CN101235330A - Synthetic base oil and preparation process thereof - Google Patents
Synthetic base oil and preparation process thereof Download PDFInfo
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- CN101235330A CN101235330A CNA2007103060979A CN200710306097A CN101235330A CN 101235330 A CN101235330 A CN 101235330A CN A2007103060979 A CNA2007103060979 A CN A2007103060979A CN 200710306097 A CN200710306097 A CN 200710306097A CN 101235330 A CN101235330 A CN 101235330A
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Abstract
The invention relates to a double dodecyl aromatic compound which contains slight branch in the components in synthetic base oil, and carbon number range of alkyl side chain of double dodecyl aromatic compound is from C10 to C28, from C11 to C24 is better and from C12 to C18 is the best, wherein the branch character of the double dodecyl side chain is assured by that total methyl number (TMN) which is assured by C13 nuclear magntic resonance or branch indexes (BI) which respectively are TMN=2.1-3.5 or BI=0.1-1.5, and the synthetic base oil has the advantages of high viscosity index, low volatility, excellent low-temperature character and excellent thermal stability and oxidation stability, which is particularly suitable for being oxidation stability synthetic base oil, second base oil, lubricant additive, and additive set group.
Description
Technical field
The present invention relates to contain in a kind of the composition synthetic base oil of the two alkyl aromatic compounds of slight branch, be particularly related to a kind of high viscosity index (HVI) that has concurrently, low volatility, excellent cold property, superior heat-stability and oxidative stability, and the solvent synthetic base oil of preferable additive.
Background technology
So-called synthetic base oil, poly-alpha olefins (poly α-olefin for example, be called for short PAO) lubricating base oils, be meant with chemical synthesis process prepared come out have the lubricating oil of setting the molecular structure body and having setting property, it has indispensable character such as high viscosity index (HVI), low volatility, excellent cold property, thermostability and oxidative stability usually.
In patent documentation, the several pieces of patents of invention relevant with synthetic base oil are arranged.For example, United States Patent (USP) 6,869,917 disclose a kind of PAO ucon oil, it has excellent cold property, and viscosity index be higher than 120 and Selby-NOACK (be called for short NOACK) volatility about 4% to 12% characteristic, be applicable to lubricating oil as the heavy gas oil engine.
United States Patent (USP) 5,600,025 discloses a kind of synthetic base oil that contains straight chain formula alkylphenol, and it has the characteristic that when low temperature lubricating oil and additive are non-crystallizable or do not have wax to exist.
United States Patent (USP) 3,173,965 disclose a kind of two alkylbenzene (dialkylbenzene that contain, the preparation method of synthetic base oil abbreviation DAB), by two step alkylation processs, and in the presence of liquid acid catalysts such as hydrofluoric acid, aluminum chloride, boron trifluoride, make described DAB synthetic base oil.The MV minium viscosity index of this DAB synthetic base oil is 95, and yield point is no more than 15 (9.4 ℃); But compare with the PAO ucon oil, synthetic the lubricating of PAO still has more excellent cold property, and the MV minium viscosity index is 120.
United States Patent (USP) 4,148,834 further point out to use aluminum chloride, alchlor to improve with the viscosity index of hydrofluoric acid as the prepared DAB synthetic base oil of catalyzer in two above-mentioned step alkylation processs.
United States Patent (USP) 3,288,716 disclose a kind of alkanisation product, have at least 90 minimal viscosity index, rotate simulation viscosity (CCS) at-40 ℃ of down cold axles and are no more than 25, and 000cSt, yield point are at least-70 ℃ and the characteristic of flashing point at least 430 .
United States Patent (USP) 4,011,166 disclose carry out polymerization and alkylation reaction by short chain straight chain formula alpha-olefin and benzene after, make and have the more alkanisation product of high viscosity index (HVI).But the cold property of this alkanisation product is not good, and especially carbon number is at C
14Or when above, improving yield point has its difficulty.
United States Patent (USP) 6,491,809 disclose the preparation method of another kind of DAB synthetic base oil, optionally in the presence of the solid catalyst, make described DAB synthetic base oil by linear alpha-olefin and benzene reaction at the type body; And, realize the isomerization of alkyl group side chain is minimized by use type body catalysts selective, make prepared DAB synthetic base oil have the carbon of high-load especially alkyl bond-2 position linearity (2-linear) isomer, and the characteristic that possesses high viscosity index (HVI) and higher yield point.
In addition, the viscosity index of synthetic base oil is higher than 120, is one of key property of synthetic base oil, and this characteristic has become the important indicator that high standard GIII in synthetic base oil and the mineral base oil or low specification GII and GI separate.
As previously mentioned, the PAO ucon oil has and is higher than 120 viscosity index and excellent cold property, and the highest GIII mineral base oil of tool, except that cold property a little the inferior position, also has the advantage of high viscosity index (HVI), is enough to contend with the PAO ucon oil.
But, even PAO ucon oil and GIII mineral base oil have above-mentioned excellent specific property, for additive the not good shortcoming of solvability is arranged still but, usually need contain ester class second base oil or other by use contains oxygen base oil (for example, oil soluble polyene glycol (PAG) or polarity base oil) and promotes the solvency power for additive.
