CN101654526B - Method for manufacturing rubber processing oil - Google Patents
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- CN101654526B CN101654526B CN 200910170401 CN200910170401A CN101654526B CN 101654526 B CN101654526 B CN 101654526B CN 200910170401 CN200910170401 CN 200910170401 CN 200910170401 A CN200910170401 A CN 200910170401A CN 101654526 B CN101654526 B CN 101654526B
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Abstract
The invention provides a method for manufacturing a rubber processing oil RPO with superior permeability to the rubber polymer, less than 3 mass% of polycyclic aromatic compounds (PCA) and high security by easy process. The method is a method for manufacturing a rubber processing oil with 10-60mm<2>/s of kinematic viscosity (100 DEG C), less than 20 DEG C of flow points, 10-40 of % C[A] and less than 3 mass% of PCA content. The method is characterized in that the deasphalted oil (A) is mixed with the vacuum distillate oil (B); the deasphalted oil (A) is a specific cycloalkyl deasphalted oil (a) and/or cycloalkyl hydrogenation deasphalted oil (b) obtained by hydrogenation to the cycloalkyl deasphalted oil; the vacuum distillate oil (B) is a specific cycloalkyl vacuum distillate oil (c), cycloalkyl hydrogenation vacuum distillate oil (d) obtained by processing hydrogenation to the cycloalkyl vacuum distillate oil, cycloalkyl solvent refining vacuum distillate oil (e) non-cycloalkyl refining vacuum distillate oil after solvent performing refining and/or hydrogenation to the non-cycloalkyl vacuum distillate oil and then performing dewaxing processing according to requirements.
Description
Technical field
The present invention relates to the manufacture method of the mineral oils rubber processing oil that adds in natural rubber or synthetic rubber, particularly because of the content that reduces polycyclc aromatic compound, there is no toxicity and carinogenicity, can carry out by comparatively being easy to operation or operation the manufacture method of rubber processing oil of the rubber processing oil of operation easy to manufacture.
Background technology
The use of rubber processing oil is that the rubber manufacturing operation such as its perviousness to the rubber polymer tissue makes to mediate, extrudes, shaping is easier in order to utilize.In addition, also for improving the physical properties of rubber item.Above-mentioned rubber processing oil need to have good affinity to rubber.On the other hand, the rubber of processing has natural rubber and synthetic rubber, and synthetic rubber has kind miscellaneous.In above-mentioned rubber, particularly natural rubber and styrene butadiene rubbers (SBR) are used in a large number, in these rubber usually use contain aromatic hydrocarbons in a large number and rubber had to the process oil of high-affinity.
For obtaining such process oil, use oil as described below: using has lubricating oil distillate that the solvent of affinity obtains the underpressure distillation by crude oil maybe will reduce pressure after the residue diasphaltene to carry out as required dewaxing treatment or hydrofining to process the oil obtained to aromatic hydrocarbons to carry out extraction treatment, thus obtained so-called extract (extract).According to column chromatography analysis, the aromatics that thus obtained process oil contains 70～99 quality %, according to n-d-M ring analysis, C
abe 20～50.Because process oil contains more heavier aromatic compounds, particularly due to the problem of the carinogenicity of polycyclc aromatic compound (PCA), in Europe for the wet goods that contains the polycyclc aromatic compound (PCA) more than 3 quality %, refining degree when the base oil modulation be take in the U.S. is benchmark, and manufacturers must mark carinogenicity and could sell.Therefore, reduce to the rubber processing oil of less than 3 quality % if not the content by polycyclc aromatic compound (PCA), be difficult in fact sell.
Polycyclc aromatic compound (PCA) also can mean with the DMSO extraction component, about the rubber processing oil of DMSO extraction component less than 3 quality %, thereby disclosed, the underpressure distillation residual component is carried out the diasphaltene processing, the oil of gained is carried out to dewaxing treatment manufactures the method (patent documentation 1) that polycyclc aromatic compound (PCA) is reduced to the rubber processing oil of less than 3 quality %.But the result that reduces the DMSO extraction component of this rubber processing oil is that aniline point raises.Aniline point is the index of the content of aromatic hydrocarbons, and aniline point is high means that aromatic hydrocarbons content is low.If the aromatic hydrocarbons content in rubber processing oil reduces, oil reduces the affinity of rubber, the essential attributes of rubber processing oil, to be rubber processing oil descend to the perviousness of rubber polymer, is difficult to make the product of the physical condition that meets final rubber item.
In addition, disclosed non-carcinogenic bright stock extract and/or deasphalted oil with and process for refining, in order to make mutagen sex index (MI) less than 1, proposed will be relevant to MI characteristic as the technical scheme (patent documentation 2) of refining index.What in this patent documentation 2, use is the oil that the diasphaltene by the residue in vacuum distillation column obtain, or uses the extraction treatment by deasphalted oil to reduce the oil of aromatics or passed through the oil that this oily dewaxing treatment obtains.But, more than polycyclc aromatic compound (PCA) is estimated as 3 quality %.The relation of the MI of not mentioned above-mentioned deasphalted oil and polycyclc aromatic compound (PCA).
Proposed that perviousness to rubber polymer is high, DMSO extraction component less than 3 quality %, can solve the manufacture method (patent documentation 3) of the rubber processing oil of above-mentioned problem.But the viscosity of this rubber processing oil is high, therefore when mixing rubber, there is the poor problem of operability.So, proposed will to the deasphalted oil of decompression residue carry out solvent extraction and extract with vacuum distillate is carried out to solvent treatment debris maybe this debris is refining and the low viscosity process oil (patent documentation 4) that mixes of mineral oils base oil.But, adopt loaded down with trivial details technique in a large number in the processing of the operation such as the solvent extraction of deasphalted oil and the solvent treatment of vacuum distillate and waste.
Patent documentation 1: Japanese Patent JP-A 6-505524 communique
Patent documentation 2: Japanese Patent JP-A 7-501346 communique
Patent documentation 3: Japanese Patent Patent 2001-108354 communique
Patent documentation 4: the open WO2003/031537 communique of international monopoly
Summary of the invention
The present invention is the invention completed in order to address the above problem, and its problem is to provide the method for manufacturing superior permeability to rubber polymer, polycyclc aromatic compound (PCA) less than 3 quality %, safe rubber processing oil by comparatively being easy to operation.
