refrigerating system (flash-point is more than 140 DEG C).It addition, the preparation method that this patent only discloses a kind of refrigerator oil base oil, the kinematic viscosity being not directed to 40 DEG C is 4.0～6.0mm2The low viscosity refrigerator oil product of/s commonly used.That is: up to the present, market is 4.5～5.5mm but without 40 DEG C of kinematic viscositys2The mineral type refrigerator oil product of/s, more not adopting conventional mineral oil to prepare 40 DEG C of kinematic viscositys is 4.5～5.5mm2The bibliographical information of the refrigerator oil of/s.
Summary of the invention
The present invention provides a kind of refrigerated machine oil composition and preparation method thereof, the defect that kinematic viscosity to solve prior art refrigerator oil 40 DEG C is high.
For achieving the above object, the present invention provides a kind of refrigerated machine oil composition, oil based on the cycloalkyl light fraction obtained by petroleum distillate and paraffinic base light fraction, it is 20%～40% that described cycloalkyl light fraction accounts for the weight/mass percentage composition of described base oil, and it is 80%～60% that described paraffinic base light fraction accounts for the weight/mass percentage composition of described base oil.
Wherein, it is 30% that described cycloalkyl light fraction accounts for the weight/mass percentage composition of described base oil, and it is 70% that described paraffinic base light fraction accounts for the weight/mass percentage composition of described base oil.
Wherein, also include: account for described base oil quality 0.3%～1.0% phenol type antioxidant, amine type antioxidant or its combination.
Wherein, also include metal deactivator, and, every gram of described base oil adds the described metal deactivator of 50～100 μ g.
Wherein, also include: account for described base oil quality 1.0%～2.0% sulfur type antiwear additive or phosphorous antiwear additive or sulfur-phosphorous antiwear additive.
Wherein, also include anti-foaming agent, and, every gram of described base oil adds 1-10 μ g anti-foaming agent, described anti-foaming agent is silicon type anti-foaming agent, non-silicon type antifoamer or silicon type and the compound anti-foaming agent of non-silicon type.
Wherein, 40 DEG C of kinematic viscositys of described refrigerated machine oil composition are 4.5～5.5mm2/s；Flash-point > 140 DEG C；Falex inefficacy load > 3000N.
Wherein, described paraffinic base light fraction be paraffinic base crude oil is carried out air-distillation and decompression distillation and hydrogenated refining, the Hydrodewaxing of the lube cut that obtains, solvent refining, hydrotreatment, fractional distillation, clay-filtered in two kinds or the multiple lubricating oil light fractions that hydrocarbon composition is different, boiling point is different that obtain of multiple refining means combined treatment.
Wherein, described cycloalkyl light fraction be naphthene base crude is carried out air-distillation and decompression distillation and hydrogenated refining, the Hydrodewaxing of the lube cut that obtains, solvent refining, hydrotreatment, fractional distillation, clay-filtered in two kinds or the multiple lubricating oil light fractions that hydrocarbon composition is different, boiling point is different that obtain of multiple refining means combined treatment.
Wherein, described antioxidant is selected from the one in 2,6 ditertiary butyl p cresol, 4,4-di-2-ethylhexylphosphine oxides (2,6-di-tert-butylphenol), phenyl-a-naphthylamine, alkyl diphenylamine and more than two kinds fractions thereof.
Wherein, described antiwear additive is selected from the one in sulfide isobutene, tricresyl phosphate, t-butyl phosphate triphenylmethyl methacrylate, trithiophenyl phosphate and two kinds of combination of the above thereof.
Wherein, described metal deactivator is selected from benzotriazole derivant and/or thiadiazoles derivative.
Wherein, described metal deactivator is selected from N, N diakylaminomethylene benzotriazole, 2,5-dimercapto-1, the one in 3,4 thiadiazoles derivatives.With base oil weight for benchmark, the addition of metal deactivator is 50～100 μ g/g preferably.
Wherein, described anti-foaming agent is selected from polydimethylsiloxane, polyacrylate, the one of polymethacrylates and two kinds of combination of the above thereof.