But, use to contain the shortcoming of ester class second base oil, have the good additive solvency power though be the ester class, facile hydrolysis and Yi Yure or oxygenolysis generate acidity or sedimentable matter.Similarly, use the shortcoming of oil soluble PAG or polarity base oil,, water absorbability is arranged and compatible problem is arranged with system component and other lubricant though be to provide some performance advantage.
Therefore, synthetic base oil is higher than 120 the viscosity index and excellent cold property except that having concurrently, also has excellent additive solvency power concurrently, is the important breakthrough of synthetic base oil industry, and is very attractive.
In related prior art, a kind of " heavy alkide " by product can independent separate in the known process of being produced the sanitising agent alkylbenzene by alkene or alkane and benzene reaction comes out.This " heavy alkide " compares with petroleum derivation mineral oil, have preferable solvability, excellent cold property, superior heat-stability and oxidative stability, but, because be from sanitising agent alkylbenzene alkanisation and obtain to contain the product of isomerization structure at high proportion again, not to obtain through alkylation process, so show relatively poor viscosity index and high volatile volatile characteristic usually by two alkylbenzenes.
For example, by chain type alkene (as a tetrapropylene) institute deutero-heavy alkide, its viscosity index is not good, usually less than 30; By straight chain formula alkene institute deutero-heavy alkide, its viscosity index is also not good, and is between 40 to 110, all of inferior quality than traditional mineral oil product.Because this " heavy alkide " has these defectives,, be not suitable for being used as the substituent of cycloalkanes lubricating oil so it only is applied to do not have refrigeration oil, hot coal oil and transformer oil in the sealing barrier systems of high request for volatility and viscosity index.
Summary of the invention
For improving and break through the characteristic of existing synthetic base oil, the invention discloses a kind of synthetic base oil (being designated hereinafter simply as the synthetic base oil that contains the slight DAB of branch) that contains the two alkyl aromatic compounds of slight branch, excellent properties with known " heavy alkide ", and except that having preferable additive solvency power, excellent cold property, outside superior heat-stability and the oxidative stability, also have the characteristic of high viscosity index (HVI) and low volatility concurrently, and range of application is quite extensive, is fit to be applied to as senior synthetic base oil, second base oil, lubricant, additive and additive cover group
Another object of the present invention is to provide a kind of synthetic base oil that contains the slight DAB of branch, in the presence of solid acid catalyst, by making a kind of slight branch double alkylation thing after aromatics (for example using benzene) and alkene (the being designated hereinafter simply as slight branch alkene) reaction through the slight branch degree of control, wherein, the alkyl group side chain carbon number range of contained two alkyl aromatic compounds is C
10To C
28, but with C
11To C
24Preferable, C
12To C
18Better, and branch's characteristic of the alkyl group side chain of this synthetic base oil that contains the slight DAB of branch, be with C
13NMR (Nuclear Magnetic Resonance) spectrum by following formula (I) and (II) defined total methyl number (TMN) or branch's index (BI) determine, when the TMN number greater than 2, promptly represent alkyl group side chain that the ramose result is arranged; So, branch's characteristic of the alkyl group side chain of the synthetic base oil that contains the slight DAB of branch of the present invention is that the TMN value is greater than 2.1 and less than 3.5, but with 2.15 to 3.25 preferable, 2.2 to 3.0 better, and the BI value is greater than 0.1 and less than 1.5, but with 0.15 to 1.25 preferable, 0.2 to 1.0 better.
BI=TMN-2 (two terminal methyl) formula (II).
The synthetic base oil that contains the slight DAB of branch of the present invention, have high viscosity index (HVI), low volatility, excellent cold property, excellent thermostability and oxidative stability and have excellent additive solvency power, the minimal viscosity index is 120, upper pour point is-40 ℃, and the NOACK volatility is no more than 13%; Below-40 ℃, cold axle rotates simulation viscosity (cold crankingsimulated is abbreviated as CCS) and is not higher than 20,000cp.
The synthetic base oil that contains the slight DAB of branch of the present invention, for containing two alkyl, trialkyls or containing many alkyl alkide of more alkyl alkane, wherein greater than 85wt%, the content of monoalkyl alkide is less than 0.5wt% based on the synthetic base oil gross weight to the content of DAB based on the synthetic base oil gross weight.
The synthetic base oil that contains the slight DAB of branch of the present invention through hydrogen treatment, clay adsorption treatment or reprocessing, can improve color and apparent, and can be used for preparing lubricating oil, and its consumption is the 1wt% to 100wt% based on the lubricating oil gross weight; The lubricating oil of being prepared has excellent additive solvency power, thus can add some additive and some other base oil, so that desired various function on the specific lubricant applications to be provided.
The synthetic base oil that contains the slight DAB of branch of the present invention, when being applied to lubricating oil as base oil or additive component, its concentration range is 1% to 99%.
Slight branch used in the present invention alkene is to make through isomerization/alkylation with custom catalysts, and the position of double bond of slight branch alkene for being positioned at terminal, inside or vinylidene form, or contains above-mentioned wherein a kind of functional group's form at least for mixed state.