The inventor achieves the above object to have carried out repeatedly conscientious research, found that, can modulate superior permeability, polycyclc aromatic compound (PCA) less than 3 quality %, safe, the low viscous rubber processing oil to rubber polymer without the operations such as solvent extraction that adopt deasphalted oil, thereby complete the present invention.
That is, the present invention is the manufacture method of rubber processing oil as described below.
Kinematic viscosity under (1) 100 ℃ is 10～60mm
2/ s, yield point are below 20 ℃, %C
abe 10～40 and polycyclc aromatic compound (PCA) containing the manufacture method of the rubber processing oil of quantity not sufficient 3 quality %, the method is characterized in that, with the ratio of mass ratio 90/10～10/90 by (A) deasphalted oil and (B) vacuum distillate mix;
Described (A) deasphalted oil following by being selected from (a) and formation more than a kind (b):
(a) aniline point be below 100 ℃, %C
abe 15～50 and polycyclc aromatic compound (PCA) containing the cycloalkyl deasphalted oil of quantity not sufficient 3 quality %, this cycloalkyl deasphalted oil is to utilize propane solvent to take the condition decompression residue that underpressure distillation obtains to naphthenic base crude that the deasphalted oil yield is 10～50 quality % to carry out the deasphalted oil that diasphaltene obtains;
(b) aniline point be below 100 ℃, %C
abe 15～50 and polycyclc aromatic compound (PCA) containing the cycloalkyl hydrogenation deasphalted oil of quantity not sufficient 3 quality %, this cycloalkyl hydrogenation deasphalted oil is to utilize propane solvent to take the condition decompression residue that underpressure distillation obtains to naphthenic base crude that the deasphalted oil yield is 10～50 quality % to carry out diasphaltene, then carry out the deasphalted oil that hydrofining obtains;
Forming more than a kind of described (B) vacuum distillate following by being selected from (c)～(g):
(c) polycyclc aromatic compound (PCA) is containing the cycloalkyl vacuum distillate of quantity not sufficient 3 quality %, and this cycloalkyl vacuum distillate is by naphthenic base crude is carried out to the vacuum distillate that underpressure distillation obtains;
(d) polycyclc aromatic compound (PCA) is containing the cycloalkyl hydrogenation vacuum distillate of quantity not sufficient 3 quality %, and this cycloalkyl hydrogenation vacuum distillate is that the cycloalkyl vacuum distillate obtained by the underpressure distillation to naphthenic base crude carries out the vacuum distillate that hydrotreatment obtains;
(e) polycyclc aromatic compound (PCA) is containing the cycloalkyl solvent treatment vacuum distillate of quantity not sufficient 3 quality %, and this cycloalkyl solvent treatment vacuum distillate is that the cycloalkyl vacuum distillate obtained by the underpressure distillation to naphthenic base crude carries out the vacuum distillate that solvent treatment obtains;
(f) polycyclc aromatic compound (PCA) is containing the cycloalkyl solvent treatment hydrogenation vacuum distillate of quantity not sufficient 3 quality %, and this cycloalkyl solvent treatment hydrogenation vacuum distillate is that the cycloalkyl vacuum distillate that obtains by the underpressure distillation to naphthenic base crude carries out solvent treatment, then further carries out the vacuum distillate that hydrotreatment obtains;
(g) polycyclc aromatic compound (PCA) is containing the refining vacuum distillate of the non-cycloalkyl of quantity not sufficient 3 quality %, and the refining vacuum distillate of this non-cycloalkyl is to carry out solvent treatment and/or hydrofining, carry out as required the vacuum distillate that dewaxing treatment obtains again by the vacuum distillate to polybase crude and/or paraffinic crude.
(2) manufacture method of the rubber processing oil of record in above-mentioned (1), wherein, with the ratio of mass ratio 80/20～20/80 by cycloalkyl deasphalted oil (a) be selected from mixing more than a kind of cycloalkyl hydrogenation vacuum distillate (d), cycloalkyl solvent treatment distilled oil (e) and cycloalkyl solvent treatment hydrogenation vacuum distillate (f), and the kinematic viscosity of rubber processing oil under 100 ℃ is 10～55mm
2/ s, aniline point are below 100 ℃.
(3) manufacture method of the rubber processing oil of record in above-mentioned (1) or (2), wherein, the mutagen sex index of rubber processing oil is less than 1, benzo [a] pyrene containing quantity not sufficient 1 quality ppm, and benzo [a] pyrene, benzo [e] pyrene, benzo [a] anthracene,
, benzo [b] fluoranthene, benzo [j] fluoranthene, benzo [k] fluoranthene and dibenzo [a, h] anthracene the summation of content be below 10 quality ppm.
Utilize the present invention, can play following special result: the operations such as solvent extraction of loaded down with trivial details deasphalted oil without the operation through loaded down with trivial details and offal treatment etc., can manufacture rubber processing oil by comparatively being easy to operation, prepared rubber processing oil safe, to the perviousness of rubber polymer also high, mixed rubber oil impregnate (bleed) etc. can not occur and viscosity low, can significantly improve operability in the time of therefore in mixing rubber.
Embodiment
(rubber processing oil)
The rubber processing oil of mineral oils usually be take the lubricating oil distillate that derives from crude oil and is the raw material modulation.Lubricating oil distillate can be used as to the normal pressure residue after the air distillation of crude oil carry out underpressure distillation and vacuum distillate or as to underpressure distillation and the decompression residue carry out the deasphalted oil that diasphaltene forms and obtain.Method as separate various constituents from lubricating oil distillate, have solvent extraction, if adopt, aromatic hydrocarbon compound had and selects the solvent of affinity to carry out solvent extraction, can be from lubricating oil distillate the separating aromatic hydrocarbon.But, aromatic hydrocarbon compound is had and selects the solvent of affinity higher to the affinity of polycyclc aromatic compound (PCA), if therefore by conventional extracting operation, extract aromatic hydrocarbon compound, can contain a large amount of PCA.If can from this extraction oil, remove PCA, can obtain good process oil, but this is usually very difficult and uneconomical.The inventor is few, safe to PCA, to the perviousness of rubber polymer, the manufacture method of high and low viscosity, rubber processing oil that operability is good is studied, found that, by adjusting underpressure distillation condition and diasphaltene condition and by these conditional combinations, without the solvent extractable matter (extract) that adopts deasphalted oil, even do not adopt the solvent treatment thing (debris) of vacuum distillate according to practical situation, can effectively manufacture rubber processing oil yet.