Wherein, described anti-foaming agent is selected from polyether-modified silicone oil and/or mean molecule quantity 60000 or above silicone oil.
And, for achieving the above object, the preparation method of a kind of refrigerated machine oil composition, comprise the following steps:
Step 1: oil based on the cycloalkyl light fraction that petroleum distillate is obtained and paraffinic base light fraction mixing, it is 20%～40% that described cycloalkyl light fraction accounts for the weight/mass percentage composition of described base oil, and it is 80%～60% that described paraffinic base light fraction accounts for the weight/mass percentage composition of described base oil；And
Step 2: mixed described cycloalkyl light fraction forms described refrigerated machine oil composition with described paraffinic base light fraction.
Wherein, also include before step 1: paraffinic base crude oil is carried out air-distillation and decompression distillation, hydrogenated refining, the Hydrodewaxing of the lube cut that obtains, solvent refining, hydrotreatment, fractional distillation, clay-filtered in two kinds or multiple refining means combined treatment obtain the paraffinic base light fraction that hydrocarbon composition is different, boiling point is different.
Wherein, also include before step 1: naphthene base crude is carried out air-distillation and decompression distillation, hydrogenated refining, the Hydrodewaxing of the lube cut that obtains, solvent refining, hydrotreatment, fractional distillation, clay-filtered in two kinds or the cycloalkyl light fraction that hydrocarbon composition is different, boiling point is different that obtains of multiple refining means combined treatment.
Wherein, also include: in step 1, mixing accounts for the phenol type antioxidant of the 0.3%～1.0% of described base oil quality, amine type antioxidant or its combination.
Wherein, also include: hybrid metal passivator in step 1, and, every gram of described base oil adds the described metal deactivator of 50～100 μ g.
Wherein, also include: in step 1, mixing accounts for sulfur type antiwear additive or phosphorous antiwear additive or the sulfur-phosphorous antiwear additive of the 1.0%～2.0% of described base oil quality.
Wherein, also it is included in: step 1 mixes anti-foaming agent, and, every gram of described base oil adds 1-10 μ g anti-foaming agent, described anti-foaming agent is silicon type anti-foaming agent, non-silicon type antifoamer or silicon type and the compound anti-foaming agent of non-silicon type.
The effect of the present invention:
Compared with prior art, low (40 DEG C of kinematic viscositys are 4.5～5.5mm to the refrigerated machine oil composition viscosity of the present invention2/ s), pour point is low, flash-point is high (more than 140 DEG C), good and with cold-producing medium (R600a) the intersolubility of lubricity and thermal stability is excellent, in kind of refrigeration cycle, high-flash and stronger greasy property can improve the refrigerating efficiency of refrigeration compressor, it is ensured that run steadily in the long term.Refrigerated machine oil composition provided by the invention is oil based on conventional mineral oil, involved technical process is simple and environmentally-friendly, yield is high, cost is low, described compositions can reach other similar synthesis type refrigerator oil same performance, and be more easy to than artificial oil produce, economic worth higher, easily realize industrial-scale production.
Detailed description of the invention
The present invention provides a kind of low viscosity refrigerated machine oil composition.Involved base oil is mainly in harmonious proportion forms with the excellent cycloalkyl of cryogenic property and viscous warm nature, the good paraffin base lubricating oil appropriate fractions of lubricity, and said composition viscosity is low, and (40 DEG C of kinematic viscositys are 4.5～5.5mm2/ s), pour point is low, flash-point is high (more than 140 DEG C), good and with cold-producing medium (R600a) the intersolubility of lubricity and thermal stability is excellent.
The present invention provides a kind of refrigerated machine oil composition, oil based on the cycloalkyl light fraction obtained by petroleum distillate and paraffinic base light fraction, it is 20%～40% that described cycloalkyl light fraction accounts for the weight/mass percentage composition of described base oil, and it is 80%～60% that described paraffinic base light fraction accounts for the weight/mass percentage composition of described base oil.
Wherein, it is 30% that described cycloalkyl light fraction accounts for the weight/mass percentage composition of described base oil, and it is 70% that described paraffinic base light fraction accounts for the weight/mass percentage composition of described base oil.