The prepared slight branch of the present invention alkene can be selected from C
10, C
11, C
12, C
13, C
14Or C
15Wherein a kind of or wherein two kinds or above different carbon numbers mix.
The prepared slight branch of the present invention alkene can obtain to invest the alkene of desired branch characteristic or obtain or obtain or obtain to invest by alkanisation and isomerization process through dehydrogenation again with the isoalkane that known technology production commonly used invests desired branch characteristic the alkene of desired branch characteristic by Structural Isomerismization after the alkanes dehydrogenation reaction by isomerized linear formula alpha-olefin.
The prepared slight branch of the present invention alkene, oligomerization cooperation that can be by alkene is with the alkene that obtain to invest desired branch characteristic, and oligomerization cooperation that for example can be by hexene, octene is with obtaining; Also can obtain to invest the alkene of desired branch characteristic by other chemical action, for example obtain by known technology Fischer Tropsch reaction; Or obtain to invest the alkene of desired branch characteristic by the olefin of different branches characteristic, for example, obtain to invest the alkene of desired branch characteristic with a chain type alkene in conjunction with selected straight chain formula alpha-olefin.
Description of drawings
The schema that Figure 1A is directly generated by isomerisation of olefin for the slight branch of explanation alkene.
Figure 1B is the then schema that generates of isomerization behind the alkene for explanation slight branch alkene by dehydrating alkanes.
The schema that Fig. 1 C is generated by the isoalkane dehydrogenation with required branch characteristic for the slight branch of explanation alkene.
Fig. 1 D for explanation slight branch alkene by the original place isomerisation of olefin after and carry out the schema of alkylation reaction with benzene.
Fig. 2 is the explanatory view of relation between explanation total methyl number (TMN) and the branch's index (BI).
Fig. 3 depicts the relation of TMN value to the viscosity index of the embodiment of the invention, and its maximum TMN value is outer to be inserted to 3.5 to reach minimal viscosity index 120.
Embodiment
Synthetic base oil disclosed in this invention is a kind of synthetic base oil that contains the two alkyl aromatic compounds of slight branch, and this paper is called the synthetic base oil that contains the slight DAB of branch.Wherein, the method for making of two alkyl aromatic compounds, being to use aromatics and slight ramose alkene is raw material, and according to the wherein a kind of alkylation process shown in Figure 1A, Figure 1B, Fig. 1 C or Fig. 1 D, in the presence of solid acid catalyst, after making aromatics and slight ramose olefine reaction, and make slight branch double alkylation produce product.
In of the present invention pair of alkyl aromatic compound method for making, employed aromatics, has the aromatic ring part, usually preferred phenyl ring, also can be selected from benzene, toluene, ethylbenzene, p-Xylol, two phenoxide, diphenyl, anisole, naphthalene and methylnaphthalene wherein a kind of aromatics or any can with the said derivative of slight branch olefin alkylation.But, because the alkylation degree finally can influence the performance that contains the synthetic base oil of the slight DAB of branch of the present invention, so except benzene, other aromatic selecting for use must be careful to avoid restriction or to change alkylating degree.
Employed slight branch alkene is to make through isomerization/alkylation with custom catalysts, and the position of double bond of slight branch alkene for being positioned at terminal, inside or vinylidene form, or being a mixed state and containing above-mentioned wherein a kind of functional group's form at least.
In known technology, carbon family is with methyl, methylene radical, methyne, connects these four kinds of structure formations of four carbon atom family (quaternary) and be present in any hydrocarbon polymer.Wherein, the characteristic description of methyl groups, appointment and quantity are determined, can use United States Patent (USP) the 5th, 922, No. 922 disclosed infrared spectrum analysis methods or use NMR (Nuclear Magnetic Resonance) spectrum (H
1And C
13) or other known technology finish and analyze and measure.
The present invention is to use C
13Magnetic nuclear resonance method and utilize the DEPT technology to assert and specify the C of methyl groups
13After the chemical shift, in experimental error 5%,, contrast total aliphatic carbon zone remaining in the spectrum again with its displacement area integral.Wherein, when the structure of setting alkyl group side chain is complete straight chain,, equal 2 (being TMN=2) so define total methyl number (TMN) because only see two terminal methyl carbon.On the contrary, any TMN value represents promptly that greater than 2 alkyl group side chain has the ramose result.Therefore,, the value of branch's index (BI) can be obtained, the branch degree of DAB among the present invention can be directly reflected by deducting 2 among the TMN.
So, use above-mentioned C
13During nuclear magnetic resonance spectroscopy, be by following formula (I) and (II) total methyl number (TMN) or branch's index (BI) branch's characteristic of determining alkyl group side chain of definition, when the TMN number greater than 2, promptly represent alkyl group side chain that the ramose result is arranged.
BI=TMN-2 (two terminal methyl) formula (II).
In synthetic lubricating base oil field, the branch of known applications alkyl group side chain, whether can weigh intermolecular is linear structure, the branch of also known alkyl group side chain structure, can reduce or reduce intermolecular viscosity index significantly, and also can have a negative impact other physical propertiess such as NOACK volatility.