In the present invention, by the ratio with mass ratio 90/10～10/90, by following rubber processing oil constituent (A) with (B), mix, can obtain rubber processing oil.As composition (A), can exemplify and be selected from following (a) and the deasphalted oil more than a kind (b).
(a) aniline point be below 100 ℃, %C
abe 15～50 and polycyclc aromatic compound (PCA) containing the cycloalkyl deasphalted oil of quantity not sufficient 3 quality %, the normal pressure residue that this cycloalkyl deasphalted oil normally obtains by the air distillation to naphthenic base crude carries out underpressure distillation, utilize propane solvent to take condition that the deasphalted oil yield is 10～50 quality % carries out to the decompression residue of above-mentioned acquisition the deasphalted oil that diasphaltene obtains;
(b) aniline point be below 100 ℃, %C
abe 15～50 and polycyclc aromatic compound (PCA) containing the cycloalkyl hydrogenation deasphalted oil of quantity not sufficient 3 quality %, the normal pressure residue that this cycloalkyl hydrogenation deasphalted oil normally obtains by the air distillation to naphthenic base crude carries out underpressure distillation, utilize propane solvent to take condition that the deasphalted oil yield is 10～50 quality % carries out diasphaltene, then carries out the deasphalted oil that hydrofining obtains the decompression residue of above-mentioned acquisition;
As composition (B), can exemplify the vacuum distillate more than a kind that is selected from following (c)～(g).
(c) polycyclc aromatic compound (PCA) is containing the cycloalkyl vacuum distillate of quantity not sufficient 3 quality %, and this cycloalkyl vacuum distillate is by naphthenic base crude is carried out to the vacuum distillate that underpressure distillation obtains;
(d) polycyclc aromatic compound (PCA) is containing the cycloalkyl hydrogenation vacuum distillate of quantity not sufficient 3 quality %, and this cycloalkyl hydrogenation vacuum distillate is that the cycloalkyl vacuum distillate obtained by the underpressure distillation to naphthenic base crude carries out the vacuum distillate that hydrotreatment obtains;
(e) polycyclc aromatic compound (PCA) is containing the cycloalkyl solvent treatment vacuum distillate of quantity not sufficient 3 quality %, and this cycloalkyl solvent treatment vacuum distillate is that the cycloalkyl vacuum distillate obtained by the underpressure distillation to naphthenic base crude carries out the vacuum distillate that solvent treatment obtains;
(f) polycyclc aromatic compound (PCA) is containing the cycloalkyl solvent treatment hydrogenation vacuum distillate of quantity not sufficient 3 quality %, and this cycloalkyl solvent treatment hydrogenation vacuum distillate is that the cycloalkyl vacuum distillate that obtains by the underpressure distillation to naphthenic base crude carries out solvent treatment, then further carries out the vacuum distillate that hydrotreatment obtains;
(g) polycyclc aromatic compound (PCA) is containing the refining vacuum distillate of the non-cycloalkyl of quantity not sufficient 3 quality %, and the refining vacuum distillate of this non-cycloalkyl is to carry out solvent treatment and/or hydrofining, carry out as required the vacuum distillate that dewaxing treatment obtains again by the vacuum distillate to polybase crude and/or paraffinic crude.
Rubber processing oil constituent (A) and blending ratio (B) are in the scope of mass ratio 90/10～10/90.If 80/20～20/80, the easy rubber processing oil of modulation specifications, therefore particularly preferably.
In the present invention, the kinematic viscosity of rubber processing oil under 100 ℃ is 10～60mm
2/ s, preferably 10～55mm
2/ s, more preferably 20～40mm
2/ s.If the kinematic viscosity under 100 ℃ is less than 10mm
2/ s, evaporate quality change and increase, and the rubber after mediating is too soft, can't make the good rubber of balance of properties.On the other hand, if surpass 60mm
2/ s, the operability of process oil being mixed to rubber descends, and the reduced viscosity effect deficiency of mixed rubber item.
Yield point is below 20 ℃, preferably below 0 ℃.If yield point is high, when low temperature, be difficult to operation.
%C
abe 10～40, preferably 15～40, more preferably 15～30.%C
aless than 10 o'clock, the solvency power of rubber processing oil, with the intermiscibility of rubber, descend, the physical property of rubber item worsens.On the other hand, if %C
asurpass 40, obviously the physical property of rubber item can descend.
Cause deformity from the entanglement of the gene information of the cell of the animal that avoids making comprising the mankind and plant or bring out the angle of cancer, make polycyclc aromatic compound (PCA) containing quantity not sufficient 3 quality %.If reduce the content of polycyclc aromatic compound (PCA), the content of other aromatics also descends, and may cause detrimentally affect to solvability or the performance of rubber.PCA content is less than 2 quality % preferably, more preferably less than 1 quality %.
In addition, the angle of and environment healthy to protect mankind, be preferably the mutagen sex index less than 1, benzo [a] pyrene contain quantity not sufficient 1 quality ppm, and benzo [a] pyrene, benzo [e] pyrene, benzo [a] anthracene,
, benzo [b] fluoranthene, benzo [j] fluoranthene, benzo [k] fluoranthene and dibenzo [a, h] anthracene the summation of content be below 10 quality ppm.If the mutagen sex index is more than 1, or the content of benzo [a] pyrene is more than 1 quality ppm, or the summation of the content of described benzo [a] pyrene etc. surpasses 10 quality ppm, and carcinogenic danger is high, therefore not good.