Wherein, also include: account for described base oil quality 0.3%～1.0% phenol type antioxidant, amine type antioxidant or its combination.
Wherein, also include metal deactivator, and, every gram of described base oil adds the described metal deactivator of 50～100 μ g.
Wherein, also include: account for described base oil quality 1.0%～2.0% sulfur type antiwear additive or phosphorous antiwear additive or sulfur-phosphorous antiwear additive.
Wherein, also include anti-foaming agent, and, every gram of described base oil adds 1-10 μ g anti-foaming agent, described anti-foaming agent is silicon type anti-foaming agent, non-silicon type antifoamer or silicon type and the compound anti-foaming agent of non-silicon type.
Wherein, 40 DEG C of kinematic viscositys of described refrigerated machine oil composition are 4.5～5.5mm2/s；Flash-point > 140 DEG C；Falex inefficacy load > 3000N.
Wherein, described paraffinic base light fraction be paraffinic base crude oil is carried out air-distillation and decompression distillation and hydrogenated refining, the Hydrodewaxing of the lube cut that obtains, solvent refining, hydrotreatment, fractional distillation, clay-filtered in two kinds or the multiple lubricating oil light fractions that hydrocarbon composition is different, boiling point is different that obtain of multiple refining means combined treatment.
Wherein, described cycloalkyl light fraction be naphthene base crude is carried out air-distillation and decompression distillation and hydrogenated refining, the Hydrodewaxing of the lube cut that obtains, solvent refining, hydrotreatment, fractional distillation, clay-filtered in two kinds or the multiple lubricating oil light fractions that hydrocarbon composition is different, boiling point is different that obtain of multiple refining means combined treatment.
Wherein, described antioxidant is selected from the one in 2,6 ditertiary butyl p cresol, 4,4-di-2-ethylhexylphosphine oxides (2,6-di-tert-butylphenol), phenyl-a-naphthylamine, alkyl diphenylamine and more than two kinds fractions thereof.
Wherein, described antiwear additive is selected from the one in sulfide isobutene, tricresyl phosphate, t-butyl phosphate triphenylmethyl methacrylate, trithiophenyl phosphate and two kinds of combination of the above thereof.
Wherein, described metal deactivator is selected from benzotriazole derivant and/or thiadiazoles derivative.
Wherein, described metal deactivator is selected from N, N diakylaminomethylene benzotriazole, 2,5-dimercapto-1, the one in 3,4 thiadiazoles derivatives.With base oil weight for benchmark, the addition of metal deactivator is 50～100 μ g/g preferably.
Wherein, described anti-foaming agent is selected from polydimethylsiloxane, polyacrylate, the one of polymethacrylates and two kinds of combination of the above thereof.
Wherein, described anti-foaming agent is selected from polyether-modified silicone oil and/or mean molecule quantity 60000 or above silicone oil.
And, the preparation method of a kind of refrigerated machine oil composition, comprise the following steps:
Step 1: oil based on the cycloalkyl light fraction that petroleum distillate is obtained and paraffinic base light fraction mixing, it is 20%～40% that described cycloalkyl light fraction accounts for the weight/mass percentage composition of described base oil, and it is 80%～60% that described paraffinic base light fraction accounts for the weight/mass percentage composition of described base oil；And
Step 2: mixed described cycloalkyl light fraction forms described refrigerated machine oil composition with described paraffinic base light fraction.
Wherein, also include before step 1: paraffinic base crude oil is carried out air-distillation and decompression distillation, hydrogenated refining, the Hydrodewaxing of the lube cut that obtains, solvent refining, hydrotreatment, fractional distillation, clay-filtered in two kinds or multiple refining means combined treatment obtain the paraffinic base light fraction that hydrocarbon composition is different, boiling point is different.
Wherein, also include before step 1: naphthene base crude is carried out air-distillation and decompression distillation, hydrogenated refining, the Hydrodewaxing of the lube cut that obtains, solvent refining, hydrotreatment, fractional distillation, clay-filtered in two kinds or the cycloalkyl light fraction that hydrocarbon composition is different, boiling point is different that obtains of multiple refining means combined treatment.