In addition, slight branch alkene can be straight-chain molecule or is the single substituting group of branching molecule, disubstituted or three substituting group mixtures, and the various branches characteristic of slight branch alkene is according to above-mentioned C
13The defined total methyl number of NMR (Nuclear Magnetic Resonance) spectrum method (TMN) or branch's index (BI) are definite, as shown in Figure 2.
Therefore, the present invention is by branch's characteristic of the slight branch of control alkene, can make the prepared synthetic base oil that contains the slight DAB of branch possess the excellent properties of all requirements, comprise have high viscosity index (HVI), low NOACK volatility, excellent cold property, excellent thermostability and oxidative stability and have excellent additive solvency power, the minimal viscosity index is 120, upper pour point is-40 ℃, the NOACK volatility is no more than 13%, below-40 ℃, cold axle rotates simulation viscosity (CCS) and is not higher than 20,000cp.
Be not less than 120 for reaching viscosity index, the slight branch alkene in the DAB base oil of the present invention, as shown in Figure 3, its TMN value should be between 2.1 to 3.5, and wherein, the TMN value is between 2.15 to 3.25 preferable, and is better between 2.2 to 3.0; And corresponding BI value is between 0.1 to 1.5, and wherein, the BI value is between 0.15 to 1.25 preferable, and is better between 0.25 to 1.0.
The branch of alkyl branch or slight branch alkene can be connected on any carbon of aliphatic olefin hydrocarbon chain in the molecule, may be by methyl, ethyl, propyl group or similar alkyl, or above-mentioned mixture.The alkene functional group of slight branch of the present invention alkene can be terminal (or α), vinylidene or inside (internal) form, or contains R
1R
2-C=C-R
3R
4The mixture of functionality.
Wherein, alleged " terminal/alpha-olefin " is meant coincidence formula R
1-CH=CH
2(R
2, R
3, R
4=H) alkene.
Alleged " vinylidene " is meant coincidence formula R
1R
2-C=CH
2(R
3, R
4=H) alkene.
Alleged " inner alkene " is meant coincidence formula R
1R
2-C=CR
3R
4The alkene of (at least one aliphatics, non-hydrogen group is connected on the alkene functional group).
With regard to the NOACK volatility, during the synthetic base oil that contains the slight DAB of branch of the present invention was formed, total carbon number must surpass C
26, but with C
28Better, and concentration surpasses 90%.Wherein, the chain length of alkyl group side chain is required to be C at least
10, or C
11More than preferable, make the NOACK volatility be no more than 13%.When the chain length of alkyl group side chain is long more, can make the synthetic base oil that contains the slight DAB of branch of the present invention have high viscosity index (HVI) more.
The preparation method of slight branch alkene, comprise: generate by dehydrating alkanes, or according to United States Patent (USP) 4,855,527 disclosed methods, carrying out the alkane/olefin isomerization by structure selectivity catalyzer such as ZSM-5 and ZSM-23 makes, or make by the described alkylation process of Figure 1A to Fig. 1 D, being included in the solid acid Alkanizing catalyst exists down, carry out isomerization and subsequently or alkylation simultaneously make, or make slight branch alkene reach desired branch's characteristic with other known technology preparation.
In addition, when using alkylation process to prepare synthetic base oil of the present invention to form, be used for the solid catalyst of alkylation process, can select similar catalyzer such as clay, amorphism silica or zeolite for use, but be not that finger only is limited to above-mentioned catalyzer.
According to the above, the characteristic that contains the synthetic base oil of the slight DAB of branch of the present invention, meet or surmount heavy alkide and the disclosed product of other aforementioned techniques every key property that is beyond one's reach, comprise high viscosity index (HVI), low volatility, excellent cold property, and excellent thermostability and oxidative stability.These dominances make the synthetic base oil that contains the slight DAB of branch of the present invention can be used as senior synthetic lubricating base oil and use, or use all suitable as base oil, second base oil or additive separately.
The synthetic base oil that contains the slight DAB of branch of the present invention, can further pass through hydrogen treatment, clay adsorption treatment or known technology processes and improves its color and external appearance characteristic, and can will get rid of as remaining impurities such as moisture content or catalyzer etc., making the fluid that is more suitable for hypersensitivity and key application, or make the insulation/cable liquid and the refrigeration oil that need have utmost point excellent electric character.
The synthetic base oil that contains the slight DAB of branch of the present invention also can improve or promotes performance by adding in the market such as antioxidant the normal additive that uses, with the demand of the specified property of satisfying the demand.
Following table 1 listed embodiment and comparative example further illustrated the excellent specific property that contains the synthetic base oil of the slight DAB of branch of the present invention, but category of the present invention is not to be only limited in the embodiment.Wherein, to be to use benzene and slight branch alkene be raw material to embodiment 1 to implementing 4, and (mordenite) be alkylation catalyst with mordenite, make benzene and slight branch's olefine reaction after, make slight branch double alkylation produce product.