The aniline point of rubber processing oil is preferably below 100 ℃.If aniline point surpasses 100 ℃, with the intermiscibility of rubber, descend, therefore not good, more preferably below 90 ℃.
The evaporation mass change of rubber processing oil is preferably below 0.5%.If the evaporation mass change surpasses 0.5%, the operability of process oil being mixed to rubber descends, and mixed rubber can descend because the oil content evaporation causes the physical property of rubber item when sulfuration.
(deasphalted oil)
What form that the cycloalkyl deasphalted oil (a) of composition (A) of one of composition base material of above-mentioned rubber processing oil and cycloalkyl hydrogenation deasphalted oil (b) used is that aniline point is, %C below 100 ℃
abe 15～50, polycyclc aromatic compound (PCA) is containing the deasphalted oil of quantity not sufficient 3 quality %.If it is not aniline point surpasses 100 ℃, to the perviousness of rubber, descend with the intermiscibility of rubber, therefore good.More preferably below 90 ℃, particularly preferably below 80 ℃.%C
aif less than 15, the obvious perviousness to rubber can descend, therefore not good.On the other hand, if surpass 50, the rubber after mediating is too soft, therefore not good.More preferably 15～40.From preventing the angle of carinogenicity, polycyclc aromatic compound (PCA) content is preferably lower concentration as much as possible.
In addition, as deasphalted oil (a) and (b), if adopt the kinematic viscosity had under 100 ℃, be 50～100mm
2the deasphalted oil of the proterties that the aromatic component that/s, yield point be below 10 ℃, obtain by Studies by Chromatography is 60～95 quality %, the easy rubber processing oil of the above-mentioned proterties of modulation, therefore better.
The deasphalted oil of composition (A) also can be used (a) and (b) both mixtures.Now, mixture must meet above-mentioned physical property.During mixing, if meet the physical property as mixture, (a) and (b) physical property separately can not meet to a certain extent above-mentioned physical property.
In propane deasphalting, if by the mixture of propane monomer or propane and the butane (mass ratio of propane/butane: 5/5～9/1) as propane solvent (also referred to as propane), it is contacted with the decompression residue, solvent components is extracted into propane solvent, and the pitch composition does not dissolve and be separated.If propane solvent is removed in evaporation from the propane solvent components, can obtain the To Propane Deasphalting Oil of having removed the pitch composition from the decompression residue.By the condition with deasphalted oil yield 10～50 quality %, the decompression residue from naphthenic base crude is carried out to propane deasphalting, can obtain the To Propane Deasphalting Oil with desired proterties.
Propane deasphalting usually in solvent ratio, be to carry out under the ratio of the solvent/stock oil condition that is 5～8, preferably 6～7.In addition, extracting operation carries out in extraction tower, and its temperature is generally 60～70 ℃ at tower top, can the formation temperature gradient in tower to improve selectivity.Extracting pressure remains on the level higher than the vapour pressure of solvent, when suppressing the solvent evaporation, is extracted.
In this operation, must set yield, the aniline point that makes deasphalted oil is below 100 ℃, %C
abe 15～50, polycyclc aromatic compound (PCA) is containing quantity not sufficient 3 quality %.Can regulate deasphalted oil yield and aforesaid operations condition, the deasphalted oil that there is desired proterties with acquisition.
(hydrogenation deasphalted oil)
In order further to obtain high-quality deasphalted oil, perhaps obtaining not meeting under the diasphaltene oil condition of above-mentioned proterties, can be to this deasphalted oil hydrogenation, thus the hydrogenation deasphalted oil that its quality is improved obtained, or obtain the hydrogenation deasphalted oil that meets above-mentioned proterties.
If will further carry out hydrofining and improve the mixture base material of the hydrogenation deasphalted oil of quality as rubber processing oil modulation use To Propane Deasphalting Oil, the snappiness of mixture further improves, therefore better.Particularly, when polycyclc aromatic compound (PCA) content of To Propane Deasphalting Oil surpasses 3 quality %, can this content be reduced to less than 3 quality % by hydrofining.
While carrying out the hydrofining processing, can adopt and the metals such as the nickel more than a kind, cobalt, molybdenum are carried on to the catalyzer that the carriers such as aluminum oxide or silica-alumina form, at hydrogen pressure 5～15MPa, 320～410 ℃ of temperature, liquid space velocity (LHSV) 0.5～5Hr
-1condition under processed.As the proterties of hydrogenation deasphalted oil, aniline point is preferably in the scope below 100 ℃ low as much as possible, %C
abe preferably in 15～50 scope large as much as possible.
As process oil or its base material, used in the past be all to the underpressure distillation residue from paraffinic crude or polybase crude carry out diasphaltene, use solvent that aromatic hydrocarbons is had to an affinity to carry out extraction treatment to the deasphalted oil cut of above-mentioned acquisition and extract (extract), if but use the above-mentioned deasphalted oil from naphthenic base crude or its hydrogenation deasphalted oil, can save extract, solvent extraction step deasphalted oil used in a large number for the manufacture of in the past in the manufacture of rubber processing oil, and can produce in a large number.
(vacuum distillate)
If to naphthenic base crude carry out underpressure distillation (normally to the naphthenic base crude air distillation and the normal pressure residue carry out underpressure distillation), can when obtaining above-mentioned decompression residue, obtain vacuum distillate.This cycloalkyl vacuum distillate can be mixed to modulate rubber processing oil of the present invention with above-mentioned cycloalkyl deasphalted oil, the deasphalted oil of cycloalkyl hydrogenation or their mixture.Now, the polycyclc aromatic compound of cycloalkyl vacuum distillate (PCA), containing quantity not sufficient 3 quality %, can be used as composition (c).