Wherein, also include: in step 1, mixing accounts for the phenol type antioxidant of the 0.3%～1.0% of described base oil quality, amine type antioxidant or its combination.
Wherein, also include: hybrid metal passivator in step 1, and, every gram of described base oil adds the described metal deactivator of 50～100 μ g.
Wherein, also include: in step 1, mixing accounts for sulfur type antiwear additive or phosphorous antiwear additive or the sulfur-phosphorous antiwear additive of the 1.0%～2.0% of described base oil quality.
Wherein, also it is included in: step 1 mixes anti-foaming agent, and, every gram of described base oil adds 1-10 μ g anti-foaming agent, described anti-foaming agent is silicon type anti-foaming agent, non-silicon type antifoamer or silicon type and the compound anti-foaming agent of non-silicon type.
Specifically, refrigerator oil base oil provided by the invention is the lube cut (paraffinic base, cycloalkyl) crude oil carrying out air-distillation and decompression distillation and obtaining, suitable hydrogenated refining, Hydrodewaxing, solvent refining, hydrotreatment, fractional distillation, clay-filtered in two kinds or multiple refining means combined treatment, obtain multiple lubricating oil light fractions that hydrocarbon composition is different, boiling point is different, and by adjusting the boiling spread of multiple light distillates, the relation of balance viscosity and flash-point, reasonably optimizing composition structure, is mixed according to proper proportion.The refrigerator oil base oil of the present invention, it is adopt paraffinic base light fraction (CN103820146A) and cycloalkyl light fraction (CN101747934A) to carry out Mixed adjustment in the ratio of 80%～60%:20%～40%, the scope of boiling point provides respectively in table 1 below and table 2, makes Basic oil Viscosity and flash-point reach application claims by different ratio mixing.Reasonably optimizing composition structure is to be obtained paraffinic base and cycloalkyl light fraction, adjusted mixed proportion by the preparation method of above-mentioned two patent application, is formed structure by rational different hydrocarbons, finally realize application claims in base oil.
In the present invention, the refrigerator oil base oil provided is by having the lubricating oil light fraction of paraffinic base characteristic and having that the lubricating oil light fraction of cycloalkyl characteristic is mixed to be formed.
In refrigerator oil base oil provided by the invention, described in there is paraffinic base characteristic the preparation method of lubricating oil light fraction can referring to patent CN103820146A " a kind of optical fiber ointment fill with oil and preparation method thereof ".The lube cut prepared in the method, here only select boiling range scope at (260～280 DEG C), (light fraction of 300～320 DEG C, its character is in Table 1.
Table 1 paraffin base lubricating oil light fraction
In refrigerator oil base oil provided by the invention, the preparation method of the described lubricating oil light fraction with cycloalkyl characteristic is referring to patent CN101747934A " preparation method of a kind of anti-evolving-gas additive of transformer oil ", the naphthene base lubrication oil fraction prepared in the method, its character is in Table 2.
Table 2 naphthene base lubrication oil fraction
In the present invention, main body of oil based on paraffinic base light fraction, based on its addition weight of oil 80%～60% time, it is possible to ensure the higher viscosity index (VI) of base oil, CP% value content, more than 50%, even if the low-molecular-weight R600a cold-producing medium dilution of lubricated property difference, also ensures that the lubricity that oil product is enough.This wherein, again with the light fraction of (300～320 DEG C) for main constituent, it is ensured that the thermal stability that base oil is good；The light fraction of (260～280 DEG C) is auxiliary element, and the viscosity being used for adjusting (290～360 DEG C) component reaches 4.5～5.5mm2/s；Meanwhile, based on cycloalkyl fraction oil composition component, based on its addition weight of oil 20%～40% time, it is possible to ensure that base oil contains rational CA% value, does not affect the dissolution characteristics of oil product, can also improve basis oil flash, it is ensured that the lubricity that base oil is enough simultaneously.
Refrigerator oil provided by the invention is to be mixed formed by cycloalkyl, paraffin base lubricating oil appropriate fractions, and its base oil feature is in Table 3.