Table 1
| Numbering | Make product | Solid acid catalyst/alkene (Olefin) source |
| Embodiment 1 | C 12Base DAB | Mordenite (Mordenite)/IV |
| Embodiment 2 | C 12Base DAB | Mordenite /IV |
| Comparative example 1 | C 12 | Mordenite /M |
| Comparative example 2 | C 12 | Mordenite/1: 1C 10(S)/C 14(M) |
| Comparative example 3 | C 12 | Referring to United States Patent (USP) 6,491,809 |
| Embodiment 3 | C 14Base DAB | Mordenite/M |
| Embodiment 4 | C 14Base DAB | Mordenite /IV |
| Comparative example 4 | C 14 | Mordenite/M |
| Comparative example 5 | C 12/C 14/C 16 | Mordenite/1: 1: 1C 14(M)/C 12(S)/C 16(S) |
| Comparative example 6 | The heavy alkide | Hydrofluoric acid/three polybutene |
| Comparative example 7 | The heavy alkide | Hydrofluoric acid/tetrapropylene |
| Comparative example 8 | 4 cSt PAO | -- |
| Comparative example 9 | 6 cSt PAO | -- |
| Comparative example 10 | The GIII mineral base oil | -- |
| Comparative example 11 | The GII mineral base oil | -- |
Annotate: " IV " representative source is Innovene company in the hurdle, alkene (Olefin) source
" M " representative source is Mitsubishi
Chemical company
" S " representative source is Shell company
With benzene (Benzene) and dodecylene (C
12, originating is Innovene company, it consists of 85% alpha-olefin and 11%C
12Prop up chain type and vinylidene alkene) be material, in the presence of the solid acid catalyst of 80% mordenite (mordenite) and 20% aluminum oxide (alumina), (weight hourly space velocity) is WHSV=2h in weight hourly space velocity
-1And reactor inlet temperature is to react under 210 ℃ the condition to make reaction mixture, removes in the distillation mode and isolates C after single alkylbenzene in the reaction mixture is lower than 0.5wt%
12Base DAB, and use nucleus magnetic resonance (NMR) and other analytical procedure that it is qualitative, analytical results is shown in table 2 and table 4.
Wherein,
With benzene and dodecylene (C
12, originating is Innovene company, it consists of 85% alpha-olefin and 11%C
12Chain type and vinylidene alkene) be material, except that reactor inlet temperature is 190 ℃, react according to step/process conditions of embodiment 1, after the reaction with C
12Base DAB separates, and with the qualitative method of embodiment 1 employing that it is qualitative, and analytical results is as shown in table 2.
With tetradecene (C
14, originating is Mitsubishi Chemical company) and be material, the isomerization C that after the zeolite catalyst isomerization, obtains consisting of 4% alpha-olefin and surpass 75% chain type and vinylidene alkene
14Alkene.Again with benzene and the isomerization C that has made
14Alkene is material, except that reactor inlet temperature is 200 ℃, react according to step/process conditions of embodiment 1, after the reaction with C
14Base DAB separates, and with the qualitative method of embodiment 1 employing that it is qualitative, and analytical results is shown in table 3 and table 4.
With benzene and tetradecene (C
14, originating is Innovene company, it consists of 74% alpha-olefin and 18%C
14Chain type and vinylidene alkene) be material, except that reactor inlet temperature is 220 ℃, react according to step/process conditions of embodiment 1, after the reaction with C
14Base DAB separates, and with the qualitative method of embodiment 1 employing that it is qualitative, and analytical results is as shown in table 3.
Comparative example 1
With benzene and tetradecene (C
14The source is Mitsubishi Chemical company, it consists of 95% alpha-olefin and 3% chain type and vinylidene alkene) be material, except that reactor inlet temperature is 190 ℃, step/process conditions according to embodiment 1 is reacted, after the reaction alkide DAB is separated, and with the qualitative method of embodiment 1 employing that it is qualitative, and analytical results is as shown in table 2.
Comparative example 2
With benzene and ratio 1: 1 ten carbene (C
10, originating is Shell company, it consists of 95% alpha-olefin and 3% chain type and vinylidene alkene) and tetradecene (C
14The source is Mitsubishi Chemical company, it consists of 95% alpha-olefin and 3% chain type and vinylidene alkene) be material, except that reactor inlet temperature is 170 ℃, step/process conditions according to embodiment 1 is reacted, after the reaction alkide DAB is separated, and with the qualitative method of embodiment 1 employing that it is qualitative, and analytical results is as shown in table 2.
Comparative example 3
With reference to the content of above-mentioned United States Patent (USP) 6,491,809, be material with benzene and pure alpha-olefin, reaction makes alkide DAB in the presence of mordenite, and with the qualitative method of embodiment 1 employing that it is qualitative, and analytical results is as shown in table 2.
Comparative example 4
With benzene and tetradecene (C
14The source is Mitsubishi Chemical company, it consists of 94% alpha-olefin and 4% chain type and vinylidene alkene) be material, except that reactor inlet temperature is 180 ℃, step/process conditions according to embodiment 1 is reacted, after the reaction alkide DAB is separated, and with the qualitative method of embodiment 1 employing that it is qualitative, and analytical results is as shown in table 3.