Usually, using such as being selected from the one kind or two or more of furfural, phenol, METHYLPYRROLIDONE etc. has the vacuum distillate that the solvent of affinity is 300～700 ℃ of left and right to normal pressure conversion boiling point to be extracted to aromatic hydrocarbons, polycyclc aromatic compound (PCA) content is adjusted to less than 3 quality %, by thus obtained debris for the manufacture of process oil.But, the vacuum distillate of polycyclc aromatic compound (PCA) containing quantity not sufficient 3 quality % arranged in deriving from the vacuum distillate of naphthenic base crude.Therefore in the present invention, at first can adopt the cycloalkyl vacuum distillate of this polycyclc aromatic compound (PCA) containing quantity not sufficient 3 quality %, it is mixed with above-mentioned deasphalted oil, thus the modulation rubber processing oil.So, can omit solvent extraction (or solvent treatment) operation of the vacuum distillate usually used in the manufacture of rubber processing oil.
For the cycloalkyl vacuum distillate, while wanting further to improve its quality, or the polycyclc aromatic compound of vacuum distillate (PCA) content is 3 quality % when above, can carry out hydrogenation or solvent extraction to improve quality, PCA content is adjusted to less than 3 quality %.If the PCA content of thus obtained vacuum distillate is less than 3 quality % also, can be used as cycloalkyl hydrogenation vacuum distillate (d) or cycloalkyl solvent treatment vacuum distillate (e).
In addition, also can use to the cycloalkyl vacuum distillate carry out that two kinds of solvent treatment and hydrogenation are processed and PCA containing the vacuum distillate of quantity not sufficient 3 quality %.Though the order of solvent treatment and hydrogenation be any processing formerly all can, can not carry out hydrotreatment to unwanted composition but carry out hydrogenation after solvent treatment, comparatively economical, therefore commonly used.The derivative of thus obtained vacuum distillate is cycloalkyl solvent treatment hydrogenation vacuum distillate (f).
In addition, can also be to polybase crude, paraffinic crude air distillation and the normal pressure residue carry out underpressure distillation, thus obtained vacuum distillate (non-cycloalkyl vacuum distillate) is mixed with above-mentioned cycloalkyl deasphalted oil, the deasphalted oil of cycloalkyl hydrogenation or their mixture, use as the base material for modulating rubber processing oil of the present invention.Therefore the polycyclc aromatic compound of non-cycloalkyl vacuum distillate (PCA) content must carry out solvent treatment and/or hydrofining lower than 3 quality %, carries out as required dewaxing treatment.Thus, can obtain polycyclc aromatic compound (PCA) containing the refining vacuum distillate (g) of the non-cycloalkyl of quantity not sufficient 3 quality %.The yield point of the refining vacuum distillate of non-cycloalkyl is preferably below 10 ℃.
Vacuum distillate (c)～(g) or derivatives thereof is mainly the oil in order to mix in the situation that do not damage the good proterties as rubber processing oil of above-mentioned To Propane Deasphalting Oil or its hydrogenation deasphalted oil to be adjusted viscosity, both can use separately, also can be by two or more mixes in the proper ratio, uses with the form of mixture arbitrarily.While using with the form of mixture of more than two kinds, the obvious less than 3 quality % of the PCA content of mixture.
As vacuum distillate (c)～(g) or derivatives thereof, if use the kinematic viscosity under 1 00 ℃ of physical property except PCA content, be 4～35mm
2/ s, %C
athe aromatic component that be 3～30, aniline point is below 120 ℃, by Studies by Chromatography, obtains is more than 10 quality %, yield point is the oil below 10 ℃, and the easy rubber processing oil of the above-mentioned proterties of modulation, therefore better.
In addition, when modulation has the vacuum distillate (c)～(g) of above-mentioned proterties and derivative thereof, by operation appropriate combination such as underpressure distillation, hydrotreatment, solvent treatment and dewaxings, with suitable order, processed.
More specifically, to crude oil atmospheric distillation and normal pressure residue while carrying out underpressure distillation, can suitably set the working conditions such as collecting temperature, collection capacity, quantity of reflux and temperature thereof that distillate cut, thereby obtain the vacuum distillate with above-mentioned proterties.Underpressure distillation is preferably that to take air distillation residue (also referred to as the normal pressure residue) be raw material, is scaled normal pressure at the terminal of distilled oil and carries out under the condition more than 500 ℃.
In the time of can't obtaining the vacuum distillate of above-mentioned proterties, or obtain more high-quality vacuum distillate for the snappiness that improves mixture, can carry out hydrofining processing or solvent treatment and process.
Cycloalkyl hydrogenation vacuum distillate (d) can obtain by operation as described below: at the nickel by more than a kind, cobalt, molybdenum isoreactivity metal, be carried under the existence of the catalyzer that the carriers such as aluminum oxide or silica-alumina form, at hydrogen pressure 5～15MPa, 300～400 ℃ of temperature, liquid space velocity (LHSV) 1～5Hr
-1condition under the cycloalkyl vacuum distillate is carried out to the hydrofining processing.
Cycloalkyl solvent treatment vacuum distillate (e) be use to aromatic hydrocarbons have the solvent of affinity to be extracted the cycloalkyl vacuum distillate and oil.As aromatic hydrocarbons being had to the solvent of selecting affinity, can exemplify furfural, phenol, METHYLPYRROLIDONE etc., choice for use one kind or two or more extraction the wherein removed aromatic component.Can adopt the purification condition of conventional lubricant base in this solvent treatment operation, for example, when using furfural as extraction solvent, can contact with solvent under the condition of 60～155 ℃ of temperature, solvent/oil ratio (volumetric ratio)=1/1～3/1 left and right.Thus, can obtain the cycloalkyl solvent treatment vacuum distillate (e) with desired proterties with the form of debris.
In addition, when the cycloalkyl vacuum distillate is carried out to solvent treatment and two kinds of processing of hydrofining, usually after solvent treatment, carry out the hydrofining processing.Solvent treatment and hydrofining can be carried out under condition same as described above.