Table 3 base oil representative property
In order to improve the serviceability of the refrigerated machine oil composition of the present invention further, in refrigerator oil base oil provided by the invention, improve thermal oxidation stability by adding currently known multiple Refrigerant Oil Additive, improve greasy property and control foaming, reduction running noise etc..
Described antioxidant can be phenolic antioxidant generally in the art, amine type antioxidant in the present invention, or their compound.One in DBPC 2,6 ditertiary butyl p cresol, 4,4-di-2-ethylhexylphosphine oxide (2,6-di-tert-butylphenol), phenyl-a-naphthylamine, alkyl diphenylamine and more than two kinds components thereof.Angularly consider from effect and economy, based on its addition the 0.3%～1.0% of weight of oil.
Described antiwear additive can be generally in the art phosphorous, containing S antiwear additive or their compound.One in sulfide isobutene, tricresyl phosphate, t-butyl phosphate triphenylmethyl methacrylate, trithiophenyl phosphate and two kinds of combination of the above thereof.A small amount of interpolation (with base oil weight for benchmark) 1.0%～2.0% can be effectively improved lubricity and the stability of compositions.
In the refrigerated machine oil composition of the present invention, described metal deactivator can be benzotriazole derivant and/or thiadiazoles derivative, such as N, N diakylaminomethylene benzotriazole, 2,5-dimercapto-1, the one in 3,4 thiadiazoles derivatives.With base oil weight for benchmark, the addition of metal deactivator is 50～100 μ g/g preferably.
Described anti-foaming agent can be silicon type generally in the art, non-silicon type or compound anti-foaming agent, selected from one and two kinds of combination of the above thereof of polydimethylsiloxane, polyacrylate, polymethacrylates, silicon type and non-silicon type complex.With base oil weight for benchmark, the polyether-modified silicone oil of described anti-foaming agent preferred content 1～10 μ g/g and/or mean molecule quantity 60000 or silicone oil above.
In order to further illustrate the features and advantages of the present invention, below in conjunction with embodiment, the present invention is described in further detail.But the present invention is not by any restriction of these examples.The additive adopted in the embodiment of the present invention is commercially available industrialization commodity, and to Additive Production, business does not limit.
Embodiment
In the present invention, the base oil adopted is the combination of the cycloalkyl through multiple hydrofinishing group technology and paraffin base lubricating oil light fraction, and this refrigerator oil base oil preferably 40 DEG C of kinematic viscositys are 4.5～5.5mm2/s；Pour point, floc point <-50 DEG C, the biphase temperature <-20 DEG C that dissolves each other；Flash-point > 140 DEG C；CA% value is 2%～6%；Viscosity index (VI) > 60.Base oil is made to have higher heat stability and low temperature properties.Additive adopts commercially available antioxidant, metal deactivator, antiwear additive and anti-foaming agent, dissimilar additive composite, substantially increases lubricity and the thermal oxidation stability of refrigerator oil product.
Refrigerator oil provided by the invention is analyzed with refrigerator oil (alkylbenzene) conventional in the market.Result is in Table 4.
Component A: have the lubricating oil light fraction of cycloalkyl characteristic, 40 DEG C of kinematic viscositys are 9.86mm2/s。
Component B: have the lubricating oil light fraction of paraffinic base characteristic, 40 DEG C of kinematic viscositys are 4.87mm2/s。
Component C: have the lubricating oil light fraction of cycloalkyl characteristic, 40 DEG C of kinematic viscositys are 10.71mm2/s。
Component D: have the lubricating oil light fraction of paraffinic base characteristic, 40 DEG C of kinematic viscositys are 3.82mm2/s。
Table 4
Effect from above example, comparative example, hydrocarbon forms refrigerator oil rational in infrastructure and has more excellent heat stability and greasy property, in kind of refrigeration cycle, high-flash and stronger greasy property can improve the refrigerating efficiency of refrigeration compressor, it is ensured that run steadily in the long term.