Comparative example 5
With benzene and ratio 1: 1: 1 tetradecene (C
14, originating is Mitsubishi Chemical company, it consists of 95% alpha-olefin and 5% chain type and vinylidene alkene), dodecylene (C
12, originating is Shell company, it consists of 95% alpha-olefin and 5% chain type and vinylidene alkene) and cetene (C
16The source is Shell company, it consists of 95% alpha-olefin and 5% chain type and vinylidene alkene) be material, except that reactor inlet temperature is 200 ℃, step/process conditions according to embodiment 1 is reacted, after the reaction alkide DAB is separated, and with the qualitative method of embodiment 1 employing that it is qualitative, and analytical results is as shown in table 3.
In order to illustrate that alkene has the importance of slight branch degree, again with embodiment 1 and 3 further with commercialization DAB, the PAO of comparative example 6-11 and mineral oil relatively, result such as table 4.
Comparative example 6 and 7
With benzene and three polybutene (BT, comparative example 6) or tetrapropylene (PT, comparative example 7) is raw material, use hydrofluoric acid to be catalyzer, after reacting under the commercialization processing procedure, the monoalkyl alkide is isolated heavy alkide product together with removing between the intermediate of DAB and monoalkyl alkide, and with the qualitative method of embodiment 1 employing that it is qualitative, and analytical results is as shown in table 4.
Comparative example 8-11
Selected commercialization sample P AO 4 ucon oils (comparative example 8), PAO 6 ucon oils (comparative example 9), GIII mineral base oil (comparative example 10) or GII mineral base oil (comparative example 12) are relatively.Wherein, the composition and the catalyzer of sample are listed in table 1, and branch's characteristic, viscosity characteristics and the performance data of process conditions, alkene/alkyl group side chain are listed in table 4.
Table 2
| Embodiment and | Embodiment | 1 | |
Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Process conditions and branch's characteristic | ||||||
| Catalyzer | Mordenite | Mordenite | Mordenite | Mordenite | Mordenite | |
| The pan feeding temperature, ℃ | 210 | 190 | 190 | 170 | |
| Alpha-olefin, min | 85％ | 85％ | 95％ | 95％ | 100％ |
| Branched-chain alkene | 11％ | 11％ | 3％ | 3％ | |
| TMN (1) | 2.36 | 2.21 | 2.09 | 2.03 | 2.0 0 |
| BI(1) | 0.36 | 0.21 | 0.09 | 0.03 | |
| Viscosity transitivity data | |||||
| 40 ℃ of viscosity, cSt | 22.2 | 22.3 | 22.2 | 22.1 | 21.16 |
| VI | 123 | 127 | 131 | 132 | 130 |
| Yield point, ℃ | -59 | -53 | -41 | -22 | -9 |
| CCS，cp@-40℃ (2) | 7,000 | 14,000 | Freezing | Freezing | Not report |
| Structural analysis | |||||
| The ortho position | 9％ | 7％ | 7％ | 5％ | 5％ |
| Between the position | 40％ | 29％ | 27％ | 13％ | 5％ |
| Contraposition | 51％ | 65％ | 65％ | 82％ | 90％ |
| 2,2 linear isomers (3) | 12.0％ | 25.0％ | 40.0％ | 55.0％ | ＞50％ |
| Performance data | |||||
| NOACK(4) | 10％ | 9％ | 8.5％ | 8.3％ | Not report |
| Aniline point, ℃ (5) | 78 | 80 | 80 | 80 | Not report |
| (1) BI/TMN-is by C 13The nucleus magnetic resonance integration is determined | |||||
| (2) CCS: cold axle rotates simulation viscosity: ASTM D5293 | |||||
| (3) the gas chromatograph is measured | |||||
| (4)NOACK：ASTM D5800B | |||||
| (5) aniline point: ASTM D611 | |||||
Table 3
| | Embodiment | 3 | |
Comparative example 4 | Comparative example 5 |
| Process conditions and branch's characteristic | |||||
| Catalyzer | Mordenite | Mordenite | Mordenite | Mordenite | |
| The pan feeding temperature, ℃ | 200 | 220 | 180 | 200 | |
| Alpha-olefin, |
4％ | 74％ | 94％ | 95％ | |
| Prop up chain type and vinylidene alkene | 75％ | 18％ | 4％ | 5％ | |
| TMN (1) | 2.65 | 2.5 | 2.07 | 2.12 | |
| BI (1) | 0.65 | 0.5 | 0.07 | 0.12 | |
| Viscosity transitivity data | |||||
| 40 ℃ of viscosity, cSt | 34.9 | 29.8 | 29.4 | 29.9 | |
| VI | 125 | 126 | 149 | 147 | |
| Yield point, ℃ (ASTM D5950) | -58 | -40 | 0 | -22 | |
| CCS，cp@-40℃ | 17,000 | 14,500 | Freezing | Freezing | |
| Structural analysis | |||||
| The ortho position | 7％ | 9％ | 6％ | 7％ | |
| Between the position | 23％ | 38％ | 19％ | 21％ | |
| Contraposition | 69％ | 52％ | 75％ | 72％ | |
| 2,2 linear isomers (2) | 1.6％ | 7.4％ | 41.9％ | 35％ | |
| Performance data | |||||
| NOACK(3) | 6.3％ | 7.6％ | 3.8％ | 3.6％ | |
| (1) BI/TMN-is by C 13The nucleus magnetic resonance integration is determined | |||||
| (2) gas chromatograph is measured | |||||
| (3)NOACK：ASTM D5800B |
Table 4. compares with the characteristic of commercialization DAB, PAO and mineral base oil product
| | Embodiment | 1 | |