If to the polybase crude underpressure distillation and the mixed base vacuum distillate or the paraffinic crude underpressure distillation and the paraffinic base vacuum distillate also carry out solvent treatment and/or hydrofining, carry out as required again dewaxing treatment, thereby polycyclc aromatic compound (PCA) content is adjusted to less than 3 quality %, can similarly it be mixed with above-mentioned deasphalted oil and/or hydrogenation deasphalted oil with cycloalkyl vacuum distillate etc., be modulated into rubber processing oil of the present invention.Refining and non-cycloalkyl vacuum distillate that obtain is generically and collectively referred to as non-cycloalkyl and makes with extra care vacuum distillate (g) thus.With the cycloalkyl vacuum distillate similarly, if the refining kinematic viscosity of vacuum distillate (g) under 100 ℃ of non-cycloalkyl is 4～35mm
2/ s, %C
athe aromatic component that be 3～30, aniline point is below 120 ℃, by Studies by Chromatography, obtains is more than 10 quality %, yield point is below 10 ℃, and the easy rubber processing oil of the above-mentioned proterties of modulation, therefore better.
Solvent treatment and/or hydrofining, again carry out dewaxing treatment as required and polycyclc aromatic compound (PCA) can obtain the multiple vacuum distillate of different physical property containing the refining vacuum distillate (g) of the non-cycloalkyl of quantity not sufficient 3 quality %, they can distinguish use separately, but also two or more mixes use.In addition, as mentioned above, non-cycloalkyl is made with extra care vacuum distillate (g) also can mix use in the proper ratio with above-mentioned cycloalkyl vacuum distillate (c)～(f) etc.
For mixed base vacuum distillate and paraffinic base vacuum distillate, the normal pressure residue is carried out to underpressure distillation, obtain vacuum distillate that normal pressure conversion boiling point is 300～700 ℃ after, used the solvent treatment that has the solvent of affinity to extract to aromatic hydrocarbons to process.As aromatic hydrocarbons being had to the solvent of selecting affinity, can exemplify furfural, phenol, METHYLPYRROLIDONE etc., choice for use one kind or two or more extraction the wherein removed aromatic component.Can adopt the purification condition of conventional lubricant base in this solvent treatment operation, for example, when using furfural as extraction solvent, can contact with solvent under the condition of 60～155 ℃ of temperature, solvent/oil ratio (volumetric ratio)=1/1～3/1 left and right.The debris that thus obtained polycyclc aromatic compound (PCA) content is reduced to less than 3 quality % can be used as the refining vacuum distillate (g) of non-cycloalkyl.
In addition, for above-mentioned vacuum distillate, after being carried out to the solvent treatment processing, it can further carry out the hydrofining processing, now, this hydrofining is processed and can be carried under the existence of the catalyzer that the carriers such as aluminum oxide or silica-alumina form, at hydrogen pressure 5～15MPa, 300～400 ℃ of temperature, liquid space velocity (LHSV) 1～5Hr at the nickel by more than a kind, cobalt, molybdenum isoreactivity metal
-1condition under carry out.
For additional better proterties, after having carried out solvent treatment and/or hydrofining, can also carry out the dewaxing treatment such as solvent dewaxing or Hydrodewaxing.Solvent dewaxing for example can be in methyl ethyl ketone/toluene Mixed Solvent be carried out under the condition of solvent/oil ratio (volumetric ratio)=1/1～5/1, temperature-10～-40 ℃, and Hydrodewaxing can be at hydrogen pressure 5～15MPa, 300～400 ℃ of temperature, LHSV 1～5Hr under the existence of zeolite catalyst
-1condition under carry out.
By the deasphalted oil (a) of (A) by above acquisition and (b) with the vacuum distillate (c)～(g) of (B) with mass ratio 90/10～10/90, particularly preferably 80/20～20/80 ratio is mixed, and can manufacture the rubber processing oil with desired proterties.In addition, the preferred manufacture method with the rubber processing oil mixed with aforementioned proportion more than a kind of the vacuum distillate (d)～(f) of (B) by the deasphalted oil (a) of (A).So, because do not use cycloalkyl hydrogenation deasphalted oil (b), so, without the program of carrying out hydrogenation, very economical, also can have the rubber processing oil of polycyclc aromatic compound (PCA) containing fine qualities such as quantity not sufficient 2 quality % with comparatively cheap price modulation in addition.The manufacture method of preferred rubber processing oil is the method that cycloalkyl deasphalted oil (a) is mixed with aforementioned proportion with cycloalkyl hydrogenation vacuum distillate (d) and/or cycloalkyl solvent treatment vacuum distillate (e).
[embodiment]
Below based on embodiment and comparative example, the present invention will be described in more detail, but the present invention is not subject to the restriction of embodiment.
The confession formation testing (rubber processing oil) of modulation embodiment and comparative example, measure its physical property, estimates its performance.
When modulation supplies formation testing, the air distillation residue of ten thousand degree (Wandoo) crude oil that at first Australia as naphthenic base crude produced and Arabic lightweight (Arabian light) crude oil that produces as Saudi Arabia of paraffinic crude carries out underpressure distillation, underpressure distillation cut and decompression residue to gained further carry out diasphaltene, hydrofining or solvent treatment, as described below being modulated into for studying the base material for formation testing (rubber processing oil) of embodiment and comparative example.
Using underpressure distillation and the normal pressure conversion boiling point cut that is 360～590 ℃ as the collection of underpressure distillation distilled oil,, using cycloalkyl vacuum distillate (N-VD) as the vacuum distillate collection from ten thousand degree crude oil, using paraffinic base vacuum distillate (P-VD) as the vacuum distillate collection from Arabian light.
Cycloalkyl and paraffinic base decompression residue are carried out to propane deasphalting with the solvent of propane content 100% with the condition of solvent ratio 6.0 respectively.For ten thousand degree crude oil residue (cycloalkyl decompression residue), the yield of deasphalted oil is set as to 25%, for Arabian light residue (paraffinic base decompression residue), the yield of deasphalted oil is set as to 30%, correspondingly the tower top temperature of extraction tower is adjusted into to 60～70 ℃ and turns round.From ten thousand degree crude oil, cycloalkyl deasphalted oil (N-BS) is reclaimed in extraction, and from Arabian light, paraffinic base deasphalted oil (P-BS) is reclaimed in extraction.The deasphalted oil of like this decompression residue being carried out to propane deasphalting and obtaining is called as so-called bright stock, is used as manufacturing the raw material of lubricating oil base.