The effect of the present invention:
Refrigerated machine oil composition provided by the invention is oil (need not add any synthesis hydrocarbon materials or modifying agent) based on conventional mineral oil, and this refrigerated machine oil composition has following good characteristic:
(1) viscosity is low, and its 40 DEG C of kinematic viscositys are 4.5～5.5mm2/ s, has good energy-saving effect；
(2) pour point is less than-50 DEG C, has good low temperature flowability；
(3) biphase temperature of dissolving each other is less than-20 DEG C, it was shown that said composition contains appropriate effectively aromatic compound, the intermiscibility good with hydrocarbon coolant, and additive has good dissolubility；
(4) flash-point is not less than 140 DEG C.
(5) Flaex sintering load is more than 3000N, has good lubricity.
(6) good and with cold-producing medium (R600a) the intersolubility of lubricity and thermal stability is excellent.
(7) technical process involved in the present invention is simple and environmentally-friendly, yield is high, the prepared totally-enclosed refrigerated machine oil composition of mineral type can reach other similar synthesis type refrigerator oil same performance, and be more easy to than artificial oil produce, economic worth higher, easily realize industrial-scale production.
(8) present invention is applicable to cycloalkyl, paraffinic base crude oil fraction.
The present invention is not restricted to the described embodiments, and can come preferably according to above-mentioned reconciliation scheme and practical condition.
Certainly; the present invention also can have other various embodiments; when without departing substantially from present invention spirit and essence thereof, those of ordinary skill in the art can make various corresponding change and deformation according to the present invention, but these change accordingly and deform the protection domain that all should belong to the claims in the present invention.
Claims (22)
1. a refrigerated machine oil composition, it is characterized in that, oil based on the cycloalkyl light fraction obtained by petroleum distillate and paraffinic base light fraction, it is 20%～40% that described cycloalkyl light fraction accounts for the weight/mass percentage composition of described base oil, and it is 80%～60% that described paraffinic base light fraction accounts for the weight/mass percentage composition of described base oil.
2. refrigerated machine oil composition according to claim 1, it is characterised in that it is 30% that described cycloalkyl light fraction accounts for the weight/mass percentage composition of described base oil, it is 70% that described paraffinic base light fraction accounts for the weight/mass percentage composition of described base oil.
3. refrigerated machine oil composition according to claim 1, it is characterised in that also include: account for described base oil quality 0.3%～1.0% phenol type antioxidant, amine type antioxidant or its combination.
4. refrigerated machine oil composition according to claim 1, it is characterised in that also include metal deactivator, and, every gram of described base oil adds the described metal deactivator of 50～100 μ g.
5. refrigerated machine oil composition according to claim 1, it is characterised in that also include: account for described base oil quality 1.0%～2.0% sulfur type antiwear additive or phosphorous antiwear additive or sulfur-phosphorous antiwear additive.
6. refrigerated machine oil composition according to claim 1, it is characterized in that, also include anti-foaming agent, and, adding 1-10 μ g anti-foaming agent in every gram of described base oil, described anti-foaming agent is silicon type anti-foaming agent, non-silicon type antifoamer or silicon type and the compound anti-foaming agent of non-silicon type.
7. refrigerated machine oil composition according to claim 1, it is characterised in that 40 DEG C of kinematic viscositys of described refrigerated machine oil composition are 4.5～5.5mm2/s；Flash-point > 140 DEG C；Falex inefficacy load > 3000N.
8. refrigerated machine oil composition according to claim 1, it is characterized in that, described paraffinic base light fraction be paraffinic base crude oil is carried out air-distillation and decompression distillation and hydrogenated refining, the Hydrodewaxing of the lube cut that obtains, solvent refining, hydrotreatment, fractional distillation, clay-filtered in two kinds or the multiple lubricating oil light fractions that obtain of multiple refining means combined treatment.
9. refrigerated machine oil composition according to claim 1, it is characterized in that, described cycloalkyl light fraction be naphthene base crude is carried out air-distillation and decompression distillation and hydrogenated refining, the Hydrodewaxing of the lube cut that obtains, solvent refining, hydrotreatment, fractional distillation, clay-filtered in two kinds or the multiple lubricating oil light fractions that obtain of multiple refining means combined treatment.