Comparative example 6 | Comparative example 7 | Comparative example 8 | Comparative example 9 | Comparative example 10 | Comparative example 11 |
| Form | C12 DAB | C14 DAB | BT heavy alkide | PT | PAO | 4 | |
GIII | GII |
| TMN | 2.36 | 2.65 | ～4 | ～5 | |||||
| 40 ℃ of viscosity of ISO viscosity grade, cSt VI yield point, ℃ NOACK (1) aniline point, ℃ (2) | 22 22.2 123 -59 9％ 78 | 32 34.9 125 -58 4％ 87 | 46 48.7 20 -43 ＞30％ 71 | 46-68 53.7 4 -35 ＞30％ 67 | 15-22 17 124 -73 13％ 118 | 32 30 135 -61 7％ 125 | 22 19 127 -18 14％ 120 | 22 20.4 102 -14 26％ 115 | |
| (1) NOACK volatility: ASTM D5800B (2) aniline point: ASTM D611 | |||||||||
According to the result of table 1-3, the viscosity index of embodiment 1-4 is respectively 123,127,125 and 126; Upper pour point is respectively-59 ℃ ,-53 ℃ ,-58 ℃ and-40 ℃; The Selby-NOACK volatility is respectively 10%, 9%, 6.3% and 7.6%; And cold axle rotation simulation viscosity (CCS) is respectively 7,000cp, 14,000cp, 17,000cp and 14,500cp under-40 ℃.Wherein, CCS be the test lubricant at low temperatures transmitting capacity and make engine start the index of ability smoothly.
So, embodiment 1-2 and the 3-4 explanation synthetic base oil that contains the slight DAB of branch of the present invention meets high viscosity index (HVI), low NOACK volatility, excellent cold property, excellent thermostability and the characteristic of oxidative stability, the minimal viscosity index is 120, upper pour point is-40 ℃, the NOACK volatility is no more than 13%, below-40 ℃, cold axle rotates simulation viscosity (CCS) and is not higher than 20,000cp.
Comparative example 1-3 uses mordenite and commercial C
12Straight chain formula alpha-olefin (but comparative example 3 uses pure alpha-olefin), make prepared DAB have the carbon of high-load alkyl bond-2 position linearity (2-linear) isomer and have high viscosity index (HVI), but the cold axle under-40 ℃ rotates simulation viscosity (CCS), and good cold property can't be provided.
Same situation, the cold axle of comparative example 4-5 under-40 ℃ rotates simulation viscosity (CCS), and good cold property can't be provided.
In addition, comparative result according to the process conditions of showing 2-3, branch's characteristic, viscosity transitivity, the present invention is by increasing the branch's characteristic and the processing procedure pan feeding temperature of alkene charging, can produce the DAB that has the high viscosity index and have better CCS character under-40 ℃ under high yield.This effect has broken through the blind spot of known technology, because the branch of known alkyl group side chain can reduce the reactivity of alkene at the solid acid alkylating processing procedure in known technology, and can make synthetic base oil reduce viscosity index significantly.
Secondly, according to the results of structural analysis of table 2-3, when temperature increase, a position DAB isomer can increase, and this is that the product of thermodynamics preference is theoretical consistent with a position isomer, still between a DAB isomer there is no major contribution for the improvement of cold property.Yet the carbon of contraposition isomer and alkyl bond-2 position linearity (2-linear) isomer is the source that is considered to high viscosity index (HVI) in known technology, but when significantly reducing, does not but influence or reduce the viscometric properties of of the present invention pair of alkylbenzene composition significantly.
For further confirming the ramose influence, under lesser temps (200 ℃), carry out alkylated reaction with isomerise linear olefinic hydrocarbons in advance according to implementing 3, learn except that can making prepared DAB tool desirable viscosity index also have better cold property (yield point is by-40 ℃ to-58 ℃).And, reduce the generation that temperature of reaction can be improved the problem of catalyst aging and reduce side reaction.
Analyze comparative example 5 from table 3 again, comparative example 5 uses the linear alpha-olefin mixture to prepare DAB, but thisly be usually used in improveing and the technology of optimizing synthetic base oil characteristic, only can on some degree, improve yield point, but can't provide improvement for the cold axle rotation simulation viscosity (CCS) under-40 ℃.
According to the result of table 4, embodiment 1 (C
12Base DAB) with embodiment 3 (C
14Base DAB) accords with or surpasses the key property of PAO and GIII/GII hydrocracking product, comprise high viscosity index (HVI), low volatility, excellent cold property, and additive solvability (determining), make it be suitable as senior synthetic base oil by aniline point.