With the aluminium oxide catalyst that carries cobalt/molybdenum at hydrogen pressure 10MPa, 350 ℃ of temperature, liquid space velocity 1.0Hr
-1condition under described cycloalkyl vacuum distillate (N-VD) and cycloalkyl deasphalted oil (N-BS) are carried out respectively to hydrofining, obtain the hydrotreatment oil of cycloalkyl hydrogenation vacuum distillate (N-VD-H) as N-VD, obtain the hydrotreatment oil of cycloalkyl hydrogenation deasphalted oil (N-BS-H) as N-BS.
Then, with furfural, described cycloalkyl vacuum distillate (N-VD) is carried out to solvent treatment.Solvent ratio is made as to 1.0, and the adjustment extraction temperature makes to reach 80% as the yield of the debris of treated oil, obtains the solvent-refined oil of cycloalkyl solvent treatment vacuum distillate (N-VD-F) as the cycloalkyl vacuum distillate (N-VD) of ten thousand degree crude oil.
In addition, under condition same as described above, this N-VD-F is further carried out to hydrofining, obtain cycloalkyl solvent treatment hydrogenation vacuum distillate (N-VD-FH).
Then, after the paraffinic base vacuum distillate (P-VD) from paraffinic crude is carried out to solvent treatment and hydrofining, further carry out solvent dewaxing.Will be as the 500neutral lubricant base of the commercial articles of Japan Energy (Japan Energy) Co., Ltd. as the refining vacuum distillate (P-VD-FHW) of paraffinic base.
The proterties for formation testing (rubber processing oil) modulation base oil N-BS, N-BS-H, P-BS, N-VD, N-VD-H, N-VD-F, N-VD-FH, P-VD and P-VD-FHW oil separately of modulation is shown in table 1 as mentioned above.The yield point of P-BS and P-VD is quite high, under room temperature, is solid state.In addition, the aniline point of P-BS, P-VD, P-VD-FHW is high.The PCA content of N-BS, N-VD is slightly less than 3.0%, and the PCA content of P-VD is more than 3.0%.
In addition, the first letter of the letter abbreviations of each base oil is the crude oil kind, and N representative ring alkyl, P mean paraffinic base, and 2 letters afterwards are that the deasphalted oil of decompression residue is denoted as to BS, and vacuum distillate is denoted as to VD.Then, for the oil that has further carried out hydrofining, solvent extraction and dewaxing treatment, according to the order of processing, add respectively H, F and W.
[table 1]
Mix according to the ratio (quality %) shown in the top of table 2 with the base oil of table 1, be modulated into the confession formation testing (rubber processing oil) of embodiment 1～9 and comparative example 1～4.For formation testing, measure physical property, and study rubber simultaneously, the JIS K6383 " test method of synthetic rubber SBR " etc. of take is its performance of benchmark evaluation for each.Physical property measurement result and evaluation result are shown in table 2.
[table 2]
In addition, in the present invention, the test of physical property measurement and performance evaluation is carried out by the following method.
kinematic viscosity
Method by JIS K2283-1993 defined is measured.
yield point
Method by JIS K2269-1987 defined is measured.
％C
A
The method of %CA by ASTM D2140-97 defined, be that so-called n-d-M ring analysis is calculated.
aniline point
Method by JIS K2256-1998 defined is measured.
the aromatic component obtained by Studies by Chromatography
Method by ASTM D2007-98 defined is measured.
polycyclc aromatic compound (PCA) concentration
Polycyclc aromatic compound (PCA) concentration is passed through the IP346 of BP association (version in 1992) test method determination as the DMSO extraction component.
the evaporation mass change
Calculate by the method that is defined as benchmark with JIS K2207 " 6.9 evaporation test method ", that is, keep, after 3 hours, measuring the quality change amount of sample in the Tempeerature-constant air groove of 163 ℃, calculate its percentage with respect to the quality of the front sample of heating.
mutagen sex index (MI)
Method by ASTM E1687-98 defined is measured.
the content of benzo [a] pyrene and benzo [a] pyrene, benzo [e] pyrene, benzo [a] anthracene,
, benzo
the summation of the content of [b] fluoranthene, benzo [j] fluoranthene, benzo [k] fluoranthene and dibenzo [a, h] anthracene (below
total content referred to as benzo [a] pyrene etc.)
By separate-GCMS of alumina column (SIM) method, measure.Use the 500mg Solid-Phase Extraction to use post as alumina column, by the heptane wash-out, remove saturated composition, then by toluene wash-out separating aromatic composition, analyze for GCMS.
The performance evaluation of process oil is as described below carries out: the conventional SBR formula (JIS K6383 " test method of synthetic rubber SBR ") of take is benchmark, at first the Synergist S-421 95 shown in table 3 is mixed, mediates by mixing ratio, make on approbation rubber, tested to estimate the performance of rubber.In addition, use the JSR1500 of Japan Synthetic Rubber Co. Ltd as SBR, use the Synergist S-421 95 of commercial goods as other.Sulfuration adopts vulcanizing press to carry out under the condition of 160 ℃, 20 minutes.
[table 3]
| Synergist S-421 95 | Mixing ratio (mass parts) |
| SBR | 100 |
| Process oil | 40 |
| Carbon black | 50 |
| Zinc oxide | 3 |
| Stearic acid | 2 |
| Vulcanization accelerator | 1 |
| Sulphur | 2 |
Below, carry out by the following method the performance evaluation of gained vulcanized rubber article.
hardness
Method by JIS K6301 " vulcanized rubber physical test method " defined is measured.
tensile strength, 300% tensile stress, elongation
Method by JIS K6251 " stretching test method of vulcanized rubber " defined is measured.
tearing strength
Method by JIS K6252 " the tear test method of vulcanized rubber " defined is measured.
have or not oil impregnate
Observe the outward appearance of at room temperature placing after 3 days by visual inspection, observe and have or not oil impregnate.
As shown in Table 2, embodiment 1～9 all meets the characteristic as rubber processing oil.On the other hand, comparative example 1 and 2 yield point are too high, can not say oil.In addition, in performance evaluation, comparative example 1 and 2 rubber are observed oil impregnate, so performance is also poor, can't use.The yield point of comparative example 3 is in inadequate available level, but PCA content has surpassed 3.0%, observes oil impregnate in performance evaluation, therefore not good.The yield point of comparative example 4 is high, also observes oil impregnate in performance evaluation, is difficult to use in practicality.