10. refrigerated machine oil composition according to claim 3, it is characterized in that, described antioxidant selected from 2,6 ditertiary butyl p cresol, 4, one in 4-di-2-ethylhexylphosphine oxide (2,6-di-tert-butylphenol), phenyl-a-naphthylamine, alkyl diphenylamine and more than two kinds fractions thereof.
11. refrigerated machine oil composition according to claim 5, it is characterised in that described antiwear additive is selected from the one in sulfide isobutene, tricresyl phosphate, t-butyl phosphate triphenylmethyl methacrylate, trithiophenyl phosphate and two kinds of combination of the above thereof.
12. refrigerated machine oil composition according to claim 4, it is characterised in that described metal deactivator is selected from benzotriazole derivant and/or thiadiazoles derivative.
13. refrigerated machine oil composition according to claim 12, it is characterised in that described metal deactivator is selected from N, N diakylaminomethylene benzotriazole, 2,5-dimercapto-1, the one in 3,4 thiadiazoles derivatives.With base oil weight for benchmark, the addition of metal deactivator is 50～100 μ g/g preferably.
14. refrigerated machine oil composition according to claim 6, it is characterised in that described anti-foaming agent is selected from polydimethylsiloxane, polyacrylate, the one of polymethacrylates and two kinds of combination of the above thereof.
15. refrigerated machine oil composition according to claim 6, it is characterised in that described anti-foaming agent is selected from polyether-modified silicone oil and/or mean molecule quantity 60000 or above silicone oil.
16. the preparation method of a refrigerated machine oil composition, it is characterised in that comprise the following steps:
Step 1: oil based on the cycloalkyl light fraction that petroleum distillate is obtained and paraffinic base light fraction mixing, it is 20%～40% that described cycloalkyl light fraction accounts for the weight/mass percentage composition of described base oil, and it is 80%～60% that described paraffinic base light fraction accounts for the weight/mass percentage composition of described base oil；And
Step 2: mixed described cycloalkyl light fraction forms described refrigerated machine oil composition with described paraffinic base light fraction.
17. the preparation method of the refrigerated machine oil composition according to claim 16, it is characterized in that, also include before step 1: paraffinic base crude oil is carried out air-distillation and decompression distillation, hydrogenated refining, the Hydrodewaxing of the lube cut that obtains, solvent refining, hydrotreatment, fractional distillation, clay-filtered in two kinds or multiple refining means combined treatment obtain the paraffinic base light fraction that hydrocarbon composition is different, boiling point is different.
18. the preparation method of refrigerated machine oil composition according to claim 16, it is characterized in that, also include before step 1: naphthene base crude is carried out air-distillation and decompression distillation, hydrogenated refining, the Hydrodewaxing of the lube cut that obtains, solvent refining, hydrotreatment, fractional distillation, clay-filtered in two kinds or the cycloalkyl light fraction that hydrocarbon composition is different, boiling point is different that obtains of multiple refining means combined treatment.
19. the preparation method of the refrigerated machine oil composition according to claim 16, it is characterised in that also include: mixing accounts for the phenol type antioxidant of the 0.3%～1.0% of described base oil quality, amine type antioxidant or its combination in step 1.
20. the preparation method of the refrigerated machine oil composition according to claim 16, it is characterised in that also include: hybrid metal passivator in step 1, and, every gram of described base oil adds the described metal deactivator of 50～100 μ g.
21. the preparation method of the refrigerated machine oil composition according to claim 16, it is characterised in that also include: mixing accounts for sulfur type antiwear additive or phosphorous antiwear additive or the sulfur-phosphorous antiwear additive of the 1.0%～2.0% of described base oil quality in step 1.
22. the preparation method of the refrigerated machine oil composition according to claim 16, it is characterized in that, also it is included in: step 1 mixes anti-foaming agent, and, adding 1-10 μ g anti-foaming agent in every gram of described base oil, described anti-foaming agent is silicon type anti-foaming agent, non-silicon type antifoamer or silicon type and the compound anti-foaming agent of non-silicon type.
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| CN105779078B (en) | 2018-10-16 |
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