And commercialization DAB, the PAO of comparative example 6-11 and mineral base oil product have low/unacceptable volatility, compare with the DAB of the present invention's preparation, and its viscosity index is nothing like.
Cooperate the branch of TMN shown in Figure 2 and BI to concern, further specify alkene branch characteristic/category of embodiment 1-4 and comparative example 1-7 again with table 5.Wherein, the two alkylbenzenes that contain the alkyl group side chain of higher carbon number obviously provide higher viscosity index.High TMN value of the present invention (2.5-2.6) C
14The C of base DAB and low TMN value (2.1-2.4)
12Viscosity index (VI) value of base DAB is more or less the same.Higher TMN value is considered to higher alkyl group side chain branch.In addition, can reach in the present invention describes desired branch degree by the alkene that mixes different B I group can be understood.
Alkene branch characteristic/category of table 5. embodiment 1-4 and comparative example 1-7
| TMN | BI | Known embodiment | Example |
| 2 | 0 | Linear alpha-alkene | BI＜0.1; Comparative example 1-5 |
| 3 | 1 | Hexene hydrocarbon dipolymer | 0.1＜BI＜1; Embodiment 1-4 |
| 4 | 2 | Butylene hydrocarbon trimer | Comparative example 6 |
| 5 | 3 | Propylene hydrocarbon tetramer | Comparative example 7 |
Claims (14)
1, a kind of synthetic base oil is characterized in that, contain the two alkyl aromatic compounds of slight branch during it is formed, and the alkyl group side chain carbon number range of described pair of alkyl aromatic compound is by C
10To C
28, branch's characteristic of this alkyl group side chain wherein is by C
13Total methyl number (TMN) that NMR (Nuclear Magnetic Resonance) spectrum is determined be greater than 2.1 less than 3.5 or branch's index (BI) be less than 1.5 greater than 0.1.
2, synthetic base oil as claimed in claim 1, wherein, the content of described pair of alkyl aromatic compound is benchmark with described synthetic base oil gross weight, accounts for 85wt% at least.
3, synthetic base oil as claimed in claim 1, wherein, described pair of alkyl aromatic compound is the wherein a kind of of two alkylbenzenes, toluene, two phenoxide, diphenyl, anisole, naphthalene or methylnaphthalene compound.
4, synthetic base oil as claimed in claim 1, wherein, the alkyl group side chain carbon number range of described pair of alkyl aromatic compound is by C
11To C
24
5, synthetic base oil as claimed in claim 1, wherein, the alkyl group side chain carbon number range of described pair of alkyl aromatic compound is by C
12To C
18
6, synthetic base oil as claimed in claim 1, wherein, the TMN value of described pair of alkyl aromatic compound is 2.15 to 3.25, the BI value is 0.15 to 1.25.
7, synthetic base oil as claimed in claim 1, wherein, the TMN value of described pair of alkyl aromatic compound is 2.2 to 3.0, the BI value is 0.2 to 1.0.
8, synthetic base oil as claimed in claim 1, wherein, the minimal viscosity index of described synthetic base oil is 120, and upper pour point is-40 ℃, the Selby-NOACK volatility for be not higher than 13% and-40 ℃ of down cold axles rotate simulation viscosity (CCS) and be not higher than 20,000cp.
9, synthetic base oil as claimed in claim 1, wherein, described synthetic base oil further comprises straight chain formula or the synthetic alkide of a chain type.
10, synthetic base oil as claimed in claim 1, wherein, described synthetic base oil further comprises lubricating oil additive or is selected from poly-alpha olefins and/or the second class synthetic base oil of mineral base oil.
11, a kind of method for preparing synthetic base oil as claimed in claim 1, this method uses aromatics and slight ramose alkene to be raw material, in the presence of solid acid catalyst, make to make behind aromatics and the slight ramose olefine reaction by isomerization or alkylation process and contain the two alkyl aromatic compounds of slight branch, wherein, the alkene functional group of described alkene is straight chain formula, terminal form, vinylidene form, internal form, side chain form or its form of mixtures.
12, the preparation method of synthetic base oil as claimed in claim 11, wherein, employed solid acid catalyst is clay, noncrystalline silica or zeolite.
13, the preparation method of synthetic base oil as claimed in claim 11, wherein, described alkene makes by following steps:
A. isomerization alkane is produced isoalkane;
B. the isoalkane product dehydrogenation generation that contains with gained contains the monoolefine product;
C. the monoolefine product that contains of gained is removed diene by selective hydration, with the monoolefine of branch's characteristic conforms particular requirement of producing alkyl group side chain.
14, the preparation method of synthetic base oil as claimed in claim 11, wherein, described alkene is the monoolefine of branch's characteristic conforms particular requirement of the alkyl group side chain that makes by following wherein a kind of step:
(1) by the structure selectivity reaction alkene oligomerization is closed and/or isomerization;
(2) by carrying out the Fischer-Tropsch reaction; Or
(3) by mixing a straight chain formula and a chain type alkene.
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| US9868912B2 (en) | 2013-03-29 | 2018-01-16 | Jx Nippon Oil & Energy Corporation | Method for producing lubricant oil base oil |
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