Example of the present invention is good as the balance of properties of rubber processing oil, and PCA content is below 3.0%, to environment also safety, can be used for the stretching, extension of rubber etc.
Claims (3)
1. the manufacture method of a rubber processing oil, the kinematic viscosity of this rubber processing oil under 100 ℃ is 10～60mm
2/ s, yield point are below 20 ℃, %C
abe 10～40 and polycyclc aromatic compound (PCA) containing quantity not sufficient 3 quality %, it is characterized in that, will (A) deasphalted oil and (B) vacuum distillate mixing with the ratio of mass ratio 90/10～10/90;
Described (A) deasphalted oil following by being selected from (a) and forming more than a kind and carrying out solvent extraction without the solvent that aromatic hydrocarbons is had to affinity (b):
(a) aniline point be below 100 ℃, %C
abe 15～50 and polycyclc aromatic compound (PCA) containing the cycloalkyl deasphalted oil of quantity not sufficient 3 quality %, this cycloalkyl deasphalted oil is to utilize propane solvent to take the condition decompression residue that underpressure distillation obtains to naphthenic base crude that the deasphalted oil yield is 10～50 quality % to carry out the deasphalted oil that diasphaltene obtains;
(b) aniline point be below 100 ℃, %C
abe 15～50 and polycyclc aromatic compound (PCA) containing the cycloalkyl hydrogenation deasphalted oil of quantity not sufficient 3 quality %, this cycloalkyl hydrogenation deasphalted oil is to utilize propane solvent to take the condition decompression residue that underpressure distillation obtains to naphthenic base crude that the deasphalted oil yield is 10～50 quality % to carry out diasphaltene, then carry out the deasphalted oil that hydrofining obtains;
Forming more than a kind of described (B) vacuum distillate following by being selected from (c)～(g):
(c) polycyclc aromatic compound (PCA) is containing the cycloalkyl vacuum distillate of quantity not sufficient 3 quality %, and this cycloalkyl vacuum distillate is by naphthenic base crude is carried out to the vacuum distillate that underpressure distillation obtains;
(d) polycyclc aromatic compound (PCA) is containing the cycloalkyl hydrogenation vacuum distillate of quantity not sufficient 3 quality %, and this cycloalkyl hydrogenation vacuum distillate is that the cycloalkyl vacuum distillate obtained by the underpressure distillation to naphthenic base crude carries out the vacuum distillate that hydrotreatment obtains;
(e) polycyclc aromatic compound (PCA) is containing the cycloalkyl solvent treatment vacuum distillate of quantity not sufficient 3 quality %, and this cycloalkyl solvent treatment vacuum distillate is that the cycloalkyl vacuum distillate obtained by the underpressure distillation to naphthenic base crude carries out the vacuum distillate that solvent treatment obtains;
(f) polycyclc aromatic compound (PCA) is containing the cycloalkyl solvent treatment hydrogenation vacuum distillate of quantity not sufficient 3 quality %, and this cycloalkyl solvent treatment hydrogenation vacuum distillate is that the cycloalkyl vacuum distillate that obtains by the underpressure distillation to naphthenic base crude carries out solvent treatment, then further carries out the vacuum distillate that hydrotreatment obtains;
(g) polycyclc aromatic compound (PCA) is containing the refining vacuum distillate of the non-cycloalkyl of quantity not sufficient 3 quality %, and the refining vacuum distillate of this non-cycloalkyl is to carry out solvent treatment and/or hydrofining, carry out as required the vacuum distillate that dewaxing treatment obtains again by the vacuum distillate to polybase crude and/or paraffinic crude.
2. the manufacture method of rubber processing oil as claimed in claim 1, it is characterized in that, with the ratio of mass ratio 80/20～20/80 by cycloalkyl deasphalted oil (a) be selected from mixing more than a kind of cycloalkyl hydrogenation vacuum distillate (d), cycloalkyl solvent treatment distilled oil (e), cycloalkyl solvent treatment hydrogenation vacuum distillate (f), and the kinematic viscosity of rubber processing oil under 100 ℃ is 10～55mm
2/ s, aniline point are below 100 ℃.
3. the manufacture method of rubber processing oil as claimed in claim 1 or 2, is characterized in that, the mutagen sex index of rubber processing oil is less than 1, benzo [a] pyrene containing quantity not sufficient 1 quality ppm, and benzo [a] pyrene, benzo [e] pyrene, benzo [a] anthracene,
, benzo [b] fluoranthene, benzo [j] fluoranthene, benzo [k] fluoranthene and dibenzo [a, h] anthracene the summation of content be below 10 quality ppm.
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| JP2013216805A (en) * | 2012-04-10 | 2013-10-24 | Showa Denko Kk | Rubber compounding oil and method for producing the same |
| JP5882828B2 (en) | 2012-05-07 | 2016-03-09 | 東レ・ダウコーニング株式会社 | Rubber additive and rubber composition comprising the same |
| JP2013241518A (en) * | 2012-05-21 | 2013-12-05 | Showa Denko Kk | Rubber compounding oil and method for manufacturing the same |
| CN105907421B (en) * | 2016-06-21 | 2017-08-29 | 中国海洋石油总公司 | A kind of preparation method of low-viscosity environment-friendly rubber oil |
| CN115651697A (en) * | 2022-11-15 | 2023-01-31 | 中国海洋石油集团有限公司 | C A Aromatic rubber plasticizer with value not less than 20% and preparation method thereof |
| CN115678594A (en) * | 2022-11-15 | 2023-02-03 | 中国海洋石油集团有限公司 | High viscosity and high C A Aromatic-based rubber plasticizer and preparation method thereof |
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| CN115651698A (en) * | 2022-11-15 | 2023-01-31 | 中国海洋石油集团有限公司 | High-aromatic-hydrocarbon aromatic-base rubber plasticizer and preparation method thereof |
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